Hydrogen‐Localization Transfer Regulation in 3D COFs Enhances Photocatalytic Acetylene Semi‐Hydrogenation to Ethylene
Pei Huang, Mingyi Yang, Shuai‐Bing Zhang, Zehui Li, Han Zhang, Si‐Miao Wang, Yan‐Yu Peng, Mi Zhang, Shun‐Li Li, Meng Lu, Ya‐Qian Lan
Abstract
Abstract In this work, a series of new crystalline three‐dimensional covalent organic frameworks (3D COFs) based on [8+4] construction was designed and successfully realized efficient photocatalytic acetylene (C 2 H 2 ) hydrogenation to ethylene (C 2 H 4 ). By regulating the hydrogen‐localization transfer effect in these 3D COFs, the Cz−Co−COF−H containing cobalt glyoximate active centers exhibited excellent C 2 H 2 ‐to‐C 2 H 4 performance, with an average C 2 H 4 yield of 1755.33 μmol g −1 h −1 in pure C 2 H 2 , also showed near 100 % conversion of C 2 H 2 in 1 % C 2 H 2 contained crude C 2 H 4 mixtures (industry‐relevant conditions), and finally obtain polymer grade C 2 H 4 . In contrast, the Cz−Co−COF−BF 2 only showed one fifth activity due to lack of hydrogen‐localization transfer. The density functional theory (DFT), projected density of states (PDOS) and molecular dynamics “slow‐growth” kinetic calculations based on precise 3D COF structures confirmed that the rapid hydrogen species transfer, enhanced water dissociation and suitable C 2 H 2 adsorption in COFs jointly contributed efficient photocatalytic acetylene hydrogenation (PAH). This work provides new opportunity towards rational design and development of crystalline photocatalysts for C 2 H 2 hydrogenation.