Details

Autor(en) / Beteiligte

• Lu, Jia‐Ni
• Liu, Jing‐Jing
• Dong, Long‐Zhang
• Lin, Jiao‐Min
• Yu, Fei
• Liu, Jiang
• Lan, Ya‐Qian

Titel

Synergistic Metal‐Nonmetal Active Sites in a Metal‐Organic Cage for Efficient Photocatalytic Synthesis of Hydrogen Peroxide in Pure Water

Ist Teil von

• Angewandte Chemie International Edition, 2023-09, Vol.62 (36), p.e202308505-n/a

Auflage

International ed. in English

Ort / Verlag

Germany: Wiley Subscription Services, Inc

Erscheinungsjahr

2023

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• Photocatalytic synthesis of hydrogen peroxide (H2O2) is a potential clean method, but the long distance between the oxidation and reduction sites in photocatalysts hinders the rapid transfer of photogenerated charges, limiting the improvement of its performance. Here, a metal‐organic cage photocatalyst, Co14(L−CH3)24, is constructed by directly coordinating metal sites (Co sites) used for the O2 reduction reaction (ORR) with non‐metallic sites (imidazole sites of ligands) used for the H2O oxidation reaction (WOR), which shortens the transport path of photogenerated electrons and holes, and improves the transport efficiency of charges and activity of the photocatalyst. Therefore, it can be used as an efficient photocatalyst with a rate of as high as 146.6 μmol g−1 h−1 for H2O2 production under O2‐saturated pure water without sacrificial agents. Significantly, the combination of photocatalytic experiments and theoretical calculations proves that the functionalized modification of ligands is more conducive to adsorbing key intermediates (*OH for WOR and *HOOH for ORR), resulting in better performance. This work proposed a new catalytic strategy for the first time; i.e., to build a synergistic metal‐nonmetal active site in the crystalline catalyst and use the host–guest chemistry inherent in the metal‐organic cage (MOC)to increase the contact between the substrate and the catalytically active site, and finally achieve efficient photocatalytic H2O2 synthesis. Two stable CoII‐based metal‐organic cages are efficient catalysts for photocatalytic synthesis of H2O2 in pure water and O2 or air atmospheres. The metal‐nonmetal active site operates synergistically during photocatalytic H2O2 synthesis and the reaction substrate can more fully contact the catalytically active site through host–guest chemistry of cages, ultimately achieving a high H2O2 production rate.