Flexible Units Induced Three-Dimensional Covalent Organic Frameworks with a Heteromotif Molecular Junction for Photocatalytic H₂O₂ Production

Liao, Jia-Peng1; Zhang, Mi1; Huang, Pei1; Dong, Long-Zhang1; Ma, Tian-Tian1; Huang, Guo-Zhang2; Liu, Yu-Fei1; Lu, Meng1; Li, Shun-Li1; Lan, Ya-Qian1

2024-02-22

10.1021/acscatal.3c06078

ACS CATALYSIS   影响因子和分区

2155-5435

In recent years, significant progress has been achieved in the field of three-dimensional covalent organic frameworks (3D COFs). However, there is still a great challenge to use flexible building units to synthesize high-connectivity 3D COFs. In this work, we showed that [6 + 3] 3D COFs could be constructed by inducing highly flexible planar building blocks from C-3 antitriangular prismed 3D building blocks. Herein, two 3D COFs with spn topology based on flexible cyclotriphosphazene units were constructed and denoted as TAA/TAB-CTP-COF, and their redox ability and photophysical features can be finely regulated by the coupled functional group, such as benzene and triazine groups. As a result, the redox heteromotif molecular junction TAA-CTP-COF with fully exposed active sites achieved high photocatalytic production of hydrogen peroxide (H2O2) with a yield of 1041 mu M h(-1) without any additional photosensitizers, organic scavengers, or cocatalysts. Furthermore, in the presence of an electron donor, the production rate of H2O2 could reach up to 2221 mu M h(-1), exhibiting one of the best performances for photocatalytic H2O2 production in the field of crystalline materials. This work showcases the potential of using flexible building blocks in building 3D COFs and highlights the versatility and efficacy of metal-free COFs in solar energy conversion.

covalent organic frameworks three-dimensional structures redox heteromotif molecular junction hydrogen peroxide photocatalysis

SCI ; EI

英语

其他

National Natural Science Foundation of China[2023YFA1507204] ; National Key R&D Program of China["22225109","22071109","22105080","22201083"] ; NSFC[BX20220115] ; China National Postdoctoral Program for Innovative Talents["2021M701270","2020M682748"] ; China Postdoctoral Science Foundation["2023A1515010779","2023A1515010928"] ; Guangdong Basic and Applied Basic Research Foundation[202102020209]

Chemistry

Chemistry, Physical

WOS:001174396300001

AMER CHEMICAL SOC

Web of Science

1.South China Normal Univ, Sch Chem, Guangzhou 510006, Guangdong, Peoples R China
2.Southern Univ Sci & Technol, Dept Chem, Guangdong Prov Key Lab Catalyt Chem, Shenzhen 518055, Guangdong, Peoples R China

Liao, Jia-Peng,Zhang, Mi,Huang, Pei,et al. Flexible Units Induced Three-Dimensional Covalent Organic Frameworks with a Heteromotif Molecular Junction for Photocatalytic H₂O₂ Production[J]. ACS CATALYSIS,2024,14(6).

Liao, Jia-Peng.,Zhang, Mi.,Huang, Pei.,Dong, Long-Zhang.,Ma, Tian-Tian.,...&Lan, Ya-Qian.(2024).Flexible Units Induced Three-Dimensional Covalent Organic Frameworks with a Heteromotif Molecular Junction for Photocatalytic H₂O₂ Production.ACS CATALYSIS,14(6).

Liao, Jia-Peng,et al."Flexible Units Induced Three-Dimensional Covalent Organic Frameworks with a Heteromotif Molecular Junction for Photocatalytic H₂O₂ Production".ACS CATALYSIS 14.6(2024).