文献类型：期刊文献

英文题名：A novel thiophene-linked metalloporphyrin conjugated polymer: a highly efficient trifunctional electrocatalyst for overall water splitting and oxygen reduction

作者：Lu, Song[1];Ying, Jiadi[1];Liu, Tiancun[1];Wang, Yeqing[1];Guo, Min[1];Shen, Qi[1];Li, Qing[2];Wu, Yong[3];Zhao, Yafei[4];Yu, Zhixin[1]

机构：[1]Shaoxing Univ, Inst New Energy, Sch Chem & Chem Engn, Shaoxing 312000, Peoples R China;[2]Mohamed bin Zayed Univ Artificial Intelligence, Dept Machine Learning, Masdar 999041, Abu Dhabi, U Arab Emirates;[3]Dalian Univ Technol, Sch Chem, Dalian 116024, Peoples R China;[4]Henan Univ Sci & Technol, Sch Phys & Engn, Luoyang 471023, Peoples R China

年份：2024

卷号：12

期号：28

起止页码：17676

外文期刊名：JOURNAL OF MATERIALS CHEMISTRY A

收录：SCI-EXPANDED(收录号：WOS:001261712800001)、、EI(收录号：20242716563334)、Scopus(收录号：2-s2.0-85197854174)、WOS

基金：This work was supported by the starting grant of Shaoxing University, the National Natural Science Foundation of China (No. 22208220), and the Zhejiang Provincial Natural Science Foundation of China (No. LQ23B030005).

语种：英文

外文关键词：Atoms - Catalyst activity - Catalytic oxidation - Conjugated polymers - Density functional theory - Design for testability - Electrocatalysts - Electrolytic reduction - Oxygen - Porphyrins - Precious metals

外文摘要：It is highly desirable to design high performance trifunctional electrocatalysts for the hydrogen evolution reaction, oxygen evolution reaction, and oxygen reduction reaction (HER/OER/ORR). Herein, we designed a thiophene-linked porphyrin (TP) conjugated polymer that serves as a substrate for anchoring single transition metal atoms (TM-N4/TP) employed in the HER, OER and OER by density functional theory (DFT) calculations. It is demonstrated that TM atoms can be stably anchored onto TP and exhibit excellent electrochemical stability. Notably, Co-N4/TP exhibits an overpotential (eta) of 0.07 V for the HER, following the Volmer-Heyrovsky mechanism with an ultralow energy barrier of 0.15 eV under acid conditions. Meanwhile, Co-N4/TP demonstrates low eta for both the OER and ORR, with eta OER/eta ORR = 0.24/0.42 V, which is comparable to those of the noble-metal benchmark catalysts for the OER and ORR. Therefore, Co-N4/TP emerges as a trifunctional catalyst for overall water splitting and oxygen reduction. The oxidation state and magnetism of metal atoms were demonstrated to correlate with the catalytic activity on TM-N4/TP. Machine learning (ML) analysis indicates that the d band center (epsilon d) is the most crucial feature for HER activity on TM-N4/TP. Moreover, it was observed that OER or ORR activity cannot be determined by a sole descriptor, and the feature importance is tunable in the OER or ORR process. This work highlights a novel family of highly efficient multifunctional catalysts for renewable energy applications based on thiophene-linked metalloporphyrin conjugated polymers. A thiophene-linked porphyrin (TP) conjugated polymer that serves as a support for anchoring single transition metal atoms (TM-N4/TP) exhibits trifunctional merit for the HER/OER/ORR.