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Induced activation of the commercial Cu/ZnO/Al2O3 catalyst for the steam reforming of methanol

Nature Catalysis volume 5, pages 99–108 (2022)Cite this article

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Abstract

The surface structure of heterogeneous catalysts is closely associated with their catalytic performance. Current efforts for structural modification mainly focus on improving the catalyst synthesis details. Here we reveal an induced activation strategy to manipulate the catalyst surface reconstruction process by controlling the composition of reducing agents at the activation stage. Exposing the commercial Cu/ZnO/Al2O3 catalyst to a H2/H2O/CH3OH/N2 mixture at 300 °C and atmospheric pressure is found to accelerate the migration of ZnOx species onto the surface of metallic Cu0 nanoparticles via an adsorbate-induced strong metal–support interaction. Such a morphological evolution improves the long-term stability by threefold and results in more abundant Cu–ZnOx interfacial sites with catalytic activity enhanced by twofold towards the methanol steam reforming reaction.

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Fig. 1: MSR activities of Cu/ZnO/Al2O3 after different activation treatments.
Fig. 2: Microscopy characterizations of activated Cu/ZnO/Al2O3.
Fig. 3: Electronic property of Cu/ZnO/Al2O3 activated with different procedures.
Fig. 4: Mechanism analysis of the MSR reaction over Cu/ZnO/Al2O3.

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The data that support the findings of this study are available from the corresponding authors on reasonable request. Source data are provided with this paper.

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Acknowledgements

This work is supported by the National Natural Science Foundation of China (22078089, M.Z.; 21908054, Z.X.; and 22075076, Z.X.), Program for Professor of Special Appointment (Eastern Scholar) at Shanghai Institutions of Higher Learning (M.Z. and S.D.), Shanghai Sailing Program (19YF1410600, M.Z.), Shanghai Rising-star Program (20QA1402400, S.D.), Shanghai Municipal Science and Technology Major Project (2018SHZDZX03, S.D.) and Fundamental Research Funds for the Central Universities, the Programme of Introducing Talents of Discipline to Universities (B16017, S.D.). The research at Lehigh University is supported by the Center for Understanding & Control of Acid Gas-Induced Evolution of Materials for Energy, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under grant DE-SC0012577 (I.E.W.). X-ray absorption spectroscopy measurements were carried out at the Shanghai Synchrotron Radiation Facility. We thank P. F. Liu and Y. W. Liu at East China University of Science and Technology for the help with X-ray absorption spectroscopy characterization. Additional support was provided by the Frontiers Science Center for Materiobiology and Dynamic Chemistry and the Feringa Nobel Prize Scientist Joint Research Center.

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Author notes

  1. These authors contributed equally: Didi Li, Fang Xu, Xuan Tang, Sheng Dai.

Authors and Affiliations

  1. State Key Laboratory of Chemical Engineering, School of Chemical Engineering, East China University of Science and Technology, Shanghai, China

    Didi Li, Fang Xu, Xianglin Liu, Zhi Xu & Minghui Zhu

  2. Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Centre, Frontiers Science Center for Materiobiology and Dynamic Chemistry, Institute of Fine Chemicals, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai, China

    Xuan Tang & Sheng Dai

  3. Operando Molecular Spectroscopy & Catalysis Laboratory, Department of Chemical and Biomolecular Engineering, Lehigh University, Bethlehem, PA, United States

    Tiancheng Pu & Israel E. Wachs

  4. Key Laboratory of Pressure Systems and Safety, Ministry of Education, East China University of Science and Technology, Shanghai, China

    Pengfei Tian & Fuzhen Xuan

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  1. Didi Li
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Contributions

D.L., Z.X., I.E.W. and M.Z. conceived the idea and designed the present work. D.L. and T.P. synthesized the catalysts and performed the catalyst characterization. F. Xu, X.L., P.T. and F. Xuan conducted the DFT calculations. X.T. and S.D. performed the aberration-corrected STEM measurements. Data were discussed among all coauthors. D.L. and M.Z. wrote the paper with contributions from all authors.

Corresponding authors

Correspondence to Zhi Xu, Israel E. Wachs or Minghui Zhu.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–43, Notes 1–5, Scheme 1 and Tables 1–10.

Supplementary Data 1

All optimized structures.

Supplementary Data 2

The most stable models among all optimized structures.

Source data

Source Data Fig. 1

Activity, stability and in situ X-ray diffraction.

Source Data Fig. 2

STEM–EELS.

Source Data Fig. 3

Quasi in situ X-ray photoelectron spectroscopy and in situ CO DRIFTS.

Source Data Fig. 4

In situ temperature-programmed DRIFTS and DFT.

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Li, D., Xu, F., Tang, X. et al. Induced activation of the commercial Cu/ZnO/Al2O3 catalyst for the steam reforming of methanol. Nat Catal 5, 99–108 (2022). https://doi.org/10.1038/s41929-021-00729-4

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