合理调整金属单原子(SAs)的配位环境是提高其催化性能的有效途径,但迄今为止仍是一个挑战。
该文中,研究人员报告了一种新的错位沉积策略,用于制备不同配位的双金属异质SAs。系统表征结果表明,合成的双金属杂SAs(以Cu和Co为例)通过Cu–C4和Co–N4配位键连接到分级碳载体上。密度泛函理论研究表明,不对称部署的CuC4和CoN4位点之间的强协同作用导致显著的极化电荷分布,即CuC4和CoN4位点周围的电子积累和缺陷。
得到的CuC4/CoN4@HC与铜基和钴基SA催化剂相比,催化剂在底物吸附和O2活化方面表现出显著增强的能力,在芳香醛的氧化酯化反应中实现了优异的催化性能。
附:英文原文
Title: Dual-Metal Hetero-Single-Atoms with Different Coordination for Efficient Synergistic Catalysis
Author: Xin Zhao, Fengliang Wang, Xiang-Peng Kong, Ruiqi Fang, Yingwei Li
Issue&Volume: September 23, 2021
Abstract: Rationally tailoring the coordination environments of metal single atoms (SAs) is an effective approach to promote their catalytic performances, which, however, remains as a challenge to date. Here, we report a novel misplaced deposition strategy for the fabrication of differently coordinated dual-metal hetero-SAs. Systematic characterization results imply that the as-synthesized dual-metal hetero-SAs (exemplified by Cu and Co) are affixed to a hierarchical carbon support via Cu–C4 and Co–N4 coordination bonds. Density functional theory studies reveal that the strong synergistic interactions between the asymmetrically deployed CuC4 and CoN4 sites lead to remarkably polarized charge distributions, i.e., electron accumulation and deficiency around CuC4 and CoN4 sites, respectively. The obtained CuC4/CoN4@HC catalyst exhibits significantly enhanced capability in substrate adsorption and O2 activation, achieving superior catalytic performances in the oxidative esterification of aromatic aldehydes in comparison with the Cu- and Co-based SA counterparts.
DOI: 10.1021/jacs.1c06349
Source: https://pubs.acs.org/doi/10.1021/jacs.1c06349
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