Proton‐Mediated Topological Interlayer Shift in 2D Covalent Organic Frameworks for Efficient Photocatalysis
Abstract
AbstractThe interlayer carriers dynamics are of significance in optoelectronic applications of 2D donor‐acceptor (D‐A) covalent organic frameworks (COFs), while are challenged by the delicate control over the inherently variable and sensitive interlayer interaction. Present work demonstrates an efficient proton‐mediation strategy that allows for the precise regulation of interlayer shift of 2D D‐A COFs for facilitated charge transfer and exciton dissociation. Exemplified by three imine‐linked D‐A COFs (IMDA), mild proton‐mediation generates an eclipsed AA stacking (IMDA‐AA) featuring in‐plane D‐A pairs and fully overlapping D‐A π‐conjugations, while excessive proton‐mediation disrupts these conjugations, resulting in a slipped AA stacking (IMDA‐SAA) with out‐of‐plane D‐A pairs. Further analysis reveals that the interlayer topology of eclipsed AA stacking of IMDA favors for the synergistically optimized charge transfer dynamics, including enhanced intralayer charge transport with reduced exciton binding energy, and boosted interlayer exciton dissociation. IMDA‐AA COF delivers an improved hydrogen evolution rate up to 171.2 mmol g−1h−1 under visible light illumination in the presence of 1.5 wt.% Pt co‐catalysts, which is as far as is known the highest value among the reports of 2D COFs based photocatalysis. Present work will provide an important avenue of addressing the topology‐governed charge transfer dynamics within COFs for solar energy conversion.
Article Details
Authors (17)
Yazhou Shuang
State Key Laboratory of Solidification Processing Center for Nano Energy Materials School of Materials Science and Engineering Northwestern Polytechnical University and Shaanxi Joint Laboratory of Graphene (NPU) Xi'an 710072 China
Yirong Zhang
1Institute for Translational Medicine on Cell Fate and Disease, Shanghai Ninth People's Hospital, Key Laboratory of Cell Differentiation and Apoptosis of National Ministry of Education, Department of Pathophysiology, Shanghai Jiao Tong University School of Medicine, Shanghai, China
Hongkang Wang
State Key Laboratory of Solidification Processing Center for Nano Energy Materials School of Materials Science and Engineering Northwestern Polytechnical University and Shaanxi Joint Laboratory of Graphene Xi'an 710072 P. R. China
Longyang Li
State Key Laboratory of Solidification Processing Center for Nano Energy Materials School of Materials Science and Engineering Northwestern Polytechnical University and Shaanxi Joint Laboratory of Graphene Xi'an 710072 P. R. China
Xueli Hao
State Key Laboratory of Rare Earth Resource Utilization Changchun Institute of Applied Chemistry Chinese Academy of Sciences Changchun Jilin 130022 P. R. China
Zelin Ma
State Key Laboratory of Solidification Processing Center for Nano Energy Materials School of Materials Science and Engineering Northwestern Polytechnical University and Shaanxi Joint Laboratory of Graphene (NPU) Xi'an 710072 China
Shiyuan Wang
Jiulong Wang
State Key Laboratory of Solidification Processing Center for Nano Energy Materials School of Materials Science and Engineering Northwestern Polytechnical University and Shaanxi Joint Laboratory of Graphene (NPU) Xi'an 710072 China
Fang Wang
Xiubo Yang
Analytical & Testing Center Northwestern Polytechnical University Xi'an 710072 China
Pengfei Guo
The Hong Kong University of Science and Technology , , , ,
Fei Xu
Hongyue Wang
China Electronic Product Reliability and Environmental Testing Research Institute 2 , Guangzhou,
Qian Ye
Wei Liu
Jie Jian
Hongqiang Wang