Lead selenide (PbSe) nanostructures with well-defined star-shaped morphology are successfully fabricated via a facile organometallic synthetic route from the reaction of tetraphenyl lead (Ph4Pb) with triphenylphosphine selenide (Ph3PSe) in dibenzylamine (DBA) with the assistance of oleic acid (OA) and oleylamine (OAm) at 220 °C for 30 min. The structure and shape of the nanocrystals are investigated by techniques of XRD, SEM, TEM, HRTEM, SAED, and EDX, and it is interesting that the obtained PbSe nanostars present Pb-rich features, although the PbSe nanostars are still in typical rock salt phase. Experimental investigations and ATR-FTIR studies demonstrate that the media of DBA, OA, and OAm with an order OA > DAB > OAm play important roles in the growth of the PbSe nanostars with well-defined shapes because the media not only serve as solvents but capping materials. The synergetic effects of the media are also favorable for the growth of PbSe nanocrystals with the well-defined star-shaped morphologies in the current reaction system. Meanwhile, varied PbSe nanostructures with cubic, side-cut cubic, and octahedral shapes can be fabricated by regulating the relevant reaction conditions, and all of these nanostructures prepared in the procedures demonstrate Pb-rich features due to the selective capping effects of the media to the exposed Pb(II) ions. It is confirmed that the specific shape and geometry of the nanostructures can be tuned by controlling the exposed crystal surfaces and/or the corresponding compositions via the variation of reaction conditions in the media.

Uniform four-coordinate nonequilibrium MnS nanowires mainly in zincblende structure, other than the stable rock-salt phase, are reported for the first time. The MnS nanowires are grown via a solution–solid–solid model from the reaction of a Mn(II) source with dibenzyl disulfide in oleylamine at 180–200 °C catalyzed by Ag2S nanocrystals in a body-centered cubic (bcc) fast-ionic phase transformed from their low-temperature monoclinic form. Investigations show that most of the zincblende MnS nanowires are grown along the ⟨112⟩ zone axis but a small proportion grow along the ⟨111⟩ZB/⟨0001⟩Wur axis with zincblende/defect-section and/or wurtzite/defect-section superlattices connected with the stems along the ⟨112⟩ direction. The nanowires have a tendency to grow straight at relatively low reaction temperature for short reaction times but twist at high temperature for long reaction times. Meanwhile, relatively high temperatures and long times favor the transition of the MnS nanowires in the zincblende phase to the corresponding thermodynamic ones in rock-salt form. Interestingly, even small increases in reaction pressure (1–2 atm) sensitively influence the growth of the MnS nanowires from zincblende to wurtzite form in the present catalytic system although low-pressure changes commonly do not have an obvious effect on condensed matter. In addition, the optical and magnetic properties of the zincblende MnS nanowires were studied, and they are varied largely from the bulk.

Indium antimonide (InSb) enables diverse applications in electronics and optoelectronics. However, to date, there has not been a report on the synthesis of InSb nanowires (NWs) via a solution-phase strategy. Here, we demonstrate for the first time the preparation of high-quality InSb NWs with twinning superlattices from a mild solution-phase synthetic environment from the reaction of commercial triphenylantimony with tris(2,4-pentanedionato)-indium(III). This reaction occurs at low temperatures from 165 to 195 °C (optimized at ∼180 °C), which is the lowest temperature reported for the growth of InSb NWs to date. Investigations reveal that the InSb NWs are grown via a solution–liquid–solid (SLS) mechanism due to the catalysis of the initially formed indium droplets in the mild solution-phase reaction system. The twinning superlattices in the InSb NWs are determined with a pseudoperiodic length of ∼42 monolayers, which result from an oscillating self-catalytic growth related to the periodical fluctuation between reduction rate of In and Sb sources in the route. The optical pump-terahertz probe spectroscopic measurement suggests that the InSb NWs have potential for applications in high-speed optoelectronic nanodevices.Keywords: group III−V semiconductor nanowire; growth mechanism; Indium antimonide (InSb); oscillatory growth; solution-phase synthetic route; solution−liquid−solid growth model; twin-plane superlattice; twinning superlattice;

A facile colloidal chemistry method is reported for synthesis of uniform Bi2S3 nanorods in a mixed solution of oleylamine with other organic amines including n-dodecylamine (C12), n-octylamine (C8), and n-hexylamine (C6). The nanorod length can be tuned through the carbon-chain length of these amines and importantly multigrams of Bi2S3 nanorods can be readily synthesized in a single scaled-up batch. Current–voltage (I–V) measurements showed that the Bi2S3 nanorods, obtained from both the small and large-scale batches or ones with different chain-length amines, exhibit fast light response characteristics (at the sub-second scale) with an obviously enhanced photocurrent (or photoconductivity) under broad-spectrum white light or monochromatic visible light of different wavelengths. The as-obtained nanorods, as determined by time-dependent current (I–t) curves, also exhibit excellent photoresponsive stability and reproducibility with the on–off switch of light. The photoconductivity enhancement in the Bi2S3 nanorods is assigned to the efficient electron–hole pair separation due to a hole-trapping mechanism. These results indicate the promising potential of Bi2S3 nanorods for optoelectronic device applications including photodetection (sensing), optical switch, photocatalysis, and photovoltaics within the visible spectrum range.

Transition metal phosphides have received considerable interest for electrochemical energy storage/conversion and catalysis. In this work, we designed a unique hybrid of NiCoP nanoparticles adhered on quasi-planar structured graphene by assembling 8.5 nm ternary NiCoP nanoparticles on graphene through a solution-phase self-assembly strategy. The NiCoP catalyst in the form of small-size particles wrapped in graphene provided more active sites, a buffer for volume alteration and enhanced conductivity for electrochemical reactions. Typically, the hybrid catalyst demonstrates a high specific capacity of around 532 mA h g−1, excellent cycling stability and superior rate performance when the hybrid material is evaluated as an anode material for lithium-ion batteries, and it shows excellent electrochemical properties with a specific capacitance of 646 F g−1 at 4 A g−1, maintaining 91% of this initial value after 2000 cycles functioning as a supercapacitor.

AbstractMoSe2 as a typical transition metal dichalcogenide holds great potential for energy storage and catalysis but its performance is largely limited by its poor conductivity. Bi2Se3 nanosheets, a kind of topological insulators, possess gapless edges on boundary and show metallic character on surface. According to the principle of complementary, a novel integrated quasiplane structure of MoSe2/Bi2Se3 hybrids is designed with artistic heteronanostructures via a hot injection in colloidal system. Interestingly, the heteronanostructures are typically constituted by single-layer Bi2Se3 hexagonal nanoplates evenly enclosed by small ultrathin hierarchical MoSe2 nanosheets on the whole surfaces. X-ray photoelectron spectroscopy investigations suggest obvious electron transfer from Bi2Se3 to MoSe2, which can help to enhance the conductivity of the hybrid electrode. Especially, schematic energy band diagrams derived from ultraviolet photoelectron spectroscopy studies indicate that Bi2Se3 has higher EF and smaller Φ than MoSe2, further confirming the electronic modulation between Bi2Se3 and MoSe2, where Bi2Se3 serves as an excellent substrate to provide electrons and acts as channels for high-rate transition. The MoSe2/Bi2Se3 hybrids demonstrating a low onset potential, small Tafel slope, high current density, and long-term stability suggest excellent hydrogen evolution reaction activity, whereas a high specific capacitance, satisfactory rate capability, and rapid ions diffusion indicate enhanced supercapacitor performance.

The metastable semiconductor phase allows for the exploration of unusual properties and functionalities of abnormal structures, although it is often difficult to prevent thermodynamic transformations to lower energy structures from higher, unfavored energy states. Here, we show for the first time the preparation of high-quality ultralong metastable zincblende (ZB)–MnSe nanowires with a four-coordinate structure via solution–solid–solid (SSS) growth in a mild solution-phase synthetic environment (120–220 °C) in the presence of a trace amount of Ag(I). The metastable ZB-MnSe nanowires are stabilized kinetically due to the catalysis of early formed body-centered cubic (bcc) fast-ionic (superionic) Ag2Se nanocrystals from the Ag(I) source, and the ZB-MnSe nanowires grow epitaxially along the ⟨110⟩ axis rather than the ⟨111⟩ axis, as commonly observed for typical four-coordinate Grimm–Sommerfeld bonding solids. Our method provides a new route for the growth of metastable nanostructures.

Transition metal dichalcogenides (MX2, where M = Mo or W and X = S or Se) have been regarded as some of the best alternatives for noble metal-free electrocatalysts for the hydrogen evolution reaction (HER). A tremendous number of attempts have mainly focused on the maximization of the number of active edge sites and the conductivity of MX2-based electrocatalysts to enhance HER performance. However, for MX2-based electrocatalysts, the acceleration of the kinetic process to improve HER performance has been neglected until now. Here we report a colloidal epitaxial growth strategy for synthesizing MoSe2–NiSe nanohybrids with well-defined heterointerfaces that are constructed by in situ growth of metallic NiSe nanocrystallites on the MoSe2 nanosheets. These high-quality vertical heteronanostructures with band alignment give rise to the electrons being transferred from the metallic NiSe nanocrystallites to the MoSe2 matrix, achieving the electronic modulation of the MoSe2–NiSe nanohybrids for efficient electrocatalytic activity. The MoSe2–NiSe nanohybrids exhibit excellent HER catalytic properties with a low onset potential of −150 mV, a large cathodic current density (10 mA cm–2 at an overpotential of 210 mV), and a small Tafel slope of 56 mV per decade. The greatly enhanced electrocatalytic properties were attributed to the electronic structure modulation from the synergetic interactions between NiSe nanocrystallites and MoSe2 nanosheets. We anticipate that the construction of hybrid structures will be a powerful tool for creating high-performance electrocatalysts in solids.

Ultralong orthorhombic Sb2Se3 nanowires have been successfully fabricated via an alternative facile organometallic synthetic route from the reaction of triphenylantimony(III) with dibenzyldiselenide in oleylamine at 180–240 °C without any other additives. The formation and growth mechanism of the Sb2Se3 nanowires is intensively investigated, and it is found that the anisotropic growth of the nanowires with almost constant diameters is resulted from the synergistic effects of the intrinsic property of the orthorhombic crystal structure and the weak binding assistance of oleylamine, and the length of the nanowires can be elongated easily by increasing reaction time in the synthetic route. Moreover, the photothermal response of the Sb2Se3 nanowires is first evaluated under illumination of UV light (320–390 nm), and it is especially noted that the Sb2Se3 nanowires exhibit highly enhanced photothermal responses (more than two times the intensity) as compared to the bulk Sb2Se3. In addition, the Sb2Se3 nanowires show excellent light-to-heat performance, which is superior to that of the nanostructured titanium dioxide and silicon powder under the same conditions.Keywords: anisotropic growth and mechanism; light-to-heat effect; new coupling reaction and mechanism; organometallic synthesis; photothermal response; ultralong Sb2Se3 nanowire;

Advances in the photocurrent conversion of two-dimensional (2D) transition metal dichalcogenides have enabled the realization and application of ultrasensitive and broad-spectral photodetectors. The requirements of previous devices constantly drive for complex technological implementation, resulting in limits in scale and complexity. Furthermore, the development of large-area and low-cost photodetectors would be beneficial for applications. Therefore, we demonstrate a novel design of a heterojunction photodetector based on solution-processed ultrathin MoSe2 nanosheets to satisfy the requirements of its application. The photodetector exhibits a high sensitivity to visible–near infrared light, with a linear dynamic range over 124 decibels (dB), a detectivity of ~1.2 × 1012 Jones, and noise current approaching 0.1 pA·Hz–1/2 at zero bias. Significantly, the device shows an ultra-high response speed up to 30 ns with a 3-dB predicted bandwidth over 32 MHz, which is far better than that of most of the 2D nanostructured and solution-processable photodetectors reported thus far and is comparable to that of commercial Si photodetectors. Combining our results with material-preparation methods, together with the methodology of device fabrication presented herein, can provide a pathway for the large-area integration of low-cost, high-speed photodetectors.

Phosphorous-rich FeP2/C nanohybrids are synthesized via the pyrolysis of ferrocene (Fe(C5H5)2) and red phosphorus in an evacuated and sealed quartz tube at 500 °C. The nanohybrids contain orthorhombic FeP2 with conical carbon tubes. Based on the calculated electroactive surface area, the performance of the FeP2/C nanohybrids as a novel non-noble metal electrocatalyst for hydrogen evolution reaction (HER) in 0.50 M H2SO4 is investigated. These nanohybrids show good catalytic activity and stability in the acidic medium and might serve as a promising new class of non-noble metal catalysts for practical HER.

Carbon-coated transition-metal phosphide (TMPs@C) nanocomposites, including Ni5P4@C nanoparticles and CoP@C nanorods, have been fabricated via a simply developed synthetic route from the reaction of organometallic sources with triphenylphosphine (PPh3) in a sealed quartz tube. These nanocomposites as anode materials for lithium-ion batteries (LIBs) exhibit excellent rate capability and highly stable cycling performances. Typically, the Ni5P4@C nanoparticles present 612 mA h g−1 after 100 cycles at 0.2C, 462 mA h g−1 after 200 cycles at 1.0C and 424 mA h g−1 at 5.0C, and the CoP@C nanorods demonstrate 654 mA h g−1 after 100 cycles at 0.2C, 530 mA h g−1 after 200 cycles at 1.0C, and 384 mA h g−1 at 5.0C, respectively, which would be of great potential in energy storage and conversion.

Transition-metal phosphides (TMPs) have been proved to be of great importance in electrochemical energy conversion and Li-ion storage. In this work, we have designed a useful one-pot hot-solution colloidal synthetic route for synthesizing a new kind of unique hybrid nanostructures (the Ni12P5/CNT nanohybrids) by direct in situ growth of Ni12P5 nanocrystals onto oxidized multiwall carbon nanotubes (CNTs). The CNTs can improve the conductivity of the hybrids and effectively prevent the aggregation of Ni12P5 nanoparticles in the cycle process. When they are evaluated as a novel non-noble-metal hydrogen evolution reaction (HER) catalyst operating in acidic electrolytes, the Ni12P5/CNT nanohybrids exhibit an onset overpotential as low as 52 mV and a Tafel slope of 56 mV dec−1 and only require overpotentials of 65 and 129 mV to attain current densities of 2 and 10 mA cm−2, respectively. Moreover, they also exhibit enhanced electrochemical performance for lithium-ion batteries serving as an anode material; the Ni12P5/CNT nanohybrids show a high capacity, excellent cycling stability and good rate performance. Their unusual properties arise from a synergetic effect between Ni12P5 and CNTs.

The design and synthesis of robust, high-performance and low-cost three-dimensional (3D) hierarchical structured materials for the electrochemical reduction of water to generate hydrogen is of great significance for practical water splitting applications. In this study, we develop an in situ space-confined method to synthesize an MoS2-based 3D hierarchical structure, in which the MoS2 nanosheets grow in the confined nanopores of metal–organic frameworks (MOFs)-derived 3D carbons as electrocatalysts for efficient hydrogen production. Benefiting from its unique structure, which has more exposed active sites and enhanced conductivity, the as-prepared MoS2/3D nanoporous carbon (3D-NPC) composite exhibits remarkable electrocatalytic activity for the hydrogen evolution reaction (HER) with a small onset overpotential of ∼0.16 V, large cathodic currents, small Tafel slope of 51 mV per decade and good durability. We anticipate that this in situ confined growth provides new insights into the construction of high performance catalysts for energy storage and conversion.

Cu2SnSe3–Au heteronanostructures have been successfully synthesized for the first time using a seed-mediated growth method. Such new Cu2SnSe3–Au heteronanostructures demonstrate enhanced and broadened optical absorption in the Vis-NIR region. We have also investigated the optoelectronic and photocatalytic properties of the Cu2SnSe3–Au heteronanostructures and proposed a mechanism to illustrate the improved photocurrent and photocatalytic performance as compared to bare Cu2SnSe3.

Monodisperse CuFeSe2 nanocrystals of high quality have been successfully synthesized for the first time using a hot-solution injection method from the reaction of metallic acetylacetonates with diphenyl diselenide (Ph2Se2) in oleylamine with addition of oleic acid at 255 °C for 90 min. The characterizations of X-ray diffraction, electron microscopy, and compositional analysis reveal that the resulting CuFeSe2 nanocrystals are of tetragonal phase with a stoichiometric composition. The CuFeSe2 nanocrystals exhibit well-defined quasi-cubic shape with an average size of ∼18 nm, and their shape can be tuned from quasi-cubes to quasi-spheres by adjusting the reaction parameters. Magnetic measurement reveals that the as-synthesized CuFeSe2 nanocrystals are ferromagnetic and paramagnetic at 4 and 300 K, respectively. Additionally, the current–voltage (I–V) behavior of the CuFeSe2 nanocrystals suggests that they are promising candidates for application in optoelectronics and solar energy conversion.Keywords: eskebornite; magnetic property; monodisperse CuFeSe2 nanocrystal; narrow bandgap semiconductor; optoelectronic property; organometallic synthesis; photodetector; ternary selenide

•CoP@C nanocables was prepared via an alternative facile and fast synthetic route.•The strategy can be applied for the fabrication of many more TMPs and composites.•The nanocables exhibit high catalytic HER activity with stable cycling performance.•The C-coating ensures fast electron transport and effect restriction of corrosion.Cobalt monophosphide@C (CoP@C) core–shell nanocables are successfully synthesized via a one-step fast reaction of cobalt(II) acetylacetonate [Co(acac)2] and triphenyl phosphine (PPh3) in a sealed tube at 400 °C for 1 h. The electrocatalytic property of the CoP@C nanocables towards the hydrogen evolution reaction (HER, for the production of molecular hydrogen from water) has been investigated in the current work and it is found that the CoP@C nanocables exhibit a high electrochemical performance and excellent cycling stability. Moreover, investigations show that the carbon coating ensures a fast electron transport and effective restriction of corrosion during the catalytic process. We believe that the CoP@C nanocables would be promising candidates for electrochemical hydrogen production catalyst.

Nanorod-FeP@C composites are synthesized via a one-pot solution reaction of ferrocene (Fe(C5H5)2) with excess triphenylphosphine (PPh3) in sealed vacuum tubes at 390 °C, in which PPh3 is used as both the phosphorus source and solvent in the reaction. The structure and lithium storage performance of the as-prepared nanorod-FeP@C composites are intensively characterized, and it is interesting that the composites exhibit an increased capacity during cycling serving as anode materials for lithium-ion batteries (LIBs). Meanwhile, mechanism investigations reveal that the capacity increase of the composites results from a hysteretic lithiation of the nanostructured FeP phase due to the coating of the carbon shell in the composites. Meanwhile, cyclic stability investigation shows that the composites have a very good cyclic stability that shows potential for the composites with a long lifespan as a promising kind of anode material.

Single crystalline copper selenide (Cu2−xSe) nanocrystals (NCs) with well-defined octahedral morphology are successfully synthesized by a colloidal hot-solution injection method from the reaction of anhydrous CuCl with Ph2Se2 under argon flow, in which 1-octadecene (ODE) and oleylamine (OAm) are used as solvent and surfactant, respectively. The Cu2−xSe octahedral nanostructures are characterized by XRD, SEM, TEM, HRTEM, SAED, EDS, FT-IR and XPS and it is found that they are in the cubic phase with high quality. The growth process of the nanostructures is investigated and it is noted that reaction temperature, reaction time and capping surfactant OAm play significant roles in controlling the morphologies of the final products. Meanwhile, the current–voltage (I–V) behavior of the as-prepared octahedral Cu2−xSe nanostructures is explored for the first time and it is found that the Cu2−xSe octahedral nanostructures are promising candidates for application in photodetection and related areas.

A new rapid and low temperature hydrothermal process has been developed to synthesize one-dimensional (1D) single-crystalline SbSI microrods at 160 °C for 4 h with high quality. Moreover, a first individual SbSI microrod based photodetector equipped with indium–tin-oxide (ITO) electrodes is constructed on a SiO2/Si substrate. The resulting device displays a remarkable response to visible light with an on–off ratio up to 727, a detectivity of 2.3 × 108 Jones, a noise equivalent power of 1.7 × 10−10 W/Hz1/2 and fast response/recovery times (<0.3 s).

MoSe2 nanosheets have been extensively pursued due to the outstanding properties of this typical layered transition metal dichalcogenide (LTMD). In this work, we report a facile, fast strategy to synthesize scalable hierarchical ultrathin MoSe2−x (x ∼ 0.47) nanosheets. The nanosheets possess 2–5 Se–Mo–Se atomic layers and were synthesised through a bottom-up colloidal route within 20 mins under mild conditions from the reaction of MoO2(acac)2 with dibenzyl diselenide. The as-obtained hierarchical ultrathin MoSe2−x nanosheets are Mo-rich with a Se vacancy and show excellent HER performance with a small overpotential of ∼170 mV, large cathodic currents, and a Tafel slope of 98 mV per decade. Such high performance has been attributed to the unique structure of the Se vacancy defect, large surface area, as well as the enhanced conductivity. Meanwhile, the pathway can be extended as a general strategy to prepare other metal selenides, such as ultrathin WSe2 and SnSe nanosheets, and PbSe nanocrystals. It will also pave a new way to synthesize scalable nanostructured materials for intriguing nanodevices and large-scale applications.

A facile catalytic growth route was developed for the low-temperature solution synthesis of Ag2S–CdS matchstick-like heteronanostructures in oleylamine, which are composed of a Ag2S spherical head and a CdS rod-like stem. Ag2S nanoseeds acted as an effective catalyst for the growth of CdS nanorods and remained at the tip of the resultant nanorods, leading to the formation of Ag2S–CdS heterostructures with a matchstick shape. The diameter of the Ag2S heads and the length of the CdS stems could be easily controlled by varying the molar ratios of the Ag/Cd precursors. The differential scanning calorimetry (DSC) and variable-temperature X-ray diffraction (XRD) studies confirmed that Ag2S catalytic seeds underwent a phase change, that is, they were in a high-temperature superionic conducting cubic structure during the CdS nanorod growth and then converted to a low-temperature monoclinic crystal structure as the reaction was cooled to room temperature. The influence of synthetic temperature on the product morphology was investigated and the morphological evolution at different growth stages was monitored using transmission electron microscopy (TEM). Furthermore, the growth kinetics of the Ag2S–CdS matchstick-like heteronanostructures, including the dissolution, nucleation and growth of CdS within the Ag2S catalyst, was reasonably discussed on the basis of the structural characteristics of the superionic cubic Ag2S catalyst and the low solubility of CdS in Ag2S derived from the Ag2S–CdS binary phase diagram.

The fabrication of hexapod-like ternary PbSexS1–x nanostructures has been reported via an alternative organometallic route from reaction of Pb(II) salt with triphenylphosphine selenide (Ph3PSe) and dibenzyl disulfide (DBDS) in dibenzylamine (DBA) with addition of oleic acid (OA) at 260 °C. The shape, structure, and composition of the nanostructured hexapods are investigated and determined by techniques of XRD, SEM, TEM, Raman, HRTEM, SAED, XPS, EDX, and HAADF-STEM, and the obtained ternary nanostructured hexapods are of typical rock salt phase with Pb-rich features without phase separation, and their compositions could be systematically regulated by facile variations of reaction parameters. Investigations reveal that the successful fabrication of the ternary hexapods with tunable compositions is resulted from the effective selection of Se and S sources of Ph3PSe and DBDS that have similar reactivity in the current reaction system along with small lattice mismatch between the two end members of PbSe and PbS. Generally, the relations between the composition and lattice parameters for the ternary nanostructures obtained in DBA with varied addition of OA exhibit linear slops that are consistent well with Vegard’s law. Interestingly, intensive investigations show that the nanostructures are mainly gradiently alloyed nanostructures with somewhat chalcogen–element segregations or disorders rather than homogeneously alloyed solid-state solutions due to kinetic limitation for short reaction time even though thermodynamics is feasible in the system, and also, high concentration of S element in the feedstocks tends to relative high density of disorders in the ternary nanostructures. Based on the revealing of the formation mechanism for the nanostructures with varied microstructures, the ternary PbSexS1–x hexapods can be tuned from gradient alloys with segregations to approximately homogeneous via enlongating reaction time. In addition, the photolysis of the nanostructures to lead oxysulfate and oxyselenate species is evidenced at ambient condition via Raman detection although they are stable at −190 °C.

Lead selenide (PbSe) nanostructures with well-defined star-shaped morphology are successfully fabricated via a facile organometallic synthetic route from the reaction of tetraphenyl lead (Ph4Pb) with triphenylphosphine selenide (Ph3PSe) in dibenzylamine (DBA) with the assistance of oleic acid (OA) and oleylamine (OAm) at 220 °C for 30 min. The structure and shape of the nanocrystals are investigated by techniques of XRD, SEM, TEM, HRTEM, SAED, and EDX, and it is interesting that the obtained PbSe nanostars present Pb-rich features, although the PbSe nanostars are still in typical rock salt phase. Experimental investigations and ATR-FTIR studies demonstrate that the media of DBA, OA, and OAm with an order OA > DAB > OAm play important roles in the growth of the PbSe nanostars with well-defined shapes because the media not only serve as solvents but capping materials. The synergetic effects of the media are also favorable for the growth of PbSe nanocrystals with the well-defined star-shaped morphologies in the current reaction system. Meanwhile, varied PbSe nanostructures with cubic, side-cut cubic, and octahedral shapes can be fabricated by regulating the relevant reaction conditions, and all of these nanostructures prepared in the procedures demonstrate Pb-rich features due to the selective capping effects of the media to the exposed Pb(II) ions. It is confirmed that the specific shape and geometry of the nanostructures can be tuned by controlling the exposed crystal surfaces and/or the corresponding compositions via the variation of reaction conditions in the media.

The catalytic mechanism offers an efficient tool to produce crystalline semiconductor nanowires, in which the choice, state, and structure of catalysts are active research issues of much interest. Here we report a novel solution–solid–solid (SSS) mechanism for nanowire growth catalyzed by solid-phase superionic conductor nanocrystals in low-temperature solution. The preparation of Ag2Se-catalyzed ZnSe nanowires at 100–210 °C is exampled to elucidate the SSS model, which can be extendable to grow other II–VI semiconductor (e.g., CdSe, ZnS, and CdS) nanowires by the catalysis of nanoscale superionic-phase silver or copper(I) chalcogenides (Ag2Se, Ag2S, and Cu2S). The exceptional catalytic ability of these superionic conductors originates from their structure characteristics, known for high-density vacancies and fast mobility of silver or copper(I) cations in the rigid sublattice of Se2– or S2– ions. Insights into the SSS mechanism are provided based on the formation of solid solution and the solid-state ion diffusion/transport at solid–solid interface between catalyst and nanowire.

Multi-step shaped CdTe nanowires with a zinc blende phase have been synthesized from the reaction of CdCl2 with diphenyl ditelluride in oleylamine with the assistance of tris(2-ethylhexyl) phosphate (TEHP) at 240 °C for 1 h. The one-dimensional CdTe nanostructured nanowires are observed with lengths up to 20 μm and about 250–300 nm in diameter. Investigations show that TEHP plays an important role in the growth of the nanowires with rough surfaces. The growth process of the nanowires is studied and it is found that the growth of the multi-step nanowires results from the spontaneous aggregation and assembly of small-sized flying saucer-like nanostructures along the axial direction under an oriented attachment growth regime with the assistance of TEHP. Meanwhile, the electrical and photoelectrical properties of the as-prepared CdTe nanowires are investigated and the nanowires exhibit p-type electrical characteristics. More importantly, a distinct strong photoelectric response is observed in a typical individual nanowire at room temperature since the photocurrent is over 60 times that of dark current at white light illumination.

Nanoporous Au–Pd bimetallic foams with a large BET surface area of 20.19 m2 g−1 have been successfully achieved via a mild hydrothermal process (100 °C) in the presence of dextran, which serves as both surfactant and reductant. X-Ray diffraction measurements confirm that the foams are bimetals with a face-centered cubic (fcc) structure, and electron microscopies show that the foams are composed of interlaced necklaces assembled from granular nanocrystals. The formation mechanism of the porous nanostructures has been clearly deduced from the measurements of Energy-dispersive X-ray spectroscopy (EDS) on different positions of some typical necklaces. The nanoporous bimetallic foams could catalyze the reduction of 2-nitrophenol to 2-aminophenol quite effectively at room temperature, and also exhibit good surface enhanced Raman spectroscopic (SERS) activity with Rhodamine 6G, which implies that the foams would be of great potential in catalysis and SERS applications.

Gold nanoplates in high yields have been successfully achieved via a two-step temperature-raising process through the reduction of hydrogen tetrachloroaurate in diethylene glycol in the presence of cetyltrimethylammonium bromide (CTAB) and poly vinyl pyrrolidone (PVP) at 180–200 °C for 35 min. X-Ray diffraction measurements showed that the gold samples are pure face-centered cubic (fcc) phase with a preferred orientation of <111> direction. Scanning and transmission electron microscopies demonstrated that the samples are trigonal and hexagonal plates and the selected area electron diffraction pattern indicated that the main plane of the product is the (111) plane. The reaction parameters of temperature, time, and quantity of CTAB and PVP were studied and it is found that they play important roles in the morphology and size of the product, and the two-step temperature-raising process advances the yield of gold nanoplates up to 90%. The UV-vis-NIR spectroscopic investigation demonstrated that the gold nanoplates have a strong adsorption band in the near-infrared region (∼800 nm). Meanwhile, the surface enhanced Raman spectrum property of Rhodamine 6G on the gold nanoplates was also investigated and the Raman scattering of Rhodamine 6G has been enhanced with an enhancement factor of ∼1 × 105.

Etched gold nanoplates have been successfully synthesized through a simple and green hydrothermal reaction, which was conducted in the presence of dextran at 130 °C for 24h. Scanning and transmission electron microscopy (SEM and TEM) demonstrated that the as-synthesized products are generally etched nanoplates and the electron diffraction (ED) pattern clearly showed that they are highly [111] oriented with a hexagonal nature. X-ray diffraction measurements indicated that the etched gold nanoplates are a pure face-centered cubic (fcc) phase with a preferred orientation in the <111> direction. Energy-dispersive X-ray spectroscopy (EDS) revealed that the product is only composed of elemental gold. The influences of the reaction parameters have been studied and it was found that the concentrations of dextran and HAuCl4, as well as the reaction temperature, play important roles in the control of morphology in the products. In addition, the formation mechanism of the etched gold nanoplates has also been revealed. The etched gold nanoplates could catalyze the reduction of 2-nitroaniline quite effectively and the reproducibility of the surface enhanced Raman spectrum (SERS) property of Rhodamine 6G on the etched gold nanoplates has also been investigated.

Gamma phase indium selenide (γ-In2Se3) hierarchical flowerlike architectures have been facilely synthesized for the first time via the reaction of indium chloride and selenium powders with the assistance of ascorbic acid at 220 °C for 20 h in an ethanol-solvothermal system, in which ascorbic acid acts as both reducing and capping agent. SEM, TEM and HRTEM investigations show that these flowerlike In2Se3 architectures with hexagonal γ-phase structures are composed of thin sheet-like nanocrystals. The detailed time-dependent experiments illustrate that flowerlike architectures evolve from solid spheres via an Ostwald ripening process and the effects of the concentration of ascorbic acid and indium precursor on the phase and morphology evolution of In2Se3 flowerlike architectures are intensively studied. Meanwhile, the electrical property of the γ-In2Se3 film is investigated and the conductivity of the film is 2.6 × 10−6 S cm−1. Considering the difficulty in the preparation of indium selenides arising from various phases and versatile stoichiometries, the successful synthesis of pure In2Se3 in this work would be of much scientific significance.

The synthesis of InP nanofibers via a new Ullmann-type reaction of indium nanoparticles with tri(m-tolyl)phosphine (P(PhMe)3) was typically performed to illustrate an alternative route for the preparation of nanostructured metal phosphides, including III–V (13–15) and transition-metal phosphides. Triarlyphosphine compounds such as other two tri(m-tolyl)phosphine isomers, diphenyl(p-tolyl)phosphine, and triphenylphosphine were comparably employed to synthesize InP nanocrystals. From the aspect of the carbonization of triarlyphosphines, Raman spectroscopy and thermo-gravimetric analysis (TGA) investigations of the InP products showed that the stability of these triarlyphosphines conformed to the order of tri(p-tolyl)phosphine ≈ tri(o-tolyl)phosphine < diphenyl(p-tolyl)phosphine < tri(m-tolyl)phosphine < triphenylphosphine. The correlation between the stability of triarlyphosphines and the growth of InP nanocrystals was investigated, and experimental results showed that the relatively stable triarlyphosphines (tri(m-tolyl)phosphine and triphenylphosphine) were favorable for the preparation of one-dimensional (1D) InP nanostructures (nanofibers and nanowires). The reactivity (stability) of triarlyphosphines was also compared with those of P(SiMe3)3 (typically see: J. M. Nedeljković, O. I. Mićić, S. P. Ahrenkiel, A. Miedaner and A. J. Nozik, J. Am. Chem. Soc., 2004, 126, 2632) and P(C8H17)3 (C. Qian, F. Kim, L. Ma, F. Tsui, P. D. Yang and J. Liu, J. Am. Chem. Soc., 2004, 126, 1195) according to the difference in preparative temperature for phosphide synthesis. Raman and photoluminescence properties of the as-synthesized InP nanocrystals were further studied, and the synthetic mechanism of our method was reasonably investigated by GC-MS analysis. Moreover, the current route was successfully extended to prepare GaP, MnP, CoP and Pd5P2 nanocrystals.

Novel one-dimensional (1D) hierarchical multilayered indium nanostructures were successfully synthesized via chemical reduction of InCl3·4H2O with Zn powder or foils in small alcohols, including methanol, ethanol, n-propyl alcohol, and the mixture of these alcohols. Electron diffraction (ED) and high-resolution transmission electronic microscopy (HRTEM) analyses revealed that the interesting multilayered nanostructures were grown from the assembly of elliptic indium monolayers along the [110] direction and the monolayer-density of the multilayered nanostructures was controllable by changing the alkyl-chain length of small alcohols. The TEM investigations for indium nanostructures obtained at different reaction stages revealed that the 1D hierarchical multilayered nanostructures gradually evolve from solid indium nanorods. On the basis of the TEM investigations and binary eutectic phase diagram of In−Zn, we proposed that the interesting evolvement of nanorods into 1D multilayered nanostructures resulted from the consumption of Zn incorporated in indium nanorods and the ripening of indium nanostructures with increasing the reaction time. In the synthesis, polycrystalline Zn powder or foils acted as both reducing reagent and epitaxial growth substrate, because of the electrode potential difference and lattice match between tetragonal In(110) plane and hexagonal Zn(110) plane, and a seed-mediated epitaxial growth led to the formation of indium nanorods/nanowires at the early reaction stage with the aid of a small quantity of water. The hierarchical multilayered indium nanostructures were further used as effective reductant and support to prepare bimetal In−Ag and In−Pd nanocomposites, which exhibited evident surface-enhanced Raman spectrum (SERS) effect and high catalytic activity in Suzuki cross-coupling reaction, respectively.

Novel one-dimensional (1D) angle-shaped zinc blende ZnSe nanostructures with an angle of 70.5° have been synthesized from the reaction of ZnCl2 with Se, in a mixture of ethanol and oleic acid under mild solvothermal conditions at 205 °C for 12 to 30 h. This is the first report on the fabrication of angle-shaped nanostructures with such a 70.5° angle for nanostructured materials including group II−VI nanocrystals. Investigations reveal that the 70.5° angle-shaped nanostructures are formed from two branches, or arms, growing along the zinc blende [1̅11̅] and [111̅] directions. The end of one branch is exposed to a positive Zn2+ ion charged surface, and the end of the other branch is exposed to a negative Se2− surface. This forms interesting nanostructures with a specific angle of 70.5° because of the kinetic conditions relevant to the use of oleic acid with a high viscosity along with the anisotropy of the ZnSe crystal. Electron microscopic investigations demonstrate that the 1D ZnSe nanostructures are dominated by alternating twins and other stacking faults at the scale of several nanometers along the whole length. These twins and faults result in quantum effects, leading to an intense blue shift in the photoluminescence spectrum for the as-synthesized ZnSe sample.

Group III–V (13–15, III = Ga, In, and V = P, As) semiconductor nanocrystals were effectively obtained via a developed Ullmann reaction route through the reactions of preformed nanoscale metallic indium or commercial gallium with triphenylphosphine (PPh3) and triphenylarsine (AsPh3) in sealed vacuum quartz tubes under moderate conditions at 320–400 °C for 8–24 h. The developed synthetic strategy in sealed vacuum tubes extends the synthesis of III–V semiconductor materials, and the air-stable PPh3 and AsPh3 with low toxicity provide good alternative pnicogen precursors for the synthesis of III–V nanocrystals. The analysis of XRD, ED and HRTEM established the production of one-dimensional (1D) metastable wurtzite (W) InP, InAs and GaP nanostructures in the zinc blende (ZB) products. Further investigations showed that 1D W nanostructures resulted from kinetic effects under the moderate synthetic conditions employed and the steric effect of PPh3 and AsPh3, and that the tendency for the synthesis of III–V nanocrystals was in the orders of IIIP > IIIAs and GaV > InV on the basis of experiments and thermodynamic calculations. Meanwhile, the microstructures and growth mechanism of the III–V nanocrystals were investigated.

A biomolecule-assisted synthetic route has been developed for the preparation of orthorhombic lanthanide hydroxycarbonate crystals with interesting assembly features, using various amino acids as capping ligands for the synthesis. Reaction mechanism to the materials is proposed. The biomolecule additives played an important role in modifying the microstructures, and the morphology of crystals could be spindly, spherical, and dumbbell-like. Thermal analysis indicated that the as-prepared cerium hydroxycarbonate was stable below 240 °C, and NdOHCO3 was stable below 400 °C. The CeOHCO3 sample showed intensive broad band emission centered at 370 nm, which may be used as a next-generation black-light material to control pests. Fluorescence of the materials is dependent on the structure. Therefore, simply alternating reaction parameters would vary microstructures and tune the optical properties of the materials.

A hydrothermal process is reported for the preparation of rare earth hydroxycarbonates LnOHCO3 (Ln = Pr, Sm, Dy, Y) with hierarchical structures, such as dumbbell nanorod clusters, stacked lamellae and patched rods. All the hydroxycarbonate samples show fluorescence, and the emission wavelengths and intensity may be different for different samples. The hydroxycarbonate samples are generally stable under 380 °C, but will decompose to the respective oxides at higher temperatures. The oxides are tested for catalytic conversion of carbon monoxide to carbon dioxide. It reveals that all the rare earth oxides are active to the catalytic reaction, and Sm2O3 shows superior catalytic performance to the other oxides.Rare earth hydroxycarbonates' LnOHCO3 (Ln = Pr, Sm, Dy, Y) superstructures have been synthesized through a hydrothermal process. The materials with hierarchical structures are assembled from anisotropic subunits, and the reaction and growth mechanisms of the lanthanide hydroxycarbonates along with their luminescent properties have been investigated using techniques of XRD, SEM, TEM, FESEM, ED, IR, TGA and PL. The derived rare earth oxides from the hydroxycarbonates are firstly investigated for the catalytic conversion of carbon monoxide to carbon dioxide, showing effective catalytic performance at relatively low temperature.

A facile one-step aqueous reducing synthetic method has been reported for the preparation of noble metal nanocrystals (or colloid) of palladium through the reduction of in situ generated aldehyde ammonia from the hydrolyzation of hexamethylenetetramine with the help of sodium oleate in water under mild conditions. The as-obtained nanocrystals were monodispersed in water with narrow size distribution, and their mean size could be tuned from 3 to 8 nm rationally. The developed synthetic route has been extended to other noble metals including Au, Ag, and Pt and bimetallic Pd−Pt nanocrystals. Meanwhile, the catalytic activities of the Pd nanocrystals were tested in aqueous media, and typically dechlorination of aryl chloride and Suzuki cross-coupling reaction are selected as model reactions. Investigations demonstrated that the Pd nanocrystals have good catalytic performance since both dehalogenation and cross-coupling reaction have high yields under current mild conditions. The results suggest that the Pd nanocrystals possess a range of potential applications including the degradation of aryl halide contaminants and the selective construction of carbon−carbon bonds for the formation of various biaryls, pharmaceuticals, and advanced materials.

A general biomolecule-assisted synthetic route has been developed for the synthesis of nanostructured inorganic crystals. In this work, CdS hierarchical dendrites were hydrothermally prepared through the reactions of cadmium chloride with thiourea in the presence of various amino acids and investigated in terms of change of size and shape by varying growth parameters for the sulfide crystals. X-ray diffraction demonstrated that the as-fabricated CdS dendrites were in wurtzite (hexagonal) phase, and electronic diffraction further determined that the CdS dendrites were in hexagonal form with single-crystal nature. The experiments revealed that both amino acids and thiourea play an important role in the formation of the hierarchical crystals. Meanwhile, a possible growth mechanism is proposed, based on the investigations.

Porous MgO nanoplates have been successfully synthesized using a single-step Mg(NO3)2 solution calcination route without the assistance of any other additions. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) explorations indicated that the sizes of these nanoplates were ranging from 100 to 300 nm and the pores in them had diameters of about 2–50 nm. Nitrogen adsorption measurements for the prepared porous MgO nanoplates showed that the products had a BET (Brunauer–Emmett–Teller) surface area of 190 m2 g−1. PL (photoluminescence) spectrum of the products exhibited a visible light emission. Based on these investigations, the products were expected to find wide applications in biologic, catalytic and optoelectronic fields. Thermogravimetric (TG) analysis provided insight into the decomposition process of the Mg(NO3)2 solution precursor. A possible growth mechanism of the products was also explained.

One single-step self-assembly route has been developed for the fabrication of coral-like MgO microcrystals from porous nanoparticles via a calcination route, in which dextran is used as soft template, and Mg(NO3)2 solution acts as the magnesium source throughout the entire process. Experiments show that the amount of dextran, the concentration of Mg(NO3)2 solution and using different Mg sources play an important role in the growth of the products. The coordinative effect in the dextran–Mg(NO3)2 complex was explored by Fourier transform infrared spectral analysis. A possible growth mechanism is also discussed.

A solution evaporation route has been successfully developed for the growth of copper nitrate hydroxide microcrystals using copper nitrate solution as the starting material in the absence of any surfactants or templates. The products were characterized by X-ray diffraction (XRD), infrared (IR) spectrum, scanning electron microscopy (SEM) and thermogravimetric (TG) analysis measurements. Controlled experiments suggested that the reaction temperature and solution concentration played an important role on the formation of the products. A possible formation mechanism of the products was also proposed.

Wurtzite CdSe dendrites were synthesized by an UV-irradiation photochemical reaction. The products were characterized by X-ray powder diffraction, transmission electron microscope, X-ray photoelectron spectroscopy, UV–vis spectra, Raman spectroscopy and photoluminescence spectroscopy. The electron microscope images showed that most of the dendrites had a width of around 1 μm with lengths of up to 3 μm. The formation of wurtzite CdSe dendrites can be explained as a self-assembly growth from early-formed particles under reduction conditions.

Pure hexagonal aluminum nitride (AlN) nanowhiskers have been successfully synthesized by directly reacting AlCl3 with NaN3 in non-solvent system at the low temperature of 450 °C for 24 h. The obtained products are characterized by X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, high-resolution transmission electron microscopy and selected area electron diffraction, which show that the obtained products are hexagonal phase AlN nanowhiskers with width from 10 to 80 nm and length up to several micrometers. The influencing factors of the formation of AlN nanowhiskers were discussed and a possible growth mechanism for AlN nanowhiskers was proposed. Additionally, the study on the corresponding optical properties and catalytic properties is also carried out.

Carbon-coated transition-metal phosphide (TMPs@C) nanocomposites, including Ni5P4@C nanoparticles and CoP@C nanorods, have been fabricated via a simply developed synthetic route from the reaction of organometallic sources with triphenylphosphine (PPh3) in a sealed quartz tube. These nanocomposites as anode materials for lithium-ion batteries (LIBs) exhibit excellent rate capability and highly stable cycling performances. Typically, the Ni5P4@C nanoparticles present 612 mA h g−1 after 100 cycles at 0.2C, 462 mA h g−1 after 200 cycles at 1.0C and 424 mA h g−1 at 5.0C, and the CoP@C nanorods demonstrate 654 mA h g−1 after 100 cycles at 0.2C, 530 mA h g−1 after 200 cycles at 1.0C, and 384 mA h g−1 at 5.0C, respectively, which would be of great potential in energy storage and conversion.

Active, durable and cost-effective electrocatalysts for hydrogen evolution reaction (HER) are of critical importance to the area of renewable energy. Despite the rapid development of alternative materials, platinum-based materials are still the most efficient catalysts for the HER. In this work, we report a facile strategy to construct a hybrid material comprising monodisperse CuPdPt nanocrystals loaded on pretreated Ketjen carbon. Significantly, this hybrid catalyst exhibited superior electrocatalytic activity and durability. The CuPdPt/C catalyst can achieve a factor of 701 enhancement in mass activity at −0.1 V vs. RHE compared with the commercial Pt/C catalyst and it can endure at least 20000 cycles with negligible activity loss. Impressively, the total platinum content in the hybrid catalyst is merely about 0.095 wt%. More importantly, this reported strategy can be readily extended to design other high-performance platinum-based nanomaterials for applications in catalysis and energy conversion.

Nanoporous Au–Pd bimetallic foams with a large BET surface area of 20.19 m2 g−1 have been successfully achieved via a mild hydrothermal process (100 °C) in the presence of dextran, which serves as both surfactant and reductant. X-Ray diffraction measurements confirm that the foams are bimetals with a face-centered cubic (fcc) structure, and electron microscopies show that the foams are composed of interlaced necklaces assembled from granular nanocrystals. The formation mechanism of the porous nanostructures has been clearly deduced from the measurements of Energy-dispersive X-ray spectroscopy (EDS) on different positions of some typical necklaces. The nanoporous bimetallic foams could catalyze the reduction of 2-nitrophenol to 2-aminophenol quite effectively at room temperature, and also exhibit good surface enhanced Raman spectroscopic (SERS) activity with Rhodamine 6G, which implies that the foams would be of great potential in catalysis and SERS applications.

Phosphorous-rich FeP2/C nanohybrids are synthesized via the pyrolysis of ferrocene (Fe(C5H5)2) and red phosphorus in an evacuated and sealed quartz tube at 500 °C. The nanohybrids contain orthorhombic FeP2 with conical carbon tubes. Based on the calculated electroactive surface area, the performance of the FeP2/C nanohybrids as a novel non-noble metal electrocatalyst for hydrogen evolution reaction (HER) in 0.50 M H2SO4 is investigated. These nanohybrids show good catalytic activity and stability in the acidic medium and might serve as a promising new class of non-noble metal catalysts for practical HER.

Group III–V (13–15, III = Ga, In, and V = P, As) semiconductor nanocrystals were effectively obtained via a developed Ullmann reaction route through the reactions of preformed nanoscale metallic indium or commercial gallium with triphenylphosphine (PPh3) and triphenylarsine (AsPh3) in sealed vacuum quartz tubes under moderate conditions at 320–400 °C for 8–24 h. The developed synthetic strategy in sealed vacuum tubes extends the synthesis of III–V semiconductor materials, and the air-stable PPh3 and AsPh3 with low toxicity provide good alternative pnicogen precursors for the synthesis of III–V nanocrystals. The analysis of XRD, ED and HRTEM established the production of one-dimensional (1D) metastable wurtzite (W) InP, InAs and GaP nanostructures in the zinc blende (ZB) products. Further investigations showed that 1D W nanostructures resulted from kinetic effects under the moderate synthetic conditions employed and the steric effect of PPh3 and AsPh3, and that the tendency for the synthesis of III–V nanocrystals was in the orders of IIIP > IIIAs and GaV > InV on the basis of experiments and thermodynamic calculations. Meanwhile, the microstructures and growth mechanism of the III–V nanocrystals were investigated.

A facile catalytic growth route was developed for the low-temperature solution synthesis of Ag2S–CdS matchstick-like heteronanostructures in oleylamine, which are composed of a Ag2S spherical head and a CdS rod-like stem. Ag2S nanoseeds acted as an effective catalyst for the growth of CdS nanorods and remained at the tip of the resultant nanorods, leading to the formation of Ag2S–CdS heterostructures with a matchstick shape. The diameter of the Ag2S heads and the length of the CdS stems could be easily controlled by varying the molar ratios of the Ag/Cd precursors. The differential scanning calorimetry (DSC) and variable-temperature X-ray diffraction (XRD) studies confirmed that Ag2S catalytic seeds underwent a phase change, that is, they were in a high-temperature superionic conducting cubic structure during the CdS nanorod growth and then converted to a low-temperature monoclinic crystal structure as the reaction was cooled to room temperature. The influence of synthetic temperature on the product morphology was investigated and the morphological evolution at different growth stages was monitored using transmission electron microscopy (TEM). Furthermore, the growth kinetics of the Ag2S–CdS matchstick-like heteronanostructures, including the dissolution, nucleation and growth of CdS within the Ag2S catalyst, was reasonably discussed on the basis of the structural characteristics of the superionic cubic Ag2S catalyst and the low solubility of CdS in Ag2S derived from the Ag2S–CdS binary phase diagram.

Nanorod-FeP@C composites are synthesized via a one-pot solution reaction of ferrocene (Fe(C5H5)2) with excess triphenylphosphine (PPh3) in sealed vacuum tubes at 390 °C, in which PPh3 is used as both the phosphorus source and solvent in the reaction. The structure and lithium storage performance of the as-prepared nanorod-FeP@C composites are intensively characterized, and it is interesting that the composites exhibit an increased capacity during cycling serving as anode materials for lithium-ion batteries (LIBs). Meanwhile, mechanism investigations reveal that the capacity increase of the composites results from a hysteretic lithiation of the nanostructured FeP phase due to the coating of the carbon shell in the composites. Meanwhile, cyclic stability investigation shows that the composites have a very good cyclic stability that shows potential for the composites with a long lifespan as a promising kind of anode material.

The synthesis of InP nanofibers via a new Ullmann-type reaction of indium nanoparticles with tri(m-tolyl)phosphine (P(PhMe)3) was typically performed to illustrate an alternative route for the preparation of nanostructured metal phosphides, including III–V (13–15) and transition-metal phosphides. Triarlyphosphine compounds such as other two tri(m-tolyl)phosphine isomers, diphenyl(p-tolyl)phosphine, and triphenylphosphine were comparably employed to synthesize InP nanocrystals. From the aspect of the carbonization of triarlyphosphines, Raman spectroscopy and thermo-gravimetric analysis (TGA) investigations of the InP products showed that the stability of these triarlyphosphines conformed to the order of tri(p-tolyl)phosphine ≈ tri(o-tolyl)phosphine < diphenyl(p-tolyl)phosphine < tri(m-tolyl)phosphine < triphenylphosphine. The correlation between the stability of triarlyphosphines and the growth of InP nanocrystals was investigated, and experimental results showed that the relatively stable triarlyphosphines (tri(m-tolyl)phosphine and triphenylphosphine) were favorable for the preparation of one-dimensional (1D) InP nanostructures (nanofibers and nanowires). The reactivity (stability) of triarlyphosphines was also compared with those of P(SiMe3)3 (typically see: J. M. Nedeljković, O. I. Mićić, S. P. Ahrenkiel, A. Miedaner and A. J. Nozik, J. Am. Chem. Soc., 2004, 126, 2632) and P(C8H17)3 (C. Qian, F. Kim, L. Ma, F. Tsui, P. D. Yang and J. Liu, J. Am. Chem. Soc., 2004, 126, 1195) according to the difference in preparative temperature for phosphide synthesis. Raman and photoluminescence properties of the as-synthesized InP nanocrystals were further studied, and the synthetic mechanism of our method was reasonably investigated by GC-MS analysis. Moreover, the current route was successfully extended to prepare GaP, MnP, CoP and Pd5P2 nanocrystals.