Wang Yicheng, Zhang Qiyu, Wang Chenxu, Zhang Yating, Hu Chao
School of Chemical Engineering and Technology, Xi'an Jiaotong University, Xi'an, 710049, P. R. China.
College of Chemistry and Chemical Engineering, Xi'an University of Science and Technology, Xi'an, 710054, P. R. China.
Chem Asian J. 2025 Feb 3;20(3):e202401250. doi: 10.1002/asia.202401250. Epub 2024 Dec 12.
The utilization of renewable energy for electrocatalytic carbon dioxide reduction reaction (CORR) represents a pivotal technology in sustainable carbon conversion. Single-atom catalysts (SACs) featuring transition metal-nitrogen-carbon (M-N-C) structures have demonstrated exceptional electrocatalytic efficacy in CORR by maximizing atom efficiency. Nevertheless, further investigation is warranted to optimize the catalytic performance of SACs through the selection of suitable carbon sources and supports, as well as the modulation of the microenvironment surrounding individual metal atoms. In this study, a sulfur-doped Ni-N-C catalyst was prepared using a two-step strategy involving metal ion adsorption and thermal decomposition, with porous ion exchange resin serving as the carbon source. Due to the uniform distribution of single atom active centers on the resin-based carbon support and sulfur doping, this catalyst efficiently converts CO into CO with a Faradaic efficiency exceeding 90 % within the range of -0.69~-1.29 V (vs. RHE), reaching a maximum value of 97.7 % (-0.79 V vs. RHE). Theoretical calculations indicate that second-shell sulfur doping effectively promotes coupled transfer of protons and electrons, leading to a significant reduction in Gibbs free energy barriers for CORR intermediate products.
利用可再生能源进行电催化二氧化碳还原反应（CORR）是可持续碳转化中的一项关键技术。具有过渡金属-氮-碳（M-N-C）结构的单原子催化剂（SACs）通过最大化原子效率，在CORR中展现出卓越的电催化效能。然而，仍需进一步研究，通过选择合适的碳源和载体以及调节单个金属原子周围的微环境来优化SACs的催化性能。在本研究中，采用两步法策略制备了硫掺杂的Ni-N-C催化剂，该策略包括金属离子吸附和热分解，使用多孔离子交换树脂作为碳源。由于单原子活性中心在树脂基碳载体上均匀分布且存在硫掺杂，该催化剂在-0.69~-1.29 V（相对于可逆氢电极，RHE）范围内能高效地将CO转化为CO，法拉第效率超过90%，在-0.79 V（相对于RHE）时达到最大值97.7%。理论计算表明，第二壳层硫掺杂有效地促进了质子和电子的耦合转移，导致CORR中间产物的吉布斯自由能垒显著降低。
