Affiliation:
1. State Key Laboratory of Fine Chemicals Frontiers Science Center for Smart Materials Oriented Chemical Engineering School of Chemical Engineering Dalian University of Technology Dalian 116024 P. R. China
2. Laboratory of Materials Modification by Laser Ion and Electron Beams, Ministry of Education Dalian University of Technology Dalian 116024 P. R. China
3. Center of Artificial Photosynthesis for Solar Fuels and Department of Chemistry School of Science Westlake University Hangzhou 310024 P. R. China
4. School of Engineering Sciences in Chemistry Biotechnology and Health KTH Royal Institute of Technology Stockholm 10044 Sweden
Abstract
AbstractPhotoredox catalysis is a green solution for organics transformation and CO2 conversion into valuable fuels, meeting the challenges of sustainable energy and environmental concerns. However, the regulation of single‐atomic active sites in organic framework not only influences the photoredox performance, but also limits the understanding of the relationship for photocatalytic selective organic conversion with CO2 valorization into one reaction system. As a prototype, different single‐atomic metal (M) sites (M2+ = Fe2+, Co2+, Ni2+, Cu2+, and Zn2+) in hydrogen‐bonded organic frameworks (M‐HOF) backbone with bridging structure of metal‐nitrogen are constructed by a typical “two‐in‐one” strategy for superior photocatalytic CN coupling reactions integrated with CO2 valorization. Remarkably, Zn‐HOF achieves 100% conversion of benzylamine oxidative coupling reactions, 91% selectivity of N‐benzylidenebenzylamine and CO2 conversion in one photoredox cycle. From X‐ray absorption fine structure analysis and density functional theory calculations, the superior photocatalytic performance is attributed to synergic effect of atomically dispersed metal sites and HOF host, decreasing the reaction energy barriers, enhancing CO2 adsorption and forming benzylcarbamic acid intermediate to promote the redox recycle. This work not only affords the rational design strategy of single‐atom active sites in functional HOF, but also facilitates the fundamental insights upon the mechanism of versatile photoredox coupling reaction systems.
Funder
National Natural Science Foundation of China
Fundamental Research Funds for the Central Universities
Subject
Electrochemistry,Condensed Matter Physics,Biomaterials,Electronic, Optical and Magnetic Materials
Cited by
9 articles.
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