Tierui Zhang

Core–Satellite Nanocomposite Catalysts Protected by a Porous Silica Shell: Controllable Reactivity, High Stability, and Magnetic Recyclability

The development of more efficient and stable catalysts hasbeen an increasingly important goal for chemists andmaterials scientists for both economic and environmentalreasons. Much attention has been paid recently to nano-particlesoftransitionmetals,particularlynoblemetals,asaresult of significant progress in synthetic methods forcontrollingtheircomposition,size,andshape.Thisdevelop-ment should lead to the design of catalysts with superiorperformance that take advantage of nanoparticles highsurface-to-volume ratio and their shape-dependent surfacestructure.

Graphene‐Supported Ultrafine Metal Nanoparticles Encapsulated by Mesoporous Silica: Robust Catalysts for Oxidation and Reduction 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.

Formation of Hollow Silica Colloids through a Spontaneous Dissolution–Regrowth Process

tence of a large number of silicate species and their rich chemical interactions makes the dissolution and growth of silica challenging to study. However, this complexity also provides enormous opportunities for the development of materials with new structures and functionalities. For example, systematic investigation of the dissolution and formation of silica nanoparticles has made it possible to control the nucleation and growth, and subsequently the crystal size and shape, of zeolite materials. [4–6] Herein, we report that amorphous silica colloids, when dispersed in an aqueous solution of NaBH4, undergo a spontaneous morphology change from solid to hollow spheres. Concurrent but separate coredissolution and shell-growth processes appear to be responsible to the formation of the hollow structures. Besides the interesting fundamental aspects of this spontaneous process, this work also provides an effective self-templated route for the preparation of hollow silica nanostructures, which may find immediate applications in fields such as catalysis and drug delivery. [7–12] Since silica can coat many nanostructures through simple sol–gel processes, our discovery also allows convenient transformation of core–shell particles into yolk– shell structures, which are promising for use as nanoscale reactors and controlled-release vehicles. Compared to widely adopted methods using polymer beads and micelle and

Carbon quantum dots/TiO2 composites for efficient photocatalytic hydrogen evolution

Carbon quantum dots modified P25 TiO2 composites (CQDs/P25) with a “dyade”-like structure were prepared via a facile one-step hydrothermal reaction. CQDs/P25 exhibited improved photocatalytic H2 evolution under UV-Vis and visible light (λ > 450 nm) irradiation without loading any noble metal cocatalyst, compared to pure P25. A possible mechanism of the photocatalytic H2 production activity over CQDs/P25 was proposed based on detailed measurements of the transient photocurrent response, surface photovoltage and hydroxyl radicals. CQDs play dual roles on the improved photocatalytic activity of CQDs/P25. Under UV-Vis light irradiation CQDs act as an electron reservoir to improve the efficient separation of the photoinduced electron–hole pairs of P25. However, under visible light irradiation CQDs act as a photosensitizer to sensitize P25 into a visible light response “dyade” structure for H2 evolution.

Well‐Dispersed ZIF‐Derived Co,N‐Co‐doped Carbon Nanoframes through Mesoporous‐Silica‐Protected Calcination as Efficient Oxygen Reduction Electrocatalysts

A well-dispersed Co,N co-doped carbon nanoframework (Co,N-CNF) with hierarchically porous structure is successfully synthesized from zeolitic imidazolate framework (ZIF) precursors via a mesoporous-silica-protected calcination strategy. By preventing the irreversible fusion and aggregation during the high-temperature pyrolysis step with this protection strategy, the Co,N-CNF exhibits comparable oxygen reduction reaction (ORR) catalytic activity to that of commercial Pt catalysts with the same loading.

Nitrogen-Doped Porous Carbon Nanosheets Templated from g-C3N4 as Metal-Free Electrocatalysts for Efficient Oxygen Reduction Reaction

Nitrogen-doped porous carbon nanosheets (N-CNS) are synthesized by hydrothermal carbon coating of g-C3 N4 nanosheets followed by high-temperature treatment in N2 . g-C3 N4 serves as a template, nitrogen source, and porogen in the synthesis. This approach yields N-CNS with a high nitrogen content and comparable oxygen reduction reaction catalytic activities to commercial Pt/C catalysts in alkaline media.

Alkali-Assisted Synthesis of Nitrogen Deficient Graphitic Carbon Nitride with Tunable Band Structures for Efficient Visible-Light-Driven Hydrogen Evolution

A facile synthetic strategy for nitrogen-deficient graphitic carbon nitride (g-C3 Nx ) is established, involving a simple alkali-assisted thermal polymerization of urea, melamine, or thiourea. In situ introduced nitrogen vacancies significantly redshift the absorption edge of g-C3 Nx , with the defect concentration depending on the alkali to nitrogen precursor ratio. The g-C3 Nx products show superior visible-light photocatalytic performance compared to pristine g-C3 N4 .

Smart Utilization of Carbon Dots in Semiconductor Photocatalysis

Efficient capture of solar energy will be critical to meeting the energy needs of the future. Semiconductor photocatalysis is expected to make an important contribution in this regard, delivering both energy carriers (especially H2 ) and valuable chemical feedstocks under direct sunlight. Over the past few years, carbon dots (CDs) have emerged as a promising new class of metal-free photocatalyst, displaying semiconductor-like photoelectric properties and showing excellent performance in a wide variety of photoelectrochemical and photocatalytic applications owing to their ease of synthesis, unique structure, adjustable composition, ease of surface functionalization, outstanding electron-transfer efficiency and tunable light-harvesting range (from deep UV to the near-infrared). Here, recent advances in the rational design of CDs-based photocatalysts are highlighted and their applications in photocatalytic environmental remediation, water splitting into hydrogen, CO2 reduction, and organic synthesis are discussed.

Defect‐Rich Ultrathin ZnAl‐Layered Double Hydroxide Nanosheets for Efficient Photoreduction of CO2 to CO with Water

Defect-rich ultrathin ZnAl-layered double hydroxide nanosheets are successfully prepared. Under UV-vis irradiation, these nanosheets are superior efficient catalysts for the photoreduction of CO2 to CO with water. The formed oxygen vacancies lead to the formation of coordinatively unsaturated Zn(+) centers within the nanosheets, responsible for the very high photocatalytic activities.

Bi2O2(OH)(NO3) as a desirable [Bi2O2]2+ layered photocatalyst: strong intrinsic polarity, rational band structure and {001} active facets co-beneficial for robust photooxidation capability

Developing high-performance photocatalytic materials is of huge significance and highly desirable for fulfilling the pressing need in environmental remediation. In this work, we demonstrate the use of bismuth nitrate Bi2O2(OH)(NO3) as an absorbing photocatalyst, which integrates multiple superiorities, like a [Bi2O2]2+ layered configuration, a non-centrosymmetric (NCS) polar structure and highly reactive {001} facets. Bi2O2(OH)(NO3) nanosheets are obtained by a facile one-pot hydrothermal route using Bi(NO3)3·5H2O as the sole raw material. Photocatalysis assessment revealed that Bi2O2(OH)(NO3) holds an unprecedented photooxidation ability in contaminant decomposition, far out-performing the well-known photocatalysts BiPO4, Bi2O2CO3, BiOCl and P25 (commercial TiO2). Particularly, it displays a universally powerful catalytic activity against various stubborn industrial contaminants and pharmaceuticals, including phenol, bisphenol A, 2,4-dichlorophenol and tetracycline hydrochloride. In-depth experimental and density functional theory (DFT) investigations co-uncovered that the manifold advantages, such as large polarizability and rational band structure, as well as exposed {001} active facets, induced robust generation of strong oxidating superoxide radicals (˙O2−) in the conduction band and hydroxyl radicals (˙OH) in the valence band, thus enabling Bi2O2(OH)(NO3) to have a powerful and durable photooxidation capability. Bi2O2(OH)(NO3) also presents high photochemical stability. This work not only rendered a highly active and stable photocatalyst for practical applications, but also laid a solid foundation for future initiatives aimed at designing new photoelectronic materials by manipulating multiple advantageous factors.