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A stable low-temperature H2-production catalyst by crowding Pt on α-MoC

Abstract

The water–gas shift (WGS) reaction is an industrially important source of pure hydrogen (H2) at the expense of carbon monoxide and water1,2. This reaction is of interest for fuel-cell applications, but requires WGS catalysts that are durable and highly active at low temperatures3. Here we demonstrate that the structure (Pt1–Ptn)/α-MoC, where isolated platinum atoms (Pt1) and subnanometre platinum clusters (Ptn) are stabilized on α-molybdenum carbide (α-MoC), catalyses the WGS reaction even at 313 kelvin, with a hydrogen-production pathway involving direct carbon monoxide dissociation identified. We find that it is critical to crowd the α-MoC surface with Pt1 and Ptn species, which prevents oxidation of the support that would cause catalyst deactivation, as seen with gold/α-MoC (ref. 4), and gives our system high stability and a high metal-normalized turnover number of 4,300,000 moles of hydrogen per mole of platinum. We anticipate that the strategy demonstrated here will be pivotal for the design of highly active and stable catalysts for effective activation of important molecules such as water and carbon monoxide for energy production.

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Fig. 1: Structural characterization and WGS performance of the Pt/α-MoC catalysts.
Fig. 2: WGS performance of the Pt/α-MoC catalysts and the typical WGS catalysts.
Fig. 3: Reaction route study.
Fig. 4: Stability of the Pt/α-MoC catalysts for the WGS reaction.

Data availability

The main data supporting the findings of this study are available within the paper and its Supplementary Information. Additional data are available from the corresponding authors upon reasonable request.

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Acknowledgements

This work received financial support from the Natural Science Foundation of China (21725301, 21932002, 21821004, 91645115, 51622211, 21577013, 21707015, 21872014, 21902018), the National Key R&D Program of China (2017YFB0602200, 2017YFA0700103, 2018YFA0305800), and the Beijing Outstanding Young Scientist Program (BJJWZYJH01201914430039). The X-ray absorption spectroscopy and X-ray diffraction experiments were conducted at the Shanghai Synchrotron Radiation Facility and the Beijing Synchrotron Radiation Facility. The Pt L3 edge X-ray absorption spectroscopy for 0.02 wt% Pt/α-MoC was conducted at beamline10-BM, MRCAT operations, Advanced Photon Source under contract number DEAC02-06CH11357. The AP-XPS experiments were conducted in Swiss Light Source synchrotron. D.M. acknowledges support from the Tencent Foundation through the XPLORER PRIZE.

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Contributions

D.M. conceived the project. D.M., W.Z., M.F.-S. and C.S. supervised the study. Xiao Zhang and M.Z. performed most of the reactions. M.X., A.L., J.S. and W.Z. performed the electron microscopy study. M.Z., Xiaochen Zhang, L.A. and J.A.v.B. did the NAP-XPS experiments. M.Z., J.Y. and B.C. did the TKA experiments. Y.D., M.P., C.Y., W.W., X.G., Z.J., S.Y. and A.J.K. performed the X-ray structure characterization (XAS and XRD) and analysis. S.Y. contributed to the calculation of the cost targets profile of the Au- or Pt-based WGS catalysts. M.Z., M.B. and J.X. did the XPS experiments. R.G., X.W. and Y.-W.L. did the DFT calculations. S.C. did the low-temperature reaction evaluation experiments. Xiao Zhang, M.Z., Y.D., W.Z., M.F.-S. and D.M. wrote the paper. All the authors discussed and revised the paper.

Corresponding authors

Correspondence to Chuan Shi or Wu Zhou or Ding Ma.

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The authors declare no competing interests.

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Peer review information Nature thanks Matteo Cargnello and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Information

This file contains Supplementary Figures S1-S19 and Supplementary Tables S1 and S2.

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Zhang, X., Zhang, M., Deng, Y. et al. A stable low-temperature H2-production catalyst by crowding Pt on α-MoC. Nature 589, 396–401 (2021). https://doi.org/10.1038/s41586-020-03130-6

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