Lei Haitao, Zhang Qingxin, Liang Zuozhong, Guo Hongbo, Wang Yabo, Lv Haoyuan, Li Xialiang, Zhang Wei, Apfel Ulf-Peter, Cao Rui
Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an, 710119, China.
Ruhr-Universität Bochum, Fakultät für Chemie und Biochemie, Anorganische Chemie I, Universitätsstrasse 150, 44801, Bochum, Germany.
Angew Chem Int Ed Engl. 2022 Jun 13;61(24):e202201104. doi: 10.1002/anie.202201104. Epub 2022 Apr 19.
Integrating molecular catalysts into designed frameworks often enables improved catalysis. Compared with porphyrin-based frameworks, metal-corrole-based frameworks have been rarely developed, although monomeric metal corroles are usually more efficient than porphyrin counterparts for the electrocatalytic oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). We herein report on metal-corrole-based porous organic polymers (POPs) as ORR and OER electrocatalysts. M-POPs (M=Mn, Fe, Co, Cu) were synthesized by coupling metal 10-phenyl-5,15-(4-iodophenyl)corrole with tetrakis(4-ethynylphenyl)methane. Compared with metal corrole monomers, M-POPs displayed significantly enhanced catalytic activity and stability. Co-POP outperformed other M-POPs by achieving four-electron ORR with a half-wave potential of 0.87 V vs. RHE and reaching 10 mA cm OER current density at 340 mV overpotential. This work is unparalleled to develop and explore metal-corrole-based POPs as electrocatalysts.
将分子催化剂整合到设计的框架中通常能够实现更好的催化效果。与基于卟啉的框架相比，基于金属咕啉的框架很少被开发，尽管单体金属咕啉在电催化氧还原反应（ORR）和析氧反应（OER）中通常比卟啉类似物更有效。我们在此报告基于金属咕啉的多孔有机聚合物（POPs）作为ORR和OER电催化剂。通过将金属10-苯基-5,15-（4-碘苯基）咕啉与四（4-乙炔基苯基）甲烷偶联合成了M-POPs（M = Mn、Fe、Co、Cu）。与金属咕啉单体相比，M-POPs表现出显著增强的催化活性和稳定性。Co-POP优于其他M-POPs，在相对于可逆氢电极（RHE）的半波电位为0.87 V时实现四电子ORR，并在340 mV过电位下达到10 mA cm的OER电流密度。这项工作在开发和探索基于金属咕啉的POPs作为电催化剂方面是无与伦比的。
