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Published June 9, 2025 | In Press
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Improving Mass Transport and Charge Transfer in COF‐Based Photocatalysts with Three‐Dimensional Ordered Macropores for Benzylamine Oxidation and Hydrogen Evolution

Sun, Lijuan1
Yan, Weicheng1
Wang, Weikang1
Wang, Lele1
Osella, Silvio2, 3 ORCID icon
Liang, Guijie4
Goddard, William A., III3 ORCID icon
Zbořil, Radek5
Zhou, Yazhou6
Yang, Juan1
Liu, Qinqin1
  • 1. ROR icon Jiangsu University
  • 2. ROR icon University of Warsaw
  • 3. ROR icon California Institute of Technology
  • 4. ROR icon Hubei University of Arts and Science
  • 5. ROR icon Technical University of Ostrava
  • 6. ROR icon Max Planck Institute for Polymer Research

Abstract

Covalent organic frameworks (COFs) have shown promise as photocatalysts for chemical transformations. However, their dense micropores and poor pore connectivity hinder mass transport and charge separation/transfer, limiting their efficiency. Herein, we develop a one-step self-sacrificing template strategy to synthesize three-dimensional ordered macroporous COFs (3DOM-COFs). This approach uniquely integrates in situ Tp–Tta COF crystallization with synchronized degradation of polystyrene templates under solvothermal conditions. This method introduces unreported kinetic match between template decomposition and framework growth. Such a confined growth mechanism leads to structurally robust and highly ordered macroporosity without post-processing. 3DOM architecture enables uniform dispersion of fine ZnCdS nanoparticles for the generation a 3DOM-COF based S-scheme heterojunction, which exhibits remarkable performance in the oxidation of benzylamine (BA) for simultaneous N-benzylbenzaldimine production with 99% selectivity at a rate of 15.1 mmol g−1 h−1 and H2 generation with a rate of 17.8 mmol g−1 h−1. The 3DOM architecture confers 50-fold faster mass transport than bulk COFs, while the heterojunction facilitates directional charge separation and interface charge transfer. Density functional theory calculations confirm that the heterojunction optimizes reaction thermodynamics by lowering the potential energy barriers of BA activation. The work pioneers a template-concurrent synthesis paradigm, resolving COFs' critical pore engineering challenges.

Copyright and License

© 2025 The Author(s). Angewandte Chemie International Editionpublished by Wiley-VCH GmbH. This is an open access article underthe terms of the Creative Commons Attribution License, whichpermits use, distribution and reproduction in any medium, providedthe original work is properly cited.

Acknowledgement

This work was financially supported by the Program for the National Natural Science Foundation of China (22472069), and the Postgraduate Research Innovation Program of Jiangsu Province (KYCX23_3710). Y.Z thanks financial support of the DFG (grant 514772236). R. Z acknowledges the support from the European Union's Horizon 2020 project SAN4Fuel (HORIZON-WIDERA-2021-ACCESS-03–01: 101079384). W.A.G thanks the US National Science Foundation (CBET 2311117) for funding. S.O. thanks the National Science Centre, Poland (grant no. UMO-2023/50/E/ST4/00197). The computation was carried out with the support of the Interdisciplinary Center for Mathematical and Computational Modeling at the University of Warsaw (ICM UW) under grants no. G83-28 and GB80-24. The authors acknowledge Polish high-performance computing infrastructure PLGrid for awarding this project access to the LUMI supercomputer, owned by the EuroHPC Joint Undertaking, hosted by CSC (Finland) and the LUMI consortium through PLL/2023/05/016760.

Open access funding enabled and organized by Projekt DEAL.

Conflict of Interest

The authors declare no conflict of interest.

Data Availability

The data that support the findings of this study are available on request from the corresponding author. The data are not publicly available due to privacy or ethical restrictions.

Supplemental Material

Supporting Information

Additional details

Identifiers Funding Caltech Custom Metadata
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July 23, 2025
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July 23, 2025