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Negative Effects of Dopants on Copper–Ceria Catalysts for CO Preferential Oxidation Under the Presence of CO2 and H2O

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Abstract

The effects of non-reducible dopants on copper–ceria catalysts for the preferential oxidation of carbon monoxide (CO PROX) were experimentally investigated by adding a non-reducible rare-earth element into the ceria support. Gadolinium-doped cerium oxides were synthesized by a combustion method as a support material for the copper–ceria catalytic system. Various compositions of the catalysts, i.e., CuO/Ce1−xGdxO2−δ (x = 0, 0.05, 0.1, 0.13, 0.18, 0.25 and 0.35), were prepared. The physical, structural, redox and surface chemical properties of the prepared catalysts were characterized by inductively coupled plasma mass spectrometry (ICP-MS), N2 isotherms, X-ray diffraction (XRD), Raman spectroscopy, transmission electron microscopy (TEM), H2 temperature-programmed reduction (H2-TPR) and X-ray photoelectron spectroscopy (XPS) analyses. To investigate the influence of the dopants on the CO PROX, an activity test was conducted for each sample under a reactant stream containing CO, H2, CO2 and H2O. Negative effects of the dopants on the CO PROX activity were experimentally observed. Several characteristics on the catalysts induced by the insertion of dopants caused the effects. The presence of the non-reducible dopants on the surface hindered the efficiency of the redox equilibrium between copper and cerium, which is the essential process for CO PROX. Surface oxygen vacancies, generated by the introduction of foreign dopants, were not beneficial to the CO PROX activity. Copper species on the catalysts might be penetrated through these vacancies and protected as non-reactive reduced form in these vacancies.

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Acknowledgements

This work was supported by the New & Renewable Energy Core Technology Program of the Korea Institute of Energy Technology Evaluation and Planning (KETEP) granted financial resource from the Ministry of Trade, Industry & Energy, Republic of Korea (No. 20153010031930). Also, this work was supported by the Global Frontier R&D Program on Center for Multiscale Energy System funded by the National Research Foundation under the Ministry of Science, ICT & Future, Korea (2011–0031569). Additionally, the authors with to thank Saudi Aramco, Saudi Arabia for the financial assistance and permission to publish results.

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  1. Department of Mechanical Engineering, Korea Advanced Institute of Science and Technology, 291 Daehak-ro, Yuseong-gu, Daejeon, 34141, Republic of Korea

    Jiwoo Oh & Joongmyeon Bae

  2. Department of Materials Science and Engineering, Korea Advanced Institute of Science and Technology, 291 Daehak-ro, Yuseong-gu, Daejeon, 34141, Republic of Korea

    Jeong Do Yoo & WooChul Jung

  3. Department of Mechanical Science and Engineering, University of Illinois at Urbana-Champaign, 1206 West Green Street, Urbana, 61801, IL, USA

    Keunsoo Kim

  4. Advanced Nano Surface Research Group, Korea Basic Science Institute, 169-148 Gwahak-ro, Daejeon, 34133, Republic of Korea

    Hyung Joong Yun

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  1. Jiwoo Oh
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Oh, J., Yoo, J.D., Kim, K. et al. Negative Effects of Dopants on Copper–Ceria Catalysts for CO Preferential Oxidation Under the Presence of CO2 and H2O. Catal Lett 147, 2987–3003 (2017). https://doi.org/10.1007/s10562-017-2188-0

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