Body-Centered-Cubic-Kernelled Ag₁₅Cu₆ Nanocluster with Alkynyl Protection: Synthesis, Total Structure, and CO₂ Electroreduction

Journal of the American Chemical Society, Год журнала: 2022, Номер 145(6), С. 3401 - 3407

Опубликована: Дек. 21, 2022

While atomically monodisperse nanostructured materials are highly desirable to unravel the size- and structure-catalysis relationships, their controlled synthesis atomic-level structure determination pose challenges. Particularly, copper-containing precise alloy nanoclusters potential catalyst candidates for electrochemical CO2 reduction reaction (eCO2RR) due high abundance tunable catalytic activity of copper. Herein, we report total an alkynyl-protected 21-atom AgCu nanocluster [Ag15Cu6(C≡CR)18(DPPE)2]-, denoted as Ag15Cu6 (HC≡CR: 3,5-bis(trifluoromethyl)phenylacetylene; DPPE: 1,2-bis(diphenylphosphino)ethane). The single-crystal X-ray diffraction reveals that consists Ag11Cu4 metal core exhibiting a body-centered cubic (bcc) structure, which is capped by 2 Cu atoms, Ag2DPPE motifs, 18 alkynyl ligands. Interestingly, cluster exhibits excellent eCO2RR with CO faradaic efficiency (FECO) 91.3% at -0.81 V (vs reversible hydrogen electrode, RHE), much higher than (FECO: 48.5% -0.89 vs RHE) Ag9Cu6 bcc structure. Furthermore, shows superior stability no significant decay in current density FECO during long-term operation 145 h. Density functional theory calculations reveal de-ligated can expose more space pair dual metals efficient active sites formation.

Язык: Английский

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Copper Doping Boosts Electrocatalytic CO₂ Reduction of Atomically Precise Gold Nanoclusters

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(50), С. 27407 - 27414

Опубликована: Дек. 6, 2023

Unraveling the atomistic synergistic effects of nanoalloys on electrocatalytic CO2 reduction reaction (eCO2RR), especially in presence copper, is paramount importance. However, this endeavor encounters significant challenges due to lack crystallographically determined atomic-level structure appropriate monometallic and bimetallic analogues. Herein, we report a one-pot synthesis characterization AuCu nanoalloy cluster catalyst, [Au15Cu4(DPPM)6Cl4(C≡CR)1]2+ (denoted as Au15Cu4). Single-crystal X-ray diffraction analysis reveals that Au15Cu4 comprises two interpenetrating incomplete, centered icosahedra (Au9Cu2 Au8Cu3) protected by six DPPM, four halide, one alkynyl ligand. The its closest monometal structural analogue, [Au18(DPPM)6Br4]2+ Au18), model systems, enable elucidation Au Cu eCO2RR. results reveal an excellent eCO2RR catalyst gas diffusion electrode-based membrane electrode assembly (MEA) cell, exhibiting high CO Faradaic efficiency (FECO) >90%, substantially higher than undoped Au18 (FECO: 60% at −3.75 V). exhibits industrial-level partial current density up −413 mA/cm2 V with CO2-fed MEA, which 2-fold Au18. functional theory (DFT) calculations demonstrate are induced doping, where exposed pair dual sites was suggested for launching process. Besides, DFT simulations these special synergistically coordinate moderate shift d-state, thus enhancing overall catalytic performance.

Язык: Английский

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Stepwise structural evolution toward robust carboranealkynyl-protected copper nanocluster catalysts for nitrate electroreduction

Science Advances, Год журнала: 2024, Номер 10(18)

Опубликована: Май 1, 2024

Atomically precise metal nanoclusters (NCs) are emerging as idealized model catalysts for imprecise nanoparticles to unveil their structure-activity relationship. However, the directional synthesis of robust NCs with accessible catalytic active sites remains a great challenge. In this work, we achieved bulky carboranealkynyl-protected copper NCs, monomer

Язык: Английский

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Planar Core and Macrocyclic Shell Stabilized Atomically Precise Copper Nanocluster Catalyst for Efficient Hydroboration of C–C Multiple Bond

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(23), С. 16295 - 16305

Опубликована: Май 30, 2024

Atomically precise metal nanoclusters (NCs) have become an important class of catalysts due to their catalytic activity, high surface area, and tailored active sites. However, the design development bond-forming reaction based on copper NCs are still in early stages. Herein, we report synthesis atomically nanocluster with a planar core unique shell, [Cu45(TBBT)29(TPP)4(C4H11N)2H14]2+ (Cu45) (TBBT: 4-tert-butylbenzenethiol; TPP: triphenylphosphine), yield via one-pot reduction method. The resulting structurally well-defined Cu45 is highly efficient catalyst for hydroboration alkynes alkenes. Mechanistic studies show that single-electron oxidation situ-formed ate complex enables formation boryl-centered radicals under mild conditions. This work demonstrates promise as C–B heteroatom reactions. compatible wide range alkenes functional groups producing hydroborated products.

Язык: Английский

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Visible-Light Photocatalytic Reduction of Aryl Halides as a Source of Aryl Radicals

Molecules, Год журнала: 2022, Номер 27(17), С. 5364 - 5364

Опубликована: Авг. 23, 2022

Aryl- and heteroaryl units are present in a wide variety of natural products, pharmaceuticals, functional materials. The method for reduction aryl halides with ubiquitous distribution is highly sought after late-stage construction various aromatic compounds. visible-light-driven to radicals by electron transfer provides an efficient, simple, environmentally friendly the This review summarizes recent progress generation metal complexes, organic compounds, semiconductors as catalysts, alkali-assisted reaction system. ability mechanism visible light induced systems summarized, intending illustrate comprehensive introduction this research topic readers.

Язык: Английский

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Size Effects of Atomically Precise Gold Nanoclusters in Catalysis

Precision Chemistry, Год журнала: 2023, Номер 1(1), С. 14 - 28

Опубликована: Март 15, 2023

The emergence of ligand-protected, atomically precise gold nanoclusters (NCs) in recent years has attracted broad interest catalysis due to their well-defined atomic structures and intriguing properties. Especially, the formulas NCs provide an opportunity study size effects at level without complications by polydispersity conventional nanoparticles that obscures relationship between size/structure Herein, we summarize catalytic precise, thioate-protected range tens hundreds metal atoms. reactions include electrochemical catalysis, photocatalysis, thermocatalysis. With sizes structures, fundamentals underlying are analyzed, such as surface area, electronic properties, active sites. In reactions, one or more factors may exert simultaneously, hence leading different catalytic-activity trends with change NCs. summary literature work disentangles fundamental mechanisms provides insights into effects. Future studies will lead further understanding shed light on sites ultimately promote catalyst design level.

Язык: Английский

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Atomically Precise Defective Copper Nanocluster Catalysts for Highly Selective C−C Cross‐Coupling Reactions

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(26)

Опубликована: Май 2, 2023

Abstract Point defects in nanoparticles have long been hypothesized to play an important role governing the particle's electronic structure and physicochemical properties. However, single point material systems usually exist with other heterogeneities, obscuring chemical of effects. Herein, we report synthesis novel atomically precise, copper hydride nanoclusters (NCs), [Cu 28 H 10 (C 7 S) 18 (TPP) 3 ] ( Cu ; TPP: triphenylphosphine; C S: o ‐thiocresol) a defined defect gram scale via one‐pot reduction method. The acts as highly selective catalyst for C−C cross‐couplings. work highlights potential defective NCs model investigating individual defects, correlating physiochemical properties, rationally designing new nanoparticle catalysts.

Язык: Английский

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Nanocluster Surface Microenvironment Modulates Electrocatalytic CO₂ Reduction

Advanced Materials, Год журнала: 2023, Номер 36(13)

Опубликована: Дек. 19, 2023

The catalytic activity and product selectivity of the electrochemical CO

Язык: Английский

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Cu₂₆ Nanoclusters with Quintuple Ligand Shells for CO₂ Electrocatalytic Reduction

Chemistry of Materials, Год журнала: 2023, Номер 35(15), С. 6123 - 6132

Опубликована: Июль 27, 2023

Copper nanostructures represent an important class of materials in CO2 electrocatalytic reduction (CO2ER) reactions, but deciphering their molecular structures, especially those with multiple and irregular organic–inorganic interfaces, remains a grand challenge. Through comprehensive characterization 26-nuclei copper nanocluster [Cu26(DPPE)3(CF3CO2)8(CH3O)2(tBuC≡C)4H11]+ (DPPE is 1,2-bis(diphenylphosphino)ethane), which stabilized by quintuple ligand shells phosphine, carboxylic acid, alcohol, alkynyl, hydride, we demonstrate this work the efficiency hybrid ligands controlling geometrical arrangements, electronic catalytic performance nanoclusters. The diverse cluster endow it peculiar geometric structure distinct and, more importantly, delicate surface structure. As result, displays high CO2ER to CO reaction.

Язык: Английский

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Metal‐Organic Framework Supported Copper Photoredox Catalysts for Iminyl Radical‐Mediated Reactions

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(21)

Опубликована: Март 10, 2023

Visible-light copper photocatalysis has recently emerged as a viable technology for building sustainable synthetic processes. To broaden the applications of phosphine-ligated copper(I) complexes, we describe herein an effective metal-organic framework (MOF)-supported photocatalyst multiple iminyl radical-mediated reactions. Due to site isolation, heterogenized photosensitizer significantly higher catalytic activity than its homogeneous counterpart. Using hydroxamic acid linker immobilize species on MOF supports affords heterogeneous catalysts with high recyclability. The post-synthetic modification sequence surfaces allows preparation previously unavailable monomeric species. Our findings highlight potential using MOF-based systems address fundamental challenges in development methodologies and mechanistic investigations transition-metal photoredox catalysis.

Язык: Английский

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