Structural Relaxation Enabled by Internal Vacancy Available in a 24-Atom Gold Cluster Reinforces Catalytic Reactivity

Abstract

Unveiling the mystery of the contribution of nonsurface or noninterface sites in a catalyst to its catalytic performance remains a great challenge because of the difficulty in capturing precisely structural information (surface plus inner) encoded in the catalyst. This work attempts to elucidate the critical role of the internal vacancy in an atomically precise 24-atom gold cluster in regulating the catalytic performance on the hydrogenation reaction of CO 2 . The experiment results show that the Au 24 cluster with internal vacancy can mitigate sintering and exhibit high catalytic activity under relatively harsh reaction conditions, in contrast to the structurally similar Au 25 cluster without internal vacancy. Our computational study suggests that the internal vacancy in Au 24 provides the cluster with much more structural flexibility, which may be crucial to resisting the aggregation of the cluster and further postponing the deactivation. The hydrogenation and coupling stages of the reaction intermediates are proposed to explain the potential reaction pathway of CO 2 with H 2 on the Au 24 catalyst with internal vacancy.

Catalytically potent and selective clusterzymes for modulation of neuroinflammation through single-atom substitutions

“…10 and 11) 54,55 . Previous work mainly focused on the atomic substitutions of Au 25 using noble metals for catalytic reactions of hydrogen and CO/CO 2 [56][57][58][59] . Our work herein constructively hypothesized and demonstrated that Au 25 can possess various unique enzyme-like activity modulated by single-atom substitution with non-precious metals like Cu and Cd, instead of Pt, in the geometric structure.…”

Contributions of Internal Atoms of Atomically Precise Metal Nanoclusters to Catalytic Performances

“…Naturally, a question is whether the internal vacancies (or referred to as internal defects) in catalysts might potentially affect the catalytic properties. To address this, the catalytic performances of the [Au 24 (PPh 3 ) 10 (SC 2 H 4 Ph] 5 Cl 2 ] + nanocluster with an internal vacancy and the [Au 25 (PPh 3 ) 10 (SC 2 H 4 Ph] 5 Cl 2 ] 2+ nanocluster without an internal vacancy for both homogeneous and heterogeneous reactions were compared [57–59] . Notably, the difference between Au 24 and Au 25 is one‐central‐atom loss in Au 24 .…”

“…Au 24 with the internal vacancy and Au 25 without the internal vacancy were first exploited as heterogeneous catalysts for the catalytic hydrogenation of CO 2 [57] . Interestingly, the Au 24 catalyst showed higher catalytic activity and stability under relatively harsh reaction conditions than the Au 25 catalyst (Figure 5c, d).…”

Cd-driven surface reconstruction and photodynamics in gold nanoclusters

“…[13][14][15][16][17][18] It has been recognized that substituting one or more gold atoms in either the core or the motifs with other metals can tune the overall performances of the parent nanoclusters. [19][20][21][22][23][24][25][26] Therefore, it has become possible to access the previous inaccessible metal synergy in the bimetallic nanoclusters at the atomic-precision.…”