4.7 Article Proceedings Paper

Production of hydrogen from methanol steam reforming using CuPd/ZrO2 catalysts - Influence of the catalytic surface on methanol conversion and CO selectivity

Journal

INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
Volume 46, Issue 33, Pages 17490-17499

Publisher

PERGAMON-ELSEVIER SCIENCE LTD
DOI: 10.1016/j.ijhydene.2020.04.040

Keywords

Methanol steam reforming; Palladium; Copper; Catalytic surface; Synthesis conditions; Catalyst design

Funding

  1. European Union [303476]
  2. Project PEMFC-SUDOE [SOE1/P1/E0293]
  3. European Regional Development Fund
  4. European Regional Development Fund (ERDF), through COMPETE2020 -Programa Operacional Competitividade e Internacionalizacao (POCI) [POCI-01-0145-FEDER-006939, UID/EQU/00511/2013]
  5. FCT -Fundacaeo para a Cie-ncia e a Tecnologia
  6. North Portugal Regional Operational Programme (NORTE 2020) under the Portugal 2020 Partnership Agreement through the European Regional Development Fund (ERDF) [NORTE-01-0145FEDER-000005 - LEPABE-2-ECO-INNOVATION]

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This study investigates the application of bimetallic catalysts in methanol steam reforming. By impregnating copper and Pd in different sequences, the surface composition of the catalyst was successfully tuned, resulting in improved methanol conversion and reforming selectivity.
Electricity generation for mobile applications by proton exchange membrane fuel cells (PEMFCs) is typically hindered by the low volumetric energy density of hydrogen. Nevertheless, nearly pure hydrogen can be generated in-situ from methanol steam reforming (MSR), with Cu-based catalysts being the most common MSR catalysts. Cu-based catalysts display high catalytic performance, even at low temperatures (ca. 250 degrees C), but are easily deactivated. On the other hand, Pd-based catalysts are very stable but show poor MSR selectivity, producing high concentrations of CO as by-product. This work studies bimetallic catalysts where Cu was added as a promoter to increase MSR selectivity of Pd. Specifically, the surface composition was tuned by different sequences of Cu and Pd impregnation on a monoclinic ZrO2 support. Both methanol conversion and MSR selectivity were higher for the catalyst with a CuPd-rich surface compared to the catalyst with a Pd-rich surface. Characterization analysis indicate that the higher MSR selectivity results from a strong interaction between the two metals when Pd is impregnated first (likely an alloy). This sequence also resulted in better metallic dispersion on the support, leading to higher methanol conversion. A H-2 production rate of 86.3 mmol h(-1) g(-1) was achieved at low temperature (220 degrees C) for the best performing catalyst. (C) 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

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