Cai Yuqi, Zhou Xiaocheng, Wang Yu, Li Yafei
Jiangsu Key Laboratory of New Power Batteries, Jiangsu Collaborative Innovation Centre of Biomedical Functional Materials, School of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, China.
ACS Omega. 2024 Jul 9;9(29):32167-32174. doi: 10.1021/acsomega.4c04465. eCollection 2024 Jul 23.
Exploring effective ways to detect intermediates during the electrochemical CO reduction reaction (CORR) process is pivotal for understanding reaction pathways and underlying mechanisms. Recently, two-dimensional FeN-embedded graphene has received increasing attention as a promising catalyst for CORR. Here, by means of density functional theory computations combined with the non-equilibrium Green's function (NEGF) method, we proposed a detection device to evaluate the performance of FeN-embedded graphene in intermediates detection during the CORR process. Our results reveal that the four key intermediates, including *COOH, *OCHO, *CHO, and *COH, can be chemisorbed on FeN-embedded graphene with high adsorption energies and appropriate charge transfer. The computed current-voltage (-) characteristics and transmission spectra suggest that the adsorption of these intermediates induces significant type-dependent changes in currents and transmission coefficients of FeN-embedded graphene. Remarkably, the FeN-embedded graphene is more sensitive to *COOH and *COH than to *OCHO and *CHO within the entire bias window. Consequently, our theoretical study indicates that the FeN-embedded graphene can effectively detect the key intermediates during the CORR process, providing a practical scheme for identifying catalytic reaction pathways and elucidating underlying reaction mechanisms.
探索在电化学CO还原反应（CORR）过程中检测中间体的有效方法对于理解反应途径和潜在机制至关重要。最近，二维FeN嵌入石墨烯作为一种有前景的CORR催化剂受到了越来越多的关注。在此，通过密度泛函理论计算结合非平衡格林函数（NEGF）方法，我们提出了一种检测装置，用于评估FeN嵌入石墨烯在CORR过程中检测中间体的性能。我们的结果表明，包括COOH、OCHO、CHO和COH在内的四种关键中间体可以以高吸附能和适当的电荷转移化学吸附在FeN嵌入石墨烯上。计算得到的电流-电压（-）特性和透射光谱表明，这些中间体的吸附会引起FeN嵌入石墨烯的电流和透射系数发生显著的类型依赖性变化。值得注意的是，在整个偏置窗口内，FeN嵌入石墨烯对COOH和COH比对OCHO和CHO更敏感。因此，我们的理论研究表明，FeN嵌入石墨烯可以有效地检测CORR过程中的关键中间体，为识别催化反应途径和阐明潜在反应机制提供了一种实用方案。
