Atomically precise metal nanoclusters as catalysts for electrocatalytic CO₂ reduction

Green Chemistry, Journal Year: 2023, Volume and Issue: 26(1), P. 122 - 163

Published: Oct. 12, 2023

Electrochemical CO 2 reduction using metal nanoclusters has attracted much attention because it can convert into several organic compounds renewable energy sources.

Language: Английский

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Nanocluster Surface Microenvironment Modulates Electrocatalytic CO₂ Reduction

Advanced Materials, Journal Year: 2023, Volume and Issue: 36(13)

Published: Dec. 19, 2023

The catalytic activity and product selectivity of the electrochemical CO

Language: Английский

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Carboxylate-Protected “Isostructural” Cu₂₀ Nanoclusters as a Model System: Carboxylate Effect on Controlling Catalysis

Chemistry of Materials, Journal Year: 2024, Volume and Issue: 36(2), P. 1004 - 1012

Published: Jan. 10, 2024

Several recent studies have demonstrated the great promise of ligand-protected atomically precise copper nanoclusters in driving various chemical transformation processes. The insights into key factors controlling catalytic performance clusters at molecular level are highly desirable but difficult to gain. Herein, we report synthesis and comprehensive characterization two novel Cu20 nanoclusters, with formulae Se@Cu20(PhSe)12(PPh3)2(C6H5COO)6 (Cu20-1) Se@Cu20(PhSe)12(PPh3)2(CF3COO)6 (Cu20-2), which proved be candidates clarifying structure property relationship catalysis. As revealed by single-crystal X-ray analysis, structures share an identical metal skeleton similar ligand distributions only difference being carboxylate ligands on surface: C6H5COO for Cu20-1 while CF3COO Cu20-2. Surprisingly, such small distinctions cause a 16-fold activity leap reduction 4-nitrophenol 4-aminophenol. electronic resulting distinct, accounts their distinct performances. This work not provides model system highlight importance catalysis but, more importantly, is also expected simulate research attention engineering modulate physicochemical properties carboxylate-functionalized beyond

Language: Английский

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Thiacalix[4]arene Etching of an Anisotropic Cu₇₀H₂₂ Intermediate for Accessing Robust Modularly Assembled Copper Nanoclusters

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(5), P. 3545 - 3552

Published: Jan. 26, 2024

Atom-precise metal nanoclusters (NCs) with large bulk (nuclearity >60) are important species for insight into the embryonic phase of nanoparticles and their top-down etching synthesis. Herein, we report a metastable rod-shaped 70-nuclei copper-hydride NC, [Cl@Cu

Language: Английский

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Promoting CO2 Electroreduction to Hydrocarbon Products via Sulfur‐Enhanced Proton Feeding in Atomically Precise Thiolate‐Protected Cu Clusters

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(48)

Published: Aug. 22, 2024

Abstract Thiolate‐protected Cu clusters with well‐defined structures and stable low‐coordinated + species exhibit remarkable potential for the CO 2 RR are ideal model catalysts establishing structure‐electrocatalytic property relationships at atomic level. However, extant employed in predominantly yield 2e − products. Herein, two 4 (MMI) 8 ( t BuS) (MMI=2‐mercapto‐1‐methylimidazole) prepared to investigate synergistic effect of adjacent S sites on RR. can reduce deep‐reduced products a 91.0 % Faradaic efficiency (including 53.7 CH ) while maintaining stability. Conversely, shows preference C 2+ products, achieving maximum FE 58.5 current density 152.1 mA⋅cm −2 . In situ XAS ex XPS spectra reveal preservation during RR, extensively enhancing adsorption capacity *CO intermediate. Moreover, kinetic analysis theoretical calculations confirm that facilitate H O dissociation into *H species, which directly participate protonation process *CHO. This study highlights important role Cu−S dual provides mechanistic insights pathway

Language: Английский

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Dipropyne‐Modified N‐Heterocyclic Carbene Stabilized Atomically Precise Copper(I) Nanocluster Catalysts for CO₂ Electroreduction

Advanced Functional Materials, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 25, 2025

Abstract Atomically precise copper(I) nanoclusters with stable active sites are highly sought‐after catalysts for the electrocatalytic CO₂ reduction reaction (CO₂RR), providing an exceptional platform to elucidate structure–activity relationships. However, rational synthesis of robust copper as effective electrocatalysts and understanding relationship between a more realistic site its performance remain significant challenge due their inherent instability. Here, novel dipropyne‐modified NHC ligand is elaborately devised two atomically nanoclusters, [Cu 17 H 6 (NHC ) 4 (dppm) ] 3+ ( Cu17a Ph Cu17b ), both exhibiting distinct unique square orthobicupola Cu core J 28 , Johnson solid). The σ‐ π‐bonding ligands imparts ultrahigh stability while coordination pattern μ 7 ‐ η σ 1 : π 2 facilitates exposure neighboring atoms, generating accessible catalytic sites. Electrocatalytic CO experiments show that achieves highest Faradaic efficiency ethylene production among reported nanoclusters. tandem mechanism RR elucidated through combination theoretical calculations attenuated total reflection‐surface‐enhanced IR absorption spectroscopy (ATR‐SEIRAS). This work not only introduces synthesizing but also offers critical insights into molecular design principles catalysts.

Language: Английский

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Machine Learning Potential for Copper Hydride Clusters: A Neutron Diffraction-Independent Approach for Locating Hydrogen Positions

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: March 15, 2025

Determining hydrogen positions in metal hydride clusters remains a formidable challenge, which relies heavily on unaffordable neutron diffraction. While machine learning has shown promise, only one deep learning-based method been proposed so far, diffraction data for training, limiting its general applicability. In this work, we present an innovative strategy─SSW-NN (stochastic surface walking with neural network)─a robust, non-neutron diffraction-dependent technique that accurately predicts positions. Validated against copper clusters, SSW-NN proved effective where X-ray or DFT predictions are available. It offers superior accuracy, efficiency, and versatility across different hydrides, including silver alloy systems, currently without any references. This approach not establishes new research paradigm but also provides universal solution localization other fields constrained by sources.

Language: Английский

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Atomically Precise Cu Nanoclusters: Recent Advances, Challenges, and Perspectives in Synthesis and Catalytic Applications

Nano-Micro Letters, Journal Year: 2024, Volume and Issue: 17(1)

Published: Dec. 3, 2024

Abstract Atomically precise metal nanoclusters are an emerging type of nanomaterial which has diverse interfacial metal–ligand coordination motifs that can significantly affect their physicochemical properties and functionalities. Among that, Cu have been gaining continuous increasing research attentions, thanks to the low cost, diversified structures, superior catalytic performance for various reactions. In this review, we first summarize recent progress regarding synthetic methods atomically modes between several typical ligands then discuss applications these with some explicit examples explain atomical-level structure–performance relationship. Finally, current challenges future perspectives critical thoughts elaborated. We hope review not only provide a whole picture advances synthesis nanoclusters, but also points out visions in rapidly booming field.

Language: Английский

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Size‐Dependent Carbon Dioxide Reduction Activity of Copper Nanoparticle and Nanocluster Electrocatalysts

ChemNanoMat, Journal Year: 2024, Volume and Issue: 10(5)

Published: March 12, 2024

Abstract The electrochemical carbon dioxide (CO 2 ) reduction reaction (CRR, which can convert CO into useful compounds at room temperature and ambient pressure by using electricity derived from renewable energy source), has been attracting attention in recent years. This is because it compounds, pertinent to establishing a next‐generation recycling‐oriented society. However, further improvement of the electrocatalyst required improve its activity, selectivity, durability. Among these, copper (Cu) synthesize various hydrocarbons most studied for CRR over many In particular, regarding ligand‐protected Cu particles CRR, size, shape, ligands prepared chemical be precisely controlled. this review, we summarize previous research on size‐dependence (nanoparticles nanoclusters) liquid‐phase reduction, discuss current status these studies researchers CRR.

Language: Английский

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One-pot gram-scale synthesis of robust copper nanoclusters for photocatalytic difluoroalkylarylation of alkenes

Polyoxometalates, Journal Year: 2024, Volume and Issue: 4(3), P. 9140080 - 9140080

Published: Oct. 8, 2024

Atomically precise copper nanoclusters have emerged as a promising class of catalysts for driving chemical reactions. However, the exploration nanocluster has been slow, likely due to their complex synthetic process, limited stability, and low activity under mild conditions. In this study, we present highly stable [Cu₈(S₂CN(CH₃)₂)₆(PPh₃)₄]²⁺ (where S₂CN(CH₃)₂ is dimethyldithiocarbamate PPh₃ triphenylphosphine) that exhibits facile protocol high photocatalytic performance. The cluster can be easily obtained by reducing Cu(S₂CN(CH₃)₂)₂ with (PPh₃)₂CuBH₄ in presence 3,5-bis(trifluoromethyl)pyrazole one-pot reaction, even yielding gram-scale product through one-step process. A comprehensive experimental theoretical characterization provides deep understanding its atomic electronic structure, which also explains stability irradiation treatment. Importantly, enables photo-catalytic difluoroalkylarylation alkenes at room temperature, resulting wide range difluoromethyl compounds This study not only presents an efficient strategy accessing atomically robust structures, but highlights potential rapidly constructing molecular complexity material economy.

Language: Английский

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