Molecularly Engineered Covalent Organic Frameworks for Hydrogen Peroxide Photosynthesis

Mingpu Kou; Yongye Wang; Yixue Xu; Liqun Ye; Yingping Huang; Baohua Jia; Hui Li; Jiaqi Ren; Yu Deng; Jiahao Chen; Ying Zhou; Kai Lei; Li Wang; Wei Liu; Hongwei Huang; Tianyi Ma

doi:10.1002/anie.202200413

Molecularly Engineered Covalent Organic Frameworks for Hydrogen Peroxide Photosynthesis

Angew Chem Int Ed Engl. 2022 May 2;61(19):e202200413. doi: 10.1002/anie.202200413. Epub 2022 Feb 25.

Authors

Mingpu Kou¹, Yongye Wang¹, Yixue Xu^{1

2}, Liqun Ye^{1

2}, Yingping Huang³, Baohua Jia^{4

5}, Hui Li^{4

5}, Jiaqi Ren¹, Yu Deng¹, Jiahao Chen⁶, Ying Zhou⁶, Kai Lei⁷, Li Wang¹, Wei Liu^{1

2}, Hongwei Huang⁸, Tianyi Ma^{4

5}

Affiliations

¹ College of Materials and Chemical Engineering, Key Laboratory of Inorganic Nonmetallic Crystalline and Energy Conversion Materials, China Three Gorges University, Yichang, 443002, China.
² Hubei Three Gorges Laboratory, 443007, Yichang, China.
³ Engineering Research Center of Eco-environment in Three Gorges Reservoir Region, Ministry of Education, China Three Gorges University, Yichang, 443002, China.
⁴ Centre for Translational Atomaterials, Swinburne University of Technology, Hawthorn, VIC 3122, Australia.
⁵ School of Science, RMIT University, Melbourne, VIC 3000, Australia.
⁶ State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, School of Oil & Natural Gas Engineering, Southwest Petroleum University, 610500, Chengdu, China.
⁷ Key Laboratory of Material Chemistry for Energy Conversion and Storage (Ministry of Education), Hubei Key Laboratory of Material Chemistry and Service Failure, Wuhan National Laboratory for Optoelectronics, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology (HUST), Luoyu Road, Wuhan, 430074, China.
⁸ Beijing Key Laboratory of Materials Utilization of Nonmetallic Minerals and Solid Wastes, School of Materials Science and Technology, China University of Geosciences, Beijing, 100083, P. R. China.

Abstract

Synthesizing H₂ O₂ from water and air via a photocatalytic approach is ideal for efficient production of this chemical at small-scale. However, the poor activity and selectivity of the 2 e^- water oxidation reaction (WOR) greatly restricts the efficiency of photocatalytic H₂ O₂ production. Herein we prepare a bipyridine-based covalent organic framework photocatalyst (denoted as COF-TfpBpy) for H₂ O₂ production from water and air. The solar-to-chemical conversion (SCC) efficiency at 298 K and 333 K is 0.57 % and 1.08 %, respectively, which are higher than the current reported highest value. The resulting H₂ O₂ solution is capable of degrading pollutants. A mechanistic study revealed that the excellent photocatalytic activity of COF-TfpBpy is due to the protonation of bipyridine monomer, which promotes the rate-determining reaction (2 e^- WOR) and then enhances Yeager-type oxygen adsorption to accelerate 2 e^- one-step oxygen reduction. This work demonstrates, for the first time, the COF-catalyzed photosynthesis of H₂ O₂ from water and air; and paves the way for wastewater treatment using photocatalytic H₂ O₂ solution.

Keywords: Bipyridine; COFs; Environmental Chemistry; H2O2; Photosynthesis.

MeSH terms

Hydrogen Peroxide / chemical synthesis*
Metal-Organic Frameworks*
Oxygen
Photosynthesis
Water

Substances

Metal-Organic Frameworks
Water
Hydrogen Peroxide
Oxygen