Bimetallic Sites for Catalysis: From Binuclear Metal Sites to Bimetallic Nanoclusters and Nanoparticles

Chemical Reviews, Год журнала: 2023, Номер 123(8), С. 4855 - 4933

Опубликована: Март 27, 2023

Heterogeneous bimetallic catalysts have broad applications in industrial processes, but achieving a fundamental understanding on the nature of active sites at atomic and molecular level is very challenging due to structural complexity catalysts. Comparing features catalytic performances different entities will favor formation unified structure-reactivity relationships heterogeneous thereby facilitate upgrading current In this review, we discuss geometric electronic structures three representative types (bimetallic binuclear sites, nanoclusters, nanoparticles) then summarize synthesis methodologies characterization techniques for entities, with emphasis recent progress made past decade. The supported nanoparticles series important reactions are discussed. Finally, future research directions catalysis based and, more generally, prospective developments both practical applications.

Язык: Английский

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Atomically Precise Copper Nanoclusters for Highly Efficient Electroreduction of CO₂ towards Hydrocarbons via Breaking the Coordination Symmetry of Cu Site

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(36)

Опубликована: Июль 20, 2023

Abstract We propose an effective highest occupied d‐orbital modulation strategy engendered by breaking the coordination symmetry of sites in atomically precise Cu nanocluster (NC) to switch product CO 2 electroreduction from HCOOH/CO higher‐valued hydrocarbons. An well‐defined 6 NC with symmetry‐broken Cu−S N 1 active (named (MBD) , MBD=2‐mercaptobenzimidazole) was designed and synthesized a judicious choice ligand containing both S atoms. Different previously reported high HCOOH selectivity NCs 3 sites, structure shows Faradaic efficiency toward hydrocarbons 65.5 % at −1.4 V versus reversible hydrogen electrode (including 42.5 CH 4 23 C H ), partial current density −183.4 mA cm −2 . Theoretical calculations reveal that can rearrange 3d orbitals as d‐orbital, thus favoring generation key intermediate *COOH instead *OCHO favor *CO formation, followed hydrogenation and/or C−C coupling produce This is first attempt regulate mode atom for generation, provides new inspiration designing efficient RR towards highly‐valued products.

Язык: Английский

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Chemical Flexibility of Atomically Precise Metal Clusters

Chemical Reviews, Год журнала: 2024, Номер 124(11), С. 7262 - 7378

Опубликована: Май 2, 2024

Ligand-protected metal clusters possess hybrid properties that seamlessly combine an inorganic core with organic ligand shell, imparting them exceptional chemical flexibility and unlocking remarkable application potential in diverse fields. Leveraging to expand the library of available materials stimulate development new functionalities is becoming increasingly pressing requirement. This Review focuses on origin from structural analysis, including intra-cluster bonding, inter-cluster interactions, cluster-environments metal-to-ligand ratios, thermodynamic effects. In introduction, we briefly outline explain differences commonalities M(I)/M(I/0) coinage clusters. Additionally, distinguish bonding characteristics atoms core, which give rise their distinct flexibility. Section 2 delves into categories, theories related following sections 3 7, primarily elucidate mechanisms trigger flexibility, dynamic processes transformation, resultant alterations structure, ensuing modifications physical–chemical properties. 8 presents notable applications have emerged utilizing assemblies. Finally, section 9, discuss future challenges opportunities within this area.

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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Single-atom tailored atomically-precise nanoclusters for enhanced electrochemical reduction of CO2-to-CO activity

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Фев. 28, 2024

Abstract The development of facile tailoring approach to adjust the intrinsic activity and stability atomically-precise metal nanoclusters catalysts is great interest but remians challenging. Herein, well-defined Au 8 modified by single-atom sites are rationally synthesized via a co-eletropolymerization strategy, in which uniformly dispersed nanocluster co-entrenched on poly-carbazole matrix. Systematic characterization theoretical modeling reveal that functionalizing single-atoms enable altering electronic structures clusters, amplifies their electrocatalytic reduction CO 2 ~18.07 fold compared isolated clusters. rearrangements structure not only strengthen adsorption key intermediates *COOH, also establish favorable reaction pathway for reaction. Moreover, this strategy fixing cross-linked polymer networks efficiently deduce performance deactivation caused agglomeration during catalytic process. This work contribute explore improvement

Язык: Английский

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Sulfur-doping tunes p-d orbital coupling over asymmetric Zn-Sn dual-atom for boosting CO2 electroreduction to formate

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Март 5, 2025

The interaction of p-d orbitals at bimetallic sites plays a crucial role in determining the catalytic reactivity, which facilitates modulation charges and enhances efficiency CO2 electroreduction process. Here, we show ligand co-etching approach to create asymmetric Zn-Sn dual-atom (DASs) within metal-organic framework (MOF)-derived yolk-shell carbon frameworks (named Zn1Sn1/SNC). DASs comprise one Sn center (p-block) partially doped with sulfur Zn (d-block) N coordination, facilitating coupling between dimer. N-Zn-Sn-S/N arrangement displays an distribution atoms, leading stable adsorption configuration HCOO* intermediates. In H-type cell, Zn1Sn1/SNC exhibits impressive formate Faraday 94.6% -0.84 V. flow electronic architecture high accessibility, current density -315.2 mA cm-2 -0.90 Theoretical calculations ideal affinity lower reduction barrier, thus improve overall reduction.

Язык: Английский

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Understanding the Role of Potential and Cation Effect on Electrocatalytic CO₂ Reduction in All-Alkynyl-Protected Ag₁₅ Nanoclusters

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Янв. 8, 2025

Atomically precise metal nanoclusters (NCs) have emerged as an intriguing class of model catalysts for electrochemical CO2 reduction reactions (CO2RR). However, the interplay between interface environment (e.g., potential, cation concentration) and electron–proton transfer (ET/PT) kinetics─particularly in alkynyl-protected NCs─remains poorly understood. Here, we combined first-principles simulations experiments to investigate role potential effect on CO2RR performance a prototype all-alkynyl-protected Ag15(C≡C–CH3)+ cluster. Our revealed that applied triggers elimination alkynyl ligand via sequentially breaking two π-type Ag–C bonds one σ-type bond expose catalytically active Ag sites, barrier breakage monotonically decreases with lowering potential. Furthermore, show introducing inner-sphere Na+ ions greatly enhances *CO2 activation promotes proton generate *COOH *CO by forming Na+–CO2(*COOH) complexes, while competitive hydrogen evolution reaction (HER) from water dissociation is suppressed, thus dramatically improving selectivity electroreduction. The measurements further validated our predictions, where CO Faradaic efficiency (FECO) current density (jCO) pronounced dependence concentration. At optimal concentration 0.1 M NaCl, FECO can reach up ∼96%, demonstrating crucial cations promoting CO2RR. findings provide vital insights into atomic-level mechanism Ag15 NCs highlight important electrolyte governing electron/proton kinetics.

Язык: Английский

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Atomically Precise Silver Clusters Stabilized by Lacunary Polyoxometalates with Photocatalytic CO₂ Reduction Activity

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(7)

Опубликована: Дек. 28, 2023

Abstract The syntheses of atomically precise silver (Ag) clusters stabilized by multidentate lacunary polyoxometalate (POM) ligands have been emerging as a promising but challenging research direction, the combination redox‐active POM and will render them unexpected geometric structures catalytic properties. Herein, we report successful construction two structurally‐new POM‐stabilized Ag clusters, TBA 6 H 14 (DPPB) 4 (CH 3 CN) 9 [Ag 24 (Si 2 W 18 O 66 ) ] ⋅ 10CH CN 9H ( {Ag } , TBA=tetra‐ n ‐butylammonium, DPPB=1,4‐Bis(diphenylphosphino)butane) Na (H O) 27 8CH 10H ), using facile one‐pot solvothermal approach. Under otherwise identical synthetic conditions, molecular could be readily tuned addition different organic ligands. In both compounds, central trefoil‐propeller‐shaped 14+ 17+ bearing 10 delocalized valence electrons are three C‐shaped {Si units. femtosecond/nanosecond transient absorption spectroscopy revealed rapid charge transfer between core Both compounds pioneeringly investigated catalysts for photocatalytic CO reduction to HCOOH with high selectivity.

Язык: Английский

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Atomically precise metal nanoclusters as catalysts for electrocatalytic CO₂ reduction

Green Chemistry, Год журнала: 2023, Номер 26(1), С. 122 - 163

Опубликована: Окт. 12, 2023

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

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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