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Toward Activity Origin of Electrocatalytic Hydrogen Evolution Reaction on Carbon‐Rich Crystalline Coordination Polymers
Author(s) -
Wang Lihuan,
Tranca Diana C.,
Zhang Jian,
Qi Yanpeng,
Sfaelou Stavroula,
Zhang Tao,
Dong Renhao,
Zhuang Xiaodong,
Zheng Zhikun,
Seifert Gotthard
Publication year - 2017
Publication title -
small
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 3.785
H-Index - 236
eISSN - 1613-6829
pISSN - 1613-6810
DOI - 10.1002/smll.201700783
Subject(s) - catalysis , electrocatalyst , hydride , protonation , metal , carbon fibers , active site , inorganic chemistry , hydrogen , materials science , chemistry , electrochemistry , organic chemistry , electrode , ion , composite material , composite number
The fundamental understanding of electrocatalytic active sites for hydrogen evolution reaction (HER) is significantly important for the development of metal complex involved carbon electrocatalysts with low kinetic barrier. Here, the MS x N y (M = Fe, Co, and Ni, x / y are 2/2, 0/4, and 4/0, respectively) active centers are immobilized into ladder‐type, highly crystalline coordination polymers as model carbon‐rich electrocatalysts for H 2 generation in acid solution. The electrocatalytic HER tests reveal that the coordination of metal, sulfur, and nitrogen synergistically facilitates the hydrogen ad‐/desorption on MS x N y catalysts, leading to enhanced HER kinetics. Toward the activity origin of MS 2 N 2 , the experimental and theoretical results disclose that the metal atoms are preferentially protonated and then the production of H 2 is favored on the MN active sites after a heterocoupling step involving a N‐bound proton and a metal‐bound hydride. Moreover, the tuning of the metal centers in MS 2 N 2 leads to the HER performance in the order of FeS 2 N 2 > CoS 2 N 2 > NiS 2 N 2 . Thus, the understanding of the catalytic active sites provides strategies for the enhancement of the electrocatalytic activity by tailoring the ligands and metal centers to the desired function.