Citation: Xin-Lou Yang, Jieying Hu, Hao Zhong, Qia-Chun Lin, Zhiqing Lin, Lai-Hon Chung, Jun He. Building metal-thiolate sites and forming heterojunction in Hf- and Zr-based thiol-dense frameworks towards stable integrated photocatalyst for hydrogen evolution[J]. Chinese Chemical Letters, ;2025, 36(7): 110120. doi: 10.1016/j.cclet.2024.110120 shu

Building metal-thiolate sites and forming heterojunction in Hf- and Zr-based thiol-dense frameworks towards stable integrated photocatalyst for hydrogen evolution

Xin-Lou Yang ^{a, b} ,
Jieying Hu ^b ,
Hao Zhong ^b ,
Qia-Chun Lin ^b ,
Zhiqing Lin ^b ,
Lai-Hon Chung ^{a, b, *,} ,
Jun He ^{a, b, *,}

a.
Guangdong Provincial Laboratory of Chemistry and Fine Chemical Engineering Jieyang Center, Jieyang 515200, China
b.
School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou 510006, China

laihonchung@gdut.edu.cn

junhe@gdut.edu.cn

Received Date: 29 April 2024
Revised Date: 23 May 2024
Accepted Date: 13 June 2024
Available Online: 13 June 2024

Figures(4)

Photocatalytic water splitting for hydrogen evolution reaction (HER) has emerged as one of the most promising approaches for solar energy utilization. Porous easily functionalized metal-organic framework (MOF) represents a rising crystalline material for photocatalytic application. Yet, most MOFs still face challenges like chemical instability in solution media, no photosensitization, and ambiguous active sites. Herein, thiol-dense Hf- or Zr-based porous frameworks (Hf-, Zr-TBAPy-8SH) were prepared as platforms for facile construction of HER active sites by anchoring transition metal (TM) ions as well as forming heterojunction with nanoscale semiconductor (CdS). The highest HER rate of 8.15 mmol g^–1 h^–1 by Co(Ⅱ)-loaded Hf-based composite highlight (1) [S^––Co] motifs as competent HER site, (2) match heterojunction outweighing traditional photosensitizer-mediated HER, (3) regulating electron density of metal-oxo cluster as a way to harness HER activity. This study firstly demonstrates synergy of Hf-oxo clusters, thiol functionalities and heterojunction as an easy yet controllable strategy to form integrated photocatalyst.
- Metal-organic frameworks,
- Thiols,
- Metal-thiolate,
- Photocatalytic hydrogen production,
- Heterojunction
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