Atomically Precise Metal-Metal Oxide Interface in Polyoxometalate-Noble Metal Hybrid Clusters.

Metal-metal oxide hybrid materials, typically composed of metal nanoparticles anchored on metal oxides matrix, are devoted enormous attentions as famous heterogeneous catalysts. The interactions between noble metals and metal oxides as well as their interfaces have been proven to be the origin of their excellent catalytic performance. Deep understandings on the interactions between noble metals and metal oxides at atomic precision, thus to precisely assess their contributions to catalysis, can serve as basic principles for catalyst design.

Fluorescent Enhancement of [AgS] Microplates by Mechanical Force Induced Crystallinity Breaking.

Mechanofluorochromic materials are a type of "smart" material because of their adjustable fluorescent properties under external mechanical force, making them significant members of the materials family. However, as the fluorescent characteristics of these materials highly depend on their microstructures, the still insufficiently in-depth research linking molecular structures to light emission motivates researchers to explore the fluorescent properties of these materials under external stimuli. In this work, based on synthetic [AgS] microplates, we explore a fascinating mechanical-induced photoluminescent enhancement phenomenon.

Directional surface plasmon polariton scattering using single magnetic nanoparticles.

Directional surface plasmon polaritons (SPPs) are expected to promote the energy efficiency of plasmonic devices, via limiting the energy in a given spatial domain. The directional scattering of dielectric nanoparticles induced by the interference between electric and magnetic responses presents a potential candidate for directional SPPs. Magnetic nanoparticles can introduce permeability as an extra manipulation, whose directional scattered SPPs have not been investigated yet.

Reconstruction Filters Improving the Spatial Resolution and Signal-to-Noise Ratio of Surface Plasmon Resonance Microscopy.

Benefitting from high sensitivity, real-time, and label-free imaging, surface plasmon resonance microscopy (SPRM) has become a powerful tool for dynamic detection of nanoparticles. However, the evanescent propagation of surface plasmon polaritons (SPPs) induces interference between scattered and launched SPPs, which deteriorates the spatial resolution and signal-to-noise ratio (SNR). Due to the simplicity and fast processing, image reconstruction based on deconvolution has shown the feasibility of improving the spatial resolution of SPRM imaging.

Modulating Catalytic Activity and Stability of Atomically Precise Gold Nanoclusters as Peroxidase Mimics via Ligand Engineering.

Metal nanoclusters (NCs), composed of a metal core and protecting ligands, show promising potentials as enzyme mimics for producing fuels, pharmaceuticals, and valuable chemicals, etc. Herein, we explore the critical role of ligands in modulating the peroxidase mimic activity and stability of Au NCs. A series of Au(SR) NCs with various thiolate ligands [SR = -acetyl-l-cysteine (NAC), 3-mercaptopropionic acid (MPA), or 3-mercapto-2-methylpropanoic acid (MMPA)] are utilized as model catalysts.

Supercrystal engineering of atomically precise gold nanoparticles promoted by surface dynamics.

The controllable packing of functional nanoparticles (NPs) into crystalline lattices is of interest in the development of NP-based materials. Here we demonstrate that the size, morphology and symmetry of such supercrystals can be tailored by adjusting the surface dynamics of their constituent NPs. In the presence of excess tetraethylammonium cations, atomically precise [Au(SR)] NPs (where SR is a thiolate ligand) can be crystallized into micrometre-sized hexagonal rod-like supercrystals, rather than as face-centred-cubic superlattices otherwise.

Cation polymer-induced aggregation of water-soluble Au(I)-thiolate complexes and their photoluminescence properties.

Au(I)-thiolate complexes are a new class of aggregation-induced emission (AIE) material. Here we demonstrate a new aggregation strategy of water-soluble Au(I)-thiolate complexes induced by cationic polymers at optimized pH values. The generated AIE shows longer wavelengths than the emission induced by other methods.

Revealing the composition-dependent structural evolution fundamentals of bimetallic nanoparticles through an inter-particle alloying reaction.

Alloy nanoparticles represent one of the most important metal materials, finding increasing applications in diverse fields of catalysis, biomedicine, and nano-optics. However, the structural evolution of bimetallic nanoparticles in their full composition spectrum has been rarely explored at the molecular and atomic levels, imparting inherent difficulties to establish a reliable structure-property relationship in practical applications. Here, through an inter-particle reaction between [Au(SR)] and [Ag(SR)] nanoparticles or nanoclusters (NCs), which possess the same number of metal atoms, but different atomic packing structures, we reveal the composition-dependent structural evolution of alloy NCs in the alloying process at the molecular and atomic levels.

Effects of nanoparticle sizes, shapes, and permittivity on plasmonic imaging.

Plasmonic imaging has exhibited superiority in label-free and fast detection to single nanoparticles due to its high sensitivity and high temporal resolution, which plays an important role in environmental monitoring and biomedical research. As containing plenty of information associated with particle features, plasmonic imaging has been used for identifying the particle sizes, shapes, and permittivity. Yet, the effects of the nanoparticle features on plasmonic imaging are not investigated, which hinders the in-depth understanding to plasmonic imaging and its applications in particle identification.

Progresses in synthetic technology development for the production of L-lactide.

L-Lactide is an intermediate for the industrial production of polylactic acid (PLA). The chemical and optical purities of lactide determine the quality of the prepared PLA. It is of great challenge to synthesize L-lactide efficiently with high chemical and optical purities under the conditions applicable for industrial production.

Diversification of Metallic Molecules through Derivatization Chemistry of Au Nanoclusters.

Derivatization is the fine chemistry that can produce chemical compounds from similar precursors and has been widely used in the field of organic synthesis to achieve diversification of molecular properties and functionalities. Ligand-protected metal nanoclusters (NCs) are metallic molecules with a definite molecular formula, well-defined molecular structure, and molecular-like physical and chemical properties. Unlike organic compounds, which have almost infinite species, until now only hundreds of metal NC species have been discovered, and only a few of them have been structurally resolved.

Interactions of Metal Nanoclusters with Light: Fundamentals and Applications.

The interactions of materials with light determine their applications in various fields. In the past decade, ultrasmall metal nanoclusters (NCs) have emerged as a promising class of optical materials due to their unique molecular-like properties. Herein, the basic principles of optical absorption and photoluminescence of metal NCs, their interactions with polarized light, and light-induced chemical reactions, are discussed, highlighting the roles of the core and protecting ligands/motifs of metal NCs in their interactions with light.

Unique Dual-Sites Boosting Overall CO Photoconversion by Hierarchical Electron Harvesters.

Low selectivity and poor activity of photocatalytic CO reduction process are usually limiting factors for its applicability. Herein, a hierarchical electron harvesting system is designed on CoNiP hollow nano-millefeuille (CoNiP NH), which enables the charge enrichment on CoNi dual active sites and selective conversion of CO to CH . The CoNiP serves as an electron harvester and photonic "black hole" accelerating the kinetics for CO -catalyzed reactions.

Revealing the etching process of water-soluble Au nanoclusters at the molecular level.

Etching (often considered as decomposition) is one of the key considerations in the synthesis, storage, and application of metal nanoparticles. However, the underlying chemistry of their etching process still remains elusive. Here, we use real-time electrospray ionization mass spectrometry to study the reaction dynamics and size/structure evolution of all the stable intermediates during the etching of water-soluble thiolate-protected gold nanoclusters (Au NCs), which reveal an unusual "recombination" process in the oxidative reaction environment after the initial decomposition process.

Ligand Design in Ligand-Protected Gold Nanoclusters.

The design of surface ligands is crucial for ligand-protected gold nanoclusters (Au NCs). Besides providing good protection for Au NCs, the surface ligands also play the following two important roles: i) as the outermost layer of Au NCs, the ligands will directly interact with the exterior environment (e.g.

Control of single-ligand chemistry on thiolated Au nanoclusters.

Diverse methods have been developed to tailor the number of metal atoms in metal nanoclusters, but control of surface ligand number at a given cluster size is rare. Here we demonstrate that reversible addition and elimination of a single surface thiolate ligand (-SR) on gold nanoclusters can be realized, opening the door to precision ligand engineering on atomically precise nanoclusters. We find that oxidative etching of [AuSR] nanoclusters adds an excess thiolate ligand and generates a new species, [AuSR].

Ligand-protected atomically precise gold nanoclusters as model catalysts for oxidation reactions.

Catalytic oxidation is an important reaction in the fine chemical industry, environment, and energy. In the past few decades, many kinds of catalysts have been produced with promising catalytic performance for oxidation reactions; however, the understanding of the mechanisms is still insufficient due to the complexity of the composition and structure of conventional catalysts. In the past several years, the community has tried to address this problem by using ligand-protected atomically precise gold nanoclusters as model catalysts.

A Photochemical Route towards Metal Sulfide Nanosheets from Layered Metal Thiolate Complexes.

Synthesizing nanomaterials with anisotropic architectures, especially two-dimensional (2D) nanosheets (NSs), is a key focus of materials science research. Metal sulfide nanosheets (MSNSs) are typically obtained involving exfoliation of bulk metal sulfides with layered structures. The synthesis of NSs of intrinsically non-layered metal sulfides has received relatively less attention.

Aurophilic Interactions in the Self-Assembly of Gold Nanoclusters into Nanoribbons with Enhanced Luminescence.

Aurophilic interactions (Au ⋅⋅⋅Au ) are crucial in directing the supramolecular self-assembly of many gold(I) compounds; however, this intriguing chemistry has been rarely explored for the self-assembly of nanoscale building blocks. Herein, we report on studies on aurophilic interactions in the structure-directed self-assembly of ultrasmall gold nanoparticles or nanoclusters (NCs, <2 nm) using [Au (SR) ] (SR=thiolate ligand) as a model cluster. The self-assembly of NCs is initiated by surface-motif reconstruction of [Au (SR) ] from short SR-[Au -SR] units to long SR-[Au -SR] (x>2) staples accompanied by structure modification of the intrinsic Au kernel.

Evolution of thiolate-stabilized Ag nanoclusters from Ag-thiolate cluster intermediates.

The synthesis of atomically precise thiolate-stabilized silver (Ag) nanoclusters is the subject of intense research interest, yet the formation mechanism of such nanoclusters remains obscure. Here, electrospray ionization mass spectrometry is successfully applied to monitor the reaction intermediates formed during the sodium-borohydride-reduction of silver 4-tert-butylbenzenethiolate (AgSPh-tBu). We demonstrate a unique evolution route to thiolate-stabilized Ag nanoclusters mediated by Ag-thiolate clusters.

Thiolate-Mediated Photoinduced Synthesis of Ultrafine Ag S Quantum Dots from Silver Nanoparticles.

Photoinduced syntheses offer significant advantages over conventional thermal strategies, including improved control over reaction kinetics and low synthesis temperatures, affording nanoparticles with nontrivial and thermodynamically unstable structures. However, the photoinduced syntheses of non-metallic nanocrystalline products (such as metal sulfides) have not yet been reported. Herein, we demonstrate the first photoinduced synthesis of ultrafine (sub-2 nm) Ag S quantum dots (QDs) from Ag nanoparticles at 10 °C.

Controllable Synthesis of Ultrathin Transition-Metal Hydroxide Nanosheets and their Extended Composite Nanostructures for Enhanced 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.

Copper(I) cysteine complexes: efficient earth-abundant oxidation co-catalysts for visible light-driven photocatalytic H2 production.

A copper(i) cysteine complex generated by mixing Cu(ii) ions with cysteine in aqueous solution greatly enhanced the activity of CdSe photocatalysts for H2 production in aqueous solution under visible light excitation. The complex can enhance the H2 evolution rate by as much as 150 times, by acting as an oxidation co-catalyst and increasing charge carrier lifetimes. The copper(i) cysteine complex can also be applied to enhance the H2 production performance of other semiconductor photocatalyst systems, thereby affording a new research direction in the development of co-catalysts for solar hydrogen production.