Intramolecular Charge Transfer and Extended Conjugate Effects in Donor--Acceptor-Type Mesoporous Carbon Nitride for Photocatalytic Hydrogen Evolution

Sun, Zongzhao1,2; Jiang, Yabin2; Zeng, Lei2; Huang, Limin2

2019-04-05

10.1002/cssc.201802890

ChemSusChem   影响因子和分区

1864-5631

1864-564X

Inspired by donor-acceptor (D-A) polymers in organic solar cell and the extended conjugation effect, a conceptual design of D--A-type mesoporous carbon nitride with benzene or thiophene as a -spacer is proposed as an efficient photocatalyst for hydrogen evolution. The photocatalyst was successfully synthesized by a one-pot thermopolymerization based on nucleophilic substitution and a Schiff-base chemical reaction. On the molecular level, the insertion of an in-plane benzene as a -spacer by forming covalent bonds C=N (acceptor) and C-N (donor) interrupts the continuity of tri-s-triazine units and maintains the intrinsic - conjugated electronic system. Synchronously, the enlarged electron delocalization and the intramolecular charge transfer induced by polarization provide force-directed migration of electrons, leading to boosted optical absorption capability and enhanced photogenerated carrier separation. With the synergistic effects of the mesoporous structure and excellent optical and electronic properties, a fivefold increase in the H-2 evolution rate compared with that of pristine g-C3N4 was achieved with robust performance. In addition, other simple aromatic heterocyclic compounds (e.g., pyridine, thiophene and furan)-based D--A structures with a higher hydrogen evolution rate (up to sevenfold increase) were also explored to broaden the application for the design of novel photocatalysts.

charge transfer donor-acceptor systems hydrogen evolution mesoporous materials photocatalysis

SCI ; EI

英语

通讯

Basic Research Fund of Shenzhen[JCYJ20150507170334573]

Chemistry ; Science & Technology - Other Topics

Chemistry, Multidisciplinary ; Green & Sustainable Science & Technology

WOS:000467235500005

WILEY-V C H VERLAG GMBH

20191306683938

Benzene ; Carbon nitride ; Charge transfer ; Conceptual design ; Electronic properties ; Hydrogen ; Light absorption ; Nitrides ; Organic polymers ; Organic solar cells ; Photocatalysis ; Solar cells ; Solar power generation ; Thiophene

Solar Power:615.2 ; Light/Optics:741.1 ; Chemical Reactions:802.2 ; Chemical Products Generally:804 ; Organic Polymers:815.1.1

Web of Science

1.Harbin Inst Technol, Sch Chem & Chem Engn, Harbin 150001, Heilongjiang, Peoples R China
2.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Guangdong, Peoples R China

Sun, Zongzhao,Jiang, Yabin,Zeng, Lei,et al. Intramolecular Charge Transfer and Extended Conjugate Effects in Donor--Acceptor-Type Mesoporous Carbon Nitride for Photocatalytic Hydrogen Evolution[J]. ChemSusChem,2019,12(7):1325-1333.

Sun, Zongzhao,Jiang, Yabin,Zeng, Lei,&Huang, Limin.(2019).Intramolecular Charge Transfer and Extended Conjugate Effects in Donor--Acceptor-Type Mesoporous Carbon Nitride for Photocatalytic Hydrogen Evolution.ChemSusChem,12(7),1325-1333.

Sun, Zongzhao,et al."Intramolecular Charge Transfer and Extended Conjugate Effects in Donor--Acceptor-Type Mesoporous Carbon Nitride for Photocatalytic Hydrogen Evolution".ChemSusChem 12.7(2019):1325-1333.