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Photocatalytic uphill conversion of natural gas beyond the limitation of thermal reaction systems

Abstract

Dry reforming of methane is one of the key reactions to exploit natural gas feedstocks by their catalytic conversion to synthesis gas (CH4 + CO2 → 2H2 + 2CO), which is used in the production of transportable liquid fuel. However, this reaction suffers from thermodynamic conversion limits and high thermal energy requirements. Herein we report that a SrTiO3-supported rhodium (Rh/STO) catalyst efficiently promotes methane reforming under ultraviolet light irradiation without heat supply at low temperatures, which cannot be achieved by conventional thermal catalysis. The photoexcited holes and electrons are used for CH4 oxidation over STO and CO2 reduction over rhodium, respectively. Isotope analysis clarified that the lattice oxygens (O2−) act as mediator to drive dry reforming of methane. The materials design of Rh/STO can be extended in principle to diverse uphill reactions that utilize photon energy to obtain valued products from different carbon resources.

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Fig. 1: STEM and STEM-EDXS images of the Rh/STO.
Fig. 2: The temperature dependence of DRM activity in dark and light irradiation conditions.
Fig. 3: Performance of photocatalytic DRM by various catalysts.
Fig. 4: Mechanism analysis by ESR and isotope trace experiment.
Fig. 5: Tentative mechanistic aspects of the photocatalytic DRM by Rh/STO.

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The data that support the findings of this study are available from the Article and Supplementary Information, or from the corresponding authors on reasonable request.

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Acknowledgements

This research was supported by a grant from the Japan Society for the Promotion of Science DC1 and Japan Science and Technology Agency (JST) CREST (grant no. JPMJCR15P1). We thank R. Ota and Y. Otsuka at the Center for Advanced Materials Analysis of the Tokyo Institute of Technology for helping with the inductively coupled plasma measurement.

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Authors

Contributions

S.S. conducted the experimental studies and wrote the paper. X.P. evaluated catalytic properties. A.Y. contributed to the experimental design and gave deep insight into photocatalytic reaction. R.W. and C.F. gave great advice on isotope trace experiment. Y.C. investigated the photocatalytic properties of various semiconductors. T.Y. and S.M. contributed to high magnification TEM observation. M.W.Y. and S.I. conducted KPFM analysis. T.F. contributed TEM analysis and helped manuscript organization. H.A. contributed to the X-ray photoelectron spectroscopy analysis and gave great advice for paper organization. M.M conceived this project and wrote the paper. All authors discussed the results and commented on the manuscript.

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Correspondence to Takeshi Fujita, Hideki Abe or Masahiro Miyauchi.

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Supplementary Methods, Figs. 1–10.

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Shoji, S., Peng, X., Yamaguchi, A. et al. Photocatalytic uphill conversion of natural gas beyond the limitation of thermal reaction systems. Nat Catal 3, 148–153 (2020). https://doi.org/10.1038/s41929-019-0419-z

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