Ligand‐Protected Au<sub>55</sub> with a Novel Structure and Remarkable CO<sub>2</sub> Electroreduction Performance

Wan, Xian‐Kai; Wang, Jia‐Qi; Wang, Quan‐Ming

doi:10.1002/ange.202108207

Cited by 21 publications

(7 citation statements)

References 91 publications

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“…The critical role halide plays in nanocluster synthesis was reported by Wang et al., who prepared the phosphine/thiolate-stabilized Au nanocluster, [Au 55 (PPh 3 ) 6 ( p -MBT) 24 ] 3+ ( p -MBT = 4-methylbenzene thiolate), by coreduction of Ph 3 PAu(SbF 6 ) and p -MBTAu in a “halide-free” environment . In the presence of halide under otherwise identical reduction conditions, the previously known [Au 25 ( p -MBT) 5 (Ph 3 P) 10 Cl 2 ] 2+ cluster was obtained …”

Section: Resultsmentioning

confidence: 99%

N-Heterocyclic Carbene-Stabilized Hydrido Au₂₄ Nanoclusters: Synthesis, Structure, and Electrocatalytic Reduction of CO₂

et al. 2022

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Atomically precise hydrido gold nanoclusters are extremely rare but interesting due to their potential applications in catalysis. By optimization of molecular precursors, we have prepared an unprecedented N-heterocyclic carbene-stabilized hydrido gold nanocluster, [Au 24 (NHC) 14 Cl 2 H 3 ] 3+ . This cluster comprises a dimer of two Au 12 kernels, each adopting an icosahedral shape with one missing vertex. The two kernels are joined through triangular faces, which are capped with a total of three hydrides. The hydrides are detected by electrospray ionization mass spectrometry and nuclear magnetic resonance spectroscopy, with density functional theory calculations supporting their position bridging the six uncoordinated gold sites. The reactivity of this Au 24 H 3 cluster in the electrocatalytic reduction of CO 2 is demonstrated and benchmarked against related catalysts.

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Section: Resultsmentioning

confidence: 99%

N-Heterocyclic Carbene-Stabilized Hydrido Au₂₄ Nanoclusters: Synthesis, Structure, and Electrocatalytic Reduction of CO₂

et al. 2022

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“…It should be noted that the origin of the active sites of these Au clusters for CO 2 reduction remains fairly controversial, owing to the identification of the active sites based on the DFT calculations rather than the experimental evidence. Besides, several Au n clusters with novel structures have been also reported to show superior electrochemical activity for CO 2 conversion to the gold nanoparticles with large size. − …”

Section: Electrochemical Reduction Of Co2 Over Au-based Clustersmentioning

confidence: 99%

Catalytic Conversion of CO₂ over Atomically Precise Gold-Based Cluster Catalysts

Cai

et al. 2022

ACS Catal.

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There are obstacles with using conventional nanoparticle catalysts for developing atomic-by-atom tailoring of active sites in the heterogeneous catalysis field. However, atomically precise metal clusters with precise formulas and crystallographically determined structures, which may build a bridge between single atoms and nanoparticles, may become possible to unravel the respective contributions of every atom in a cluster to its overall catalytic performances and build the structure−property relationship at an atomic-precision level. In this Review, we will first describe recent advances of CO 2 electronic reduction catalyzed by Au-based clusters including pure gold and its alloys. We will then put a particular emphasis on chemical fixation of CO 2 into organic molecules, such as alkyne, epoxide, and amine, over gold cluster catalysts. Additionally, we will concisely introduce the discovery of catalytic selectivity of the Au-based clusters in CO 2 hydrogenation toward C 1 and C 2 products. Finally, we will provide our perspectives on some issues for catalytic conversion of CO 2 over atomically precise metal clusters in future catalysis research.

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“…We found that the [Au 22 H 3 ] 3+ cluster shows higher FE toward CO than the [Au 11 ] 3+ cluster under all voltages. When more negative potentials are applied, the FE first increases and then decreases, reaching a maximum at about −0.6 V. This trend is similar to the recently reported phosphine/thiolate coprotected Au 55 cluster . The best catalytic performance of [Au 22 H 3 ] 3+ was observed at −0.6 V with an FE CO of 92.7%, which is significantly higher than that of the thiolate-protected Au 25 cluster at a similar potential .…”

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confidence: 91%

A Heteroleptic Gold Hydride Nanocluster for Efficient and Selective Electrocatalytic Reduction of CO₂ to CO

et al. 2022

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It has been a long-standing challenge to create and identify the active sites of heterogeneous catalysts, because it is difficult to precisely control the interfacial chemistry at the molecular level. Here we report the synthesis and catalysis of a heteroleptic gold trihydride nanocluster, [Au22H3(dppe)3(PPh3)8]3+ [dppe = 1,2-bis(diphenylphosphino)ethane, PPh3 = triphenylphosphine]. The Au22H3 core consists of two Au11 units bonded via six uncoordinated Au sites. The three H atoms bridge the six uncoordinated Au atoms and are found to play a key role in catalyzing electrochemical reduction of CO2 to CO with a 92.7% Faradaic efficiency (FE) at −0.6 V (vs RHE) and high reaction activity (134 A/gAu mass activity). The CO current density and FECO remained nearly constant for the CO2 reduction reaction for more than 10 h, indicating remarkable stability of the Au22H3 catalyst. The Au22H3 catalytic performance is among the best Au-based catalysts reported thus far for electrochemical reduction of CO2. Density functional theory (DFT) calculations suggest that the hydride coordinated Au sites are the active centers, which facilitate the formation of the key *COOH intermediate.

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Ligand‐Protected Au₅₅ with a Novel Structure and Remarkable CO₂ Electroreduction Performance

Cited by 21 publications

References 91 publications

N-Heterocyclic Carbene-Stabilized Hydrido Au₂₄ Nanoclusters: Synthesis, Structure, and Electrocatalytic Reduction of CO₂

N-Heterocyclic Carbene-Stabilized Hydrido Au₂₄ Nanoclusters: Synthesis, Structure, and Electrocatalytic Reduction of CO₂

Catalytic Conversion of CO₂ over Atomically Precise Gold-Based Cluster Catalysts

A Heteroleptic Gold Hydride Nanocluster for Efficient and Selective Electrocatalytic Reduction of CO₂ to CO

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Ligand‐Protected Au55 with a Novel Structure and Remarkable CO2 Electroreduction Performance

Cited by 21 publications

References 91 publications

N-Heterocyclic Carbene-Stabilized Hydrido Au24 Nanoclusters: Synthesis, Structure, and Electrocatalytic Reduction of CO2

N-Heterocyclic Carbene-Stabilized Hydrido Au24 Nanoclusters: Synthesis, Structure, and Electrocatalytic Reduction of CO2

Catalytic Conversion of CO2 over Atomically Precise Gold-Based Cluster Catalysts

A Heteroleptic Gold Hydride Nanocluster for Efficient and Selective Electrocatalytic Reduction of CO2 to CO

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Product

Resources

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Ligand‐Protected Au₅₅ with a Novel Structure and Remarkable CO₂ Electroreduction Performance

N-Heterocyclic Carbene-Stabilized Hydrido Au₂₄ Nanoclusters: Synthesis, Structure, and Electrocatalytic Reduction of CO₂

N-Heterocyclic Carbene-Stabilized Hydrido Au₂₄ Nanoclusters: Synthesis, Structure, and Electrocatalytic Reduction of CO₂

Catalytic Conversion of CO₂ over Atomically Precise Gold-Based Cluster Catalysts

A Heteroleptic Gold Hydride Nanocluster for Efficient and Selective Electrocatalytic Reduction of CO₂ to CO