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Metal–organic framework‐derived cobalt and nitrogen co‐doped porous carbon with four‐coordinated Co–N x for efficient acetylene hydrochlorination
Author(s) -
Dong Xiaobin,
Zhao Chaoyue,
Guan Qingxin,
Li Wei,
Xu Xiufang
Publication year - 2018
Publication title -
applied organometallic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.53
H-Index - 71
eISSN - 1099-0739
pISSN - 0268-2605
DOI - 10.1002/aoc.4570
Subject(s) - acetylene , chemistry , catalysis , cobalt , inorganic chemistry , carbon fibers , bimetallic strip , adsorption , vinyl chloride , pyrolysis , metal organic framework , organic chemistry , materials science , composite number , polymer , copolymer , composite material
Industrial production of vinyl chloride through acetylene hydrochlorination is a dominating technique in coal‐rich areas, but its development is severely restricted by the use of toxic mercury chloride (HgCl 2 ) catalyst. Inspired by the fact that doped carbon materials active in acetylene hydrochlorination often have good performance in the oxygen reduction reaction, a series of cobalt and nitrogen co‐doped porous carbon catalysts prepared by pyrolysis of bimetallic ZIFs based on ZIF‐8 and ZIF‐67 under N 2 were applied in acetylene hydrochlorination. The catalytic activities of the co‐doped catalysts varied with Co addition, and the highest acetylene conversion could be up to 83% with a space velocity of 2.6 ml g −1 min −1 at 220°C when a small amount of cobalt was introduced. Results of several characterizations confirmed the existence of Co–N x in the co‐doped carbons, pointing out that this coordination structure makes the catalysts have better ability to adsorb and activate C 2 H 2 . Density functional theory calculation finally proved that C atom adjacent to the N atom in Co–N 4 structure is the primary active site in co‐doped catalysts with high activity. We also conclude that the decreased N content caused by Co 2 N decomposition and the coordination structure change of Co–N x should be responsible for the gradually worsening performances of the carbon catalysts with further Co addition. Our study provides a new route for improving the performance of N‐doped carbon material in acetylene hydrochlorination and thus enhances its potential for practical application.