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Controlling activity and selectivity using water in the Au-catalysed preferential oxidation of CO in H2

Nature Chemistry volume 8, pages 584–589 (2016)Cite this article

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Abstract

Industrial hydrogen production through methane steam reforming exceeds 50 million tons annually and accounts for 2–5% of global energy consumption. The hydrogen product, even after processing by the water–gas shift, still typically contains ∼1% CO, which must be removed for many applications. Methanation (CO + 3H2 → CH4 + H2O) is an effective solution to this problem, but consumes 5–15% of the generated hydrogen. The preferential oxidation (PROX) of CO with O2 in hydrogen represents a more-efficient solution. Supported gold nanoparticles, with their high CO-oxidation activity and notoriously low hydrogenation activity, have long been examined as PROX catalysts, but have shown disappointingly low activity and selectivity. Here we show that, under the proper conditions, a commercial Au/Al2O3 catalyst can remove CO to below 10 ppm and still maintain an O2-to-CO2 selectivity of 80–90%. The key to maximizing the catalyst activity and selectivity is to carefully control the feed-flow rate and maintain one to two monolayers of water (a key CO-oxidation co-catalyst) on the catalyst surface.

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Figure 1: PROX performance and deactivation of Au/Al2O3 with water in the feed (1% CO, 1.4% O2, 60% H2, balance He).
Figure 2: High conversion PROX reactivity over Au/Al2O3.
Figure 3: Effect of SV on CO PROX catalysis over Au/Al2O3.
Figure 4: Effect of water and temperature on CO PROX catalysis over Au/Al2O3.
Figure 5: Gas-adsorption data.

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Acknowledgements

The authors kindly thank J. Kenvin (Micromeritics Instrument Corporation) and S.M.K. Shahri (Pennsylvania State University) for assistance with the measurement of the water-adsorption isotherms. The authors gratefully acknowledge the US National Science Foundation (Grant No CBET-1160217 and No. CHE-1012395) for financial support of this work. Z.C. and R.M.R. acknowledge the Department of Energy, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, Catalysis Sciences Program under grant No. DE-FG02-12ER16364 for partial funding of this research.

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Authors and Affiliations

  1. Department of Chemistry, Trinity University, San Antonio, 78212-7200, Texas, USA

    Johnny Saavedra, Todd Whittaker, Christopher J. Pursell & Bert D. Chandler

  2. Pacific Northwest National Laboratory, Richland, Washington, 99352, USA

    Johnny Saavedra

  3. Department of Chemical Engineering, The Pennsylvania State University, University Park, 16802-4400, Pennsylvania, USA

    Zhifeng Chen & Robert M. Rioux

  4. Department of Chemistry, The Pennsylvania State University, University Park, 16802-4400, Pennsylvania, USA

    Robert M. Rioux

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Contributions

J.S., B.D.C. and C.J.P. designed the catalysis experiments; J.S. performed the catalysis experiments and analysed the data; B.D.C. and C.J.P. designed the infrared spectroscopy experiments; T.W. performed the infrared spectroscopy experiments and analysed the data; B.D.C. and R.M.R. designed the gas-adsorption experiments and analysed the data; Z.C. and R.M.R. designed and performed the X-ray photoemission spectroscopy and X-ray diffraction experiments (see the Supplementary Information) and analysed the data; J.S., B.D.C., R.M.R. and C.J.P. co-wrote the paper.

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Correspondence to Bert D. Chandler.

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Saavedra, J., Whittaker, T., Chen, Z. et al. Controlling activity and selectivity using water in the Au-catalysed preferential oxidation of CO in H2. Nature Chem 8, 584–589 (2016). https://doi.org/10.1038/nchem.2494

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