中国科学院固体物理研究所伍志鲲团队报道了基于连续单非金属原子调谐的金属纳米团簇上，自下而上构建金属-有机框架Loricae用于定制催化。相关研究成果于2024年3月5日发表在《美国化学会杂志》。

将单个或多个杂金属原子引入金属纳米颗粒是改变其结构（组成）和性质的众所周知的策略。然而，表面单非金属原子掺杂具有挑战性，且很少报道。

研究人员首次开发了合成方法，实现了对超小金属纳米颗粒（金属纳米团簇，NCs）的“外科手术”式连续表面单非金属原子掺杂、置换和添加，并成功合成和表征了三种新型bcc金属NCs Au38I（S-Adm）19、Au38S（S-Adm）20和Au38IS（S-Adm:1-adamantanethiolate）。

研究人员详细研究了单个非金属原子的取代和添加对NC结构和光学性能（包括吸收和光致发光）的影响，为结构（组成）-性能的相关性提供了见解。此外，采用自下而上的方法在NC表面构建金属-有机框架（MOF），这并没有本质上改变金属-NC的结构，但导致表面配体的部分释放，并刺激金属-NC催化对硝基苯酚还原的活性。此外，表面MOF结构增强了NC的稳定性和水溶性，为通过修饰MOF官能团来调节NC催化活性提供了另一个维度。

附：英文原文

Title: Bottom-Up Construction of Metal–Organic Framework Loricae on Metal Nanoclusters with Consecutive Single Nonmetal Atom Tuning for Tailored Catalysis

Author: Qing You, He Wang, Yan Zhao, Wentao Fan, Wanmiao Gu, Hai-Long Jiang, Zhikun Wu

Issue&Volume: March 5, 2024

Abstract: The introduction of single or multiple heterometal atoms into metal nanoparticles is a well-known strategy for altering their structures (compositions) and properties. However, surface single nonmetal atom doping is challenging and rarely reported. For the first time, we have developed synthetic methods, realizing “surgery”-like, successive surface single nonmetal atom doping, replacement, and addition for ultrasmall metal nanoparticles (metal nanoclusters, NCs), and successfully synthesized and characterized three novel bcc metal NCs Au38I(S-Adm)19, Au38S(S-Adm)20, and Au38IS(S-Adm)19 (S-Adm: 1-adamantanethiolate). The influences of single nonmetal atom replacement and addition on the NC structure and optical properties (including absorption and photoluminescence) were carefully investigated, providing insights into the structure (composition)–property correlation. Furthermore, a bottom-up method was employed to construct a metal–organic framework (MOF) on the NC surface, which did not essentially alter the metal NC structure but led to the partial release of surface ligands and stimulated metal NC activity for catalyzing p-nitrophenol reduction. Furthermore, surface MOF construction enhanced NC stability and water solubility, providing another dimension for tunning NC catalytic activity by modifying MOF functional groups.

DOI: 10.1021/jacs.3c13635

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.3c13635