Reactivity and Recyclability of Ligand‐Protected Metal Cluster Catalysts for CO<sub>2</sub> Transformation

Li, Guangjun; Hou, Jin; Lei, Xiaomei; Li, Dan; Yu, Enqi; Hu, Weigang; Cai, Xiao; Liu, Xu; Chen, Mingyang; Zhu, Yan

doi:10.1002/anie.202216735

Cited by 24 publications

(25 citation statements)

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“…Chem., Int. Ed.202362e202216735 The study shows the synergy of the surface heteroatom and ligand of bimetallic clusters, in which the Cu 3 (SR) 3 surface motif of the Cu 12 Ag 17 (SR) 12 (PPh 3 ) 4 catalyst is identified as catalytic sites to enhance the formylation reaction of CO 2 with amines via improving the CO 2 capture, hydrogen transfer, and successive recombination of the intermediate and substrate. Asymmetrically Doping a Platinum Atom into a Au 38 Nanocluster for Changing the Electron Configuration and Reactivity in ElectrocatalysisLiuX.WangE.ZhouM.WanY.ZhangY.LiuH.ZhaoY.LiJ.GaoY.ZhuY. Liu, X. Wang, E. Zhou, M. Wan, Y. Zhang, Y. Liu, H. Zhao, Y. Li, J. Gao, Y. Zhu, Y. 10.1002/anie.202207685Angew.…”

Section: Key Referencesmentioning

confidence: 99%

Section: Key Referencesmentioning

confidence: 99%

“…The determined structural information on nanocluster catalysts imparts advantages in identifying active sites and exploring catalytic mechanisms, which can in turn guide the design and synthesis of high-performance catalysts. More notably, doping foreign metal atoms (i.e., heteroatoms) into a designated nanocluster is an effective strategy for tailoring its catalytic property through modulating the electronic properties, improving the structural robustness, and providing additional active sites for the absorption and activation of reactant molecules. − ,− Given structural characteristic of nanoclusters, the heteroatoms can be introduced into the surface of the parent homometal nanocluster, , in which they can directly act as active sites for improving the catalytic reactivity or cooperatively communicating with organic ligands to form surface multisites to promote the reactions occurring at different sites. The heterometallic atom can also replace the subsurface or kernel atom of the parent nanocluster, in which it can tune the electronic property through the electron transfer of subsurface/kernel heteroatoms to exterior metal atoms or vice versa, thereby imparting a substantial influence on the observed catalytic performance. ,,,, These researches bring about a new conceptual framework for understanding subnanometer-scale catalysis.…”

Section: Key Referencesmentioning

confidence: 99%

“…Recently, Li and co-workers made an extra effort to identify the active Cu 3 S 3 surface motif of the Cu 12 Ag 17 (SR) 12 (PPh 3 ) 4 cluster for the CO 2 formylation reaction with amines and found that Cu 12 Ag 17 (SR) 12 (PPh 3 ) 4 can integrate the advantages of homogeneous and heterogeneous catalysts, thereby exhibiting highly catalytic activity and recyclability . As shown in Figure a, a series of the structurally comparable cluster catalysts including Cu 12 Ag 17 (SR) 12 (PPh 3 ) 4 , Cu 12 Ag 16 Au 1 (SR) 12 (PPh 3 ) 4 , and Ag 28 Au 1 (SR) 12 (PPh 3 ) 4 (where the SR ligand is a dithiolate) were studied: Cu 12 Ag 17 (SR) 12 (PPh 3 ) 4 and Cu 12 Ag 16 Au 1 (SR) 12 (PPh 3 ) 4 comprised a MAg 12 (M = Ag or Au) core, respectively, which was stabilized by four Cu 3 (SR) 3 and four AgPPh 3 motifs, while Ag 28 Au 1 (SR) 12 (PPh 3 ) 4 had a Ag 12 Au core protected by Ag 3 (SR) 3 and AgPPh 3 motifs.…”

Section: Catalytic Performances Enhanced By Surface/subsurface Hetero...mentioning

confidence: 99%

“…(c) Time-resolved in situ FTIR spectra obtained from the reaction of CO 2 with pyrrolidine and phenylsilane catalyzed by Cu 12 Ag 17 (SR) 12 (PPh 3 ) 4 and Ag 28 Au 1 (SR) 12 (PPh 3 ) 4 , respectively. Reproduced with permission from ref . Copyright 2023 John Wiley & Sons, Inc.…”

Section: Catalytic Performances Enhanced By Surface/subsurface Hetero...mentioning

confidence: 99%

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Catalysis Synergism by Atomically Precise Bimetallic Nanoclusters Doped with Heteroatoms

2023

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Conspectus Bimetallic catalysts hold promise in tailoring the catalytic activity and selectivity of transition metals for important chemical processes due to the synergistic coupling between the constituent elements that can connect catalytical active sites. However, it remains a challenge to construct an ideal bimetallic catalyst to study the respective or cooperative effects of the two transition metals within the bimetallic catalyst on the overall catalytic performance because multiple factors are always convoluted, such as the size dispersity of particles, the inhomogeneous structure, and the unknown exact location of the two metal elements in any particle. Therefore, almost all of the current studies give rise to the statistics of the overall catalytic performance from all of the particles in a bimetallic catalyst or at least the observed performance reflects an ensemble average of all metal atoms in a particle. Atomically precise metal nanoclusters have attracted catalysis scientists since their total structures (core plus surface) were solved by single-crystal X-ray crystallography, thereby providing unparalleled opportunities to build a precise correlation of catalyst structures with catalytic properties at an atomic level. Within this field, we are interested in identifying catalytically active sites and further constructing the active sites by an atom-by-atom manipulation, which are typically challenging for conventional particle-based heterogeneous catalysts and organometallics-based complex catalysts. In this Account, we mainly focus on the extensive efforts to fundamentally understand catalysis synergy in bimetallic nanocluster catalysts doped with heterometallic atoms. We first briefly describe the design rules and chemical synthesis of atomically precise bimetallic nanoclusters doped with heteroatoms including co-reduction, atom substitution, and reconstruction as typical synthesis strategies. We then put particular emphasis on the recent research toward the synergistic effects of surface/subsurface heteroatoms of the bimetallic nanoclusters on controlling the catalytic pathways, in which a series of examples showed that catalytically active sites can be dramatically tailored by the metal heteroatoms (Ru, Cu, Ni, Cd, etc.) located on the surface or subsurface of gold nanoclusters. Other cases indicated that the catalytic activity can be driven by surface heteroatom–ligand motifs of bimetallic nanoclusters. We also discuss the remote effects of nonsurface or kernel heteroatoms located in the cores of bimetallic nanoclusters on improving the catalytic reactions directly occurring on the catalyst surface. Finally, we anticipate that the advances in this research field would not only provide in-depth insight into the intraparticle synergism in bimetallic catalysts for understanding and controlling their catalytic reactivity but also provide valuable guidelines for high-performance catalysts that can be applied in industry.

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Section: Key Referencesmentioning

confidence: 99%

Section: Key Referencesmentioning

confidence: 99%

Section: Key Referencesmentioning

confidence: 99%

Section: Catalytic Performances Enhanced By Surface/subsurface Hetero...mentioning

confidence: 99%

Section: Catalytic Performances Enhanced By Surface/subsurface Hetero...mentioning

confidence: 99%

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Catalysis Synergism by Atomically Precise Bimetallic Nanoclusters Doped with Heteroatoms

2023

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Pd₈ Nanocluster with Nonmetal‐to‐Metal‐ Ring Coordination and Promising Photothermal Conversion Efficiency

You,

Jiang,

Fan

et al. 2023

Angewandte Chemie

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Constructing ambient‐stable, single‐atom‐layered metal‐based materials with atomic precision and understanding their underlying stability mechanisms are challenging. Here, stable single‐atom‐layered nanoclusters of Pd were synthesized and precisely characterized through electrospray ionization mass spectrometry and single‐crystal X‐ray crystallography. A pseudo‐pentalene‐like Pd8 unit was found in the nanocluster, interacting with two syn PPh units through nonmetal‐to‐metal ‐ring coordination. The unexpected coordination, which is distinctly different from the typical organoring‐to‐metal coordination in half‐sandwich‐type organometallic compounds, contributes to the ambient stability of the as‐obtained single‐atom‐layered nanocluster as revealed through theoretical and experimental analyses. Furthermore, quantum chemical calculations revealed dominant electron transition along the horizontal x‐direction of the Pd8 plane, indicating high photothermal conversion efficiency (PCE) of the nanocluster, which was verified by the experimental PCE of 73.3 %. Therefore, this study unveils the birth of a novel type of compound and the finding of the unusual nonmetal‐to‐metal ‐ring coordination and has important implications for future syntheses, structures, properties, and structure–property correlations of single‐atom‐layered metal‐based materials.

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

Li,

Dong,

Liu

et al. 2024

Angewandte Chemie

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Thiolate‐protected Cu clusters with well‐defined structures and stable low‐coordinated Cu+ species exhibit remarkable potential for the CO2RR and are ideal model catalysts for establishing structure–electrocatalytic property relationships at the atomic level. However, extant Cu clusters employed in the CO2RR predominantly yield 2e− products. Herein, two model Cu4(MMI)4 and Cu8(MMI)4(tBuS)4 clusters (MMI = 2‐mercapto‐1‐methylimidazole) are prepared to investigate the synergistic effect of Cu+ and adjacent S sites on the CO2RR. Cu4(MMI)4 can reduce CO2 to deep‐reduced products with a 91.0% Faradaic efficiency (including 53.7% for CH4) while maintaining remarkable stability. Conversely, Cu8(MMI)4(tBuS)4 shows a remarkable preference for C2+ products, achieving a maximum FE of 58.5% with a C2+ current density of 152.1 mA∙cm−2. In situ XAS and ex situ XPS spectra reveal the preservation of Cu+ species in Cu clusters during CO2RR, extensively enhancing the adsorption capacity of *CO intermediates. Moreover, kinetic analysis and theoretical calculations confirm that S sites facilitate H2O dissociation into *H species, which directly participate in the protonation process on adjacent Cu sites for the protonation of *CO to *CHO. This study highlights the important role of Cu–S dual sites in Cu clusters and provides mechanistic insights into the CO2RR pathway at the atomic level.

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Reactivity and Recyclability of Ligand‐Protected Metal Cluster Catalysts for CO₂ Transformation

Cited by 24 publications

References 49 publications

Catalysis Synergism by Atomically Precise Bimetallic Nanoclusters Doped with Heteroatoms

Catalysis Synergism by Atomically Precise Bimetallic Nanoclusters Doped with Heteroatoms

Pd₈ Nanocluster with Nonmetal‐to‐Metal‐ Ring Coordination and Promising Photothermal Conversion Efficiency

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

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Reactivity and Recyclability of Ligand‐Protected Metal Cluster Catalysts for CO2 Transformation

Cited by 24 publications

References 49 publications

Catalysis Synergism by Atomically Precise Bimetallic Nanoclusters Doped with Heteroatoms

Catalysis Synergism by Atomically Precise Bimetallic Nanoclusters Doped with Heteroatoms

Pd8 Nanocluster with Nonmetal‐to‐Metal‐ Ring Coordination and Promising Photothermal Conversion Efficiency

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

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Reactivity and Recyclability of Ligand‐Protected Metal Cluster Catalysts for CO₂ Transformation

Pd₈ Nanocluster with Nonmetal‐to‐Metal‐ Ring Coordination and Promising Photothermal Conversion Efficiency

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