Zhang Yechuan, Gu Zhengxiang, Yang Huiyue, Gao Jie, Peng Fang, Yang Huajun
School of Chemistry and Materials Science, Nanjing Normal University, 210023 Nanjing, China.
School of Chemistry and Materials Science, Nanjing Normal University, 210023 Nanjing, China; Huaxi MR Research Center (HMRRC), Department of Radiology, West China Hospital, Sichuan University, Chengdu 610041, China.
J Colloid Interface Sci. 2023 Dec 15;652(Pt A):250-257. doi: 10.1016/j.jcis.2023.08.078. Epub 2023 Aug 12.
The conversion of CO to CO is one of the crucial pathways in the carbon dioxide reduction reaction (CORR). Iron and nitrogen co-doped carbon matrix (FeN) is a promising catalyst for converting COto CO with excellent activity and selectivity. However, the reactive mechanism of CORR on the FeN catalyst is not fully unveiled. For example, it is still evasive that the obtained C product is methanol and/or methane instead of CO in some cases. Herein, DFT calculation is conducted to unravel the effect from both solvent molecules and intermediates as axial groups on the selectivity of C products in CORR using FeN catalyts. Calculation results demonstrate that the FeN(H), FeN(OH), FeN(COOH), and FeN(CO) configurations are not only beneficial to the removal of CO, but also effectively suppress the hydrogen evolution reaction, whereas the FeN, FeN(CO) and FeN(HO) configurations are inclined to produce CHOH and/or CH. The mechanism studied in this work provides an inspiration of optimizing the selectivity of C products in CORR from the perspective of regulating solvent molecules and intermediates as axial groups on FeN.
CO 转化为 CO 是二氧化碳还原反应（CORR）中的关键途径之一。铁氮共掺杂碳基材料（FeN）是一种很有前景的催化剂，可将 CO 高效且选择性地转化为 CO，但 CORR 在 FeN 催化剂上的反应机理尚未完全揭示。例如，在某些情况下，所得 C 产物是甲醇和/或甲烷而非 CO 这一问题仍不明确。在此，进行密度泛函理论（DFT）计算，以揭示溶剂分子和作为轴向基团的中间体对使用 FeN 催化剂的 CORR 中 C 产物选择性的影响。计算结果表明，FeN(H)、FeN(OH)、FeN(COOH) 和 FeN(CO) 构型不仅有利于 CO 的去除，还能有效抑制析氢反应，而 FeN、FeN(CO) 和 FeN(HO) 构型则倾向于生成 CH OH 和/或 CH。本工作所研究的机理为从调节 FeN 上作为轴向基团的溶剂分子和中间体的角度优化 CORR 中 C 产物的选择性提供了思路。
