The effects of zirconia morphology on methanol synthesis from COand H2 over Cu/ZrO2 catalysts: Part I -- Steady-State Studies

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The effect of zirconia phase on the activity and selectivityof Cu/ZrO2 for the hydrogenation of CO has been investigated. Relativelypure t-ZrO2 and m-ZrO2 were prepared with high surface areas (~; 145m2/g). Copper was then deposited onto the surface of these materials byeither incipient-wetness impregnation or deposition-precipitation. For afixed Cu surface area, Cu/m-ZrO2 was tenfold more active for methanolsynthesis than Cu/t-ZrO2 from a feed of 3/1 H2/CO at 3.0 MPa andtemperatures between 473 and 523 K. Cu/m-ZrO2 also exhibited a higherselectivity to methanol. Increasing the Cu surface area on m-ZrO2resulted in further improvement in activity with minimal change inselectivity. Methanol productivity … continued below

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Rhodes, Michael J. & Bell, Alexis T. March 21, 2005.

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The effect of zirconia phase on the activity and selectivityof Cu/ZrO2 for the hydrogenation of CO has been investigated. Relativelypure t-ZrO2 and m-ZrO2 were prepared with high surface areas (~; 145m2/g). Copper was then deposited onto the surface of these materials byeither incipient-wetness impregnation or deposition-precipitation. For afixed Cu surface area, Cu/m-ZrO2 was tenfold more active for methanolsynthesis than Cu/t-ZrO2 from a feed of 3/1 H2/CO at 3.0 MPa andtemperatures between 473 and 523 K. Cu/m-ZrO2 also exhibited a higherselectivity to methanol. Increasing the Cu surface area on m-ZrO2resulted in further improvement in activity with minimal change inselectivity. Methanol productivity increased linearly for both Cu/t-ZrO2and Cu/m-ZrO2 with increasing Cu surface area. The difference in inherentactivity of each phase paralleled the stronger and larger CO adsorptioncapacity of the Cu/m-ZrO2 as quantified by CO-TPD. The higher COadsorption capacity of Cu/m-ZrO2 is attributed to the presence of a highconcentration of anionic vacancies on the surface of m-ZrO2. Suchvacancies expose cus-Zr4+ cations, which act as Lewis acid centers andenhance the Bronsted acidity of adjacent Zr-OH groups. The presence ofcus-Zr4+ sites and adjacent Bronsted acidic Zr-OH groups contributes tothe adsorption of CO as HCOO-Zr groups, which are the initial precursorsto methanol.

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  • Journal Name: Journal of Catalysis; Journal Volume: 233; Journal Issue: 1; Related Information: Journal Publication Date: 2005

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  • Report No.: LBNL--57001-Pt.-1
  • Grant Number: DE-AC02-05CH11231
  • Office of Scientific & Technical Information Report Number: 900645
  • Archival Resource Key: ark:/67531/metadc882490

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  • March 21, 2005

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  • Sept. 22, 2016, 2:13 a.m.

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  • Sept. 29, 2016, 2:31 p.m.

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Rhodes, Michael J. & Bell, Alexis T. The effects of zirconia morphology on methanol synthesis from COand H2 over Cu/ZrO2 catalysts: Part I -- Steady-State Studies, article, March 21, 2005; Berkeley, California. (https://digital.library.unt.edu/ark:/67531/metadc882490/: accessed April 24, 2024), University of North Texas Libraries, UNT Digital Library, https://digital.library.unt.edu; crediting UNT Libraries Government Documents Department.

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