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Nano Research 2024, 17(6): 4908-4915 https://doi.org/10.1007/s12274-024-6483-y
Research Article | Issue | Published: 07 February 2024

Covalent triazine frameworks modified by ultrafine Pt nanoparticles for efficient photocatalytic hydrogen production

Show Author's Information Xu Han1,§,  Xueying Ge3,§,  Wen-Wen He1( ),  Wangwang Shen1,  Tao Zhou1,  Jian-Sen Wang2,  Rong-Lin Zhong2( ),  Abdullah M. Al-Enizi4,  Ayman Nafady4,  Shengqian Ma3( )
School of Chemistry and Life Science, Advanced Institute of Materials Science, Changchun University of Technology, Changchun 130012, China
Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, College of Chemistry, Jilin University, Changchun 130021, China
Department of Chemistry, University of North Texas, 1508 W. Mulberry St. Denton, TX 76201, USA
Department of Chemistry, College of Science, King Saud University, Riyadh 11451, Saudi Arabia

§ Xu Han and Xueying Ge contributed equally to this work.

Keywords:
hydrogen evolution reaction, photocatalysts, Pt nanoparticles, covalent triazine-based framework-1 (CTF-1)
Topics:
Photocatalysts
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Han X, Ge X, He W-W, et al. Covalent triazine frameworks modified by ultrafine Pt nanoparticles for efficient photocatalytic hydrogen production. Nano Research, 2024, 17(6): 4908-4915. https://doi.org/10.1007/s12274-024-6483-y
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Abstract Full text Electronic supplementary material About this article

Pt nanoparticles (PtNPs) as active species have always been considered as one of the best semiconductor materials for photocatalytic hydrogen production. In this study, a Schottky heterojunction has been successfully constructed by evenly loading ultrafine PtNPs onto a triazine-based covalent organic frameworks (COFs). This strategy maintained the high activity of these ultra-small PtNPs while maximizing the utilization of the Pt active sites. The fabricated PtNPs@covalent triazine-based framework-1 (CTF-1) composite accomplished a significantly high rate of hydrogen evolution (20.0 mmol·g−1·h−1, apparent quantum efficiency (AQE) = 7.6%, at λ = 450 nm) with 0.40 wt.% Pt loading, giving rise to a 44-fold-increase in the efficiency of the photocatalytic hydrogen production compared to the pristine CTF-1. Theoretical calculations revealed that the strong electron transfer (Q(Pt) = −0.726 qe, in the analysis of Bader charge, Q(Pt) is the charge quantity transferred from Pt cluster to CTF-1, and qe is the unit of charge transfer quantity) between PtNPs and CTF-1 triggers a strong interaction, which makes PtNPs being firmly attached to the structure of CTF-1, thereby enabling high stability and excellent hydrogen production efficiency. Importantly, the hydrogen binding free energy (ΔGH*) of PtNPs@CTF-1 is much lower than that of the unmodified CTF-1, leading to a much lower intermediate state and hence a significant improvement in photocatalytic performance. The overall findings of this work provide a new platform to incorporate metallic NPs into COFs for the design and fabrication of highly efficient photocatalysts.


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Abstract
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Electronic supplementary material
About this article

Covalent triazine frameworks modified by ultrafine Pt nanoparticles for efficient photocatalytic hydrogen production

Show Author's information Xu Han1,§, Xueying Ge3,§, Wen-Wen He1( ), Wangwang Shen1, Tao Zhou1, Jian-Sen Wang2, Rong-Lin Zhong2( ), Abdullah M. Al-Enizi4, Ayman Nafady4, Shengqian Ma3( )
School of Chemistry and Life Science, Advanced Institute of Materials Science, Changchun University of Technology, Changchun 130012, China
Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, College of Chemistry, Jilin University, Changchun 130021, China
Department of Chemistry, University of North Texas, 1508 W. Mulberry St. Denton, TX 76201, USA
Department of Chemistry, College of Science, King Saud University, Riyadh 11451, Saudi Arabia

§ Xu Han and Xueying Ge contributed equally to this work.

Abstract

Pt nanoparticles (PtNPs) as active species have always been considered as one of the best semiconductor materials for photocatalytic hydrogen production. In this study, a Schottky heterojunction has been successfully constructed by evenly loading ultrafine PtNPs onto a triazine-based covalent organic frameworks (COFs). This strategy maintained the high activity of these ultra-small PtNPs while maximizing the utilization of the Pt active sites. The fabricated PtNPs@covalent triazine-based framework-1 (CTF-1) composite accomplished a significantly high rate of hydrogen evolution (20.0 mmol·g−1·h−1, apparent quantum efficiency (AQE) = 7.6%, at λ = 450 nm) with 0.40 wt.% Pt loading, giving rise to a 44-fold-increase in the efficiency of the photocatalytic hydrogen production compared to the pristine CTF-1. Theoretical calculations revealed that the strong electron transfer (Q(Pt) = −0.726 qe, in the analysis of Bader charge, Q(Pt) is the charge quantity transferred from Pt cluster to CTF-1, and qe is the unit of charge transfer quantity) between PtNPs and CTF-1 triggers a strong interaction, which makes PtNPs being firmly attached to the structure of CTF-1, thereby enabling high stability and excellent hydrogen production efficiency. Importantly, the hydrogen binding free energy (ΔGH*) of PtNPs@CTF-1 is much lower than that of the unmodified CTF-1, leading to a much lower intermediate state and hence a significant improvement in photocatalytic performance. The overall findings of this work provide a new platform to incorporate metallic NPs into COFs for the design and fabrication of highly efficient photocatalysts.

Keywords: hydrogen evolution reaction, photocatalysts, Pt nanoparticles, covalent triazine-based framework-1 (CTF-1)

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Publication history
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Acknowledgements

Publication history

Received: 26 October 2023
Revised: 21 December 2023
Accepted: 11 January 2024
Published: 07 February 2024
Issue date: June 2024

Copyright

© Tsinghua University Press 2024

Acknowledgements

Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (Nos. 22271022 and 21701016) and the Science and Technology Development Planning of Jilin Province (No. YDZJ202201ZYTS342). This paper was also supported by the China Scholarship Council (CSC No. 201802335014). Partial support from the Robert A. Welch Foundation (B-0027) (S.M.) and Researchers Supporting Program (No. RSP-2024R55) at King Saud University, Riyadh, Saudi Arabia is also acknowledged.

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