Enhanced Hydrogen Peroxide Photosynthesis Using X‐Packed Cocrystal Catalysts
Abstract
ABSTRACT Hydrogen peroxide (H 2 O 2 ) is an essential chemical and potent energy carrier. Its production through solar energy and metal‐free photocatalysts is desirable. Organic semiconductors, as a new generation of semiconductors, can form suitable transition state intermediates showing great ability in enhancing the efficiency and selectivity of photocatalytic H 2 O 2 generation, offering a metal‐free, green, and more economical solution. However, the smaller Frenkel exciton radius and larger exciton Coulomb binding energy lead to a constrained capacity for exciton dissociation, blocking the way of photocatalysts based on organic semiconductors. Here, we overcome the bottleneck by cocrystal engineering. A kind of cocrystal photocatalysts with X‐packing are designed and synthesized, which permit all excited states to be optically allowed due to reduced energy splitting, enhancing the exciton participation in photosynthesis of H 2 O 2 giving much more efficient singlet exciton dissociation and exciton utilization. Indeed, the X‐packed cocrystals show photosynthesis of H 2 O 2 from O 2 and H 2 O at a rate of 2.65 mmol h −1 g −1 and a solar‐chemical energy conversion efficiency of 0.42%, which can be further improved to 13.3 mmol h −1 g −1 with a hole sacrificial agent. This work seems to open a new door for high solar exciton utilization with organic semiconductors by cocrystal engineering.
Article Details
Authors (14)
Lingsong Wang
State Key Laboratory of Advanced Materials for Intelligent Sensing Key Laboratory of Organic Integrated Circuits Ministry of Education Tianjin Key Laboratory of Molecular Optoelectronic Sciences Department of Chemistry School of Science Tianjin University Tianjin China
Jingheng Deng
Beijing National Laboratory for Molecular Sciences Institute of Chemistry Chinese Academy of Sciences Beijing China
Shuyu Li
State Key Laboratory for Crop Stress Resistance and High-Efficiency Production, Shaanxi Key Laboratory of Agricultural and Environmental Microbiology, College of Life Sciences, Northwest Agriculture and Forestry University
Huapeng Liu
State Key Laboratory of Advanced Materials for Intelligent Sensing Key Laboratory of Organic Integrated Circuits Ministry of Education Tianjin Key Laboratory of Molecular Optoelectronic Sciences Department of Chemistry School of Science Tianjin University Tianjin China
Kexin Liu
Hubei Key Laboratory of Electrochemical Power Sources, College of Chemistry and Molecular Sciences
Xiaocai Lv
State Key Laboratory of Advanced Materials for Intelligent Sensing Key Laboratory of Organic Integrated Circuits Ministry of Education Tianjin Key Laboratory of Molecular Optoelectronic Sciences Department of Chemistry School of Science Tianjin University Tianjin China
Yufan Zhang
Key Laboratory of Photochemistry, Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences
Jikun Li
State Key Laboratory for Porous Metal Materials, Shaanxi Key Laboratory of New Conceptual Sensors and Molecular Materials, Shaanxi International Research Center for Soft Matter, Xi’an Key Laboratory of Sustainable Polymer Materials, School of Materials Science and Engineering
Shuming Bai
Key Laboratory of Photochemistry, Beijing National Laboratory for Molecular Sciences, Institute of Chemistry
Yongfa Zhu
Department of Chemistry
Xiaotao Zhang
Tianjin Key Laboratory of Molecular Optoelectronic Sciences, Department of Chemistry, School of Science, Tianjin University and Collaborative Innovation Center of Chemical Science and Engineering, Tianjin 300072, China
Weigang Zhu
State Key Laboratory of Advanced Materials for Intelligent Sensing Key Laboratory of Organic Integrated Circuits Ministry of Education Tianjin Key Laboratory of Molecular Optoelectronic Sciences Department of Chemistry School of Science Tianjin University Tianjin China
Jincai Zhao
Wenping Hu