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Long-range enhancements of micropollutant adsorption on metal-promoted photocatalysts

Nature Catalysis volume 7, pages 912–920 (2024) Cite this article

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Abstract

Photocatalysis can effectively degrade emerging (micro)pollutants in wastewater and achieve advanced water treatment objectives, wherein the low solar energy conversion efficiency remains a challenge. One key determinant is the effective adsorption of micropollutants, which is challenging to define, especially for photocatalysts with surface heterogeneity over different length scales and under (non-)reactive conditions. Here we report a generalizable imaging technique adCOMPEITS (adsorption-based competition-enabled imaging technique with super-resolution) and quantify the adsorption behaviours of non-fluorescent micropollutants on heterostructured Au/TiO2 photocatalysts at nanometre resolution under both non-catalytic and photo(electro)catalytic conditions. We discover a long-range enhancement of micropollutant adsorption on TiO2, which reaches micrometre-length scale and stems from the long-range surface band bending of TiO2 upon contacting metal co-catalyst. We further engineer the band bending to effectively modulate the long-range effects on molecular adsorption. The imaging technique and the scientific discoveries here should open avenues towards understanding and engineering metal-promoted photocatalysts for many applications.

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Fig. 1: AdCOMPEITS reveals long- and short-range micropollutant adsorption enhancements.
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Fig. 2: Mechanisms of adsorption enhancements.
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Fig. 3: Micropollutant adsorption under photocatalytic and photoelectrocatalytic conditions.
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Fig. 4: Band bending engineering to manipulate long-range adsorption enhancement.
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Data availability

Raw data supporting the findings of this study are available from the authors upon reasonable request. Source data are provided with this paper.

Code availability

MATLAB codes are provided as Supplementary Software 1.

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Acknowledgements

The research on semiconductor photo(electro)catalysis is supported by the US Department of Energy, Office of Science, Basic Energy Sciences, Catalysis Science Program (grant no. DE-SC0004911; P.C.). The research on super-resolution imaging of metal nanoparticles is supported by the Army Research Office (grant no. W911NF-23-1-0105). The research used Cornell Center for Materials Research Shared Facilities supported by NSF (grant no. DMR-1719875). M.Z. acknowledges the support from the National University of Singapore start-up grant, National Research Foundation Singapore (grant no. U2311D4005), Centre for Hydrogen Innovations (grant no. CHI-P2023-04) and Ministry of Education (grant no. 23-0646-A0001).

Author information

Author notes

  1. Muwen Yang

    Present address: L.E.K. Consulting, Boston, MA, USA

  2. Rong Ye

    Present address: Department of Chemical Engineering and Catalysis Science and Technology Institute, University of Michigan, Ann Arbor, MI, USA

  3. Xianwen Mao

    Present address: Department of Materials Science and Engineering, Institute of Functional Intelligent Materials, and Centre for Advanced 2D Materials, National University of Singapore, Singapore, Singapore

Authors and Affiliations

  1. Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY, USA

    Ming Zhao, Wenjie Li, Muwen Yang, Zhiheng Zhao, Rong Ye, Xianwen Mao, Paul Padgett & Peng Chen

  2. Department of Materials Science and Engineering, National University of Singapore, Singapore, Singapore

    Ming Zhao

  3. Centre for Hydrogen Innovations, National University of Singapore, Singapore, Singapore

    Ming Zhao

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Contributions

M.Z. designed and performed experiments, synthesized particles, derived kinetic models, wrote computer codes and analysed data. W.L. contributed to adCOMPEITS method development. M.Y. performed FDTD calculations and analysis. Z.Z. contributed to photocurrent measurements. R.Y., X.M. and P.P. contributed to imaging experiments. M.Z. and P.C. analysed results and wrote the manuscript. P.C. directed research. All authors contributed to discussions.

Corresponding author

Correspondence to Peng Chen.

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Competing interests

P.C. and X.M. previously filed a US patent application ‘Super-resolution optical imaging of non-fluorescent species’ (no. 16/584,219) that is pending and encompasses the adCOMPEITS method.

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Nature Catalysis thanks Johan Hofkens, Dechen Jiang and Bert M. Weckhuysen for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information (download PDF )

Supplementary Figs. 1–32, Discussion and Tables 1 and 2.

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MATLAB codes.

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Statistical source data.

Source Data Fig. 3 (download XLSX )

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Zhao, M., Li, W., Yang, M. et al. Long-range enhancements of micropollutant adsorption on metal-promoted photocatalysts. Nat Catal 7, 912–920 (2024). https://doi.org/10.1038/s41929-024-01199-0

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