The development of inexpensive electrode materials with a high volumetric capacity and long cycle-life is a central issue for large-scale lithium-ion batteries. Here, we report a nanostructured porous Fe2N anode fully encapsulated in carbon microboxes (Fe2N@C) prepared through a facile confined anion conversion from polymer coated Fe2O3 microcubes. The resulting carbon microboxes could not only protect the air-sensitive Fe2N from oxidation but also retain thin and stable SEI layer. The appropriate internal voids in the Fe2N cubes help to release the volume expansion during lithiation/delithiation processes, and Fe2N is kept inside the carbon microboxes without breaking the shell, resulting in a very low electrode volume expansion (the electrode thickness variation upon lithiation is ∼9%). Therefore, the Fe2N@C electrodes maintain high volumetric capacity (1030 mA h cm–3 based on the lithiation-state electrode volume) comparable to silicon anodes, stable cycling performance (a capacity retention of over 91% for 2500 cycles), and excellent rate performance. Kinetic analysis reveals that the Fe2N@C shows an enhanced contribution of capacitive charge mechanism and displays typical pseudocapacitive behavior. This work provides a new direction on designing and constructing nanostructured electrodes and protective layer for air unstable conversion materials for potential applications as a lithium-ion battery/capacitor electrode.Keywords: carbon encapsulation; conversion electrode; Fe2N; high volumetric capacity; Lithium-ion batteries; porous;

The solution synthesis of ternary metal oxides is difficult due to the competing hydrolysis of metal ions. There are reports of hydro-/solvothermal growth of nanoparticles, but one-dimensional (1D) nanoarrays are less common. Here, we report an alternative and general strategy to circumvent this challenge by converting the 1D binary metal oxide/hydroxide nanostructures initially grown driven by screw dislocations into ternary oxides. Using the α-GaOOH/α-Ga2O3/ZnGa2O4 wide bandgap transparent conductor materials as a demonstration, we synthesize vertical arrays of high aspect ratio α-GaOOH nanorods (NRs) on conducting substrates with controllable length for the first time using a continuous flow reactor and confirm their growth mechanism to be dislocation-driven. Then the α-GaOOH NR arrays can be converted into porous α-Ga2O3 NR arrays, which can be further converted via a solution method into porous ZnGa2O4 nanotube (NT) arrays due to the Kirkendall effect. This work presents a new and general strategy to prepare 1D nanostructure arrays of various binary and ternary oxides at low cost and large scale, and such facile solution growth and the unique structure of porous ZnGa2O4 NT arrays will facilitate their practical applications.

Metastable structural polymorphs can have superior properties and applications to their thermodynamically stable phases, but the rational synthesis of metastable phases is a challenge. Here, a new strategy for stabilizing metastable phases using surface functionalization is demonstrated using the example of formamidinium lead iodide (FAPbI3) perovskite, which is metastable at room temperature (RT) but holds great promises in solar and light-emitting applications. We show that, through surface ligand functionalization during direct solution growth at RT, pure FAPbI3 in the cubic perovskite phase can be stabilized in nanostructures and thin films at RT without cation or anion alloying. Surface characterizations reveal that long-chain alkyl or aromatic ammonium (LA) cations bind to the surface of perovskite structure. Calculations show that such functionalization reduces the surface energy and plays a dominant role in stabilizing the metastable perovskite phase. Excellent photophysics and optically pumped lasing from the stabilized single-crystal FAPbI3 nanoplates with low thresholds were demonstrated. High-performance solar cells can be fabricated with such directly synthesized stabilized phase-pure FAPbI3 with a lower bandgap. Our results offer new insights on the surface chemistry of perovskite materials and provide a new strategy for stabilizing metastable perovskites and metastable polymorphs of solid materials in general.Keywords: lead halide perovskites; Metastable polymorphs; nanolasers; perovskite photovoltaics; photophysics; surface functionalization;

We report novel two-dimensional lead halide perovskite structures templated by a unique conjugated aromatic dication, N,N-dimethylphenylene-p-diammonium (DPDA). The asymmetrically substituted primary and tertiary ammoniums in DPDA facilitate the formation of two-dimensional network (2DN) perovskite structures incorporating a conjugated dication between the PbX42– (X = Br, I) layers. These 2DN structures of (DPDA)PbI4 and (DPDA)PbBr4 were characterized by single-crystal X-ray diffraction, showing uniquely low distortions in the Pb–X–Pb bond angle for 2D perovskites. The Pb–I–Pb bond angle is very close to ideal (180°) for a 2DN lead iodide perovskite, which can be attributed to the ability of the rigid diammonium DPDA to insert into the PbX62– octahedral pockets. Optical characterization of (DPDA)PbI4 shows an excitonic absorption peak at 2.29 eV (541 nm), which is red-shifted in comparison to similar 2DN lead iodide structures. Temperature-dependent photoluminescence of both compounds reveals both a self-trapped exciton and free exciton emission feature. The reduced exciton absorption energy and emission properties are attributed to the dication-induced structural order of the inorganic PbX42– layers. DFT calculation results suggest mixing of the conjugated organic orbital component in the valence band of these 2DN perovskites. These results demonstrate a rational new strategy to incorporate conjugated organic dications into hybrid perovskites and will spur spectroscopic investigations of these compounds as well as optoelectronic applications.

Molybdenum disulfide (MoS2) is a two-dimensional material promising for electronic, optical, and catalytic applications. To fully harness its potential, functionalization is essential to controlling its properties. However, MoS2 functionalization has been mostly limited to either 1T-phase MoS2 or the edges of 2H-phase MoS2, and the chemistry of covalent functionalization on the basal plane of 2H-MoS2 is poorly understood. Here, we report a facile approach to covalently functionalize chemical vapor deposition (CVD) grown 2H-MoS2 monolayers (MLs), as well as mechanically exfoliated MoS2, via thiol conjugation at sulfur vacancies on the basal plane. Thorough characterization confirmed the functionalization by thiol molecules on MoS2 MLs, and we experimentally proved that sulfur vacancies in MoS2 MLs play a key role in the functionalization of basal planes. By the controlling of the amount of sulfur vacancies via sulfur annealing, the degree of MoS2 functionalization was effectively tuned. Because thiol conjugation partially repairs or passivates sulfur vacancies, enhanced photoluminescence response and decreased active sites for hydrogen evolution catalysis were observed for functionalized MoS2. Moreover, such functionalization can be utilized for making MoS2-based heterostructures, an example of which was demonstrated using a dithiol molecule to link MoS2 layers and PbSe quantum dots. These results provide new understanding and insights on the surface chemistry of MoS2 and open up more opportunities for MoS2 MLs with well-controlled properties and broader applications.Keywords: basal plane; ligand functionalization; monolayer; MoS2; sulfur vacancy;

Organic–inorganic hybrid perovskites attract considerable attention owing to their applications in high-efficiency solar cells and light emission. Compared with three-dimensional perovskites, two-dimensional (2D) layered hybrid perovskites have a higher exciton binding energy and potentially higher light-emission efficiency. The growth of high-quality crystalline 2D perovskites with a well-defined nanoscale morphology is desirable because they can be suitable building blocks for integrated optoelectronics and (nano)photonics. Herein, we report the facile solution growth of single-crystal microplates of 2D perovskites based on a 2-phenylethylammonium (C6H5CH2CH2NH3+, PEA) cation, (PEA)2PbX4 (X = Br, I), with a well-defined rectangular geometry and nanoscale thickness through a dissolution–recrystallization process. The crystal structures of (PEA)2PbX4 are first confirmed using single-crystal X-ray diffraction. A solution-phase transport-growth process is developed to grow microplates with a typical size of tens of micrometers and thickness of hundreds of nanometers on another clean substrate different from the substrate coated with lead-acetate precursor film. Surface-topography analysis suggests that the formation of the 2D microplates is likely driven by the wedding-cake growth mechanism. Through halide alloying, the photoluminescence emission of (PEA)2Pb(Br,I)4 perovskites with a narrow peak bandwidth is readily tuned from violet (~410 nm) to green (~530 nm).

AbstractSilicon is an extremely important technological material, but its current industrial production by the carbothermic reduction of SiO2 is energy intensive and generates CO2 emissions. Herein, we developed a more sustainable method to produce silicon nanowires (Si NWs) in bulk quantities through the direct electrochemical reduction of CaSiO3, an abundant and inexpensive Si source soluble in molten salts, at a low temperature of 650 °C by using low-melting-point ternary molten salts CaCl2–MgCl2–NaCl, which still retains high CaSiO3 solubility, and a supporting electrolyte of CaO, which facilitates the transport of O2− anions, drastically improves the reaction kinetics, and enables the electrolysis at low temperatures. The Si nanowire product can be used as high-capacity Li-ion battery anode materials with excellent cycling performance. This environmentally friendly strategy for the practical production of Si at lower temperatures can be applied to other molten salt systems and is also promising for waste glass and coal ash recycling.

With the intense interest in inorganic cesium lead halide perovskites and their nanostructures for optoelectronic applications, high-quality crystalline nanomaterials with controllable morphologies and growth directions are desirable. Here, we report a vapor-phase epitaxial growth of horizontal single-crystal CsPbX3 (X = Cl, Br, I) nanowires (NWs) and microwires (MWs) with controlled crystallographic orientations on the (001) plane of phlogopite and muscovite mica. Moreover, single NWs, Y-shaped branches, interconnected NW or MW networks with 6-fold symmetry, and, eventually, highly dense epitaxial network of CsPbBr3 with nearly continuous coverage were controllably obtained by varying the growth time. Detailed structural study revealed that the CsPbBr3 wires grow along the [001] directions and have the (100) facets exposed. The incommensurate heteroepitaxial lattice match between the CsPbBr3 and mica crystal structures and the growth mechanism of these horizontal wires due to asymmetric lattice mismatch were proposed. Furthermore, the photoluminescence waveguiding and good performance from the photodetector device fabricated with these CsPbBr3 networks demonstrated that these well-connected CsPbBr3 NWs could serve as straightforward platforms for fundamental studies and optoelectronic applications.Keywords: Cesium lead halide perovskites; nanowire networks; optoelectronic devices; vapor-phase epitaxial growth; waveguide;

MoSe2 is a promising earth-abundant electrocatalyst for the hydrogen-evolution reaction (HER), even though it has received much less attention among the layered dichalcogenide (MX2) materials than MoS2 so far. Here, a novel hydrothermal-synthesis strategy is presented to achieve simultaneous and synergistic modulation of crystal phase and disorder in partially crystallized 1T-MoSe2 nanosheets to dramatically enhance their HER catalytic activity. Careful structural characterization and defect characterization using positron annihilation lifetime spectroscopy correlated with electrochemical measurements show that the formation of the 1T phase under a large excess of the NaBH4 reductant during synthesis can effectively improve the intrinsic activity and conductivity, and the disordered structure from a lower reaction temperature can provide abundant unsaturated defects as active sites. Such synergistic effects lead to superior HER catalytic activity with an overpotential of 152 mV versus reversible hydrogen electrode (RHE) for the electrocatalytic current density of j = −10 mA cm−2, and a Tafel slope of 52 mV dec−1. This work paves a new pathway for improving the catalytic activity of MoSe2 and generally MX2-based electrocatalysts via a synergistic modulation strategy.

Magnetic skyrmions are topologically stable vortex-like spin structures that are promising for next generation information storage applications. Materials that host magnetic skyrmions, such as MnSi and FeGe with the noncentrosymmetric cubic B20 crystal structure, have been shown to stabilize skyrmions upon nanostructuring. Here, we report a chemical vapor deposition method to selectively grow nanowires (NWs) of cubic FeGe out of three possible FeGe polymorphs for the first time using finely ground particles of cubic FeGe as seeds. X-ray diffraction and transmission electron microscopy (TEM) confirm that these micron-length NWs with ∼100 nm to 1 μm diameters have the cubic B20 crystal structure. Although Fe13Ge8 NWs are also formed, the two types of NWs can be readily differentiated by their faceting. Lorentz TEM imaging of the cubic FeGe NWs reveals a skyrmion lattice phase under small applied magnetic fields (∼0.1 T) at 233 K, a skyrmion chain state at lower temperatures (95 K) and under high magnetic fields (∼0.4 T), and a larger skyrmion stability window than bulk FeGe. This synthetic approach to cubic FeGe NWs that support stabilized skyrmions opens a route toward the exploration of new skyrmion physics and devices based on similar nanostructures.Keywords: chemical vapor deposition; Cubic FeGe; Lorentz TEM; magnetic skyrmion; nanowires;

We investigate solution-grown single-crystal methylammonium lead iodide (MAPbI3) nanowires and nanoplates with spatially resolved photocurrent mapping. Sensitive perovskite photodetectors with Schottky contacts are fabricated by directly transferring the nanostructures on top of prepatterned gold electrodes. Scanning photocurrent microscopy (SPCM) measurements on these single-crystal nanostructures reveal a minority charge carrier diffusion length up to 21 μm, which is significantly longer than the values observed in polycrystalline MAPbI3 thin films. When the excitation energy is close to the bandgap, the photocurrent becomes substantially stronger at the edges of nanostructures, which can be understood by the enhancement of light coupling to the nanostructures. These perovskite nanostructures with long carrier diffusion lengths and strong photonic enhancement not only provide an excellent platform for studying their intrinsic properties but may also boost the performance of perovskite-based optoelectronic devices.Keywords: carrier diffusion length; Lead halide perovskite; nanostructures; photocurrent; photonics; scanning photocurrent microscopy;

The excellent intrinsic optoelectronic properties of methylammonium lead halide perovskites (MAPbX3, X = Br, I), such as high photoluminescence quantum efficiency, long carrier lifetime, and high gain coupled with the facile solution growth of nanowires make them promising new materials for ultralow-threshold nanowire lasers. However, their photo and thermal stabilities need to be improved for practical applications. Herein, we report a low-temperature solution growth of single crystal nanowires of formamidinium lead halide perovskites (FAPbX3) that feature red-shifted emission and better thermal stability compared to MAPbX3. We demonstrate optically pumped room-temperature near-infrared (∼820 nm) and green lasing (∼560 nm) from FAPbI3 (and MABr-stabilized FAPbI3) and FAPbBr3 nanowires with low lasing thresholds of several microjoules per square centimeter and high quality factors of about 1500–2300. More remarkably, the FAPbI3 and MABr-stabilized FAPbI3 nanowires display durable room-temperature lasing under ∼108 shots of sustained illumination of 402 nm pulsed laser excitation (150 fs, 250 kHz), substantially exceeding the stability of MAPbI3 (∼107 laser shots). We further demonstrate tunable nanowire lasers in wider wavelength region from FA-based lead halide perovskite alloys (FA,MA)PbI3 and (FA,MA)Pb(I,Br)3 through cation and anion substitutions. The results suggest that formamidinium lead halide perovskite nanostructures could be more promising and stable materials for the development of light-emitting diodes and continuous-wave lasers.

Metal fluorides and oxides can store multiple lithium ions through conversion chemistry to enable high-energy-density lithium-ion batteries. However, their practical applications have been hindered by an unusually large voltage hysteresis between charge and discharge voltage profiles and the consequent low-energy efficiency (<80%). The physical origins of such hysteresis are rarely studied and poorly understood. Here we employ in situ X-ray absorption spectroscopy, transmission electron microscopy, density functional theory calculations, and galvanostatic intermittent titration technique to first correlate the voltage profile of iron fluoride (FeF3), a representative conversion electrode material, with evolution and spatial distribution of intermediate phases in the electrode. The results reveal that, contrary to conventional belief, the phase evolution in the electrode is symmetrical during discharge and charge. However, the spatial evolution of the electrochemically active phases, which is controlled by reaction kinetics, is different. We further propose that the voltage hysteresis in the FeF3 electrode is kinetic in nature. It is the result of ohmic voltage drop, reaction overpotential, and different spatial distributions of electrochemically active phases (i.e., compositional inhomogeneity). Therefore, the large hysteresis can be expected to be mitigated by rational design and optimization of material microstructure and electrode architecture to improve the energy efficiency of lithium-ion batteries based on conversion chemistry.

Molybdenum disulfide (MoS2) is a promising nonprecious catalyst for the hydrogen evolution reaction (HER) that has been extensively studied due to its excellent performance, but the lack of understanding of the factors that impact its catalytic activity hinders further design and enhancement of MoS2-based electrocatalysts. Here, by using novel porous (holey) metallic 1T phase MoS2 nanosheets synthesized by a liquid-ammonia-assisted lithiation route, we systematically investigated the contributions of crystal structure (phase), edges, and sulfur vacancies (S-vacancies) to the catalytic activity toward HER from five representative MoS2 nanosheet samples, including 2H and 1T phase, porous 2H and 1T phase, and sulfur-compensated porous 2H phase. Superior HER catalytic activity was achieved in the porous 1T phase MoS2 nanosheets that have even more edges and S-vacancies than conventional 1T phase MoS2. A comparative study revealed that the phase serves as the key role in determining the HER performance, as 1T phase MoS2 always outperforms the corresponding 2H phase MoS2 samples, and that both edges and S-vacancies also contribute significantly to the catalytic activity in porous MoS2 samples. Then, using combined defect characterization techniques of electron spin resonance spectroscopy and positron annihilation lifetime spectroscopy to quantify the S-vacancies, the contributions of each factor were individually elucidated. This study presents new insights and opens up new avenues for designing electrocatalysts based on MoS2 or other layered materials with enhanced HER performance.

Here we report the synthesis and characterization of a family of photolabile nitroveratryl-based surfactants that form different types of supramolecular structures depending on the alkyl chain lengths ranging from 8 to 12 carbon atoms. By incorporating a photocleavable α-methyl-o-nitroveratryl moiety, the surfactants can be degraded, along with their corresponding supramolecular structures, by light irradiation in a controlled manner. The self-assembly of the amphiphilic surfactants was characterized by conductometry to determine the critical concentration for the formation of the supramolecular structures, transmission electron microscopy to determine the size and shape of the supramolecular structures, and dynamic light scattering (DLS) to determine the hydrodynamic diameter of the structures in aqueous solutions. The photodegradation of the surfactants and the supramolecular structures was confirmed using UV–vis spectroscopy, mass spectrometry, and DLS. This surfactant family could be potentially useful in drug delivery, organic synthesis, and other applications.

Organic–inorganic lead iodide perovskites are efficient materials for photovoltaics and light-emitting diodes. We report carrier decay dynamics of nanorods of mixed cation formamidinium and methylammonium lead iodide perovskites [HC(NH2)2]1–x[CH3NH3]xPbI3 (FA1–xMAxPbI3) synthesized through a simple solution method. The structure and FA/MA composition ratio of the single-crystal FA1–xMAxPbI3 nanorods are fully characterized, which shows that the mixed cation FA1–xMAxPbI3 nanorods are stabilized in the perovskite structure. The photoluminescence (PL) emission from FA1–xMAxPbI3 nanorods continuously shifts from 821 to 782 nm as the MA ratio (x) increases from 0 to 1 and is shown to be inhomogeneously broadened. Time-resolved PL from individual FA1–xMAxPbI3 nanorods demonstrates that lifetimes of mixed cation FA1–xMAxPbI3 nanorods are longer than those of the pure FAPbI3 or MAPbI3 nanorods, and the FA0.4MA0.6PbI3 displays the longest average PL lifetime of about 2 μs. These results suggest that mixed cation FA1–xMAxPbI3 perovskites are promising for high-efficiency photovoltaics and other optoelectronic applications.

The fascinating semiconducting and optical properties of monolayer and few-layer transition metal dichalcogenides, as exemplified by MoS2, have made them promising candidates for optoelectronic applications. Controllable growth of heterostructures based on these layered materials is critical for their successful device applications. Here, we report a direct low temperature chemical vapor deposition (CVD) synthesis of MoS2 monolayer/multilayer vertical heterostructures with layer-controlled growth on a variety of layered materials (SnS2, TaS2, and graphene) via van der Waals epitaxy. Through precise control of the partial pressures of the MoCl5 and elemental sulfur precursors, reaction temperatures, and careful tracking of the ambient humidity, we have successfully and reproducibly grown MoS2 vertical heterostructures from 1 to 6 layers over a large area. The monolayer MoS2 heterostructure was verified using cross-sectional high resolution transmission electron microscopy (HRTEM) while Raman and photoluminescence spectroscopy confirmed the layer-controlled MoS2 growth and heterostructure electronic interactions. Raman, photoluminescence, and energy dispersive X-ray spectroscopy (EDS) mappings verified the uniform coverage of the MoS2 layers. This reaction provides an ideal method for the scalable layer-controlled growth of transition metal dichalcogenide heterostructures via van der Waals epitaxy for a variety of optoelectronic applications.Keywords: chemical vapor deposition; graphene; heterostructures; molybdenum disulfide; SnS2; TaS2; van der Waals epitaxy

Violet electroluminescence is rare in both inorganic and organic light-emitting diodes (LEDs). Low-cost and room-temperature solution-processed lead halide perovskites with high-efficiency and color-tunable photoluminescence are promising for LEDs. Here, we report room-temperature color-pure violet LEDs based on a two-dimensional lead halide perovskite material, namely, 2-phenylethylammonium (C6H5CH2CH2NH3+, PEA) lead bromide [(PEA)2PbBr4]. The natural quantum confinement of two-dimensional layered perovskite (PEA)2PbBr4 allows for photoluminescence of shorter wavelength (410 nm) than its three-dimensional counterpart. By converting as-deposited polycrystalline thin films to micrometer-sized (PEA)2PbBr4 nanoplates using solvent vapor annealing, we successfully integrated this layered perovskite material into LEDs and achieved efficient room-temperature violet electroluminescence at 410 nm with a narrow bandwidth. This conversion to nanoplates significantly enhanced the crystallinity and photophysical properties of the (PEA)2PbBr4 samples and the external quantum efficiency of the violet LED. The solvent vapor annealing method reported herein can be generally applied to other perovskite materials to increase their grain size and, ultimately, improve the performance of optoelectronic devices based on perovskite materials.Keywords: layered perovskite; nanoplate; solvent vapor annealing; violet-light-emitting diode (LED)

Lead halide perovskite nanowires (NWs) are emerging as a class of inexpensive semiconductors with broad bandgap tunability for optoelectronics, such as tunable NW lasers. Despite exciting progress, the current organic–inorganic hybrid perovskite NW lasers suffer from limited tunable wavelength range and poor material stability. Herein, we report facile solution growth of single-crystal NWs of inorganic perovskite CsPbX3 (X = Br, Cl) and their alloys [CsPb(Br,Cl)3] and a low-temperature vapor-phase halide exchange method to convert CsPbBr3 NWs into perovskite phase CsPb(Br,I)3 alloys and metastable CsPbI3 with well-preserved perovskite crystal lattice and NW morphology. These single crystalline NWs with smooth end facets and subwavelength dimensions are ideal Fabry–Perot cavities for NW lasers. Optically pumped tunable lasing across the entire visible spectrum (420–710 nm) is demonstrated at room temperature from these NWs with low lasing thresholds and high-quality factors. Such highly efficient lasing similar to what can be achieved with organic–inorganic hybrid perovskites indicates that organic cation is not essential for light emission application from these lead halide perovskite materials. Furthermore, the CsPbBr3 NW lasers show stable lasing emission with no measurable degradation after at least 8 h or 7.2 × 109 laser shots under continuous illumination, which are substantially more robust than their organic–inorganic counterparts. The Cs-based perovskites offer a stable material platform for tunable NW lasers and other nanoscale optoelectronic devices.Keywords: cesium lead halide perovskites; nanowires; photostability; tunable lasers; vapor-phase halide exchange

We report amorphous MoSxCly as a high-performance electrocatalyst for both electrochemical and photoelectrochemical hydrogen generation. This novel ternary electrocatalyst is synthesized via chemical vapour deposition at temperatures lower than those typically used to grow crystalline MoS2 nanostructures and structurally characterized. The MoSxCly electrocatalysts exhibit stable and high catalytic activity toward the hydrogen evolution reaction, as evidenced by large cathodic current densities at low overpotentials and low Tafel slopes (ca. 50 mV decade−1). The electrocatalytic performance can be further enhanced through depositing MoSxCly on conducting vertical graphenes. Furthermore, MoSxCly can be directly deposited on p-type silicon photocathodes to enable efficient photoelectrochemical hydrogen evolution.

We report the controlled synthesis of NiCo layered double hydroxide (LDH) nanoplates using a newly developed high temperature high pressure hydrothermal continuous flow reactor (HCFR), which enables direct growth onto conductive substrates in high yield and, most importantly, better control of the precursor supersaturation and, thus, nanostructure morphology and size. The solution coordination chemistry of metal–ammonia complexes was utilized to synthesize well-defined NiCo LDH nanoplates directly in a single step without topochemical oxidation. The as-grown NiCo LDH nanoplates exhibit a high catalytic activity toward the oxygen evolution reaction (OER). By chemically exfoliating LDH nanoplates to thinner nanosheets, the catalytic activity can be further enhanced to yield an electrocatalytic current density of 10 mA cm–2 at an overpotential of 367 mV and a Tafel slope of 40 mV dec–1. Such enhancement could be due to the increased surface area and more exposed active sites. X-ray photoelectron spectroscopy (XPS) suggests the exfoliation also caused some changes in electronic structure. This work presents general strategies to controllably grow nanostructures of LDH and ternary oxide/hydroxides in general and to enhance the electrocatalytic performance of layered nanostructures by exfoliation.

Layered double hydroxides (LDHs) are a family of two-dimensional (2D) materials with layered crystal structures that have found many applications. Common strategies to synthesize LDHs lead to a wide variety of morphologies, from discrete 2D nanosheets to nanoflowers. Here, we report a study of carefully controlled LDH nanoplate syntheses using zinc aluminum (ZnAl) and cobalt aluminum (CoAl) LDHs as examples and reveal their crystal growth to be driven by screw dislocations. By controlling and maintaining a low precursor supersaturation using a continuous flow reactor, individual LDH nanoplates with well-defined morphologies were synthesized on alumina-coated substrates, instead of the nanoflowers that result from uncontrolled overgrowth. The dislocation-driven growth was further established for LDH nanoplates directly synthesized using the respective metal salt precursors. Atomic force microscopy revealed screw dislocation growth spirals, and under transmission electron microscopy, thin CoAl LDH nanoplates displayed complex contrast contours indicative of strong lattice strain caused by dislocations. These results suggest the dislocation-driven mechanism is generally responsible for the growth of 2D LDH nanostructures, and likely other materials with layered crystal structures, which could help the rational synthesis of well-defined 2D nanomaterials with improved properties.

Using dynamic cantilever magnetometry we measure an enhanced skyrmion lattice phase extending from around 29 K down to at least 0.4 K in single MnSi nanowires (NWs). Although recent experiments on two-dimensional thin films show that reduced dimensionality stabilizes the skyrmion phase, our results are surprising given that the NW dimensions are much larger than the skyrmion lattice constant. Furthermore, the stability of the phase depends on the orientation of the NWs with respect to the applied magnetic field, suggesting that an effective magnetic anisotropy, likely due to the large surface-to-volume ratio of these nanostructures, is responsible for the stabilization. The compatibility of our technique with nanometer-scale samples paves the way for future studies on the effect of confinement and surfaces on magnetic skyrmions.

Nickel–iron oxides/hydroxides are among the most active electrocatalysts for the oxygen evolution reaction. In an effort to gain insight into the role of Fe in these catalysts, we have performed operando Mössbauer spectroscopic studies of a 3:1 Ni:Fe layered hydroxide and a hydrous Fe oxide electrocatalyst. The catalysts were prepared by a hydrothermal precipitation method that enabled catalyst growth directly on carbon paper electrodes. Fe4+ species were detected in the NiFe hydroxide catalyst during steady-state water oxidation, accounting for up to 21% of the total Fe. In contrast, no Fe4+ was detected in the Fe oxide catalyst. The observed Fe4+ species are not kinetically competent to serve as the active site in water oxidation; however, their presence has important implications for the role of Fe in NiFe oxide electrocatalysts.

Analysis of protein phosphorylation remains a significant challenge due to the low abundance of phosphoproteins and the low stoichiometry of phosphorylation, which requires effective enrichment of phosphoproteins. Here we have developed superparamagnetic nanoparticles (NPs) whose surface is functionalized by multivalent ligand molecules that specifically bind to the phosphate groups on any phosphoproteins. These NPs enrich phosphoproteins from complex cell and tissue lysates with high specificity as confirmed by SDS-PAGE analysis with a phosphoprotein-specific stain and mass spectrometry analysis of the enriched phosphoproteins. This method enables universal and effective capture, enrichment, and detection of intact phosphoproteins toward a comprehensive analysis of the phosphoproteome.

Understanding crystal growth and improving material quality is important for improving semiconductors for electronic, optoelectronic, and photovoltaic applications. Amidst the surging interest in solar cells based on hybrid organic–inorganic lead halide perovskites and the exciting progress in device performance, improved understanding and better control of the crystal growth of these perovskites could further boost their optoelectronic and photovoltaic performance. Here, we report new insights on the crystal growth of the perovskite materials, especially crystalline nanostructures. Specifically, single crystal nanowires, nanorods, and nanoplates of methylammonium lead halide perovskites (CH3NH3PbI3 and CH3NH3PbBr3) are successfully grown via a dissolution-recrystallization pathway in a solution synthesis from lead iodide (or lead acetate) films coated on substrates. These single crystal nanostructures display strong room-temperature photoluminescence and long carrier lifetime. We also report that a solid–liquid interfacial conversion reaction can create a highly crystalline, nanostructured MAPbI3 film with micrometer grain size and high surface coverage that enables photovoltaic devices with a power conversion efficiency of 10.6%. These results suggest that single-crystal perovskite nanostructures provide improved photophysical properties that are important for fundamental studies and future applications in nanoscale optoelectronic and photonic devices.

The study of efficient, robust, and earth-abundant electrocatalysts for the hydrogen evolution reaction (HER) is essential for hydrogen-based energy technologies. Previous works have demonstrated that pyrite-structure materials (e.g., CoS2, NiSe2) are efficient HER catalysts. Here, we first systematically investigate the nanostructure synthesis of a series of pyrite-phase nickel phosphoselenide materials—NiP2, Se-doped NiP2 (NiP1.93Se0.07), P-doped NiSe2 (NiP0.09Se1.91), and NiSe2—through a facile thermal conversion of Ni(OH)2 nanoflakes. The similar nanostructures enable a systematic and fair comparison of their structural properties and catalytic activities for HER. We found that NiP1.93Se0.07 shows the best HER performance, followed by NiP2, NiP0.09Se1.91, and NiSe2. Se-doped NiP2 grown on carbon fiber paper can achieve an electrocatalytic current density of 10 mA cm–2 at an overpotential as low as 84 mV and a small Tafel slope of 41 mV decade–1. This study not only estabilishes Se-doped NiP2 as a competitive HER catalyst, but also demonstrates that doping or alloying of developed catalysts (especially doping with anions from another group; e.g., selenium to phosphorus) can improve the HER catalytic activity, which provides a general strategy to improve catalytic efficiencies of existing electrocatalysts for HER.Keywords: doping; electrocatalysis; hydrogen evolution reaction (HER); nickel diphosphide (NiP2); nickel diselenide (NiSe2); pyrite phase

Resurgent interest in iron pyrite (FeS2) as an earth-abundant, nontoxic semiconductor for solar applications has resulted in many attempts to grow phase-pure thin films via chemical vapor deposition (CVD). However, all thin films grown via CVD or sulfidation to date have contained marcasite phase or other iron sulfide impurities. Here, we report the use of metallic cobalt pyrite (cattierite, CoS2) thin films as an ideal substrate leading to the first direct growth of phase-pure iron pyrite thin films via atmospheric pressure CVD. This synthesis was achieved by reacting FeCl3 and ditert butyl disulfide (TBDS) at 400–450 °C. The products were confirmed as phase-pure iron pyrite using X-ray diffraction (XRD), Raman spectroscopy, and energy dispersive X-ray spectroscopy (EDS). In addition to phase-purity, the synthesis produced crystal domains >1 μm and a conformal coating 3–5 μm thick, which are attributed to the <2% lattice mismatch of the isostructural cattierite substrate. The surface was characterized by ultraviolet and X-ray photoelectron spectroscopy (UPS & XPS) and the electrical properties by electrochemical impedance spectroscopy (EIS) and Mott–Schottky analysis. The direct growth of a phase-pure iron pyrite film on a conductive substrate provides the most convenient configuration so far for potential solar cells.

Porous materials are of particular interest due to their high surface area and rich edge sites, which are favorable for applications such as catalysis. Although there are well-established strategies for synthesizing porous metal oxides (e.g., by annealing the corresponding metal hydroxides), facile and scalable routes to porous metal hydroxides and metal chalcogenides are lacking. Here, we report a simple and general strategy to synthesize porous nanosheets of metal hydroxides by selectively etching layered double hydroxide (LDH) nanoplate precursors that contain amphoteric metal and to further convert them into porous metal chalcogenides by a solution method. Using NiGa LDH as an example, we show that the thin nanoplates with high surface accessibility facilitate the topotactic conversion of NiGa LDH to β-Ni(OH)2 and further to NiSe2 with porous texture while preserving the sheet-like morphology. The converted β-Ni(OH)2 and NiSe2 are highly active for electrocatalytic oxygen evolution reaction and hydrogen evolution reaction (HER), respectively, which demonstrates the applications of such high surface area porous nanostructures with rich edge sites. Particularly, the porous NiSe2 nanosheets exhibited excellent catalytic activity toward HER with low onset overpotential, small Tafel slope, and good stability under both acidic and alkaline conditions. Overall electrochemical water splitting experiments using these porous β-Ni(OH)2 and NiSe2 nanosheets were further demonstrated. Our work presents a new strategy to prepare porous nanomaterials and to further enhance their catalytic and other applications.

In order to utilize nanostructured materials for potential solar and other energy-harvesting applications, scalable synthetic techniques for these materials must be developed. Herein we use a vapor phase conversion approach to synthesize nanowire (NW) arrays of semiconducting barium silicide (BaSi2) in high yield for the first time for potential solar applications. Dense arrays of silicon NWs obtained by metal-assisted chemical etching were converted to single-crystalline BaSi2 NW arrays by reacting with Ba vapor at about 930 °C. Structural characterization by X-ray diffraction and high-resolution transmission electron microscopy confirm that the converted NWs are single-crystalline BaSi2. The optimal conversion reaction conditions allow the phase-pure synthesis of BaSi2 NWs that maintain the original NW morphology, and tuning the reaction parameters led to a controllable synthesis of BaSi2 films on silicon substrates. The optical bandgap and electrochemical measurements of these BaSi2 NWs reveal a bandgap and carrier concentrations comparable to previously reported values for BaSi2 thin films.

We report metallic WS2 nanosheets that display excellent catalytic activity for hydrogen evolution reaction (HER) that is the best reported for MX2 materials. They are chemically exfoliated from WS2 nanostructures synthesized by chemical vapour deposition, including by using a simple and fast microwave-assisted intercalation method. Structural and electrochemical studies confirm that the simultaneous conversion and exfoliation of semiconducting 2H-WS2 into nanosheets of its metallic 1T polymorph result in facile electrode kinetics, excellent electrical transport, and proliferation of catalytically active sites.

Electrocatalysis plays a key role in the energy conversion processes central to several renewable energy technologies that have been developed to lessen our reliance on fossil fuels. However, the best electrocatalysts for these processes—which include the hydrogen evolution reaction (HER), the oxygen reduction reaction (ORR), and the redox reactions that enable regenerative liquid-junction photoelectrochemical solar cells—often contain scarce and expensive noble metals, substantially limiting the potential for these technologies to compete with fossil fuels. The considerable challenge is to develop robust electrocatalysts composed exclusively of low-cost, earth-abundant elements that exhibit activity comparable to that of the noble metals. In this review, we summarize recent progress in the development of such high-performance earth-abundant inorganic electrocatalysts (and nanostructures thereof), classifying these materials based on their elemental constituents. We then detail the most critical obstacles facing earth-abundant inorganic electrocatalysts and discuss various strategies for further improving their performance. Lastly, we offer our perspectives on the current directions of earth-abundant inorganic electrocatalyst development and suggest pathways toward achieving performance competitive with their noble metal-containing counterparts.

We report a facile chemical vapor deposition (CVD) growth of vertical heterostructures of layered metal dichalcogenides (MX2) enabled by van der Waals epitaxy. Few layers of MoS2, WS2, and WSe2 were grown uniformly onto microplates of SnS2 under mild CVD reaction conditions (<500 °C) and the heteroepitaxy between them was confirmed using cross-sectional transmission electron microscopy (TEM) and unequivocally characterized by resolving the large-area Moiré patterns that appeared on the basal planes of microplates in conventional TEM (nonsectioned). Additional photoluminescence peaks were observed in heterostructures of MoS2–SnS2, which can be understood with electronic structure calculations to likely result from electronic coupling and charge separation between MoS2 and SnS2 layers. This work opens up the exploration of large-area heterostructures of diverse MX2 nanomaterials as the material platform for electronic structure engineering of atomically thin two-dimensional (2D) semiconducting heterostructures and device applications.

Topologically stable magnetic skyrmions realized in B20 metal silicide or germanide compounds with helimagnetic order are very promising for magnetic memory and logic devices. However, these applications are hindered because the skyrmions only survive in a small temperature-field (T–H) pocket near the critical temperature Tc in bulk materials. Here we demonstrate that the skyrmion state in helimagnetic MnSi nanowires with varied sizes from 400 to 250 nm can exist in a substantially extended T–H region. Magnetoresistance measurements under a moderate external magnetic field along the long axis of the nanowires (H∥) show transitions corresponding to the skyrmion state from Tc ∼32 K down to at least 3 K, the lowest temperature in our measurement. When the field is applied perpendicular to the wire axis (H⊥), the skyrmion state was not resolvable using the magnetoresistance measurements. Our analysis suggests that the shape-induced uniaxial anisotropy might be responsible for the stabilization of skyrmion state observed in nanowires.

Understanding semiconductor surface states is critical for their applications, but fully characterizing surface electrical properties is challenging. Such a challenge is especially crippling for semiconducting iron pyrite (FeS2), whose potential for solar energy conversion has been suggested to be held back by rich surface states. Here, by taking advantage of the high surface-to-bulk ratio in nanostructures and effective electrolyte gating, we develop a general method to fully characterize both the surface inversion and bulk electrical transport properties for the first time through electrolyte-gated Hall measurements of pyrite nanoplate devices. Our study shows that pyrite is n-type in the bulk and p-type near the surface due to strong inversion and yields the concentrations and mobilities of both bulk electrons and surface holes. Further, solutions of the Poisson equation reveal a high-density of surface holes accumulated in a 1.3 nm thick strong inversion layer and an upward band bending of 0.9–1.0 eV. This work presents a general methodology for using transport measurements of nanostructures to study both bulk and surface transport properties of semiconductors. It also suggests that high-density of surface states are present on surface of pyrite, which partially explains the universal p-type conductivity and lack of photovoltage in polycrystalline pyrite.

We report the preparation and characterization of highly efficient and robust photocathodes based on heterostructures of chemically exfoliated metallic 1T-MoS2 and planar p-type Si for solar-driven hydrogen production. Photocurrents up to 17.6 mA/cm2 at 0 V vs reversible hydrogen electrode were achieved under simulated 1 sun irradiation, and excellent stability was demonstrated over long-term operation. Electrochemical impedance spectroscopy revealed low charge-transfer resistances at the semiconductor/catalyst and catalyst/electrolyte interfaces, and surface photoresponse measurements also demonstrated slow carrier recombination dynamics and consequently efficient charge carrier separation, providing further evidence for the superior performance. Our results suggest that chemically exfoliated 1T-MoS2/Si heterostructures are promising earth-abundant alternatives to photocathodes based on noble metal catalysts for solar-driven hydrogen production.

Iron pyrite (FeS2) is considered a promising earth-abundant semiconductor for solar energy conversion with the potential to achieve terawatt-scale deployment. However, despite extensive efforts and progress, the solar conversion efficiency of iron pyrite remains below 3%, primarily due to a low open circuit voltage (VOC). Here we report a comprehensive investigation on {100}-faceted n-type iron pyrite single crystals to understand its puzzling low VOC. We utilized electrical transport, optical spectroscopy, surface photovoltage, photoelectrochemical measurements in aqueous and acetonitrile electrolytes, UV and X-ray photoelectron spectroscopy, and Kelvin force microscopy to characterize the bulk and surface defect states and their influence on the semiconducting properties and solar conversion efficiency of iron pyrite single crystals. These insights were used to develop a circuit model analysis for the electrochemical impedance spectroscopy that allowed a complete characterization of the bulk and surface defect states and the construction of a detailed energy band diagram for iron pyrite crystals. A holistic evaluation revealed that the high-density of intrinsic surface states cannot satisfactorily explain the low photovoltage; instead, the ionization of high-density bulk deep donor states, likely resulting from bulk sulfur vacancies, creates a nonconstant charge distribution and a very narrow surface space charge region that limits the total barrier height, thus satisfactorily explaining the limited photovoltage and poor photoconversion efficiency of iron pyrite single crystals. These findings lead to suggestions to improve single crystal pyrite and nanocrystalline or polycrystalline pyrite films for successful solar applications.

The development of efficient and robust earth-abundant electrocatalysts for the hydrogen evolution reaction (HER) is an ongoing challenge. We report metallic cobalt pyrite (cobalt disulfide, CoS2) as one such high-activity candidate material and demonstrate that its specific morphology—film, microwire, or nanowire, made available through controlled synthesis—plays a crucial role in determining its overall catalytic efficacy. The increase in effective electrode surface area that accompanies CoS2 micro- and nanostructuring substantially boosts its HER catalytic performance, with CoS2 nanowire electrodes achieving geometric current densities of −10 mA cm–2 at overpotentials as low as −145 mV vs the reversible hydrogen electrode. Moreover, micro- and nanostructuring of the CoS2 material has the synergistic effect of increasing its operational stability, cyclability, and maximum achievable rate of hydrogen generation by promoting the release of evolved gas bubbles from the electrode surface. The benefits of catalyst micro- and nanostructuring are further demonstrated by the increased electrocatalytic activity of CoS2 nanowire electrodes over planar film electrodes toward polysulfide and triiodide reduction, which suggests a straightforward way to improve the performance of quantum dot- and dye-sensitized solar cells, respectively. Extension of this micro- and nanostructuring strategy to other earth-abundant materials could similarly enable inexpensive electrocatalysts that lack the high intrinsic activity of the noble metals.

Semiconducting higher manganese silicides (HMS), with a nominal composition of MnSi1.73, are particularly promising thermoelectric materials because of their elemental abundance, nontoxicity, and reported ZT of around 0.4 at 800 K for undoped samples. However, embedded MnSi impurities naturally form during the melt growth of HMS materials. The influences of such naturally occurring MnSi impurities within bulk HMS have yet to be carefully studied. Herein, we report the synthesis of high-purity MnSi-free single crystals of HMS by chemical vapor transport and the thermoelectric properties of consolidated HMS samples prepared by spark plasma sintering (SPS). The high purity of the HMS crystals is verified by scanning and transmission electron microscopy, electron diffraction, and synchrotron high-resolution X-ray diffraction. Despite successfully growing high purity HMS single crystals, we find that MnSi will nevertheless precipitate from HMS after SPS processing. In-situ sychrotron high-resolution X-ray diffraction experiments show that HMS are unstable at high temperatures. Despite the precipitation of MnSi inclusions within the HMS materials, we show that samples prepared from undoped single crystals of HMS exhibit higher hole mobilities owing to their higher purity, resulting in an improved maximum ZT of 0.52 ± 0.08 at 750 K.

Iron pyrite is an earth-abundant and inexpensive material that has long been interesting for electrochemical energy storage and solar energy conversion. A large-scale conversion synthesis of phase-pure pyrite nanowires has been developed for the first time. Nano-pyrite cathodes exhibited high Li-storage capacity and excellent capacity retention in Li/pyrite batteries using a liquid electrolyte, which retained a discharge capacity of 350 mAh g−1 and a discharge energy density of 534 Wh kg−1 after 50 cycles at 0.1 C rate.

We report a novel synthesis of Ti5Si3 nanoparticles (NPs) via the magnesio-reduction of TiO2 NPs and SiO2 in eutectic LiCl–KCl molten salts at 700 °C. The Ti5Si3 particle size (∼25 nm) is confined to the nanoscale due to the partial dissolution of Mg and silica in the molten salts and a subsequent heterogeneous reduction on the surface of the TiO2 NPs.

Many materials have been explored as potential hydrogen evolution reaction (HER) electrocatalysts to generate clean hydrogen fuel via water electrolysis, but none so far compete with the highly efficient and stable (but cost prohibitive) noble metals. Similarly, noble metals often excel as electrocatalytic counter electrode materials in regenerative liquid-junction photoelectrochemical solar cells, such as quantum dot-sensitized solar cells (QDSSCs) that employ the sulfide/polysulfide redox electrolyte as the hole mediator. Here, we systematically investigate thin films of the earth-abundant pyrite-phase transition metal disulfides (FeS2, CoS2, NiS2, and their alloys) as promising alternative electrocatalysts for both the HER and polysulfide reduction. Their electrocatalytic activity toward the HER is correlated to their composition and morphology. The emergent trends in their performance suggest that cobalt plays an important role in facilitating the HER, with CoS2 exhibiting highest overall performance. Additionally, we demonstrate the high activity of the transition metal pyrites toward polysulfide reduction and highlight the particularly high intrinsic activity of NiS2, which could enable improved QDSSC performance. Furthermore, structural disorder introduced by alloying different transition metal pyrites could increase their areal density of active sites for catalysis, leading to enhanced performance.

Quantum dot nanoscale semiconductor heterostructures (QDHs) are a class of materials potentially useful for integration into solar energy conversion devices. However, realizing the potential of these heterostructured systems requires the ability to identify and synthesize heterostructures with suitably designed materials, controlled size and morphology of each component, and structural control over their shared interface. In this review, we will present the case for the utility and advantages of chemically synthesized QDHs for solar energy conversion, beginning with an overview of various methods of heterostructured material synthesis and a survey of heretofore reported materials systems. The fundamental charge transfer properties of the resulting materials combinations and their basic design principles will be outlined. Finally, we will discuss representative solar photovoltaic and photoelectrochemical devices employing QDHs (including quantum dot sensitized solar cells, or QDSSCs) and examine how QDH synthesis and design impacts their performance.

We report a facile approach to perform post-growth doping of hematite (α-Fe2O3) nanostructures by depositing titanium (Ti) precursor solution and subsequent annealing in air. Using hematite nanowire photoanodes on fluorine doped tin oxide (FTO) glass substrates as a model system, the doping conditions were carefully optimized and highly photoactive hematite photoanodes were prepared at a more practically acceptable temperature of 650–700 °C than the ≥800 °C commonly used in previous works. A combination of microstructural characterization, elemental analysis, photoelectrochemical (PEC) measurements, and electrochemical impedance spectroscopy (EIS) analysis were employed to confirm the distribution of Ti atoms in hematite nanostructures and the role of Ti dopants in enhancing the photocurrent of hematite photoanodes. It was found that the Ti-treatment increases the donor concentration of hematite by about 10 fold and facilitates majority carrier transport and collection, which may account for the performance enhancement. Moreover, EIS measurements under illumination and Mott–Schottky analysis clearly showed that Ti dopants interact with the surface trap states of hematite, suggesting that surface passivation may also contribute to the improved PEC performance. This facile post-growth doping method can be applied to other hematite nanostructures such as electrochemically deposited hematite films and expanded to other dopants such as zirconium (Zr).

Nanoscience and nanotechnology impact our lives in many ways, from electronic and photonic devices to biosensors. They also hold the promise of tackling the renewable energy challenges facing us. However, one limiting scientific challenge is the effective and efficient bottom-up synthesis of nanomaterials. We can approach this core challenge in nanoscience and nanotechnology from two perspectives: (a) how to controllably grow high-quality nanomaterials with desired dimensions, morphologies, and material compositions and (b) how to produce them in a large quantity at reasonable cost. Because many chemical and physical properties of nanomaterials are size- and shape-dependent, rational syntheses of nanomaterials to achieve desirable dimensionalities and morphologies are essential to exploit their utilities. In this Account, we show that the dislocation-driven growth mechanism, where screw dislocation defects provide self-perpetuating growth steps to enable the anisotropic growth of various nanomaterials at low supersaturation, can be a powerful and versatile synthetic method for a wide variety of nanomaterials.Despite significant progress in the last two decades, nanomaterial synthesis has often remained an “art”, and except for a few well-studied model systems, the growth mechanisms of many anisotropic nanostructures remain poorly understood. We strive to go beyond the empirical science (“cook-and-look”) and adopt a fundamental and mechanistic perspective to the anisotropic growth of nanomaterials by first understanding the kinetics of the crystal growth process. Since most functional nanomaterials are in single-crystal form, insights from the classical crystal growth theories are crucial. We pay attention to how screw dislocations impact the growth kinetics along different crystallographic directions and how the strain energy of defected crystals influences their equilibrium shapes. Furthermore, such inquiries are supported by detailed structural investigation to identify the evidence of dislocations. The dislocation-driven growth mechanism not only can unify the various explanations behind a wide variety of exotic nanoscale morphologies but also allows the rational design of catalyst-free solution-phase syntheses that could enable the scalable and low cost production of nanomaterials necessary for large scale applications, such as solar and thermoelectric energy conversions, energy storage, and nanocomposites.In this Account, we discuss the fundamental theories of the screw dislocation driven growth of various nanostructures including one-dimensional nanowires and nanotubes, two-dimensional nanoplates, and three-dimensional hierarchical tree-like nanostructures. We then introduce the transmission electron microscopy (TEM) techniques to structurally characterize the dislocation-driven nanomaterials for future searching and identifying purposes. We summarize the guidelines for rationally designing the dislocation-driven growth and discuss specific examples to illustrate how to implement the guidelines. By highlighting our recent discoveries in the last five years, we show that dislocation growth is a general and versatile mechanism that can be used to grow a variety of nanomaterials via distinct reaction chemistry and synthetic methods. These discoveries are complemented by selected examples of anisotropic crystal growth from other researchers. The fundamental investigation and development of dislocation-driven growth of nanomaterials will create a new dimension to the rational design and synthesis of increasingly complex nanomaterials.

We present a general methodology for measuring the Hall effect on nanostructures with one-dimensional (1D) nanowire morphology. Relying only on typical e-beam lithography, the methodology developed herein utilizes an angled electrode evaporation technique so that the nanowire itself is a shadow mask and an intimate sidewall contact can be formed for the Hall electrodes. A six-contact electrode scheme with offset transverse contacts is utilized that allows monitoring of both the longitudinal resistivity and the Hall resistivity which is extracted from the raw voltage from the transverse electrodes using an antisymmetrization procedure. Our method does not require the use of a highly engineered lithographic process to produce directly opposing Hall electrodes with a very small gap. Hall effect measurements on semiconducting iron pyrite (FeS2) nanowire devices are validated by comparing to Hall effect measurements in the conventional Hall geometry using FeS2 plate devices. This Hall effect measurement is further extended to MnSi nanowires, and the distinct anomalous Hall effect signature is identified for the first time in chiral magnetic MnSi nanowires, a significant step toward identifying the topological Hall effect due to skyrmions in chiral magnetic nanowires.

Promising catalytic activity from molybdenum disulfide (MoS2) in the hydrogen evolution reaction (HER) is attributed to active sites located along the edges of its two-dimensional layered crystal structure, but its performance is currently limited by the density and reactivity of active sites, poor electrical transport, and inefficient electrical contact to the catalyst. Here we report dramatically enhanced HER catalysis (an electrocatalytic current density of 10 mA/cm2 at a low overpotential of −187 mV vs RHE and a Tafel slope of 43 mV/decade) from metallic nanosheets of 1T-MoS2 chemically exfoliated via lithium intercalation from semiconducting 2H-MoS2 nanostructures grown directly on graphite. Structural characterization and electrochemical studies confirmed that the nanosheets of the metallic MoS2 polymorph exhibit facile electrode kinetics and low-loss electrical transport and possess a proliferated density of catalytic active sites. These distinct and previously unexploited features of 1T-MoS2 make these metallic nanosheets a highly competitive earth-abundant HER catalyst.

If nanostructured thermoelectric materials are to be used for future energy harvesting and power generation applications, scalable production of thermoelectric nanostructures must be developed. Herein we report a vapor phase conversion method to synthesize nanowire (NW) arrays of semiconducting higher manganese silicides (HMS, or MnSi1.75) for enhanced thermoelectric applications. Dense arrays of silicon NWs obtained by metal-assisted chemical etching were converted to single-crystalline HMS NW arrays with the original nanoscale morphology preserved by reacting with Mn vapor in a sealed stainless steel reactor at 950 °C. Structural characterization by X-ray and electron diffraction and high-resolution transmission electron microscopy confirm that the converted NWs are single-crystalline NWs of HMS phases such as Mn7Si12, Mn27Si47, and Mn39Si68. Investigations of the conversion process using in situ high resolution powder X-ray diffraction (HRPXRD) and mechanistic experiments reveal that the presence of excess Si substrate underneath the Si NWs, careful control of Mn precursor, and high reaction temperature are crucial to the selective formation of HMS phase. The electrical resistivity of these HMS NWs are similar to that of the bulk HMS.Keywords: higher manganese silicides; in situ XRD; nanowire arrays; silicides; thermoelectrics;

Metal-matrix nanocomposites (MMNCs) have great potential for a wide range of applications. To provide high performance, effective nanoparticle (NP) dispersion in the liquid and NP capture within the metal grains during solidification is essential. In this work, we present the novel synthesis and structural characterization of surface-clean titanium diboride (TiB2) NPs with an average particle size of 20 nm, by ultrasonic-assisted reduction of fluorotitanate and fluoroboride salts in molten aluminum. The high-intensity ultrasonic field restricts NP growth. Using a master nanocomposite approach, the as-prepared TiB2 NPs are effectively incorporated into A206 alloys during solidification processing because of their clean surface, showing partial capture and significant grain refinement.Keywords: dispersion; metal-matrix nanocomposites; TiB2 nanoparticles; ultrasonic processing; wettability;

We report the growth, structural, and electrical characterization of single-crystalline iron pyrite (FeS2) nanorods, nanobelts, and nanoplates synthesized via sulfidation reaction with iron dichloride (FeCl2) and iron dibromide (FeBr2). The as-synthesized products were confirmed to be single-crystal phase pure cubic iron pyrite using powder X-ray diffraction, Raman spectroscopy, and transmission electron microscopy. An intermediate reaction temperature of 425 °C or a high sulfur vapor pressure under high temperatures was found to be critical for the formation of phase pure pyrite. Field effect transport measurements showed that these pyrite nanostructures appear to behave as a moderately p-doped semiconductor with an average resistivity of 2.19 ± 1.21 Ω·cm, an improved hole mobility of 0.2 cm2 V–1 s–1, and a lower carrier concentration on the order of 1018–1019 cm–3 compared with previous reported pyrite nanowires. Temperature-dependent electrical transport measurements reveal Mott variable range hopping transport in the temperature range 40–220 K and transport via thermal activation of carriers with an activation energy of 100 meV above room temperature (300–400 K). Most importantly, the transport properties of the pyrite nanodevices do not change if highly pure (99.999%) precursors are utilized, suggesting that the electrical transport is dominated by intrinsic defects in pyrite. These single-crystal pyrite nanostructures are nice platforms to further study the carrier conduction mechanisms, semiconductor defect physics, and surface properties in depth, toward improving the physical properties of pyrite for efficient solar energy conversion.Keywords: iron pyrite; nanostructure; photoelectrochemistry; photovoltaics; semiconductor transport; solar energy conversion

We report a three-dimensional (3D) mesoscale heterostructure composed of one-dimensional (1D) nanowire (NW) arrays epitaxially grown on two-dimensional (2D) nanoplates. Specifically, three facile syntheses are developed to assemble vertical ZnO NWs on CuGaO2 (CGO) nanoplates in mild aqueous solution conditions. The key to the successful 3D mesoscale integration is the preferential nucleation and heteroepitaxial growth of ZnO NWs on the CGO nanoplates. Using transmission electron microscopy, heteroepitaxy was found between the basal planes of CGO nanoplates and ZnO NWs, which are their respective (001) crystallographic planes, by the observation of a hexagonal Moiré fringes pattern resulting from the slight mismatch between the c planes of ZnO and CGO. Careful analysis shows that this pattern can be described by a hexagonal supercell with a lattice parameter of almost exactly 11 and 12 times the a lattice constants for ZnO and CGO, respectively. The electrical properties of the individual CGO–ZnO mesoscale heterostructures were measured using a current-sensing atomic force microscopy setup to confirm the rectifying p–n diode behavior expected from the band alignment of p-type CGO and n-type ZnO wide band gap semiconductors. These 3D mesoscale heterostructures represent a new motif in nanoassembly for the integration of nanomaterials into functional devices with potential applications in electronics, photonics, and energy.Keywords: 3D heterostructure; diode; epitaxy; mesoscale; nanoplate; nanowire; ZnO

Stacking faults are an important class of crystal defects commonly observed in nanostructures of close packed crystal structures. They can bridge the transition between hexagonal wurtzite (WZ) and cubic zinc blende (ZB) phases, with the most known example represented by the “nanowire (NW) twinning superlattice”. Understanding the formation mechanisms of stacking faults is crucial to better control them and thus enhance the capability of tailoring physical properties of nanomaterials through defect engineering. Here we provide a different perspective to the formation of stacking faults associated with the screw dislocation-driven growth mechanism of nanomaterials. With the use of NWs of WZ aluminum nitride (AlN) grown by a high-temperature nitridation method as the model system, dislocation-driven growth was first confirmed by transmission electron microscopy (TEM). Meanwhile numerous stacking faults and associated partial dislocations were also observed and identified to be the Type I stacking faults and the Frank partial dislocations, respectively, using high-resolution TEM. In contrast, AlN NWs obtained by rapid quenching after growth displayed no stacking faults or partial dislocations; instead many of them had voids that were associated with the dislocation-driven growth. On the basis of these observations, we suggest a formation mechanism of stacking faults that originate from dislocation voids during the cooling process in the syntheses. Similar stacking fault features were also observed in other NWs with WZ structure, such as cadmium sulfide (CdS) and zinc oxide (ZnO).Keywords: AlN nanowire; dislocation-driven growth; partial dislocation; stacking fault; wurtzite; zinc blende

We report a cobalt pyrite (cobalt disulfide, CoS2) thin film on glass as a robust, high-performance, low-cost, earth-abundant counter electrode for liquid-junction quantum dot-sensitized solar cells (QDSSCs) that employ the aqueous sulfide/polysulfide (S2–/Sn2–) redox electrolyte as the hole-transporting medium. The metallic CoS2 thin film electrode is prepared via thermal sulfidation of a cobalt film deposited on glass and has been characterized by powder X-ray diffraction and electron microscopy. Using the CoS2 counter electrode, CdS/CdSe-sensitized QDSSCs display improved short-circuit photocurrent density and fill factor, achieving solar light-to-electricity conversion efficiencies as high as 4.16%, with an average efficiency improvement of 54 (±14)% over equivalent devices assembled with a traditional platinum counter electrode. Electrochemical measurements verify that CoS2 shows high electrocatalytic activity toward polysulfide reduction, rationalizing the improved QDSSC performance. CoS2 is also less susceptible to poisoning by the sulfide/polysulfide electrolyte, a problem that plagues platinum electrodes in this application; furthermore, CoS2 exhibits excellent stability in sulfide/polysulfide electrolyte, resulting in highly reproducible performance.Keywords: cobalt pyrite (CoS2); counter electrode; electrochemistry; photovoltaic solar energy conversion; quantum dot-sensitized solar cell (QDSSC); sulfide/polysulfide electrolyte;

The increasing demands from large-scale energy applications call for the development of lithium-ion battery (LIB) electrode materials with high energy density. Earth abundant conversion cathode material iron trifluoride (FeF3) has a high theoretical capacity (712 mAh g–1) and the potential to double the energy density of the current cathode material based on lithium cobalt oxide. Such promise has not been fulfilled due to the nonoptimal material properties and poor kinetics of the electrochemical conversion reactions. Here, we report for the first time a high-capacity LIB cathode that is based on networks of FeF3 nanowires (NWs) made via an inexpensive and scalable synthesis. The FeF3 NW cathode yielded a discharge capacity as high as 543 mAh g–1 at the first cycle and retained a capacity of 223 mAh g–1 after 50 cycles at room temperature under the current of 50 mA g–1. Moreover, high-resolution transmission electron microscopy revealed the existence of continuous networks of Fe in the lithiated FeF3 NWs after discharging, which is likely an important factor for the observed improved electrochemical performance. The loss of active material (FeF3) caused by the increasingly ineffective reconversion process during charging was found to be a major factor responsible for the capacity loss upon cycling. With the advantages of low cost, large quantity, and ease of processing, these FeF3 NWs are not only promising battery cathode materials but also provide a convenient platform for fundamental studies and further improving conversion cathodes in general.

Copper (Cu) nanowires (NWs) are inexpensive conducting nanomaterials intensively explored for transparent conducting electrodes and other applications. However, the mechanism for solution growth of Cu NWs remains elusive so far. Here we show that the one-dimensional anisotropic growth of Cu NWs and nanotubes (NTs) in solution is driven by axial screw dislocations. All three types of evidence for dislocation-driven growth have been conclusively observed using transmission electron microscopy (TEM) techniques: rigorous two-beam TEM analysis that conclusively characterizes the dislocations in the NWs to be pure screw dislocations along ⟨110⟩ direction, twist contour analysis that confirms the presence of Eshelby twist associated with the dislocation, and the observation of spontaneously formed hollow NTs. The reduction–oxidation (redox) electrochemical reaction forming the Cu NWs presents new chemistry for controlling supersaturation to promote dislocation-driven NW growth. Using this understanding to intentionally manipulate the supersaturation, we have further improved the NW growth by using a continuous flow reactor to yield longer Cu NWs under much milder chemical conditions. The rational synthesis of Cu NWs with control over size and geometry will facilitate their applications.

We report for the first time the facile solution growth of α-FeF3·3H2O nanowires (NWs) in large quantity at a low supersaturation level and their scalable conversion to porous semiconducting α-Fe2O3 (hematite) NWs of high aspect ratio via a simple thermal treatment in air. The structural characterization by transmission electron microscopy shows that thin α-FeF3·3H2O NWs (typically <100 nm in diameter) are converted to single-crystal α-Fe2O3 NWs with internal pores, while thick ones (typically >100 nm in diameter) become polycrystalline porous α-Fe2O3 NWs. We further demonstrated the photoelectrochemical (PEC) application of the nanostructured photoelectrodes prepared from these converted hematite NWs. The optimized photoelectrode with a ∼400 nm thick hematite NW film yielded a photocurrent density of 0.54 mA/cm2 at 1.23 V vs reversible hydrogen electrode potential after modification with cobalt catalyst under standard conditions (AM 1.5 G, 100 mW/cm2, pH = 13.6, 1 M NaOH). The low cost, large quantity, and high aspect ratio of the converted hematite NWs, together with the resulting simpler photoelectrode preparation, can be of great benefit for hematite-based PEC water splitting. Furthermore, the ease and scalability of the conversion from hydrated fluoride NWs to oxide NWs suggest a potentially versatile and low-cost strategy to make NWs of other useful iron-based compounds that may enable their large-scale renewable energy applications.

We report the growth and structural, electrical, and optical characterization of vertically oriented single-crystalline iron pyrite (FeS2) nanowires synthesized via thermal sulfidation of steel foil for the first time. The pyrite nanowires have diameters of 4–10 nm and lengths greater than 2 μm. Their crystal phase was identified as cubic iron pyrite using high-resolution transmission electron microscopy, Raman spectroscopy, and powder X-ray diffraction. Electrical transport measurements showed the pyrite nanowires to be highly p-doped, with an average resistivity of 0.18 ± 0.09 Ω cm and carrier concentrations on the order of 1021 cm–3. These pyrite nanowires could provide a platform to further study and improve the physical properties of pyrite nanostructures toward solar energy conversion.

We report for the first time the multi-gram scale solution growth of α-aluminium fluoride trihydrate (α-AlF3·3H2O) nanorods (NRs) under low supersaturation conditions, and their conversion to porous β-AlF3 NRs. Electron microscopy analysis shows that the NRs yielded from the optimized conditions have an average length of 1.9 μm and diameter of 223 nm. Nanoparticle morphology can also be achieved by tuning the supersaturation through several experimental parameters such as [Al3+] and [HF]/[Al3+] and H2O/2-propanol vol. ratio. Moderate thermal treatment of the as-synthesized α-AlF3·3H2O NRs in air atmosphere (5 h at 500 °C) results in pure β-AlF3 porous NRs, which may be useful as catalysts.

We report a green synthesis of Cu2O nanowires and nanotubes in aqueous solution by reducing Cu2+ to Cu+ with glucose or fructosevia Fehling's reaction. The screw dislocation-driven growth of Cu2O nanowires and nanotubes is confirmed by imaging the dislocation contrast, the Eshelby twist associated with dislocations and the spontaneously formed hollow nanotubes.

We report the synthesis of CdS and CdSe nanowires (NWs) and nanoribbons (NRs) with gold catalysts by H2-assisted chemical vapor deposition. Nanopods and nanocones were obtained without catalysts at higher system pressure. Transmission electron microscopy (TEM) studies, including two-beam TEM and displaced-aperture dark-field TEM characterization, were used to investigate the NW growth mechanism. Dislocation contrast and twist contours have been routinely observed within the synthesized one-dimensional (1D) CdS and CdSe NWs, suggesting the operation of the dislocation-driven NW growth mechanism under our experimental conditions. The Burgers vectors of dislocations and the associated Eshelby twists were measured and quantified. We hypothesize that gold nanoparticles provide nucleation sites to initiate the growth of CdS/CdSe NWs and lead to the formation of dislocations that continue to drive and sustain 1D growth at a low supersaturation level. Our study suggests that the dislocation-driven mechanism may also contribute to the growth of other 1D nanomaterials that are commonly considered to grow via the vapor–liquid–solid mechanism.Keywords: CdS; CdSe; chemical vapor deposition; dislocation-driven growth; Eshelby twist; nanowire

We present a novel method for synthesizing epitaxial quantum dot-nanowire (QD-NW) heterostructures using the example of colloidal PbSe QDs decorated on furnace-grown hematite (α-Fe2O3) NWs. The direct heterogeneous nucleation of QDs on Fe2O3 NWs relies upon an aggressive surface dehydration of the as-synthesized Fe2O3 NWs at 350 °C under vacuum and subsequent introduction of colloidal reactants resulting in direct growth of PbSe QDs on Fe2O3. The synthesis is tunable: the QD diameter distribution and density of QDs on the NWs increase with increased dehydration time, and QD diameters and size distributions decrease with decreased injection temperature of the colloidal synthesis. Transmission electron microscopy (TEM) structural analysis reveals direct heteroepitaxial heterojunctions where the matching faces can be PbSe (002) and Fe2O3 (003) with their respective [11̅0] crystallographic directions aligned. This can be a general approach for integrating colloidal and furnace synthetic techniques, thus broadening possible material combinations for future high-quality, epitaxial nanoscale heterostructures for solar applications.Keywords: colloidal quantum dots on nanostructures; Fe2O3 nanowires; heterojunction; heterostructure; PbSe quantum dots; solar conversion;

Nanostructured silicon is promising for high capacity anodes in lithium batteries. The specific capacity of silicon is an order of magnitude higher than that of conventional graphite anodes, but the large volume change of silicon during lithiation and delithiation and the resulting poor cyclability has prevented its commercial application. This challenge could potentially be overcome by silicon nanostructures that can provide facile strain relaxation to prevent electrode pulverization, maintain effective electrical contact, and have the additional benefits of short lithium diffusion distances and enhanced mass transport. In this review, we present an overview of rechargeable lithium batteries and the challenges and opportunities for silicon anodes, then survey the performance of various morphologies of nanostructured silicon (thin film, nanowires/nanotubes, nanoparticles, and mesoporous materials) and their nanocomposites. Other factors that affect the performance of nanostructured silicon anodes, including solvent composition, additives, binders, and substrates, are also examined. Finally, we summarize the key lessons from the successes so far and offer perspectives and future challenges to enable the applications of silicon nanoanodes in practical lithium batteries at large scale.

We report the dislocation-driven growth of two-dimensional (2D) nanoplates. They are another type of dislocation-driven nanostructure and could find application in energy storage, catalysis, and nanoelectronics. We first focus on nanoplates of zinc hydroxy sulfate (3Zn(OH)2·ZnSO4·0.5H2O) synthesized from aqueous solutions. Both powder X-ray and electron diffraction confirm the zinc hydroxy sulfate (ZHS) crystal structure as well as their conversion to zinc oxide (ZnO). Scanning electron, atomic force, and transmission electron microscopy reveal the presence of screw dislocations in the ZHS nanoplates. We further demonstrate the generality of this mechanism through the growth of 2D nanoplates of α-Co(OH)2, Ni(OH)2, and gold that can also follow the dislocation-driven growth mechanism. Finally, we propose a unified scheme general to any crystalline material that explains the growth of nanoplates as well as different dislocation-driven nanomaterial morphologies previously observed through consideration of the relative crystal growth step velocities at the dislocation core versus the outer edges of the growth spiral under various supersaturations.

We report a general method for determining the spin polarization from nanowire materials using Andreev reflection spectroscopy implemented with a Nb superconducting contact and common electron-beam lithography device fabrication techniques. This method was applied to magnetic semiconducting Fe1–xCoxSi alloy nanowires with x̅ = 0.23, and the average spin polarization extracted from 6 nanowire devices is 28 ± 7% with a highest observed value of 35%. Local-electrode atom probe tomography (APT) confirms the homogeneous distribution of Co atoms in the FeSi host lattice, and X-ray magnetic circular dichroism (XMCD) establishes that the elemental origin of magnetism in this strongly correlated electron system is due to Co atoms.

We report the rational synthesis of α-FeOOH (goethite) nanowires following a dislocation-driven mechanism by utilizing a continuous-flow reactor and chemical equilibria to maintain constant low supersaturations. The existence of axial screw dislocations and the associated Eshelby twist in the nanowire product were confirmed using bright-/dark-field transmission electron microscopy imaging and twist contour analysis. The α-FeOOH nanowires can be readily converted into semiconducting single-crystal but porous α-Fe2O3 (hematite) nanowires via topotactic transformation. Our results indicate that, with proper experimental design, many more useful materials can be grown in one-dimensional morphologies in aqueous solutions via the dislocation-driven mechanism.

The Mn–Si binary phase diagram contains seven distinct equilibrium phases; however, to date, only two phases have been reported in nanowire (NW) morphology. We report the simple reaction of Mn vapor with a Si substrate in a H2 atmosphere to lead to the formation of NW mixtures of MnSi and three new NW phases α-Mn5Si3, β-Mn5Si3, and β-Mn3Si, with the more Mn-rich phases formed at progressively higher temperatures from 800 to 940 °C identified using electron diffraction, together with other structural characterization techniques. Furthermore, the observation of β-Mn5Si3 NWs having the D8m W5Si3 structure type, which is a structure never observed in the Mn–Si system, represents the first report of Mn5Si3 polymorphism. The purposeful use of excess metal species and intentional limitation of vaporous Si species during NW synthesis has led to the first synthesis of manganese-rich silicide NWs.Keywords: magnetic nanomaterials; manganese silicides; nanowires; polymorphism;

Thermoelectric materials can be used for solid state power generation and heating/cooling applications. The figure of merit of thermoelectric materials, ZT, which determines their efficiency in a thermoelectric device, remains low for most conventional bulk materials. Nanoscale and nanostructured thermoelectric materials are promising for increasing ZT relative to the bulk. This review introduces the theory behind thermoelectric materials and details the predicted and demonstrated enhancements of ZT in nanoscale and nanostructured thermoelectric materials. We discuss thin films and superlattices, nanowires and nanotubes, and nanocomposites, providing a ZT comparison among various families of nanocomposite materials. We provide some perspectives regarding the origin of enhanced ZT in nanoscale and nanostructured materials and suggest some promising and fruitful research directions for achieving high ZT materials for practical applications.

We present the chemical vapor deposition (CVD) reactions of the single source precursor Fe(SiCl3)2(CO)4 over Si, Ge, CoSi2/Si, and CoSi/Si substrates to explore the growth and doping processes of silicide nanowires (NWs). Careful investigation of the composition and morphology of the NW products and the intruded silicide films from which they nucleate revealed that the group IV elements (Si, Ge) in the NW products originate from both the precursor and the substrate, while the metal elements incorporated into the NWs (Fe, Co) originate from vapor phase precursor delivery. The use of a Ge growth substrate enabled the successful synthesis of Fe5Si2Ge NWs, the first report of a metal silicide−germanide alloy NW. Further, investigation of the pyrolysis of the CoSiCl3(CO)4 precursor revealed independent delivery of Co and Si species during CVD reactions. This understanding enabled a new, more robust two-precursor synthetic route to Fe1−xCoxSi alloy NWs using Fe(SiCl3)2(CO)4 and CoCl2.Keywords: chemical vapor deposition; diffusion; germanide; nanowire; silicide; single source precursor

We report the synthesis, phase transformation, and electrical property measurement of single-crystal NiGe and ε-Ni5Ge3 nanowires (NWs). NiGe NWs were spontaneously synthesized by chemical vapor deposition of GeH4 onto a porous Ni substrate without the use of intentional catalysts. The as-grown NWs of the orthorhombic NiGe phase were transformed to the hexagonal ε-Ni5Ge3 phase by thermal annealing induced Ni enrichment. This controllable conversion of germanide phases is desirable for phase-dependent property study and applications, and the observation of novel metastable ε-Ni5Ge3 phase suggests the importance of kinetic factors in such nanophase transformations. Electrical studies reveal that NiGe NWs are highly conductive, with an average resistivity of 35 ± 15 μΩ·cm, while the resistivity of ε-Ni5Ge3 NWs is more than 4 times that of the NiGe phase. NWs of nickel germanides, particularly NiGe, would be useful building blocks for germanium-based nanoelectronic devices.Keywords: nanoelectronics; nanowire; nickel germanide; phase transformation; resistivity

We report an improved method to synthesize α-Fe2O3 (hematite) nanowires (NWs) via thermal oxidation that significantly reduces reaction time while improving NW density and uniformity. Stress introduced by shot-peening the starting steel foils and the relief of such stress seem to play an important role in promoting uniform one-dimensional growth. Water vapor is also shown to strongly influence both the density and the morphology of the grown nanostructures. Furthermore, although the as-grown NWs exhibit the high average resistivity (4 × 102 ± 4 × 102 Ω·m) associated with undoped hematite, chemical vapor deposition of silane coating these NWs, followed by an annealing step, produces silicon-doped α-Fe2O3 NWs that exhibit a significantly improved average resistivity of 4 × 10–3 ± 6 × 10–3 Ω·m. High-resolution electron microscopy, elemental mapping by EDS, and further study of their electrical properties attribute the increased conductivity to lattice doping. These doped hematite NW arrays are promising candidates for potential application as photoanodes in photoelectrochemical solar cells.

We report the synthesis, structural characterization, and magnetotransport of single-crystalline nanowires of manganese monosilicide, MnSi. Bulk MnSi has unusual magnetic orderings, helimagnetism, and skyrmions at ambient pressure, and high pressure studies have revealed partial magnetic ordering and non-Fermi liquid behavior. MnSi nanowires were synthesized using chemical vapor deposition of MnCl2 onto silicon substrates. The morphology, structure, and composition of these nanowires were analyzed using electron microscopy and X-ray spectroscopy. The low-temperature magnetoresistance characteristics of MnSi nanowires reveal the first signature of helimagnetism in one-dimensional nanomaterials.

In the current examples of dislocation-driven nanowire growth, the screw dislocations that propagate one-dimensional growth originate from spontaneously formed highly defective “seed” crystals. Here we intentionally utilize screw dislocations from defect-rich gallium nitride (GaN) thin films to propagate dislocation-driven growth, demonstrating epitaxial growth of zinc oxide (ZnO) nanowires directly from aqueous solution. Atomic force microscopy confirms screw dislocations are present on the native GaN surface and ZnO nanowires grow directly from dislocation etch pits of heavily etched GaN surfaces. Furthermore, transmission electron microscopy confirms the existence of axial dislocations. Eshelby twist in the resulting ZnO nanowires was confirmed using bright-/dark-field imaging and twist contour analysis. These results further confirm the connection between dislocation source and nanowire growth. This may eventually lead to defect engineering strategies for rationally designed catalyst-free dislocation-driven nanowire growth for specific applications.

EuS nanocrystals (NCs) were doped with Gd resulting in an enhancement of their magnetic properties. New EuS and GdS single source precursors (SSPs) were synthesized, characterized, and employed to synthesize Eu1−xGdxS NCs by decomposition in oleylamine and trioctylphosphine at 290 °C. The doped NCs were characterized using X-ray diffraction, transmission electron microscopy, and scanning transmission electron microscopy, which support the uniform distribution of Gd dopants through electron energy loss spectroscopy (EELS) mapping. X-ray absorption spectroscopy (XAS) revealed the dopant ions in Eu1−xGdxS NCs to be predominantly Gd3+. NCs with a variety of doping ratios of Gd (0 ≤ x < 1) were systematically studied using vibrating sample magnetometry and the observed magnetic properties were correlated with the Gd doping levels (x) as quantified with ICP-AES. Enhancement of the Curie temperature (TC) was observed for samples with low Gd concentrations (x ≤ 10%) with a maximum TC of 29.4 K observed for NCs containing 5.3% Gd. Overall, the observed TC, Weiss temperature (θ), and hysteretic behavior correspond directly to the doping level in Eu1−xGdxS NCs and the trends qualitatively follow those previously reported for bulk and thin film samples.

We have successfully synthesized mesoporous silica-germania mixed oxide (Si1−xGexO2) with x up to 0.31 by controlling the reaction to delay hydrolysis and condensation until the precursors have sufficiently ordered around the nonionic templating agent. Small-angle X-ray diffraction (SAXS) and transmission electron microscopy (TEM) reveal disordered worm-like mesopores for all germanium concentrations investigated, with pore periodicities of 9.8 and 10.5 nm for x ≈ 0.10 and 0.20 respectively. We confirm that the germanium and silicon are homogenous on the nanoscale using scanning transmission electron microscopy (STEM) with energy dispersive X-ray (EDX) mapping. Attempts to convert the mixed mesoporous oxides to mesoporous Si1−xGex alloys via magnesiothermic reduction resulted in phase segregation.

We report the synthesis of epitaxially-hyperbranched FeSi nanowires via chemical vapor transport using FeSi2 as the source material and I2 as the transport agent. Scanning electron microscopy reveals that the nanowires have diameters ranging from 25 to 1000 nm, depending on the morphology. Structural characterization using electron diffraction, energy dispersive spectroscopy, and powder X-ray diffraction reveal that these nanowires are single-crystalline cubic FeSi with growth in the <110> direction. X-Ray photoelectron spectroscopy shows that the thin, amorphous coating on these nanostructures is comprised primarily of silicon oxide. Interestingly, these FeSi nanowires exhibit merohedral twinning, an uncommon type of twinning in nanostructures that cannot be observed using electron diffraction, with the (001) twin plane parallel to the <110> growth direction. Such merohedral twinning should generally be expected for all B20 silicide nanowires. In addition to nanowires, other morphologies including nanocombs, nanoflowers, and micron-sized crystals are also observed during the synthesis at various temperature zones of the growth substrates.

Transition metal silicides represent an extremely broad set of refractory materials that are currently employed for many applications including CMOS devices, thin film coatings, bulk structural components, electrical heating elements, photovoltaics, and thermoelectrics. Many of these applications may be improved by making 1-dimensional nanomaterials. Chemical synthesis of silicide nanowires is more complicated compared to other classes of nanomaterials due to the complex phase behaviour between metals and silicon and the complex stoichiometries and structures of their resulting compounds. Recently, several synthetic strategies have been developed to overcome this challenge resulting in increasing reports of silicide nanowires in the literature. These strategies are highlighted in this feature article, along with future synthetic challenges and a review of the applications emerging from current silicide nanowires.

Mass spectrometry (MS)-based phosphoproteomics remains challenging due to the low abundance of phosphoproteins and substoichiometric phosphorylation. This demands better methods to effectively enrich phosphoproteins/peptides prior to MS analysis. We have previously communicated the first use of mesoporous zirconium dioxide (ZrO2) nanomaterials for effective phosphopeptide enrichment. Here, we present the full report including the synthesis, characterization, and application of mesoporous titanium dioxide (TiO2), ZrO2, and hafnium dioxide (HfO2) in phosphopeptide enrichment and MS analysis. Mesoporous ZrO2 and HfO2 are demonstrated to be superior to TiO2 for phosphopeptide enrichment from a complex mixture with high specificity (>99%), which could almost be considered as a “purification”, mainly because of the extremely large active surface area of mesoporous nanomaterials. A single enrichment and Fourier transform MS analysis of phosphopeptides digested from a complex mixture containing 7% of α-casein identified 21 out of 22 phosphorylation sites for α-casein. Moreover, the mesoporous ZrO2 and HfO2 can be reused after a simple solution regeneration procedure with comparable enrichment performance to that of fresh materials. Mesoporous ZrO2 and HfO2 nanomaterials hold great promise for applications in MS-based phosphoproteomics.

We discuss a nanowire and nanotube formation mechanism in which axial screw dislocations provide self-perpetuating steps to enable one-dimensional (1D) crystal growth, unlike previously understood vapor−liquid−solid (VLS) or analogous metal-catalyzed growth. We initially found this mechanism in hierarchical pine tree PbS nanowires with helically rotating branches. We further applied it to ZnO, demonstrating that screw dislocations can drive the spontaneous formation of nanotubes, and used classical crystal growth theory to confirm that their anisotropic 1D growth is driven by dislocations. Dislocation-driven growth should be general to many materials grown in vapor or solution and is underappreciated. It will create a new dimension in the rational synthesis of nanomaterials. The resulting complex hierarchical nanostructures can be useful for solar energy conversion, and our understanding will allow large-scale synthesis of 1D nanomaterials for practical applications.

Nanoscience and nanotechnology can provide many benefits to photovoltaic and photoelectrochemical applications by combining novel nanoscale properties with processability and low cost. Taking advantage of high quality, high efficiency, yet low cost nanomaterials could potentially provide the new and transformative approaches to enable the proposed generation-III solar technologies. Nanowires are interesting because they have a long axis to absorb incident sunlight yet with a short radial distance to separate the photogenerated carriers. In this perspective, we further suggest that more “complex” nanostructures, both in the form of hierarchically branching/hyperbranching nanowire structures and in the form of multi-component nanowire heterostructures of diverse materials, are potentially even more interesting for solar energy harvesting and conversion. The common bottom-up synthetic techniques to induce branching in nanowires to form hierarchical nanowire structures are reviewed. Several potential strategies for their incorporation into solar conversion devices are discussed and some fundamental issues and future directions are identified.

The basic characteristics of nanowire growth driven by screw dislocations were investigated by synthesizing hierarchical lead sulfide (PbS) nanowire “pine trees” using chemical vapor deposition of PbCl2 and S precursors and systematically observing the effects of various growth parameters, such as hydrogen flow, temperature, pressure, and the growth substrates employed. Statistical surveys showed that the growth rate of the dislocation-driven trunk is about 6 μm/min and that of the vapor-liquid-solid (VLS) driven branch nanowire is about 1.2 μm/min under the typical reaction conditions at 600 °C, 900 Torr, and a hydrogen flow rate of 1.5 sccm. The onset of hydrogen flow plus the presence of fresh silicon have been identified as the critical ingredients for generating PbS nanowire trees reproducibly. To explain the experimental findings in the context of classical crystal growth theory, the former is suggested to create a spike in supersaturation of the actual sulfur precursor H2S and initiate dislocations with screw components that then propagate anisotropically to form the PbS nanowire trunks. Maintaining suitable hydrogen flow provides a favorable low supersaturation that promotes dislocation-driven trunk nanowire growth and enables the simultaneous VLS nanowire growth of branches. Furthermore, thermodynamic consideration and experiments showed that silicon fortuitously controls the supersaturation by reversibly reacting with H2S to form SiS2 and that SiS2 can also be a viable precursor for PbS nanowire growth. The key requirements of screw dislocation-driven nanowire growth are summarized. This study provides some general guidelines for further nanowire growth driven by screw dislocations.

Growth of extensively aligned hierarchical lead sulfide (PbS) nanowires with hyperbranched morphology has been achieved by synthesizing nanowires epitaxially on single crystal NaCl, rutile TiO2 (001), and muscovite mica in a chemical vapor deposition process. The morphology of as-grown PbS nanowires has been examined using scanning electron microscopy. Epitaxial match with the (100) plane of PbS has been observed on all substrates, and epitaxial match with PbS (111) was also observed on mica. In addition, the preferred orientation of nanowires led to particularly strong (200) reflections from PbS in powder X-ray diffraction. The potential epitaxial relationship and lattice match are proposed and discussed. PbS nanowires of the pine tree morphology can only be formed non-epitaxially in the presence of epitaxial hyperbranched clusters. The difficulty of forming epitaxial nanowire pine trees suggested that epitaxial growth might not be conducive to the creation of dislocations that drive the formation of pine tree nanowires. Electrical properties of PbS nanowires have also been investigated.

This work represents the first use of mesoporous zirconium oxide nanomaterials for highly effective and selective enrichment of phosphorylated peptides.

Single-crystal nanorods of half-metallic chromium dioxide (CrO2) were synthesized and structurally characterized. Spin-dependent electrical transport was investigated in individual CrO2 nanorod devices contacted with nonmagnetic metallic electrodes. Negative magnetoresistance (MR) was observed at low temperatures due to the spin-dependent direct tunneling through the contact barrier and the high spin polarization in the half-metallic nanorods. The magnitude of this negative magnetoresistance decreases with increasing bias voltage and temperature due to spin-independent inelastic hopping through the barrier, and a small positive magnetoresistance was found at room temperature. It is believed that the contact barrier and the surface state of the nanorods have great influence on the spin-dependent transport limiting the magnitude of MR effect in this first attempt at spin filter devices of CrO2 nanorods with nonmagnetic contacts.

We report single-crystal nanowires of magnetic semiconducting Fe1−xCoxSi alloys synthesized using a two-component single source precursor approach. Extending our previous syntheses of FeSi and CoSi nanowires from Fe(SiCl3)2(CO)4 and Co(SiCl3)(CO)4 precursors, we found that a homogeneous solution formed upon mixing these two precursors due to melting point suppression. This liquid constitutes the single-source precursor suitable for delivery through chemical vapor deposition, which enables the chemical synthesis of Fe1−xCoxSi alloy nanowires on silicon substrates covered with a thin (1–2 nm) SiO2 layer. Using scanning and transmission electron microscopy and energy dispersive X-ray spectroscopy and mapping, we demonstrate two homogenously mixed alloy nanowire samples with very different Co substitution concentrations (x): 6 ± 5%, the ferromagnetic semiconductor regime, and 44 ± 5%, the helical magnetic regime. The magnetotransport properties of these alloy nanowires are pronouncedly different from that of the host structures FeSi and CoSi, as well as from one another, and consistent with the physical properties as expected for their corresponding compositions. These novel magnetic semiconducting silicide nanowires will be important building blocks for silicon-based spintronic nanodevices.

Inspired by nature's ability to fabricate supramolecular nanostructures from the bottom-up, materials scientists have become increasingly interested in the use of biomolecules like DNA, peptides, or proteins as templates for the creation of novel nanostructures and nanomaterials. Although the advantages of self-assembling biomolecular structures clearly lie in their chemical diversity, spatial control, and numerous geometric architectures, it is challenging to elaborate them into functional hybrid inorganic–bionanomaterials without rendering the biomolecular scaffold damaged or dysfunctional. In this study, attachment of gold nanoparticles to collagen-related self-assembling peptides at L-lysine residues incorporated within the peptide sequence and the N-terminus led to metal nanoparticle-decorated fibers. After electroless silver plating, these fibers were completely metallized, creating electrically conductive nanowires under mild conditions while leaving the peptide fiber core intact. This study demonstrates the bottom-up assembly of synthetic peptidic fibers under mild conditions and their potential as templates for other complex inorganic–organic hybrid nanostructures.

With recent literature demonstrating enhancement of the thermoelectric performance of nanoscale materials relative to their corresponding bulk materials, methods to synthesize low-dimensional nanomaterials in large scale at low cost are needed. We demonstrate a method for preparing nanostructured dimagnesium silicide (Mg2Si) thermoelectric materials that are nanocomposites with MgO by the reduction of diatomaceous earth (diatoms) using a gas-displacement solid state reaction with magnesium vapor. The resulting semiconducting Mg2Si preserves the general morphology of the original diatoms and their nanosized grains at least down to the size of 30 nm. This reaction represents a possible method for the production of large quantities of low-cost nanoscale thermoelectric materials with potential for enhanced thermoelectric performance.A nanostructured Mg2Si and MgO nanocomposite thermoelectric material is synthesized in the Mg gas-displacement solid state reduction of SiO2 from diatomaceous earth. The resulting semiconducting Mg2Si nanostructures preserve the original diatom morphology, with nanosized grains at least down to the size of 30 nm.

Inspired by nature's ability to fabricate supramolecular nanostructures from the bottom-up, materials scientists have become increasingly interested in the use of biomolecules like DNA, peptides, or proteins as templates for the creation of novel nanostructures and nanomaterials. Although the advantages of self-assembling biomolecular structures clearly lie in their chemical diversity, spatial control, and numerous geometric architectures, it is challenging to elaborate them into functional hybrid inorganic–bionanomaterials without rendering the biomolecular scaffold damaged or dysfunctional. In this study, attachment of gold nanoparticles to collagen-related self-assembling peptides at L-lysine residues incorporated within the peptide sequence and the N-terminus led to metal nanoparticle-decorated fibers. After electroless silver plating, these fibers were completely metallized, creating electrically conductive nanowires under mild conditions while leaving the peptide fiber core intact. This study demonstrates the bottom-up assembly of synthetic peptidic fibers under mild conditions and their potential as templates for other complex inorganic–organic hybrid nanostructures.

Growth of extensively aligned hierarchical lead sulfide (PbS) nanowires with hyperbranched morphology has been achieved by synthesizing nanowires epitaxially on single crystal NaCl, rutile TiO2 (001), and muscovite mica in a chemical vapor deposition process. The morphology of as-grown PbS nanowires has been examined using scanning electron microscopy. Epitaxial match with the (100) plane of PbS has been observed on all substrates, and epitaxial match with PbS (111) was also observed on mica. In addition, the preferred orientation of nanowires led to particularly strong (200) reflections from PbS in powder X-ray diffraction. The potential epitaxial relationship and lattice match are proposed and discussed. PbS nanowires of the pine tree morphology can only be formed non-epitaxially in the presence of epitaxial hyperbranched clusters. The difficulty of forming epitaxial nanowire pine trees suggested that epitaxial growth might not be conducive to the creation of dislocations that drive the formation of pine tree nanowires. Electrical properties of PbS nanowires have also been investigated.

We report the synthesis of epitaxially-hyperbranched FeSi nanowires via chemical vapor transport using FeSi2 as the source material and I2 as the transport agent. Scanning electron microscopy reveals that the nanowires have diameters ranging from 25 to 1000 nm, depending on the morphology. Structural characterization using electron diffraction, energy dispersive spectroscopy, and powder X-ray diffraction reveal that these nanowires are single-crystalline cubic FeSi with growth in the <110> direction. X-Ray photoelectron spectroscopy shows that the thin, amorphous coating on these nanostructures is comprised primarily of silicon oxide. Interestingly, these FeSi nanowires exhibit merohedral twinning, an uncommon type of twinning in nanostructures that cannot be observed using electron diffraction, with the (001) twin plane parallel to the <110> growth direction. Such merohedral twinning should generally be expected for all B20 silicide nanowires. In addition to nanowires, other morphologies including nanocombs, nanoflowers, and micron-sized crystals are also observed during the synthesis at various temperature zones of the growth substrates.

Transition metal silicides represent an extremely broad set of refractory materials that are currently employed for many applications including CMOS devices, thin film coatings, bulk structural components, electrical heating elements, photovoltaics, and thermoelectrics. Many of these applications may be improved by making 1-dimensional nanomaterials. Chemical synthesis of silicide nanowires is more complicated compared to other classes of nanomaterials due to the complex phase behaviour between metals and silicon and the complex stoichiometries and structures of their resulting compounds. Recently, several synthetic strategies have been developed to overcome this challenge resulting in increasing reports of silicide nanowires in the literature. These strategies are highlighted in this feature article, along with future synthetic challenges and a review of the applications emerging from current silicide nanowires.

We have successfully synthesized mesoporous silica-germania mixed oxide (Si1−xGexO2) with x up to 0.31 by controlling the reaction to delay hydrolysis and condensation until the precursors have sufficiently ordered around the nonionic templating agent. Small-angle X-ray diffraction (SAXS) and transmission electron microscopy (TEM) reveal disordered worm-like mesopores for all germanium concentrations investigated, with pore periodicities of 9.8 and 10.5 nm for x ≈ 0.10 and 0.20 respectively. We confirm that the germanium and silicon are homogenous on the nanoscale using scanning transmission electron microscopy (STEM) with energy dispersive X-ray (EDX) mapping. Attempts to convert the mixed mesoporous oxides to mesoporous Si1−xGex alloys via magnesiothermic reduction resulted in phase segregation.

We report for the first time the multi-gram scale solution growth of α-aluminium fluoride trihydrate (α-AlF3·3H2O) nanorods (NRs) under low supersaturation conditions, and their conversion to porous β-AlF3 NRs. Electron microscopy analysis shows that the NRs yielded from the optimized conditions have an average length of 1.9 μm and diameter of 223 nm. Nanoparticle morphology can also be achieved by tuning the supersaturation through several experimental parameters such as [Al3+] and [HF]/[Al3+] and H2O/2-propanol vol. ratio. Moderate thermal treatment of the as-synthesized α-AlF3·3H2O NRs in air atmosphere (5 h at 500 °C) results in pure β-AlF3 porous NRs, which may be useful as catalysts.

We report a green synthesis of Cu2O nanowires and nanotubes in aqueous solution by reducing Cu2+ to Cu+ with glucose or fructosevia Fehling's reaction. The screw dislocation-driven growth of Cu2O nanowires and nanotubes is confirmed by imaging the dislocation contrast, the Eshelby twist associated with dislocations and the spontaneously formed hollow nanotubes.

We report a novel synthesis of Ti5Si3 nanoparticles (NPs) via the magnesio-reduction of TiO2 NPs and SiO2 in eutectic LiCl–KCl molten salts at 700 °C. The Ti5Si3 particle size (∼25 nm) is confined to the nanoscale due to the partial dissolution of Mg and silica in the molten salts and a subsequent heterogeneous reduction on the surface of the TiO2 NPs.

This work represents the first use of mesoporous zirconium oxide nanomaterials for highly effective and selective enrichment of phosphorylated peptides.

Quantum dot nanoscale semiconductor heterostructures (QDHs) are a class of materials potentially useful for integration into solar energy conversion devices. However, realizing the potential of these heterostructured systems requires the ability to identify and synthesize heterostructures with suitably designed materials, controlled size and morphology of each component, and structural control over their shared interface. In this review, we will present the case for the utility and advantages of chemically synthesized QDHs for solar energy conversion, beginning with an overview of various methods of heterostructured material synthesis and a survey of heretofore reported materials systems. The fundamental charge transfer properties of the resulting materials combinations and their basic design principles will be outlined. Finally, we will discuss representative solar photovoltaic and photoelectrochemical devices employing QDHs (including quantum dot sensitized solar cells, or QDSSCs) and examine how QDH synthesis and design impacts their performance.

Thermoelectric materials can be used for solid state power generation and heating/cooling applications. The figure of merit of thermoelectric materials, ZT, which determines their efficiency in a thermoelectric device, remains low for most conventional bulk materials. Nanoscale and nanostructured thermoelectric materials are promising for increasing ZT relative to the bulk. This review introduces the theory behind thermoelectric materials and details the predicted and demonstrated enhancements of ZT in nanoscale and nanostructured thermoelectric materials. We discuss thin films and superlattices, nanowires and nanotubes, and nanocomposites, providing a ZT comparison among various families of nanocomposite materials. We provide some perspectives regarding the origin of enhanced ZT in nanoscale and nanostructured materials and suggest some promising and fruitful research directions for achieving high ZT materials for practical applications.