Peng Xinyang, Han Jinxiu, Li Xialiang, Liu Guijun, Xu Yuhan, Peng Yuxin, Nie Shuai, Li Wenzi, Li Xinrui, Chen Zhuo, Peng Haonan, Cao Rui, Fang Yu
Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an 710119, China.
Chem Commun (Camb). 2023 Sep 7;59(72):10777-10780. doi: 10.1039/d3cc03104g.
A newly designed copper complex of 5,15-bis(pentafluorophenyl)-10,20-bis(-carborane)porphyrin (1) was synthesized and tested for the electrocatalytic hydrogen evolution reaction (HER). In acetonitrile, 1 was much more efficient than Cu 5,15-bis(pentafluorophenyl)-10,20-diphenylporphyrin (2) for electrocatalytic HER by shifting the catalytic wave to the anodic direction by 190 mV. In aqueous media, 1 also outperformed 2 by achieving higher current densities under smaller overpotentials. This enhancement was attributed to the aromatic and the strong electron-withdrawing properties of -carborane groups. This work is significant to address the crucial effects of -(-carborane) substituents of metal porphyrins on boosting the electrocatalytic HER.
合成了一种新设计的5,15-双（五氟苯基）-10,20-双（-碳硼烷）卟啉铜配合物（1），并对其进行了电催化析氢反应（HER）测试。在乙腈中，通过将催化波向阳极方向移动190 mV，配合物1在电催化HER方面比铜5,15-双（五氟苯基）-10,20-二苯基卟啉（2）效率高得多。在水性介质中，配合物1在较小过电位下实现了更高的电流密度，同样优于配合物2。这种增强归因于-碳硼烷基团的芳香性和强吸电子特性。这项工作对于解决金属卟啉的-（-碳硼烷）取代基对促进电催化HER的关键作用具有重要意义。
