文献类型： 外文期刊

作者： Xue, Ding-Ming ¹ ; Zhang, Yi-Jun ² ; Chen, Jing-Wen ³ ; Yang, Hao ⁴ ; Xie, Rui-Jie ⁵ ; Qi, Shi-Chao ⁶ ; Bu, Yuan-Qing ¹ ; Liu, Fei ⁷ ; Zhang, Hou-Hu ¹ ; Lalevee, Jacques ² ;

作者机构： 1.Minist Ecol & Environm, Nanjing Inst Environm Sci, 8 Jiangwangmiao St, Nanjing 210042, Peoples R China

2.Univ Haute alsace, CNRS, UMR IS2M 7361, F-68100 Mulhouse, Alsace, France

3.Jiangsu Acad Agr Sci, Inst Agr Facil & Equipment, Key Lab Protected Agr Engn Middle & Lower Reaches, Minist Agr & Rural Affairs, Nanjing 210014, Peoples R China

4.Yantai Univ, Sch Chem & Chem Engn, Yantai 264005, Shandong, Peoples R China

5.Xiamen Univ, Inst Flexible Elect IFE, Future Technol, Xiangan Campus,Xiangan South Rd, Xiamen 361102, Fujian, Peoples R China

6.Nanjing Tech Univ, Coll Chem Engn, Jiangsu Natl Synerget Innovat Ctr Adv Mat SICAM, State Key Lab Mat Oriented Chem Engn, Nanjing 211816, Peoples R China

7.Chinese Acad Sci, Nanjing Inst Geog & Limnol, Key Lab Lake & Watershed Sci Water Secur, Nanjing 210008, Peoples R China

8.Nanjing Univ Informat Sci & Technol, Jiangsu Collaborat Innovat Ctr Atmospher Environm, Sch Environm Sci & Engn, Jiangsu Key Lab Atmospher Environm Monitoring & Po, 219 Ningliu Rd, Nanjing 210044, Peoples R China

关键词： Molecular engineering; Covalent organic frameworks; Photosynthesis; Donor-acceptor; Hydrogen peroxide

期刊名称：CHEMICAL ENGINEERING JOURNAL （ 影响因子：13.2； 五年影响因子：13.5 ）

ISSN： 1385-8947

年卷期： 2024 年 502 卷

页码：

收录情况： SCI

摘要： Covalent organic frameworks (COFs), as a newly emerging kind of porous and crystalline materials, serve as an ideal template for hydrogen peroxide (H2O2) photosynthesis. However, the vision of achieving high efficiency and selectivity in H2O2 photosynthesis is greatly hindered by the large exciton binding energy and limited charge separation efficiency influenced by the molecular structure of the building blocks. Herein, we developed three newly designed COFs with a donor-acceptor (D-A) structure and incorporated regulatory units (fluorine, F, and methoxyl, OCH3) in the D-A pathway through molecular engineering to optimize electronic structure, the availability of activate sites, charge kinetics and O2 activation capacity. Due to electron-donating effect, OCH3functionalization (NIES-COF-3) can strengthen the intramolecular electron transfer and interaction with O2. This results in a reduction of the energy barrier of the rate-determining step (*O2 -> *OOH) and excellent O2-to-H2O2 photocatalytic activity under visible light irradiation, delivering an H2O2 production rate of 3238.4 mu mol g- 1h- 1 and a high apparent quantum yield of 3.17 %. In addition, F-functionalization (NIES-COF-2) primarily reduces the band-gap energy and improve the O2 adsorption capacity compared to unfunctionalized NIES-COF-1. This work unveils insight into the catalytic activity-optimization mechanism of molecular engineering in the D-A structure and provides important references for photocatalysts.