We report an effective and universal approach for the preparation of ultrathin single- or multiple-component transition-metal hydroxide (TMH) nanosheets with thickness below 5 nm. The unique synthesis benefits from the gradual decomposition of the preformed metal–boron (M-B, M=Fe, Co, Ni, NiCo) composite nanospheres which facilitates the formation of ultrathin nanosheets by the oxidation of the metal and the simultaneous release of boron species. The high specific surface area of the sheets associated with their ultrathin nature promises a wide range of applications. For example, we demonstrate the remarkable adsorption ability of Pb^II and As^V in waste water by the ultrathin FeOOH nanosheets. More interestingly, the process can be extended simply to the synthesis of composite structures of metal alloy hollow shells encapsulated by TMH nanosheets, which show excellent catalytic activity in the Heck reaction.

We report an effective and universal approach for the preparation of ultrathin single- or multiple-component transition-metal hydroxide (TMH) nanosheets with thickness below 5 nm. The unique synthesis benefits from the gradual decomposition of the preformed metal–boron (M-B, M=Fe, Co, Ni, NiCo) composite nanospheres which facilitates the formation of ultrathin nanosheets by the oxidation of the metal and the simultaneous release of boron species. The high specific surface area of the sheets associated with their ultrathin nature promises a wide range of applications. For example, we demonstrate the remarkable adsorption ability of Pb^II and As^V in waste water by the ultrathin FeOOH nanosheets. More interestingly, the process can be extended simply to the synthesis of composite structures of metal alloy hollow shells encapsulated by TMH nanosheets, which show excellent catalytic activity in the Heck reaction.

A robust method for epitaxial deposition of Au onto the surface of Ag nanostructures is demonstrated, which allows effective conversion of Ag nano­structures of various morphologies into Ag@Au counterparts, with the anisotropic ones showing excellent plasmonic properties comparable to the original Ag nanostructures while significantly enhanced stability. Sulfite plays a determining role in the success of this epitaxial deposition as it strongly complexes with gold cations to completely prevent galvanic replacement while it also remains benign to the Ag surface to avoid any ligand-assisted oxidative etching. By using Ag nanoplates as an example, it is shown that the corresponding Ag@Au nanoplates possess remarkable plasmonic properties that are virtually Ag-like, in clear contrast to Ag@Au nanospheres that exhibit much lower plasmonic activities than their Ag counterparts. As a result, they display high durability and activities in surface-enhanced Raman scattering applications. This strategy may represent a general platform for depositing a noble metal on less stable metal nanostructures, thus opening up new opportunities in rational design of functional metal nanomaterials for a broad range of applications.

Colloidal barium-doped TiO₂ nanocrystals have been developed that enable the highly reversible light-responsive color switching of redox dyes with excellent cycling performance and high switching rates. Oxygen vacancies resulting from the Ba doping serve as effective sacrificial electron donors (SEDs) to scavenge the holes photogenerated in TiO₂ nanocrystals under UV irradiation and subsequently promote the reduction of methylene blue to its colorless leuco form. Effective color switching can therefore be realized without relying on external SEDs, thus greatly increasing the number of switching cycles. Ba doping can also accelerate the recoloration under visible-light irradiation by shifting the absorption edge of TiO₂ nanocrystals to a shorter wavelength. Such a system can be further casted into a solid film to produce a rewritable paper on which letters and patters can be repeatedly printed using UV light and then erased by heating; this process can be repeated for many cycles and does not require additional inks.

Anisotropic nanostructures provide an additional degree of freedom for tailoring the collective properties of their ensembles. Using Fe@SiO₂ nanoellipsoids as anisotropic building blocks, herein we demonstrate a new class of magnetically responsive photonic structures whose photonic properties can be dynamically tuned by controlling the direction of the magnetic fields they are exposed to. These novel photonic structures diffract at a minimum wavelength when the field direction is perpendicular to the incident angle, and a maximum wavelength when the field is switched to parallel direction; and the diffraction intensity reaches maximum values when the fields are either parallel or perpendicular to the incident light, and decreases when the field direction is moved off-angle.

Anisotropic nanostructures provide an additional degree of freedom for tailoring the collective properties of their ensembles. Using Fe@SiO₂ nanoellipsoids as anisotropic building blocks, herein we demonstrate a new class of magnetically responsive photonic structures whose photonic properties can be dynamically tuned by controlling the direction of the magnetic fields they are exposed to. These novel photonic structures diffract at a minimum wavelength when the field direction is perpendicular to the incident angle, and a maximum wavelength when the field is switched to parallel direction; and the diffraction intensity reaches maximum values when the fields are either parallel or perpendicular to the incident light, and decreases when the field direction is moved off-angle.

Colloidal barium-doped TiO₂ nanocrystals have been developed that enable the highly reversible light-responsive color switching of redox dyes with excellent cycling performance and high switching rates. Oxygen vacancies resulting from the Ba doping serve as effective sacrificial electron donors (SEDs) to scavenge the holes photogenerated in TiO₂ nanocrystals under UV irradiation and subsequently promote the reduction of methylene blue to its colorless leuco form. Effective color switching can therefore be realized without relying on external SEDs, thus greatly increasing the number of switching cycles. Ba doping can also accelerate the recoloration under visible-light irradiation by shifting the absorption edge of TiO₂ nanocrystals to a shorter wavelength. Such a system can be further casted into a solid film to produce a rewritable paper on which letters and patters can be repeatedly printed using UV light and then erased by heating; this process can be repeated for many cycles and does not require additional inks.

The nitridation of hollow TiO₂ nanoshells and their layered assembly into electrodes for electrochemical energy storage are reported. The nitridated hollow shells are prepared by annealing TiO₂ shells, produced initially using a sol–gel process, under an NH₃ environment at different temperatures ranging from 700 to 900 °C, then assembled to form a robust monolayer film on a water surface through a quick and simple assembly process without any surface modification to the samples. This approach facilitates supercapacitor cell design by simplifying the electrochemical electrode structure by removing the need to use any organic binder or carbon-based conducting materials. The areal capacitance of the as-prepared electrode is observed to be ≈180 times greater than that of a bare TiO₂ electrode, mainly due to the enhanced electrical conductivity of the TiN phase produced through the nitridation process. Furthermore, the electrochemical capacitance can be enhanced linearly by constructing an electrode with multilayered shell films through a repeated transfer process (0.8 to 7.1 mF cm^–2, from one monolayer to 9 layers). Additionally, the high electrical conductivity of the shell film makes it an excellent scaffold for supporting other psuedocapacitive materials (e.g., MnO₂), producing composite electrodes with a specific capacitance of 743.9 F g^–1 at a scan rate of 10 mV s^–1 (based on the mass of MnO₂) and a good cyclic stability up to 1000 cycles.

Graphene nanosheet-supported ultrafine metal nanoparticles encapsulated by thin mesoporous SiO₂ layers were prepared and used as robust catalysts with high catalytic activity and excellent high-temperature stability. The catalysts can be recycled and reused in many gas- and solution-phase reactions, and their high catalytic activity can be fully recovered by high-temperature regeneration, should they be deactivated by feedstock poisoning. In addition to the large surface area provided by the graphene support, the enhanced catalytic performance is also attributed to the mesoporous SiO₂ layers, which not only stabilize the ultrafine metal nanoparticles, but also prevent the aggregation of the graphene nanosheets. The synthetic strategy can be extended to other metals, such as Pd and Ru, for preparing robust catalysts for various reactions.

Graphene nanosheet-supported ultrafine metal nanoparticles encapsulated by thin mesoporous SiO₂ layers were prepared and used as robust catalysts with high catalytic activity and excellent high-temperature stability. The catalysts can be recycled and reused in many gas- and solution-phase reactions, and their high catalytic activity can be fully recovered by high-temperature regeneration, should they be deactivated by feedstock poisoning. In addition to the large surface area provided by the graphene support, the enhanced catalytic performance is also attributed to the mesoporous SiO₂ layers, which not only stabilize the ultrafine metal nanoparticles, but also prevent the aggregation of the graphene nanosheets. The synthetic strategy can be extended to other metals, such as Pd and Ru, for preparing robust catalysts for various reactions.

TiO₂ hollow shells with well-controlled crystallinity, phase, and porosity are desirable in many applications. In photocatalysis in particular, they can provide high active surface area, reduced diffusion resistance, and improved accessibility to reactants. Here, the results from studies of the causes for the failure of a prior etching and calcination scheme to make such shells and on a newly-developed simple yet robust process for producing uniform mesoporous TiO₂ shells with precisely controllable crystallinity and phase are reported. The key finding is that base etching of the SiO₂@TiO₂ core-shell particles leads to the formation of sodium titanate species, which, if not removed, promote substantial crystal growth during calcination and destroy the structural integrity of the TiO₂ shells. A simple acid treatment of the base-etched samples may convert the sodium titanates into protonated titanates, which not only prevent the formation of the impurity phases, but also help to maintain the structural integrity of the shell and allow precise control of the TiO₂ phase and crystallinity. This new development affords convenient optimization of the structure of the hollow TiO₂ shells toward efficient photocatalysts, which outperform the commercial P25-TiO₂ in the photocatalytic decomposition of organic dye molecules.

Mesoporous hollow colloidal particles with well-defined characteristics have potential use in many applications. In liquid-phase catalysis, in particular, they can provide a large active surface area, reduced diffusion resistance, improved accessibility to reactants, and excellent dispersity in reaction media. Herein, we report the tailored synthesis of sulfated ZrO₂ hollow nanostructures and their catalytic applications in the dehydration of fructose. ZrO₂ hollow nanoshells with controllable thickness were first synthesized through a robust sol–gel process. Acidic functional groups were further introduced to the surface of hollow ZrO₂ shells by sulfuric acid treatment followed by calcination. The resulting sulfated ZrO₂ hollow particles showed advantageous properties for liquid-phase catalysis, such as well-maintained structural integrity, good dispersity, favorable mesoporosity, and a strongly acidic surface. By controlling the synthesis and calcination conditions and optimizing the properties of sulfated ZrO₂ hollow shells, we have been able to design superacid catalysts with superior performance in the dehydration of fructose to 5-hydroxymethyfurfural than the solid sulfated ZrO₂ nanocatalyst.

The crystallization of nanometer-scale materials during high-temperature calcination can be controlled by a thin layer of surface coating. Here, a novel silica-protected calcination process for preparing mesoporous hollow TiO₂ nanostructures with a high surface area and a controllable crystallinity is presented. This method involves the preparation of uniform silica colloidal templates, sequential deposition of TiO₂ and then SiO₂ layers through sol–gel processes, calcination to transform amorphous TiO₂ to crystalline anatase, and finally etching of the inner and outer silica to produce mesoporous anatase TiO₂ shells. The silica-protected calcination step allows crystallization of the amorphous TiO₂ layer into anatase nanocrystals, while simultaneously limiting the growth of anatase grains to within several nanometers, eventually producing mesoporous anatase shells with a high surface area (∼311 m² g⁻¹) and good water dispersibility upon chemical etching of the silica. When used as photocatalysts for the degradation of Rhodamine B under UV irradiation, the as-synthesized mesoporous anatase shells show significantly enhanced photocatalytic activity with greater enhancement for samples calcined at higher temperatures thanks to their improved crystallinity.

Dieser Aufsatz fasst jüngste Entwicklung auf dem Gebiet der responsiven photonischen Kristalle zusammen, einschließlich Design-, Fertigungs- und Anwendungsstrategien, z. B. als optische Schalter oder chemische und biologische Sensoren. Eine Reihe von Fertigungsmethoden für responsive photonische Strukturen ist heute verfügbar, die hauptsächlich auf Selbstorganisationsprozessen beruhen. Gegenüber Mikrofertigungsverfahren besitzen diese Ansätze die Vorteile geringerer Prozesskosten und einer besseren Produktionseffizienz, es gibt aber noch beträchtliche Herausforderungen zu bewältigen. Einige Techniken wie Schleuderbeschichtung, magnetische Aggregation und durchflussinduzierte Selbstorganisation erweisen sich hier als vielversprechend. Entscheidende Hinweise für den Entwurf neuer, verbesserter Systeme könnte das Vorbild natürlicher photonischer Strukturen bieten.

This Review summarizes recent developments in the field of responsive photonic crystal structures, including principles for design and fabrication and many strategies for applications, for example as optical switches or chemical and biological sensors. A number of fabrication methods are now available to realize responsive photonic structures, the majority of which rely on self-assembly processes to achieve ordering. Compared with microfabrication techniques, self-assembly approaches have lower processing costs and higher production efficiency, however, major efforts are still needed to further develop such approaches. In fact, some emerging techniques such as spin coating, magnetic assembly, and flow-induced self-assembly have already shown great promise in overcoming current challenges. When designing new systems with improved performance, it is always helpful to bear in mind the lessons learnt from natural photonic structures.

Nanoparticles of transition metals, particularly noble metals, are widely used in catalysis. However, enhancing their stability during catalytic reactions has been a challenge that has limited the full use of the benefits associated with their small size. In this Feature Article, a general “encapsulation and etching” strategy for the fabrication of nanocatalyst systems is introduced in which catalyst nanoparticles are protected within porous shells. The novelty of this approach lies in the use of chemical etching to assist the creation of mesopores in a protective oxide shell to promote efficient mass transfer to encapsulated metal nanoparticles. The etching process allows for the direct transformation of dense silica coatings into porous shells so that chemical species can reach the catalyst surface to participate in reactions while the shells act as physical barriers against aggregation of the catalyst particles. By using the surface-protected etching process, both yolk–shell and core–satellite type nanoreactors are synthesized and their utilization in liquid- and gas-phase catalysis is demonstrated. The thermal and chemical stability of the metallic cores during catalytic reactions is also investigated, and further work is carried out to enhance recyclability via the introduction of superparamagnetic components into the nanoreactor framework.

Core–shell structured Fe₃O₄/SiO₂/TiO₂ nanocomposites with enhanced photocatalytic activity that are capable of fast magnetic separation have been successfully synthesized by combining two steps of a sol–gel process with calcination. The as-obtained core–shell structure is composed of a central magnetite core with a strong response to external fields, an interlayer of SiO₂, and an outer layer of TiO₂ nanocrystals with a tunable average size. The convenient control over the size and crystallinity of the TiO₂ nanocatalysts makes it possible to achieve higher photocatalytic efficiency than that of commercial photocatalyst Degussa P25. The photocatalytic activity increases as the thickness of the TiO₂ nanocrystal shell decreases. The presence of SiO₂ interlayer helps to enhance the photocatalytic efficiency of the TiO₂ nanocrystal shell as well as the chemical and thermal stability of Fe₃O₄ core. In addition, the TiO₂ nanocrystals strongly adhere to the magnetic supports through covalent bonds. We demonstrate that this photocatalyst can be easily recycled by applying an external magnetic field while maintaining their photocatalytic activity during at least eighteen cycles of use.