Highly crystalline organic semiconductors are ideal materials for photocatalytic hydrogen evolution in water splitting.However,the instability and complex synthesis processes of most reported organic molecule-based ph...Highly crystalline organic semiconductors are ideal materials for photocatalytic hydrogen evolution in water splitting.However,the instability and complex synthesis processes of most reported organic molecule-based photocatalysts restrict their applications.In this study,we introduce benzo[1,2-b:4,5-bʹ]bis[1]benzothiophene-3,9-dicarboxylic acid,5,5,11,11-tetraoxide(FSOCA),a highly crystalline,stable molecular crystal that is easy to synthesize and serves as an efficient photocatalyst for the hydrogen evolution reaction.FSOCA exhibits high efficiency in sacrificial hydrogen evolution reaction(760μmol h^(−1),76 mmol g^(−1)h^(−1)at 330 mW cm^(−2);570μmol h^(−1),57 mmol g^(−1)h^(−1)at 250 mW cm^(−2)),and FSOCA remains stable during photocatalysis for up to 400 h.Experiments and theoretical studies confirmed the presence of hydrogen bonds between the sulfone group and the sacrificial agent(ascorbic acid).This interaction significantly improved the oxidation reaction kinetics and boosted the photocatalytic performance.This study presents a scalable and convenient approach to synthesize highly crystalline,active,and stable organic photocatalysts with potential applications in large-scale photocatalysis.展开更多
Crystallization is an unsolved challenge in the chemistry of covalent triazine frameworks(CTFs) due to the poorly controlled simultaneous polymerization and crystallization processes. Herein, the synthesis of crystall...Crystallization is an unsolved challenge in the chemistry of covalent triazine frameworks(CTFs) due to the poorly controlled simultaneous polymerization and crystallization processes. Herein, the synthesis of crystalline CTFs via the introduction of aliphatic amine as a dynamic modulator is reported. By optimizing the amount of aliphatic amine, the crystallization process can be controlled in an open system, resulting in the synthesis of crystalline CTFs. These crystalline CTFs exhibit much better photocatalytic hydrogen evolution performance, with highly ordered CTF-1-C3 demonstrating superior performance(10 mmol g^(-1)h^(-1)) compared with most reported CTF-1. This approach also allows for the preparation of various crystalline CTFs.展开更多
Porous organic polymers(POPs) are porous materials composed of light elements such as C, H, N, and O. The benign characters,including large surface area, good physical and chemical stability, well-defined chemical com...Porous organic polymers(POPs) are porous materials composed of light elements such as C, H, N, and O. The benign characters,including large surface area, good physical and chemical stability, well-defined chemical composition, wide ranges of monomer selection, and strong designability, have made POPs one of the frontiers in materials research. In this review, we discussed the design and synthesis of various POP materials that mainly led by Chinese scientists, including conjugated microporous polymers(CMPs), porous aromatic frameworks(PAFs), and hypercrosslinked porous polymers(HCPs), as well as crystalline POPs comprised of covalent organic frameworks(COFs) and a special class of COFs with triazine rings, covalent triazine frameworks(CTFs), and supramolecular organic frameworks(SOFs), and sorted out their main applications in adsorption, separation,catalysis, and electrochemistry fields.展开更多
基金supported by the National Natural Science Foundation of China(grant nos.21975086,22305087,and 52203259)the International S&T Cooperation Program of China(grant nos.2018YFE0117300 and 22161142005)+5 种基金the Natural Science Foundation of Hubei Province(grant no.2022CFB720)X.J.Y.and X.Y.acknowledge the support from the Huazhong University of Science and Technology(HUST)Academic Frontier Youth Team(grant no.2019QYTD11)L.M.Y.and B.Y.S.gratefully acknowledge the National Natural Science Foundation of China(21873032,22073033,21673087,and 21903032)the startup fund from HUST(2006013118 and 3004013105)the Fundamental Research Funds for the Central Universities(2019kfyRCPY116)the Innovation and Talent Recruitment Base of New Energy Chemistry and Device(B21003).
文摘Highly crystalline organic semiconductors are ideal materials for photocatalytic hydrogen evolution in water splitting.However,the instability and complex synthesis processes of most reported organic molecule-based photocatalysts restrict their applications.In this study,we introduce benzo[1,2-b:4,5-bʹ]bis[1]benzothiophene-3,9-dicarboxylic acid,5,5,11,11-tetraoxide(FSOCA),a highly crystalline,stable molecular crystal that is easy to synthesize and serves as an efficient photocatalyst for the hydrogen evolution reaction.FSOCA exhibits high efficiency in sacrificial hydrogen evolution reaction(760μmol h^(−1),76 mmol g^(−1)h^(−1)at 330 mW cm^(−2);570μmol h^(−1),57 mmol g^(−1)h^(−1)at 250 mW cm^(−2)),and FSOCA remains stable during photocatalysis for up to 400 h.Experiments and theoretical studies confirmed the presence of hydrogen bonds between the sulfone group and the sacrificial agent(ascorbic acid).This interaction significantly improved the oxidation reaction kinetics and boosted the photocatalytic performance.This study presents a scalable and convenient approach to synthesize highly crystalline,active,and stable organic photocatalysts with potential applications in large-scale photocatalysis.
基金financially supported by the National Natural Science Foundation of China(22161142005,21975086)the Science and Technology Department of Hubei Province(2019CFA008)。
基金supported by the National Natural Science Foundation of China (21975086, 52203259)the International S&T Cooperation Program of China (22161142005, 2018YFE0117300)。
文摘Crystallization is an unsolved challenge in the chemistry of covalent triazine frameworks(CTFs) due to the poorly controlled simultaneous polymerization and crystallization processes. Herein, the synthesis of crystalline CTFs via the introduction of aliphatic amine as a dynamic modulator is reported. By optimizing the amount of aliphatic amine, the crystallization process can be controlled in an open system, resulting in the synthesis of crystalline CTFs. These crystalline CTFs exhibit much better photocatalytic hydrogen evolution performance, with highly ordered CTF-1-C3 demonstrating superior performance(10 mmol g^(-1)h^(-1)) compared with most reported CTF-1. This approach also allows for the preparation of various crystalline CTFs.
文摘Porous organic polymers(POPs) are porous materials composed of light elements such as C, H, N, and O. The benign characters,including large surface area, good physical and chemical stability, well-defined chemical composition, wide ranges of monomer selection, and strong designability, have made POPs one of the frontiers in materials research. In this review, we discussed the design and synthesis of various POP materials that mainly led by Chinese scientists, including conjugated microporous polymers(CMPs), porous aromatic frameworks(PAFs), and hypercrosslinked porous polymers(HCPs), as well as crystalline POPs comprised of covalent organic frameworks(COFs) and a special class of COFs with triazine rings, covalent triazine frameworks(CTFs), and supramolecular organic frameworks(SOFs), and sorted out their main applications in adsorption, separation,catalysis, and electrochemistry fields.
