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High quantum efficiency of hydrogen production from methanol aqueous solution with PtCu–TiO2 photocatalysts

Nature Materials volume 22, pages 619–626 (2023)Cite this article

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Abstract

Methanol with 12.5 wt% H2 content is widely considered a liquid hydrogen medium. Taking into account water with 11.1 wt% H2 content, H2 synthesis from the mixture of water and methanol is a promising method for on-demand hydrogen production. We demonstrate an atomic-level catalyst design strategy using the synergy between single atoms and nanodots for H2 production. The PtCu–TiO2 sandwich photocatalyst achieves a remarkable H2 formation rate (2,383.9 µmol h–1) with a high apparent quantum efficiency (99.2%). Furthermore, the oxidation product is a high-value chemical formaldehyde with 98.6% selectivity instead of CO2, leading to a nearly zero-carbon-emission process. Detailed investigations indicate a dual role of the copper atoms: an electron acceptor to facilitate photoelectron transfer to Pt, and a hole acceptor for the selective oxidation of methanol to formaldehyde, thus avoiding over-oxidation to CO2. The synergy between Pt nanodots and Cu single atoms together reduces the activation energy of this process to 13.2 kJ mol–1.

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Fig. 1: H2 production from liquid water reforming of methanol by photocatalysis.
Fig. 2: Physical characterization of the photocatalysts.
Fig. 3: Morphology observation of the catalysts.
Fig. 4: Chemical characterization of the photocatalysts.
Fig. 5: Reaction scheme for methanol conversion.

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All data are available in the manuscript or the Supplementary Information. Source data are provided with this paper.

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Acknowledgements

We thank the Photoemission Endstation (BL10B) at the National Synchrotron Radiation Laboratory in Hefei and beamline BL11B of the Shanghai Synchrotron Radiation Facility for providing sufficient beamline time. H.W., X. Li, T.J.M., L.X. and J.T. thank the UK Engineering and Physical Sciences Research Council (EP/S018204/2), the Royal Society Newton Advanced Fellowship grant (NAF\R1\191163) and the Royal Society Leverhulme Trust Senior Research Fellowship (SRF\R1\21000153). L.X. and J.T. also thank the National Natural Science Foundation of China for a grant (22250710677).

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Authors and Affiliations

  1. Department of Chemical Engineering, University College London, London, UK

    Hui Wang, Xiyi Li, Tina Jingyan Miao, Lunqiao Xiong & Junwang Tang

  2. State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China

    Haifeng Qi, Xiaoyan Liu, Aiqin Wang & Tao Zhang

  3. Hefei National Research Center for Physical Sciences at the Microscale, Collaborative Innovation Center of Chemistry for Energy Materials, Key Laboratory of Surface and Interface Chemistry and Energy Catalysis of Anhui Higher Education Institutes, School of Chemistry and Materials Science, University of Science and Technology of China, Hefei, China

    Xiao Sun & Weixin Huang

  4. Department of Chemical and Process Engineering, University of Strathclyde, Glasgow, UK

    Shuya Jia & Xiaolei Zhang

  5. BCAST, Brunel University London, Uxbridge, UK

    Shihao Wang

  6. Industrial Catalysis Center, Department of Chemical Engineering, Tsinghua University, Beijing, China

    Junwang Tang

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  1. Hui Wang
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Contributions

J.T. designed and supervised the entire project and oversaw all discussions. H.W. conducted the catalyst preparation, sample characterizations and activity tests. H.Q. carried out the EXAFS and fitted the data. X. Li contributed to the electron paramagnetic resonance discussion. T.J.M. helped to collect data and in the discussion of UV–visible–near-infrared diffuse reflectance spectra. S.J. carried out the density functional theory calculation, and X.Z. supervised the process. X.S. collected the Ti and O EXAFS data, and W.H. supervised the process. L.X. performed the aberration-corrected HAADF-STEM. S.W. collected all the TEM data. X. Liu, A.W. and T.Z. supervised the EXAFS data collection and fitting. The manuscript was written through collective contributions from all authors. All authors approved the final version of the manuscript.

Corresponding author

Correspondence to Junwang Tang.

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Supplementary Information

Supplementary Figs. 1–35, tables 1–7, caption for video 1 and references.

Supplementary Video 1

Hydrogen generation via PtCu–TiO2.

Supplementary Data

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Source Data Fig. 2

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Wang, H., Qi, H., Sun, X. et al. High quantum efficiency of hydrogen production from methanol aqueous solution with PtCu–TiO2 photocatalysts. Nat. Mater. 22, 619–626 (2023). https://doi.org/10.1038/s41563-023-01519-y

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