近日，课题组博士生曹守福的论文“Can N, S cocoordination promote single atom catalyst performance in CO₂RR? Fe‒N₂S₂ porphyrin vs. Fe‒N₄ porphyrin”被 Small（2020年中科院SCI期刊一区Top期刊，IF=11.459）接收！该工作研究了硫氮共配位环境对单原子催化剂在二氧化碳还原过程的提升性能及作用机理。

Single atom catalysts (SACs) are promising electrocatalyts for CO₂ reduction reaction (CO₂RR), in which the coordination environment plays a crucial role in intrinsic catalytic activity. Taking the regular Fe porphyrin (Fe‒N₄ porphyrin) as a probe, our study revealed that the introduction of opposable S atoms into N coordination (Fe‒N₂S₂ porphyrin) allowed for an appropriate electronic structural optimization on active sites. On account of the additional orbitals around the Fermi level and the abundant Fe  orbital occupation after S substitution, N, S cocoordination could effectively tune SACs and thus facilitating the protonation of intermediates during CO₂RR. CO₂RR mechanisms to possible C1 products via two-, six-, and eight-electron pathways were systematically elucidated on Fe‒N₄ porphyrin and Fe‒N₂S₂ porphyrin. Fe‒N₄ porphyrin yielded the most favorable product of HCOOH with a limiting potential of -0.70 V. Fe‒N₂S₂ porphyrin exhibited low limiting potentials of -0.38 and -0.40 V for HCOOH and CH₃OH, respectively, surpassing those of most Cu-based catalysts and SACs. Hence, the N, S cocoordination might provide better catalytic environment than regular N coordination for SACs in CO₂RR. This work demonstrated Fe‒N₂S₂ porphyrin as a high-performance CO₂RR catalyst, and highlighted N, S cocoordination regulation as an effective approach to fine tune high atomically dispersed electrocatalysts.