Premium
Construction of Donor–Acceptor Heterojunctions in Covalent Organic Framework for Enhanced CO 2 Electroreduction
Author(s) -
Wu Qiao,
Mao MinJie,
Wu QiuJin,
Liang Jun,
Huang YuanBiao,
Cao Rong
Publication year - 2021
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.202004933
Subject(s) - covalent organic framework , electrocatalyst , materials science , porphyrin , faraday efficiency , covalent bond , catalysis , electrochemical reduction of carbon dioxide , intramolecular force , electrochemistry , photochemistry , chemical engineering , inorganic chemistry , chemistry , electrode , organic chemistry , carbon monoxide , engineering
Covalent organic frameworks (COFs) are promising candidates for electrocatalytic reduction of carbon dioxide into valuable chemicals due to their porous crystalline structures and tunable single active sites, but the low conductivity leads to unmet current densities for commercial application. The challenge is to create conductive COFs for highly efficient electrocatalysis of carbon dioxide reduction reaction (CO 2 RR). Herein, a porphyrin‐based COF containing donor–acceptor (D–A) heterojunctions, termed TT‐Por(Co)‐COF, is constructed from thieno[3,2‐b]thiophene‐2,5‐dicarbaldehyde (TT) and 5,10,15,20‐tetrakis(4‐aminophenyl)‐porphinatocobalt (Co‐TAPP) via imine condensation reaction. Compared with COF‐366‐Co without TT, TT‐Por(Co)‐COF displays enhanced CO 2 RR performance to produce CO due to its favorable charge transfer capability from the electron donor TT moieties to the acceptor Co‐porphyrin ring active center. The combination of strong charge transfer properties and enormous amount of accessible active sites in the 2D TT‐Por(Co)‐COF nanosheets results in good catalytic performance with a high Faradaic efficiency of CO (91.4%, − 0.6 V vs reversible hydrogen electrode (RHE) and larger partial current density of 7.28 mA cm −2 at − 0.7 V versus RHE in aqueous solution. The results demonstrate that integration of D–A heterojunctions in COF can facilitate the intramolecular electron transfer, and generate high current densities for CO 2 RR.