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Semiconductor/Covalent‐Organic‐Framework Z‐Scheme Heterojunctions for Artificial Photosynthesis
Author(s) -
Zhang Mi,
Lu Meng,
Lang ZhongLing,
Liu Jiang,
Liu Ming,
Chang JiaNan,
Li LeYan,
Shang LinJie,
Wang Min,
Li ShunLi,
Lan YaQian
Publication year - 2020
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202000929
Subject(s) - covalent bond , covalent organic framework , semiconductor , heterojunction , photocatalysis , artificial photosynthesis , electron transfer , materials science , redox , pyridine , chemical engineering , photochemistry , organic semiconductor , chemistry , nanotechnology , inorganic chemistry , optoelectronics , organic chemistry , catalysis , engineering
A strategy to covalently connect crystalline covalent organic frameworks (COFs) with semiconductors to create stable organic–inorganic Z‐scheme heterojunctions for artificial photosynthesis is presented. A series of COF–semiconductor Z‐scheme photocatalysts combining water‐oxidation semiconductors (TiO 2 , Bi 2 WO 6 , and α‐Fe 2 O 3 ) with CO 2 reduction COFs (COF‐316/318) was synthesized and exhibited high photocatalytic CO 2 ‐to‐CO conversion efficiencies (up to 69.67 μmol g −1 h −1 ), with H 2 O as the electron donor in the gas–solid CO 2 reduction, without additional photosensitizers and sacrificial agents. This is the first report of covalently bonded COF/inorganic‐semiconductor systems utilizing the Z‐scheme applied for artificial photosynthesis. Experiments and calculations confirmed efficient semiconductor‐to‐COF electron transfer by covalent coupling, resulting in electron accumulation in the cyano/pyridine moieties of the COF for CO 2 reduction and holes in the semiconductor for H 2 O oxidation, thus mimicking natural photosynthesis.