Issue 15, 2025

Vacancy-induced modulation of the interfacial properties of Au25(SCH3)18 nanoclusters supported on defective graphene

Abstract

Atomically precise metal nanoclusters (NCs) are frequently loaded onto various substrates for numerous catalytic applications, yet the interfacial interaction remains poorly understood. In this study, we performed ab initio molecular dynamics (AIMD) simulations to systematically investigate the interfacial dynamics of thiolated-protected Au25(SR)18 NCs on graphene substrates with varying vacancy defect sizes. The results revealed that when the vacancy defects feature a convex-shaped armchair edge, the vacancy edges would undergo severe reconstruction and reduce the substrate reactivity, which cannot effectively anchor the Au25 NCs and induce high mobility on graphene. In contrast, when the vacancy defects feature a concave-shaped armchair edge, the present unsaturated sp2 dangling bond imparts high reactivity to the vacancy edge, which enables strong chemical interaction with Au25 and leads to facile and spontaneous removal of the staple Au–SCH3 moiety from the protecting –S–Au–S–Au–S– motif. The etched Au25 NCs with exposed active Au sites can efficiently facilitate the electrocatalytic CO2 reduction to CO with moderate energy barriers. This work reveals the significant role of the defect edges of graphene in modulating the interfacial behavior of metal NCs, providing a promising strategy for regulating the interfacial and catalytic properties of atomically precise metal NCs.

Graphical abstract: Vacancy-induced modulation of the interfacial properties of Au25(SCH3)18 nanoclusters supported on defective graphene

Supplementary files

Article information

Article type
Paper
Submitted
07 Jan 2025
Accepted
10 Mar 2025
First published
11 Mar 2025

Nanoscale, 2025,17, 9490-9501

Vacancy-induced modulation of the interfacial properties of Au25(SCH3)18 nanoclusters supported on defective graphene

P. Zhu, Y. Chen and Q. Tang, Nanoscale, 2025, 17, 9490 DOI: 10.1039/D5NR00054H

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