Chou Pallas, Kim Lauren, Marzouk Sammer M, Sun Rui, Hartnett Alaina C, Dogutan Dilek K, Zheng Shao-Liang, Nocera Daniel G
Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, Massachusetts 02138, United States.
ACS Omega. 2022 Mar 2;7(10):8988-8994. doi: 10.1021/acsomega.2c00109. eCollection 2022 Mar 15.
Zn(II), Cu(II), and Ni(II) 5,10,15,20-tetrakis(4-fluoro-2,6-dimethylphenyl)porphyrins (TFPs) have been synthesized and characterized. The electronic spectroscopy and cyclic voltammetry of these compounds, along with the free-base macrocycle (2H-TFP), have been determined; 2H-TFP was also structurally characterized by X-ray crystallography. The Cu(II)TFP exhibits catalytic activity for the hydrogen evolution reaction (HER). The analysis of linear sweep voltammograms shows that the HER reaction of Cu(II)TFP with benzoic acid is first-order in proton concentration with an average apparent rate constant for HER catalysis of = 5.79 ± 0.47 × 10 M s.
已合成并表征了锌（II）、铜（II）和镍（II）的5,10,15,20-四（4-氟-2,6-二甲基苯基）卟啉（TFP）。已测定了这些化合物以及游离碱大环（2H-TFP）的电子光谱和循环伏安法；2H-TFP也通过X射线晶体学进行了结构表征。Cu（II）TFP对析氢反应（HER）具有催化活性。线性扫描伏安图分析表明，Cu（II）TFP与苯甲酸的HER反应在质子浓度上是一级反应，HER催化的平均表观速率常数为 = 5.79 ± 0.47 × 10 M s 。
