Tang Hui Min, Fan Wai Yip
Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543, Singapore.
ACS Omega. 2023 Feb 9;8(7):7234-7241. doi: 10.1021/acsomega.3c00412. eCollection 2023 Feb 21.
A series of mononuclear first-row transition metal pyrithione M(pyr) complexes (M = Ni(II), Mn(II), = 2; M = Co(III), Fe(III), = 3) have been prepared from the reaction of the corresponding metal salt with the sodium salt of pyrithione. Using cyclic voltammetry, the complexes have been shown to behave as proton reduction electrocatalysts albeit with varying efficiencies in the presence of acetic acid as the proton source in acetonitrile. The nickel complex displays the optimal overall catalytic performance with an overpotential of 0.44 V. An ECEC mechanism is suggested for the nickel-catalyzed system based on the experimental data and supported by density functional theory calculations.
通过相应金属盐与吡啶硫酮钠盐反应，制备了一系列单核第一行过渡金属吡啶硫酮M(pyr)配合物（M = Ni(II)、Mn(II)，= 2；M = Co(III)、Fe(III)，= 3）。利用循环伏安法表明，在乙腈中以乙酸作为质子源时，这些配合物表现为质子还原电催化剂，尽管效率各不相同。镍配合物表现出最佳的整体催化性能，过电位为0.44 V。基于实验数据并得到密度泛函理论计算支持，提出了镍催化体系的ECEC机理。
