Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an, 710119, P. R. China.
ChemSusChem. 2022 May 20;15(10):e202200086. doi: 10.1002/cssc.202200086. Epub 2022 Feb 24.
Elucidating the effects of various structural components on energy-related small molecule activation is of fundamental and practical significance. Herein the inhibition effect of positively charged substituents on the hydrogen evolution reaction (HER) was reported. With the use of Cu porphyrins 1-5 containing different numbers and locations of positively charged substituents, it was demonstrated that their electrocatalytic HER activities significantly decreased when more cationic units were located close to the Cu ion: the i /i (i is the catalytic peak current, i is the one-electron reduction peak current) value decreased from 38 with zero cationic unit to 15 with four closely located cationic units. Inspired by this result, Cu porphyrin 6, with four meso-phenyl groups each bearing a negatively charged para-sulfonic substituent, was designed. With these anionic units, 6 outperformed the other Cu porphyrins for electrocatalytic HER under the same conditions.
阐明各种结构成分对与能量相关的小分子活化的影响具有基础和实际意义。本文报道了正电荷取代基对析氢反应（HER）的抑制作用。使用含有不同数量和位置正电荷取代基的铜卟啉 1-5，证明当更多的阳离子单元靠近铜离子时，其电催化 HER 活性显著降低：i /i（i 是催化峰电流，i 是单电子还原峰电流）值从零阳离子单元时的 38 降低到四个紧密相邻阳离子单元时的 15。受此结果启发，设计了具有四个中位苯基的铜卟啉 6，每个苯基带有一个带负电荷的对位磺酸取代基。在相同条件下，这些阴离子单元使 6 比其他铜卟啉更适合电催化 HER。
