Acta Phys. -Chim. Sin. ›› 2021, Vol. 37 ›› Issue (6): 2008047.doi: 10.3866/PKU.WHXB202008047

Special Issue: Design and Fabrication of Advanced Photocatalyst

• ARTICLE • Previous Articles     Next Articles

Carboxyl-Functionalized Graphene for Highly Efficient H2-Evolution Activity of TiO2 Photocatalyst

Ping Wang1,*(), Haitao Li1, Yanjie Cao1, Huogen Yu1,2,*()   

  1. 1 School of Chemistry, Chemical Engineering and Life Sciences, Wuhan University of Technology, Wuhan 430070, China
    2 State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, Wuhan 430070, China
  • Received:2020-08-17 Accepted:2020-09-22 Published:2020-09-28
  • Contact: Ping Wang,Huogen Yu;
  • About author:Huogen Yu, Emails: (H.Y.)
    Ping Wang, Emails: (P.W.); Tel.: +86-27-87756779-8303 (P.W.)
  • Supported by:
    the National Natural Science Foundation of China(21771142);the National Natural Science Foundation of China(51872221);the Fundamental Research Funds for the Central Universities, China(WUT2019IB002)


The use of semiconductor photocatalysts (CdS, g-C3N4, TiO2, etc.) to generate hydrogen (H2) is a prospective strategy that can convert solar energy into hydrogen energy, thereby meeting future energy demands. Among the numerous photocatalysts, TiO2 has attracted significant attention because of its suitable reduction potential and excellent chemical stability. However, the photoexcited electrons and holes of TiO2 are easily quenched, leading to limited photocatalytic performance. Furthermore, graphene has been used as an effective electron cocatalyst in the accelerated transport of photoinduced electrons to enhance the H2-production performance of TiO2, owing to its excellent conductivity and high charge carrier mobility. For an efficient graphene-based photocatalyst, the rapid transfer of photogenerated electrons is extremely important along with an effectual interfacial H2-production reaction on the graphene surface. Therefore, it is necessary to further optimize the graphene microstructures (functionalized graphene) to improve the H2-production performance of graphene-based TiO2 photocatalysts. The introduction of H2-evolution active sites onto the graphene surface is an effective strategy for the functionalization of graphene. Compared with the noncovalent functionalization of graphene (such as loading Pt, MoSx, and CoSx on the graphene surface), its covalent functionalization can provide a strong interaction between graphene and organic molecules in the form of H2-evolution active sites that are produced by chemical reactions. In this study, carboxyl-functionalized graphene (rGO-COOH) was successfully modified via ring-opening and esterification reactions on the TiO2 surface by using an ultrasound-assisted self-assembly method to prepare a high-activity TiO2/rGO-COOH photocatalyst. The Fourier transform infrared (FTIR) spectra, X-ray photoelectron spectroscopy (XPS), and thermogravimetric (TG) curves revealed the successful covalent functionalization of GO to rGO-COOH by significantly enhanced ―COOH groups in FTIR and increased peak area of carboxyl groups in XPS. A series of characterizations, including X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), XPS, and UV-Vis adsorption spectra, were performed to demonstrate the successful synthesis of TiO2/rGO-COOH photocatalysts. The experimental data for the hydrogen-evolution rate showed that the TiO2/rGO-COOH displayed an extremely high hydrogen-generation activity (254.2 μmol∙h−1∙g−1), which was 2.06- and 4.48-fold higher than those of TiO2/GO and TiO2, respectively. The enhanced photocatalytic activity of TiO2/rGO-COOH is ascribed to the carboxyl groups of carboxyl-functionalized graphene, which act as effective hydrogen-generation active sites and enrich hydrogen ions owing to their excellent nucleophilicity that facilitates the interfacial hydrogen production reaction of TiO2. This study provides novel insights into the development of high-activity graphene-supported photocatalysts in the hydrogen-generation field.

Key words: Carboxyl-functionalized graphene, Carboxyl groups, TiO2, Photocatalytic H2 evolution


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