摘要 : <abstract type="main" xml:lang="en"> <title type="main">Abstract</title> <p> A strategy to covalently connect crystalline covalent organic frameworks (COFs) with semiconductors to create stable organic–inor... 展开 <abstract type="main" xml:lang="en"> <title type="main">Abstract</title> <p> 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. </p> </abstract> 收起