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Generation of oxide surface patches promoting H-spillover in Ru/(TiOx)MnO catalysts enables CO2 reduction to CO

Nature Catalysis volume 6, pages 1062–1072 (2023)Cite this article

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Abstract

The migration of reducible metal oxides (for example, TiO2) to the surface of metal nanoparticles can inhibit sintering but has a strong negative impact on the catalytic activity. Here we reveal the in situ creation of TiOx patches over an MnO support to generate effective transport channels for hydrogen spillover to form more active hydrogen species on the MnO surface which are responsible for reducing CO2 to CO, a key reaction for CO2 conversion to high-value chemicals. The Ru/(TiOx)MnO (Ru/Ti/Mn) catalyst shows a 3.3-fold increase in reverse water-gas shift performance compared with conventional Ru/MnOx catalysts. Through a combination of physicochemical methods, including in situ studies, catalytic and kinetic data, and theoretical modelling, we demonstrate that the oxide–oxide interfaces are spontaneously generated during reductive treatment in H2, contributing to the increased activity. The results open perspectives for the design of novel selective hydrogenation catalysts via the in situ creation of oxide–oxide interfaces acting as hydrogen-species transport channels.

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Fig. 1: Ru/Ti/Mn catalyst characterizations during in situ TiOx overlayer formation.
Fig. 2: Microscopy characterizations of the catalysts.
Fig. 3: CO2 reduction activities of Ru/Ti/Mn catalysts.
Fig. 4: Kinetic results and temperature-programmed experiments of the catalysts.
Fig. 5: Revealing mechanisms of enhanced CO2 reduction activity on Ru/Ti/Mn.
Fig. 6: Reaction path for hydrogen migration and the RWGS reaction.

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Data availability

Data presented in the main figures of the manuscript and the Supplementary Information are publicly available through the figshare repository (https://doi.org/10.6084/m9.figshare.24037167). The atomic coordinates of the optimized computational models are provided in Supplementary Data 1. All other relevant raw data are available from the corresponding author on reasonable request. Source data are provided with this paper.

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Acknowledgements

This work was financially supported by the NSFC of China (22172161 and 21972140), LiaoNing Revitalization Talents Program (XLYC1907053), the Dalian National Laboratory for Clean Energy (DNL202021) and the AI S&T Program of Yulin Branch, Dalian National Laboratory for Clean Energy, CAS (DNL-YLA202204). X.L. acknowledges support from the Youth Innovation Promotion Association CAS (2020179) and the National Natural Science Foundation of China (21972160). S.P. and G.C. acknowledge support from the CAS President’s International Fellowship Initiative (PIFI) programme and G.C. from the Alexander von Humboldt-Stiftung/Foundation (Humboldt Research Award). The authors thank C. Zeng from Hitachi High-Tech for his great help in atomic resolution ADF-STEM and EDS data acquisition with the Hitachi HF5000 microscope.

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Authors and Affiliations

  1. Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China

    Hui Kang, Shiyan Li, Shuwen Yu & Yuefeng Liu

  2. College of Chemical Engineering, Sichuan University, Chengdu, China

    Hui Kang & Wei Chu

  3. State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, China

    Ling Zhu & Xingchen Liu

  4. Key Laboratory of Organo-Pharmaceutical Chemistry of Jiangxi Province, Gannan Normal University, Ganzhou, China

    Ling Zhu

  5. University of Chinese Academy of Sciences, Beijing, China

    Shiyan Li

  6. Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang, China

    Yiming Niu & Bingsen Zhang

  7. Department of ChiBioFarAm,University of Messina, Messina, Italy

    Siglinda Perathoner & Gabriele Centi

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Contributions

Y.L. conceived and supervised the project. H.K. performed the catalyst preparation, most of the characterizations and the catalytic tests. L.Z. and X.L. carried out the DFT calculations and wrote the related section. S.L., Y.N., B.Z. and Y.L. performed the electron microscopy experiments. S.Y. helped with the in situ Raman experiments. W.C., S.P. and G.C. provided helpful discussions. H.K., G.C. and Y.L. analysed the data and wrote the paper. All authors contributed to the discussion and manuscript preparation.

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Correspondence to Xingchen Liu or Yuefeng Liu.

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Nature Catalysis thanks Atsushi Urakawa, Wei Zhang and Sergio Posada-Pérez for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–49, Notes 1–7, Tables 1 and 2, and references.

Supplementary Data 1

The atomic coordinates of the optimized computational models.

Source data

Source Data Fig. 1

Ex situ and in situ X-ray diffraction, Ti/Mn ratio based on XPS.

Source Data Fig. 2

Particle size statistics.

Source Data Fig. 3

Activity.

Source Data Fig. 4

Activity and reaction kinetics.

Source Data Fig. 5

In situ DRIFTS and temperature-programmed experiments.

Source Data Fig. 6

DFT calculation.

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Kang, H., Zhu, L., Li, S. et al. Generation of oxide surface patches promoting H-spillover in Ru/(TiOx)MnO catalysts enables CO2 reduction to CO. Nat Catal 6, 1062–1072 (2023). https://doi.org/10.1038/s41929-023-01040-0

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