Liu Siying, Zheng Desheng, Zhao Lei, Zhao Xiuyun, Chen Xin
Center for Computational Chemistry and Molecular Simulation, College of Chemistry and Chemical Engineering, Southwest Petroleum University, Chengdu 610500, P. R. China.
School of Computer Science, Southwest Petroleum University, Chengdu 610500, P. R. China.
Langmuir. 2023 Oct 17;39(41):14748-14757. doi: 10.1021/acs.langmuir.3c02135. Epub 2023 Oct 3.
Single-atom catalysts (SACs) are attracting global attention due to their 100% atomic utilization rate and unique properties. Rare-earth-based SACs have shown great potential in the field of electrocatalysis in recent years. In this study, the catalytic performance of four rare earth metals (REMs) anchored into N-graphene for the CORR is systematically studied by density functional theory. The calculation results of formation energy show that all REM@N-G compounds have favorable stability. In addition, the Gibbs free energy calculation results of all possible elementary reactions show that the *OCHO pathway is the optimal hydrogenation pathway for all catalysts, and they have the same potential determining step (*OCHO + e + H → *HCOOH). Meanwhile, the products of the CORR on these catalysts are different, and the product on REM@N-G (REM = La, Pr, and Nd) is CH, while the product on Ce@N-G is CHOH. In particular, Nd@N-G exhibits the best catalytic activity in this work, with a very low limiting potential of -0.38 V. These results may guide the development of rare-earth-based SACs for CORR.
单原子催化剂（SACs）因其100%的原子利用率和独特性能而备受全球关注。近年来，稀土基单原子催化剂在电催化领域展现出巨大潜力。在本研究中，通过密度泛函理论系统研究了四种锚定在N-石墨烯上的稀土金属（REMs）对CO2RR的催化性能。生成能的计算结果表明，所有REMs@N-G化合物都具有良好的稳定性。此外，所有可能基元反应的吉布斯自由能计算结果表明，*OCHO途径是所有催化剂的最佳加氢途径，且它们具有相同的决速步骤（*OCHO + e + H → *HCOOH）。同时，这些催化剂上CO2RR的产物不同，REMs@N-G（REM = La、Pr和Nd）上的产物为CH，而Ce@N-G上的产物为CHOH。特别是，Nd@N-G在本工作中表现出最佳的催化活性，其极限电位低至-0.38 V。这些结果可能会指导用于CO2RR的稀土基单原子催化剂的开发。
