Synthesis, redox properties, and catalytic hydrogen gas generation of porphycene cobalt complexes

被引：1

作者：

Zhou, Zihan ^{[1
]}

Koide, Taro ^{[1
]}

Shiota, Yoshihito ^{[3
]}

Yano, Yoshio ^{[1
]}

Xu, Ning ^{[1
]}

Ono, Toshikazu ^{[1
,2
]}

Shimakoshi, Hisashi ^{[1
]}

Yoshizawa, Kazunari ^{[3
]}

Hisaeda, Yoshio ^{[1
,2
]}

机构：

[1] Kyushu Univ, Grad Sch Engn, Dept Chem & Biochem, Nishi Ku, Moto Oka 744, Fukuoka, Fukuoka 8190395, Japan

[2] Kyushu Univ, Ctr Mol Syst CMS, Nishi Ku, Moto Oka 744, Fukuoka, Fukuoka 8190395, Japan

[3] Kyushu Univ, Inst Mat Chem & Engn, Nishi Ku, Moto Oka 744, Fukuoka 8190395, Japan

来源：

JOURNAL OF PORPHYRINS AND PHTHALOCYANINES | 2022年 / 26卷 / 03期

关键词：

porphycene; cobalt complex; hydrogen evolution reaction (HER); ligand-centered reduction; electrocatalyst; ACTIVE LIGANDS; EVOLUTION REACTIONS; FUNCTIONAL MODELS; RECENT PROGRESS; BASIS-SET; PORPHYRIN; REDUCTION; H-2; REACTIVITY; ACID;

D O I：

10.1142/S108842462250016X

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A new meso-tetrakis(3,5-di-tert-butylphenyl) substituted porphycene and its cobalt complex were synthesized and characterized. Several meso-tetraarylporphycene cobalt complexes having different substituents showed catalytic activity for the hydrogen gas evolution reaction (HER) in the presence of trifluoroacetic acid (TFA) under electrochemical reductive conditions. The electrochemical potential of the HER was -1.50V vs. Ag/AgCl in THF. The active species of this reaction were determined to be the ligand reduced species of Co(II) porphycenes. The catalytic efficiencies of the cobalt complexes of meso-aryl substituted porphycenes and meso-tetraphenylporphyrin were compared and meso-tetraphenyl porphycene cobalt complex exhibited the best current efficiency of 72%. Based on these experimental results and theoretical calculations, we proposed a possible HER mechanism of this system. A new porphycene having four 3,5-di-tert-butylphenyl groups at the meso-positions and its cobalt complex were synthesized and characterized. The electrocatalytic hydrogen evolution reaction via the ligand-centered reduction of porphycene cobalt complexes was investigated. The reaction process was revealed by experimental results and theoretical calculations and was clearly different from the system via metal-centered reduction using porphyrin cobalt complex.

引用

页码：263 / 272

页数：10

共 67 条

[1] Cobaloximes as functional models for hydrogenases. 2. proton electroreduction catalyzed by difluoroborylbis(dimethylglyoximato)cobalt(II) complexes in organic media [J].