天津大学邓意达团队近日研究了四面体配位单原子催化剂对CO₂电还原的自旋态效应。2025年6月5日出版的《美国化学会志》发表了这项成果。

活性位点的自旋状态是影响电催化剂催化性能的最重要因素之一。迄今为止，大多数调节都是在非四面体配位的金属位点上进行的，而四面体配位单原子催化剂（TCSAC）尚未得到研究。

研究组介绍了TCSAC的自旋状态与其对CO₂电还原的活性之间的相关性。TCSAC是使用ZnO作为基板制成的。TCSAC金属位点的自旋态调节催化剂和吸附中间体之间的相互作用。过渡金属（TM）磁矩与CO₂还原反应的极限电位（UL）之间存在火山关系。 

自旋态分析表明，TMs的中间自旋态更有利于CO₂的吸附和转化。中间自旋的TM-t₂轨道和吸附分子p_z轨道之间的最佳相互作用显著提高了TCSAC的催化活性。因此，与RHE相比，Fe-TCSAC在-0.9 V时实现了91.6%的高FE_CO。这些结果为四面体配位单原子催化剂的自旋态效应提供了理论依据和指导。

附：英文原文

Title: Spin-State Effect of Tetrahedron-Coordinated Single-Atom Catalysts on CO2 Electroreduction

Author: Yuan Liu, Xixi Ren, Jiajun Wang, Haozhi Wang, Zexiang Yin, Yang Wang, Wenjie Huang, Xiaolin Hu, Zhichuan J. Xu, Yida Deng

Issue&Volume: June 5, 2025

Abstract: Spin state of active sites is one of the most influencing factors for the catalytic performance of electrocatalysts. To date, most modulations are conducted on non-tetrahedrally coordinated metal sites, while tetrahedron-coordinated single-atom catalysts (TCSACs) have not been investigated yet. This article presents a correlation between the spin state of TCSACs and their activities toward CO2 electroreduction. TCSACs are made using ZnO as the substrate. The spin states of metal sites of TCSACs modulate the interactions between the catalyst and adsorbed intermediates. A volcano relationship is found between the transition metal (TM) magnetic moments and the limiting potential (UL) of the CO2 reduction reaction. Spin-state analysis indicates that the intermediate spin state of TMs is more favorable for the adsorption and conversion of CO2. Optimal interaction between the TM-t2 orbitals of the intermediate spin and the adsorbed molecule-pz orbitals significantly improves the catalytic activity of the TCSACs. As a result, Fe-TCSAC achieves a high FECO of 91.6% at 0.9 V vs RHE. These results provide a theoretical basis and guidelines for the spin-state effects of tetrahedron-coordinated single-atom catalysts.

DOI: 10.1021/jacs.4c18550

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.4c18550