Surface-Clean Au₂₅ Nanoclusters in Modulated Microenvironment Enabled by Metal–Organic Frameworks for Enhanced Catalysis

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(48), P. 22008 - 22017

Published: Nov. 21, 2022

Metal nanoclusters (NCs) with atomically precise structures have sparked interest in catalysis. Unfortunately, their high aggregation tendency and the spatial resistance of surface ligands pose significant challenges. Herein, Au25 NCs are encapsulated into isoreticular metal-organic frameworks (MOFs), namely UiO-66-X (X = H, NH2, OH, NO2), followed by removal on NCs. The resulting surface-clean NCs, protected MOF confinement, exhibit much superior activity stability respect to pristine oxidative esterification furfural. Remarkably, experimental theoretical results jointly demonstrate that diverse functional groups modulate electronic state, giving rise discriminated substrate adsorption energy Au25@UiO-66-X. As a result, electron density suitable ability dominate trend: Au25@UiO-66-NH2 > Au25@UiO-66-OH Au25@UiO-66 Au25@UiO-66-NO2. This work develops new strategy for stabilization metal pore wall-engineered MOFs enhanced

Language: Английский

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Homoleptic Alkynyl‐Protected Ag₁₅ Nanocluster with Atomic Precision: Structural Analysis and Electrocatalytic Performance toward CO₂ Reduction

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(50), P. 26136 - 26141

Published: Sept. 24, 2021

We report the fabrication of homoleptic alkynyl-protected Ag15 (C≡C-t Bu)12+ (abbreviated as ) nanocluster and its electrocatalytic properties toward CO2 reduction reaction. Crystal structure analysis reveals that possesses a body-centered-cubic (BCC) with an Ag@Ag8 @Ag6 metal core configuration. Interestingly, we found can adsorb in air spontaneously self-assembled into one-dimensional linear material during crystal growth process. Furthermore, convert CO faradaic efficiency ca. 95.0 % at -0.6 V maximal turnover frequency 6.37 s-1 -1.1 along excellent long-term stability. Finally, density functional theory (DFT) calculations disclosed Bu)11+ one alkynyl ligand stripping off from intact cluster expose uncoordinated Ag atom catalytically active site for formation.

Language: Английский

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Creation of High‐Performance Heterogeneous Photocatalysts by Controlling Ligand Desorption and Particle Size of Gold Nanocluster

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(39), P. 21340 - 21350

Published: May 26, 2021

Recently, the creation of new heterogeneous catalysts using unique electronic/geometric structures small metal nanoclusters (NCs) has received considerable attention. However, to achieve this, it is extremely important establish methods remove ligands from ligand-protected NCs while preventing aggregation NCs. In this study, ligand-desorption process during calcination was followed for metal-oxide-supported 2-phenylethanethiolate-protected gold (Au) 25-atom five experimental techniques. The results clearly demonstrate that consists ligand dissociation on surface NCs, adsorption generated compounds support and desorption support, temperatures at which these processes occurred were elucidated. Based obtained knowledge, we established a method form metal-oxide layer Au their aggregation, thereby succeeding in creating water-splitting photocatalyst with high activity stability.

Language: Английский

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Structural Engineering toward Gold Nanocluster Catalysis

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(51)

Published: Sept. 28, 2022

Abstract Atomically precise gold nanoclusters provide great opportunities to explore the relationship between structure and properties of nanogold catalysts. A nanocluster consists a metal core surface ligand shell, both shell have significant effects on catalytic properties. Thanks their structures, active site clusters can be readily identified ligands catalysis disclosed. In this Minireview, we summarize recent advances in research nanoclusters, emphasizing four strategies for constructing open sites, including by post‐treatment, bulky strategy, geometric mismatch method, heteroatom doping procedures. We also discuss activity, selectivity, stability cluster Finally, present future challenges relating catalysis.

Language: Английский

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Advanced Strategies for Stabilizing Single-Atom Catalysts for Energy Storage and Conversion

Electrochemical Energy Reviews, Journal Year: 2022, Volume and Issue: 5(3)

Published: Sept. 1, 2022

Well-defined atomically dispersed metal catalysts (or single-atom catalysts) have been widely studied to fundamentally understand their catalytic mechanisms, improve the efficiency, increase abundance of active components, enhance catalyst utilization, and develop cost-effective effectively reduce usage noble metals. Such relatively higher selectivity activity with maximum atom utilization due unique characteristics high dispersion a low-coordination environment. However, freestanding single atoms are thermodynamically unstable, such that during synthesis reactions, they inevitably tend agglomerate system energy associated large surface areas. Therefore, developing innovative strategies stabilize catalysts, including mass-separated soft landing, one-pot pyrolysis, co-precipitation, impregnation, atomic layer deposition, organometallic complexation, is critically needed. Many types supporting materials, polymers, commonly used in these fabrication techniques. Herein, we review stabilization catalyst, different methods, specific metals carriers, advantages disadvantages. In particular, this focuses on application polymers functions as carriers for atoms, synthetic templates, encapsulation agents, protection agents process. The technical challenges currently faced by summarized, perspectives related future research directions enhancement loading content, large-scale implementation proposed realize practical applications. Single-atom characterized dispersibility, weak coordination environments, selectivity, highest utilization. free area, individual usually unstable prone agglomeration reactions. researchers developed strategies, sedimentation, coprecipitation, step reduction, precipitation, This article summarizes from aspects support types, reaction its focus preparation role manufacturing main feature polymer-derived materials contain abundant heteroatoms, N, possess lone-pair electrons. These electrons can anchor through strong interactions. environment facilitate formation because enlarge average distance precursor adsorbed polymer matrix. Polymers nitrogen groups favorable candidates dispersing weakening tendency aggregation redistributing charge densities around performance. provides summary analysis current directions, mechanism sufficiently loading, implementation.

Language: Английский

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N-heterocyclic carbene coordinated metal nanoparticles and nanoclusters

Coordination Chemistry Reviews, Journal Year: 2022, Volume and Issue: 458, P. 214425 - 214425

Published: Feb. 3, 2022

Language: Английский

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Ultrasmall Coinage Metal Nanoclusters as Promising Theranostic Probes for Biomedical Applications

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(22), P. 11879 - 11898

Published: May 18, 2023

Ultrasmall coinage metal nanoclusters (NCs, <3 nm) have emerged as a novel class of theranostic probes due to their atomically precise size and engineered physicochemical properties. The rapid advances in the design applications NC-based are made possible by atomic-level engineering NCs. This Perspective article examines (i) how functions NCs for applications, (ii) probe is designed its properties affect performance, (iii) used diagnose treat various diseases. We first summarize tailored terms biocompatibility tumor targeting. focus our discussion on bioimaging-directed disease diagnosis, photoinduced therapy, nanomedicine, drug delivery, optical urinalysis. Lastly, an outlook challenges opportunities future development provided.

Language: Английский

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Eight-Electron Superatomic Cu₃₁ Nanocluster with Chiral Kernel and NIR-II Emission

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(18), P. 10355 - 10363

Published: April 27, 2023

Owing to the inherent instability caused by low Cu(I)/Cu(0) half-cell reduction potential, Cu(0)-containing copper nanoclusters are quite uncommon in comparison their Ag and Au congeners. Here, a novel eight-electron superatomic nanocluster [Cu31(4-MeO-PhC≡C)21(dppe)3](ClO4)2 (Cu31, dppe = 1,2-bis(diphenylphosphino)ethane) is presented with total structural characterization. The determination reveals that Cu31 features an chiral metal core arising from helical arrangement of two sets three Cu2 units encircling icosahedral Cu13 core, which further shielded 4-MeO-PhC≡C- ligands. first carrying eight free electrons, corroborated electrospray ionization mass spectrometry, X-ray photoelectron spectroscopy density functional theory calculations. Interestingly, demonstrates near-infrared (750-950 nm, NIR-I) window absorption second (1000-1700 NIR-II) emission, exceptional family endows it great potential biological applications. Of note, 4-methoxy groups providing close contacts neighboring clusters crucial for cluster formation crystallization, while 2-methoxyphenylacetylene leads only hydride clusters, Cu6H or Cu32H14. This research not showcases new member superatoms but also exemplifies nanoclusters, nonluminous visible range may emit luminescence deep NIR region.

Language: Английский

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A Review of State of the Art in Phosphine Ligated Gold Clusters and Application in Catalysis

Advanced Science, Journal Year: 2022, Volume and Issue: 9(15)

Published: March 25, 2022

Atomically precise gold clusters are highly desirable due to their well-defined structure which allows the study of structure-property relationships. In addition, they have potential in technological applications such as nanoscale catalysis. The structural, chemical, electronic, and optical properties ligated strongly defined by metal-ligand interaction type ligands. This critical feature renders gold-phosphine unique distinct from other ligand-protected clusters. use multidentate phosphines enables preparation varying core sizes exotic structures beyond regular polyhedrons. Weak gold-phosphorous (Au-P) bonding is advantageous for ligand exchange removal specific applications, catalysis, without agglomeration. aim this review provide a unified view present an in-depth discussion on recent advances key developments these features chemistry, Advanced characterization techniques, including synchrotron-based spectroscopy, unraveled substantial effects Au-P composition-, structure-, size-dependent properties. State-of-the-art theoretical calculations that reveal insights into experimental findings also discussed. Finally, application catalysis presented.

Language: Английский

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

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 145(6), P. 3401 - 3407

Published: Dec. 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.

Language: Английский

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