Chang Qiaowan, Liu Yumeng, Lee Ju-Hyeon, Ologunagba Damilola, Hwang Sooyeon, Xie Zhenhua, Kattel Shyam, Lee Ji Hoon, Chen Jingguang G
Department of Chemical Engineering, Columbia University, New York, New York 10027, United States.
School of Materials Science and Engineering, Kyungpook National University, Daegu 41566, Republic of Korea.
J Am Chem Soc. 2022 Sep 7;144(35):16131-16138. doi: 10.1021/jacs.2c06953. Epub 2022 Aug 25.
Single-atom catalysts (SACs) of non-precious transition metals (TMs) often show unique electrochemical performance, including the electrochemical carbon dioxide reduction reaction (CORR). However, the inhomogeneity in their structures makes it difficult to directly compare SACs of different TM for their CORR activity, selectivity, and reaction mechanisms. In this study, the comparison of isolated TMs (Fe, Co, Ni, Cu, and Zn) is systematically investigated using a series of crystalline molecular catalysts, namely TM-coordinated phthalocyanines (TM-Pcs), to directly compare the intrinsic role of the TMs with identical local coordination environments on the CORR performance. The combined experimental measurements, characterization, and density functional theory calculations of TM-Pc catalysts reveal a TM-dependent CORR activity and selectivity, with the free energy difference of Δ(*HOCO) - Δ(*CO) being identified as a descriptor for predicting the CORR performance.
非贵金属过渡金属（TMs）的单原子催化剂（SACs）通常表现出独特的电化学性能，包括电化学二氧化碳还原反应（CORR）。然而，其结构的不均匀性使得不同TM的SACs在CORR活性、选择性和反应机理方面难以直接比较。在本研究中，使用一系列晶体分子催化剂，即TM配位酞菁（TM-Pcs），系统地研究了孤立TM（Fe、Co、Ni、Cu和Zn）的比较，以直接比较具有相同局部配位环境的TMs对CORR性能的内在作用。TM-Pc催化剂的实验测量、表征和密度泛函理论计算相结合，揭示了TM依赖的CORR活性和选择性，其中Δ（*HOCO）-Δ（*CO）的自由能差被确定为预测CORR性能的描述符。
