Liu Tianyang, Jing Yu, Li Yafei
Jiangsu Co-Innovation Centre of Efficient Processing and Utilization of Forest Resources, College of Chemical Engineering, Nanjing Forestry University, Nanjing 210037, China.
Jiangsu Collaborative Innovation Centre of Biomedical Functional Materials, Jiangsu Key Laboratory of New Power Batteries, School of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, China.
J Phys Chem Lett. 2024 Jun 13;15(23):6216-6221. doi: 10.1021/acs.jpclett.4c01096. Epub 2024 Jun 5.
Heterogeneous metal-nitrogen-carbon (M-N-C) single-atom catalysts (SACs) have garnered considerable attention in the two-electron CO reduction reaction (2e-CORR). Interestingly, almost M-N-C SACs mainly produce CO, while Sb is one of the few SACs reported so far that can produce HCOOH. Nevertheless, the underlying factors for different selectivities on Sb-N-C SAC remain controversial, and the lack of in-depth understanding of limiting factors hampers further regulations. Here, by using constant-potential first-principles calculations, we revealed that the high HCOOH selectivity of Sb-N-C SAC is mainly attributed to their weak charge accumulation ability. Remarkably, considering the highly tunable geometric structure of M-N-C SACs, we provide that Sb-N-C SAC with the SbNS center is a promising candidate for CO production. Our work provides the mechanism insight into 2e-CORR selectivity and further paves the way toward electrocatalyst regulation and design.
异质金属-氮-碳（M-N-C）单原子催化剂（SACs）在双电子CO还原反应（2e-CORR）中受到了广泛关注。有趣的是，几乎所有的M-N-C SACs主要生成CO，而Sb是迄今为止报道的少数几种能够生成HCOOH的SACs之一。然而，Sb-N-C SACs具有不同选择性的潜在因素仍存在争议，并且对限制因素缺乏深入了解阻碍了进一步的调控。在此，通过恒电位第一性原理计算，我们揭示了Sb-N-C SACs对HCOOH的高选择性主要归因于其较弱的电荷积累能力。值得注意的是，考虑到M-N-C SACs具有高度可调节的几何结构，我们提出具有SbNS中心的Sb-N-C SAC是一种有前景的CO生成候选材料。我们的工作为2e-CORR选择性提供了机理见解，并进一步为电催化剂的调控和设计铺平了道路。
