Chinese Journal of Catalysis ›› 2023, Vol. 51: 124-134.DOI: 10.1016/S1872-2067(23)64475-4

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Efficient charge separation by a donor-acceptor system integrating dibenzothiophene into a porphyrin-based metal-organic framework for enhanced photocatalytic hydrogen evolution

Fei Yana,b, Youzi Zhanga,b, Sibi Liua,b, Ruiqing Zoua,b, Jahan B Ghasemic,*(), Xuanhua Lia,b,*()   

  1. aResearch & Development Institute of Northwestern Polytechnical University in Shenzhen, Shenzhen 518057, Guangdong, China
    bState Key Laboratory of Solidification Processing, Center for Nano Energy Materials, School of Materials Science and Engineering, Northwestern Polytechnical University, Xi’an 710072, Shannxi, China
    cDepartment of Chemistry, University of Tehran, District 6, Tehran, Iran
  • Received:2023-05-04 Accepted:2023-06-20 Online:2023-08-18 Published:2023-09-11
  • Contact: *E-mail: (X. Li), (J. B Ghasemi).
  • Supported by:
    Science, Technology, and Innovation Commission of Shenzhen Municipality(JCYJ008103417036);National Natural Science Foundation of China(22261142666);National Natural Science Foundation of China(52172237);Shaanxi Science Fund for Distinguished Young Scholars(2022JC-21);Research Fund of the State Key Laboratory of Solidification Processing (NPU), China(2021-QZ-02);Fundamental Research Funds for the Central Universities(3102019JC005);Fundamental Research Funds for the Central Universities(D5000220033)


The high selectivity of organic ligands and metal ions that construct metal-organic frameworks (MOFs) enables considerable richness in the MOF structure and confers them with numerous potentials, rendering MOFs extremely interesting to researchers in the field of photocatalytic hydrogen evolution. However, the severe recombination of photoinduced charge carriers significantly restricts the photocatalytic performance of the MOFs. Herein, we report a porphyrin-based donor-acceptor (D-A) MOF consisting of meso-tetra(4-carboxyphenyl) porphyrin (TCPP) donor and a thieno [3,2b:20,30-d]thiophene-S,S-dioxide (BTDO) acceptor via coordination with Zn2+ ions, and denoted as TCPP-Zn-BTDO. The charge-transfer interaction from TCPP to BTDO broadened the light absorption range of TCPP-Zn-BTDO, with a high theoretical spectral efficiency of 69.72%. The D-A structure of TCPP-Zn-BTDO effectively enhanced the internal electric field because of its large molecular dipole, which significantly improved the charge-separation efficiency. Based on the aforementioned improvements, TCPP-Zn-BTDO showed a three-fold higher photocatalytic hydrogen evolution rate than the corresponding monocomponent MOF of TCPP-Zn without the BTDO acceptor. The D-A MOF reported in this study provides a new strategy for enhancing the photocatalytic performance of MOF.

Key words: Photocatalysis, Charge separation, Porphyrin, Metal-organic framework, Donor-acceptor