中国科学技术大学江海龙团队报道了Fe和Ni单原子对在MOF衍生N掺杂碳上的非键相互作用增强CO₂电还原。相关研究成果于2021年11月15日发表在国际顶尖学术期刊《美国化学会杂志》。

单原子催化剂（SAC）具有原子利用率高的特点，在各种应用中引起了广泛的兴趣。然而，SACs中的单原子位点通常被认为是独立的单元，相邻位点之间的相互作用在很大程度上被忽略。

该文中，研究人员通过直接热解由Fe和Ni掺杂的ZnO纳米颗粒组装的MOFs，精确构建了一种新型的Fe1–Ni1–N–C催化剂，其相邻的Fe和Ni单原子对修饰在氮掺杂的碳载体上。由于相邻的Fe和Ni单原子对的协同作用，Fe1–Ni1–N–C在电催化还原CO₂方面表现出显著增强的性能，远远超过了单独Fe或Ni单原子的Fe1–N–C和Ni1–N–C。此外，在锌-二氧化碳电池中，Fe1–Ni1–N–C还具有优异的CO选择性和耐久性。理论模拟表明，在Fe1–Ni1–N–C中，单个Fe原子可以通过非键相互作用被相邻的单原子Ni高度激活，显著促进COOH*中间体的形成，从而加速CO₂的整体还原。

该研究工作为构建含有多种金属物种的单原子催化剂提供了一个通用策略，并揭示了相邻单原子之间的交流效应对改善催化性能的重要性。

附：英文原文

Title: Non-Bonding Interaction of Neighboring Fe and Ni Single-Atom Pairs on MOF-Derived N-Doped Carbon for Enhanced CO2 Electroreduction

Author: Long Jiao, Juntong Zhu, Yan Zhang, Weijie Yang, Siyuan Zhou, Aowen Li, Chenfan Xie, Xusheng Zheng, Wu Zhou, Shu-Hong Yu, Hai-Long Jiang

Issue&Volume: November 15, 2021

Abstract: Single-atom catalysts (SACs), featuring high atom utilization, have captured widespread interests in diverse applications. However, the single-atom sites in SACs are generally recognized as independent units and the interplay of adjacent sites is largely overlooked. Herein, by the direct pyrolysis of MOFs assembled with Fe and Ni-doped ZnO nanoparticles, a novel Fe1–Ni1–N–C catalyst, with neighboring Fe and Ni single-atom pairs decorated on nitrogen-doped carbon support, has been precisely constructed. Thanks to the synergism of neighboring Fe and Ni single-atom pairs, Fe1–Ni1–N–C presents significantly boosted performances for electrocatalytic reduction of CO2, far surpassing Fe1–N–C and Ni1–N–C with separate Fe or Ni single atoms. Additionally, the Fe1–Ni1–N–C also exhibits superior performance with excellent CO selectivity and durability in Zn-CO2 battery. Theoretical simulations reveal that, in Fe1–Ni1–N–C, single Fe atoms can be highly activated by adjacent single-atom Ni via non-bonding interaction, significantly facilitating the formation of COOH* intermediate and thereby accelerating the overall CO2 reduction. This work supplies a general strategy to construct single-atom catalysts containing multiple metal species and reveals the vital importance of the communitive effect between adjacent single atoms toward improved catalysis.

DOI: 10.1021/jacs.1c08050

Source: https://pubs.acs.org/doi/10.1021/jacs.1c08050