Ren-Wu Huang

Electrochemical oxidation of ethylene (C2H4) to ethylene glycol (EG) offers a sustainable route for chemical production. However, designing catalysts at the atomic level and precisely elucidating the microscopic mechanisms of catalytic processes remain a formidable challenge. Here, we report a well-defined Ag14S(4-CF3PhS)12(PPh3)8 cluster (Ag14) and its electrocatalytic performance and mechanism for the conversion of C2H4 to EG. The Ag14 supported on carbon nanotubes (Ag14/CNTs) achieved high selectivity (> 96%), EG productivity (73.43 μmol·h‒1), and turnover frequency (5.25 s‒1) at 2.4 V (vs. reversible hydrogen electrode). In situ characterization and theoretical calculations indicate that the catalytic process involves electrochemical activation of water to generate Ag-oxygen species, followed by the oxidation of C2H4 to form the intermediate ethylene oxide (EO), and eventually the ring-opening of EO to EG. The superior performance of Ag14/CNTs is attributed to the role of mixed ligands in stabilizing high-valent silver and elevating the d-band centre, thereby reducing the adsorption free energy of key intermediates and suppressing the competing oxygen evolution reaction. This work provides a foundation for developing nano-sized silver-based catalysts for the electrocatalytic conversion of C2H4 to EG.

Dendrite growth and side reactions occurring in Zn anodes hinder the development and practical application of aqueous Zn-ion batteries. Herein, for the first time, we demonstrated the use of ligand-protected Cu nanoclusters as Zn plating/stripping mediators to construct dendrite-free Zn anodes. The abundant polar functional groups (–COOH, –NH₂, and –CO–NH–) on the peripheral ligands modulated the solvation structure and regulated the transport of Zn²⁺, whereas the zincophilic Cu cores functioned as nucleating agents to guide the uniform nucleation and plating of Zn. Using such bifunctional CuNCs, the asymmetric cell achieves a coulombic efficiency of 99.40% for over 1000 cycles, and the symmetric cell exhibits low voltage hysteresis and superior cycling over 400 h with a high depth of discharge of 40%. These findings may contribute to the design of multifunctional mediators at the atomic level.

The hydroboration of alkynes into vinylboronate esters is a vital transformation, but achieving high chemoselectivity of targeted functional groups and an appreciable turnover number is a considerable challenge. Herein, we develop two dynamically regulating dual-catalytic-site copper clusters (Cu₄NC and Cu₈NC) bearing N-heterocyclic thione ligands that endow Cu₄NC and Cu₈NC catalysts with performance. In particular, the performance of microcrystalline Cu₄NC in hydroboration is characterized by a high turnover number (77786), a high chemoselectivity, high recovery and reusability under mild conditions. Mechanistic studies and density functional theory calculations reveal that, compared with the Cu₈NC catalyst, the Cu₄NC catalyst has a lower activation energy for hydroboration, accounting for its high catalytic activity. This work reveals that precisely constructed cluster catalysts with dual catalytic sites may provide a way to substantially improve catalytic properties by fully leveraging synergistic interactions and dynamic ligand effects, thus promoting the development of cluster catalysts.

Near-infrared (NIR) photothermal materials efficiently convert low-energy near-infrared light into heat and have a significant role across various domains. Herein, a copper iodine cluster node (Cu₁₄I₁₄) featuring inorganic aromaticity was assembled with porphyrinic ligands characterized by classical π-aromaticity to create a dual-aromatic crystalline MOF (denoted as Cu₁₄I₁₄-CuTPyP). Cu₁₄I₁₄-CuTPyP with extensive electron delocalization exhibited broad NIR absorption and achieved a high NIR photothermal conversion efficiency of 63.77% under 1064 nm laser irradiation; this efficiency surpassed those of most reported porphyrin assembly materials. By combining in situ Raman spectroscopy, transient absorption spectroscopy, and control experiments, we revealed that the cooperation between aromatic Cu₁₄I₁₄ and porphyrin led to an active electron transfer pathway in Cu₁₄I₁₄-CuTPyP, which consumed a considerable amount of excited-state molecules (71.4%) through ultrafast nonradiative relaxation channels (2.1 ps). In this study, our thorough investigation of the photothermal properties of bis-aromatic MOFs could aid in setting a new standard for material design.

Due to their atomically precise structure, photoluminescent copper nanoclusters (Cu NCs) have emerged as promising materials in both fundamental studies and technological applications, such as bio‐imaging, cell labeling, phototherapy, and photo‐activated catalysis. In this work, a facile strategy is reported for the synthesis of a novel Cu NCs coprotected by thiolate and phosphine ligands, formulated as [Cu₁₅(PPh₃)₆(PET)₁₃]²⁺, which exhibits bright emission in the near‐infrared (NIR) region (≈720 nm) and crystallization‐induced emission enhancement (CIEE) phenomenon. Single crystal X‐ray crystallography shows that the NC possesses an extraordinary distorted trigonal antiprismatic Cu₆ core and a, unique among metal clusters, “tri‐blade fan”‐like structure. An in‐depth structural investigation of the ligand shell combined with density functional theory calculations reveal that the extended CH···π and π‐π intermolecular ligand interactions significantly restrict the intramolecular rotations and vibrations and, thus, are a major reason for the CIEE phenomena. This study provides a strategy for the controllable synthesis of structurally defined Cu NCs with NIR luminescence, which enables essential insights into the origins of their optical properties.

Copper-based nanomaterials have attracted tremendous interest due to their unique properties in the fields of photoluminescence and catalysis. As a result, studies on the correlation between their molecular structure and their properties are of great importance. Copper nanoclusters are a new class of nanomaterials that can provide an atomic-level view of the crystal structure of copper nanoparticles. Herein, a high-nuclearity copper nanocluster with 81 copper atoms, formulated as [Cu81(PhS)46(tBuNH2)10(H)32]3+ (Cu81), was successfully synthesized and fully studied by X-ray crystallography, X-ray photoelectron spectroscopy, hydrogen evolution experiments, electrospray ionization mass spectrometry, nuclear magnetic resonance spectroscopy, and density functional theory calculations. Cu81 exhibits extraordinary structural characteristics, including (i) three types of novel epitaxial surface-protecting motifs; (ii) an unusual planar Cu17 core; (iii) a hemispherical shell, comprised of a curved surface layer and a planar surface layer; and (iv) two distinct, self-organized arrangements of protective ligands on the curved and planar surfaces. The present study sheds light on structurally unexplored copper nanomaterials and paves the way for the synthesis of high-nuclearity copper nanoclusters.

Interest has been growing in defects of halide perovskites in view of their intimate connection with key material optoelectronic properties. In perovskite quantum dots (PQDs), the influence of defects is even more apparent than in their bulk counterparts. By combining experiment and theory, we report herein a halide‐vacancy‐driven, ligand‐directed self‐assembly process of CsPbBr₃ PQDs. With the assistance of oleic acid and didodecyldimethylammonium sulfide, surface‐Br‐vacancy‐rich CsPbBr₃ PQDs self‐assemble into nanowires (NWs) that are 20–60 nm in width and several millimeters in length. The NWs exhibit a sharp photoluminescence profile (≈18 nm full‐width at‐half‐maximum) that peaks at 525 nm. Our findings provide insight into the defect‐correlated dynamics of PQDs and defect‐assisted fabrication of perovskite materials and devices.

Interest has been growing in defects of halide perovskites in view of their intimate connection with key material optoelectronic properties. In perovskite quantum dots (PQDs), the influence of defects is even more apparent than in their bulk counterparts. By combining experiment and theory, we report herein a halide‐vacancy‐driven, ligand‐directed self‐assembly process of CsPbBr₃ PQDs. With the assistance of oleic acid and didodecyldimethylammonium sulfide, surface‐Br‐vacancy‐rich CsPbBr₃ PQDs self‐assemble into nanowires (NWs) that are 20–60 nm in width and several millimeters in length. The NWs exhibit a sharp photoluminescence profile (≈18 nm full‐width at‐half‐maximum) that peaks at 525 nm. Our findings provide insight into the defect‐correlated dynamics of PQDs and defect‐assisted fabrication of perovskite materials and devices.

Although core–shell copper metal nanoclusters are important emerging materials for practical applications and fundamental scientific research, their synthesis lags behind that of gold and silver nanoclusters–challenged by copper’s much lower half-cell reduction potential, M(I)/M(0). To overcome this synthetic hurdle, we introduce a simple reaction strategy, involving the mild reducing agent borane tert-butylamine complex, to produce a core–shell superatom copper nanocluster, [Cu₆₁(S^tBu)₂₆S₆Cl₆H₁₄]⁺ (−S^tBu; tert-butyl thiolate), which is the largest Cu(0)-containing structurally-solved core–shell copper cluster to-date. The nanocluster exhibits a quasi-elongated triangular gyrobicupola (quasi-J_36,J₃₆ = Johnson solid) Cu₁₉ core and a shell held together by a novel “18-crown-6” metal-sulfide-like belt. Because of its stability, this cluster displays a single molecular ion peak in mass spectrometry measurements without any cluster fragmentation signals—a first observation of its kind for copper nanoclusters that paves the way for researchers to study nanocluster composition, charge, stability, and reaction mechanisms with atomic precision that only mass spectrometry could afford.