近日，新加坡国立大学Jianping Xie团队报道了基序编辑揭示了原子精确金属纳米簇中隐藏的活性位点，用于增强电催化。相关论文发表在2025年10月23日出版的《美国化学会志》上。

金属纳米计为催化提供了原子精确的平台，但通常需要大量的分子基序来实现纳米计的稳定性。

研究组评估了这些基序如何阻断活性位点的进入，并量化结构完整性和催化性能之间的权衡。在此基础上，研究组设计了一个基序-基序表面编辑策略，以原子精度暴露催化位点，同时保持核的完整性。使用[Au₂₅ (pMBA) ₁₈]^-纳米簇（pMBA = 对巯基苯甲酸）为模型体系，研究组选择性地用紧凑的Cu-(pMBA)₃单元取代了立体体积庞大的Au₂(pMBA)₃基序，得到了具有对称、开放表面结构的[Au₁₃Cu₄(pMBA)₁₂]^3-纳米基。

原位吸收和质谱分析揭示了与传统的共还原或配体位移不同的逐步基序交换机制，使表面重建没有核畸变。与母体材料[Au₂₅(pMBA)₁₈]（0.1 s^-1）相比，该材料的析氢周转率提高了180倍（18.8 s^-1）。根据光谱和密度泛函理论，这是由于Au₃面暴露增加和氢结合改善所致。这项工作为金属纳米材料的可编程表面工程提供了一条可推广的途径，有助于解决原子精度和催化可及性之间长期存在的矛盾。

附：英文原文

Title: Motif Editing Reveals Hidden Active Sites in Atomically Precise Metal Nanoclusters for Enhanced Electrocatalysis

Author: Zhihe Liu, Moshuqi Zhu, Bo Li, Junmei Chen, Shibo Xi, Yang-Yang Yu, Lu Xia, Lei Wang, De-en Jiang, F. Pelayo García de Arquer, Jianping Xie

Issue&Volume: October 23, 2025

Abstract: Metal nanoclusters offer atomically precise platforms for catalysis but often require bulk molecular motifs to achieve cluster stability. Here, we assess how these motifs block access to active sites and quantify trade-offs between structural integrity and catalytic performance. Based on this, we designed a motif-by-motif surface editing strategy to expose catalytic sites with atomic precision while preserving the kernel integrity of the cluster. Using [Au25(pMBA)18] nanoclusters (pMBA = para-mercaptobenzoic acid) as a model system, we selectively replace sterically bulky Au2(pMBA)3 motifs with compact Cu-(pMBA)3 units, yielding [Au13Cu4(pMBA)12]3– nanoclusters with a symmetric, open-surface architecture. In situ absorption and mass spectrometry reveals a stepwise motif exchange mechanism distinct from conventional coreduction or ligand displacement, which enables surface reconstruction without kernel distortion. The resulting clusters deliver a 180-fold enhancement in hydrogen evolution turnover frequency (18.8 s–1), compared to the parent [Au25(pMBA)18] (0.1 s–1), attributed to increased Au3 facet exposure and improved hydrogen binding, as suggested by spectroscopy and density functional theory. This work offers a generalizable route to programmable surface engineering in metal nanoclusters, contributing to advance in the longstanding paradox between atomic precision and catalytic accessibility.

DOI: 10.1021/jacs.5c08684

Source: https://pubs.acs.org/doi/full/10.1021/jacs.5c08684