Novel Inorganic-Organic Dual-Photosensitizing Dinuclear-Metal Self-Assembly System for Efficient Artificial Photosynthesis without Sacrificial Electron Donors.

Owing to the unique synergistic effect, dinuclear-metal-molecule-catalysts (DMCs) show excellent performance in catalytic fields. However, for overall photocatalytic CO reaction (CORR), it is still a challenge to construct well-matched photosensitizer (PS) components for DMCs-based photocatalysts. Inorganic-quantum-dot PS possesses capacities of multiple exciton generation and catalyzing water oxidation but is incompatible with DMCs.

Transition Metal-Gallium Intermetallic Compounds with Tailored Active Site Configurations for Electrochemical Ammonia Synthesis.

Gallium (Ga) with a low melting point can serve as a unique metallic solvent in the synthesis of intermetallic compounds (IMCs). The negative formation enthalpy of transition metal-Ga IMCs endows them with high catalytic stability. Meanwhile, their tunable crystal structures offer the possibility to tailor the configurations of active sites to meet the requirements for specific catalytic applications.

Crystal-Phase-Selective Etching of Heterophase Au Nanostructures.

Selective oxidative etching is one of the most effective ways to prepare hollow nanostructures and nanocrystals with specific exposed facets. The mechanism of selective etching in noble metal nanostructures mainly relies on the different reactivity of metal components and the distinct surface energy of multimetallic nanostructures. Recently, phase engineering of nanomaterials (PEN) offers new opportunities for the preparation of unique heterostructures, including heterophase nanostructures.

Breaking Highly Ordered PtPbBi Intermetallic with Disordered Amorphous Phase for Boosting Electrocatalytic Hydrogen Evolution and Alcohol Oxidation.

Constructing amorphous/intermetallic (A/IMC) heterophase structures by breaking the highly ordered IMC phase with disordered amorphous phase is an effective way to improve the electrocatalytic performance of noble metal-based IMC electrocatalysts because of the optimized electronic structure and abundant heterophase boundaries as active sites. In this study, we report the synthesis of ultrathin A/IMC PtPbBi nanosheets (NSs) for boosting hydrogen evolution reaction (HER) and alcohol oxidation reactions. The resulting A/IMC PtPbBi NSs exhibit a remarkably low overpotential of only 25 mV at 10 mA cm for the HER in an acidic electrolyte, together with outstanding stability for 100 h.

Metal-Organic Framework-Based Hetero-Phase Nanostructure Photocatalysts with Molecular-Scale Tunable Energy Levels.

As an effective method to modulate the physicochemical properties of materials, crystal phase engineering, especially hetero-phase, plays an important role in developing high-performance photocatalysts. However, it is still a huge challenge but significant to construct porous hetero-phase nanostructures with adjustable band structures. As a kind of unique porous crystalline materials, metal-organic frameworks (MOFs) might be the appropriate candidate, but the MOF-based hetero-phase is rarely reported.

Phase Engineering of Nanomaterials: Transition Metal Dichalcogenides.

Crystal phase, a critical structural characteristic beyond the morphology, size, dimension, facet, , determines the physicochemical properties of nanomaterials. As a group of layered nanomaterials with polymorphs, transition metal dichalcogenides (TMDs) have attracted intensive research attention due to their phase-dependent properties. Therefore, great efforts have been devoted to the phase engineering of TMDs to synthesize TMDs with controlled phases, especially unconventional/metastable phases, for various applications in electronics, optoelectronics, catalysis, biomedicine, energy storage and conversion, and ferroelectrics.

3D Noble-Metal Nanostructures Approaching Atomic Efficiency and Atomic Density Limits.

Noble metals have been widely used in catalysis, however, the scarcity and high cost of noble metal motivate researchers to balance the atomic efficiency and atomic density, which is formidably challenging. This article proposes a robust strategy for fabricating 3D amorphous noble metal-based oxides with simultaneous enhancement on atomic efficiency and density with the assistance of atomic channels, where the atomic utilization increases from 18.2% to 59.

Recent Progress on Phase Engineering of Nanomaterials.

As a key structural parameter, phase depicts the arrangement of atoms in materials. Normally, a nanomaterial exists in its thermodynamically stable crystal phase. With the development of nanotechnology, nanomaterials with unconventional crystal phases, which rarely exist in their bulk counterparts, or amorphous phase have been prepared using carefully controlled reaction conditions.

Synthesis of 2H/fcc-Heterophase AuCu Nanostructures for Highly Efficient Electrochemical CO Reduction at Industrial Current Densities.

Structural engineering of nanomaterials offers a promising way for developing high-performance catalysts toward catalysis. However, the delicate modulation of thermodynamically unfavorable nanostructures with unconventional phases still remains a challenge. Here, the synthesis of hierarchical AuCu nanostructures is reported with hexagonal close-packed (2H-type)/face-centered cubic (fcc) heterophase, high-index facets, planar defects (e.

Structural Transformation of Unconventional-Phase Materials.

The structural transformation of materials, which involves the evolution of different structural features, including phase, composition, morphology, etc., under external conditions, represents an important fundamental phenomenon and has drawn substantial research interest. Recently, materials with unconventional phases that are different from their thermodynamically stable ones have been demonstrated to possess distinct properties and compelling functions and can further serve as starting materials for structural transformation studies.

Ligand-Assisted Phase Engineering of Nanomaterials.

ConspectusThe synthesis of monodisperse colloidal nanomaterials with well-defined structures is important for both fundamental research and practical application. To achieve it, wet-chemical methods with the usage of various ligands have been extensively explored to finely control the structure of nanomaterials. During the synthesis, ligands cap the surface and thus modulate the size, shape, and stability of nanomaterials in solvents.

Seeded Synthesis of Hollow PdSn Intermetallic Nanomaterials for Highly Efficient Electrocatalytic Glycerol Oxidation.

Intermetallic nanomaterials have shown promising potential as high-performance catalysts in various catalytic reactions due to their unconventional crystal phases with ordered atomic arrangements. However, controlled synthesis of intermetallic nanomaterials with tunable crystal phases and unique hollow morphologies remains a challenge. Here, a seeded method is developed to synthesize hollow PdSn intermetallic nanoparticles (NPs) with two different intermetallic phases, that is, orthorhombic Pd Sn and monoclinic Pd Sn .

Two-Dimensional Nanomaterial-Templated Composites.

ConspectusTwo-dimensional (2D) nanomaterials have attracted increasing research interest since mechanically exfoliated graphene was obtained in 2004. The ultrathin thickness and relatively large lateral size of 2D nanomaterials render them various intriguing properties such as compelling electronic properties, ultrahigh specific surface area, excellent mechanical properties, and so on. A wide range of 2D nanomaterials, including graphene and its derivatives, transition metal dichalcogenides (TMDs), metals, , have been prepared with different compositions, structures and (crystal) phases.

Isolated Electron-Rich Ruthenium Atoms in Intermetallic Compounds for Boosting Electrochemical Nitric Oxide Reduction to Ammonia.

The direct electrochemical nitric oxide reduction reaction (NORR) is an attractive technique for converting NO into NH with low power consumption under ambient conditions. Optimizing the electronic structure of the active sites can greatly improve the performance of electrocatalysts. Herein, we prepare body-centered cubic RuGa intermetallic compounds (i.

Preparation of Amorphous SnO -Encapsulated Multiphased Crystalline Cu Heterostructures for Highly Efficient CO Reduction.

Controlling the architectures and crystal phases of metal@semiconductor heterostructures is very important for modulating their physicochemical properties and enhancing their application performances. Here, a facile one-pot wet-chemical method to synthesize three types of amorphous SnO -encapsulated crystalline Cu heterostructures, i.e.

Isoreticular Series of Two-Dimensional Covalent Organic Frameworks with the kgd Topology and Controllable Micropores.

Two-dimensional (2D) covalent organic frameworks (COFs) possess designable pore architectures but limited framework topologies. Until now, 2D COFs adopting the topology with ordered and rhombic pore geometry have rarely been reported. Here, an isoreticular series of 2D COFs with the topology and controllable pore size is synthesized by employing a -symmetric aldehyde, .

Confined Growth of Silver-Copper Janus Nanostructures with {100} Facets for Highly Selective Tandem Electrocatalytic Carbon Dioxide Reduction.

Electrocatalytic carbon dioxide reduction reaction (CO RR) holds significant potential to promote carbon neutrality. However, the selectivity toward multicarbon products in CO RR is still too low to meet practical applications. Here the authors report the delicate synthesis of three kinds of Ag-Cu Janus nanostructures with {100} facets (JNS-100) for highly selective tandem electrocatalytic reduction of CO to multicarbon products.

Preparation of Au@Pd Core-Shell Nanorods with -2H- Heterophase for Highly Efficient Electrocatalytic Alcohol Oxidation.

Controlled construction of bimetallic nanostructures with a well-defined heterophase is of great significance for developing highly efficient nanocatalysts and investigating the structure-dependent catalytic performance. Here, a wet-chemical synthesis method is used to prepare Au@Pd core-shell nanorods with a unique -2H- heterophase (: face-centered cubic; 2H: hexagonal close-packed with a stacking sequence of "AB"). The obtained -2H- heterophase Au@Pd core-shell nanorods exhibit superior electrocatalytic ethanol oxidation performance with a mass activity as high as 6.

Preparation of fcc-2H-fcc Heterophase Pd@Ir Nanostructures for High-Performance Electrochemical Hydrogen Evolution.

With the development of phase engineering of nanomaterials (PEN), construction of noble-metal heterostructures with unconventional crystal phases, including heterophases, has been proposed as an attractive approach toward the rational design of highly efficient catalysts. However, it still remains challenging to realize the controlled preparation of such unconventional-phase noble-metal heterostructures and explore their crystal-phase-dependent applications. Here, various Pd@Ir core-shell nanostructures are synthesized with unconventional fcc-2H-fcc heterophase (2H: hexagonal close-packed; fcc: face-centered cubic) through a wet-chemical seeded method.

Seeded Synthesis of Unconventional 2H-Phase Pd Alloy Nanomaterials for Highly Efficient Oxygen Reduction.

Crystal phase engineering of noble-metal-based alloy nanomaterials paves a new way to the rational synthesis of high-performance catalysts for various applications. However, the controlled preparation of noble-metal-based alloy nanomaterials with unconventional crystal phases still remains a great challenge due to their thermodynamically unstable nature. Herein, we develop a robust and general seeded method to synthesize PdCu alloy nanomaterials with unconventional hexagonal close-packed (, 2H type) phase and also tunable Cu contents.

Synthesis of Pd Sn and PdCuSn Nanorods with L1 Phase for Highly Efficient Electrocatalytic Ethanol Oxidation.

The crystal phase of nanomaterials is one of the key parameters determining their physicochemical properties and performance in various applications. However, it still remains a great challenge to synthesize nanomaterials with different crystal phases while maintaining the same composition, size, and morphology. Here, a facile, one-pot, wet-chemical method is reported to synthesize Pd Sn nanorods with comparable size and morphology but different crystal phases, that is, an ordered intermetallic and a disordered alloy with L1 and face-centered cubic (fcc) phases, respectively.

Hydrogen-Intercalation-Induced Lattice Expansion of Pd@Pt Core-Shell Nanoparticles for Highly Efficient Electrocatalytic Alcohol Oxidation.

Lattice engineering on specific facets of metal catalysts is critically important not only for the enhancement of their catalytic performance but also for deeply understanding the effect of facet-based lattice engineering on catalytic reactions. Here, we develop a facile two-step method for the lattice expansion on specific facets, i.e.

Evoking ordered vacancies in metallic nanostructures toward a vacated Barlow packing for high-performance hydrogen evolution.

Metallic nanostructures are commonly densely packed into a few packing variants with slightly different atomic packing factors. The structural aspects and physicochemical properties related with the vacancies in such nanostructures are rarely explored because of lack of an effective way to control the introduction of vacancy sites. Highly voided metallic nanostructures with ordered vacancies are however energetically high lying and very difficult to synthesize.

Bromide Ions Triggered Synthesis of Noble Metal-Based Intermetallic Nanocrystals.

Ordered intermetallic nanomaterials with a well-defined crystal structure and fixed stoichiometry facilitate the predictable control of their electronic structure and catalytic performance. To obtain the thermodynamically stable intermetallic structures, the conventional approaches with high-temperature annealing are still far from satisfactory, because of annealing-induced aggregation and sintering of nanomaterials. Herein, a general wet-chemical method is developed to synthesize a series of noble metal-based intermetallic nanocrystals, including hexagonal close-packed (hcp) PtBi nanoplates, face-centered cubic (fcc) Pd Pb nanocubes, and hcp Pd Bi nanoparticles.