Abstract
Industrial Cu/ZnO/Al2O3 or novel rate catalysts, prepared with a photochemical deposition method, were studied under functional CH3OH synthesis conditions at the set temperature (T) range of 240–350 °C, 20 bar pressure, and stoichiometric carbon dioxide/hydrogen composition. Analytical scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), X-ray adsorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) methods were systematically utilized to investigate the interfaces, measured local geometry, and chemical state electronics around the structured active sites of commercially available Cu/ZnO/Al2O3 material or synthesized Cu/ZnO. Processed Cu K-edge EXAFS analysis suggested that various Cu atom species, clusters, metallic fcc Cu, Cu oxides (Cu2O or CuO) and the Cu0.7Zn2 alloy with hexagonal crystalline particles are contained after testing. It was proposed that in addition to the model’s Cu surface area, the amount, ratio and dispersion of the mentioned bonded Cu compounds significantly influenced activity. Additionally, XPS revealed that carbon may be deposited on the commercial Cu/ZnO/Al2O3, forming the inactive carbide coating with Cu or/and Zn, which may be the cause of basicity’s severe deactivation during reactions. The selectivity to methanol decreased with increasing T, whereas more Cu0.7Zn2 inhibited the CO formation through reverse water–gas shift (RWGS) CO2 reduction.
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Acknowledgements
This work was supported by the Slovenian Research Agency (P1-0112, P1-0175, P2-152) and by the project CALIPSOplus under the Grant Agreement 730872 from the EU Framework Programme for Research and Innovation HORIZON 2020. XAS spectra measured at beamline P64 of PETRA III at DESY, Hamburg, a member of the Helmholtz Association (HGF) under project I-20160764 EC. We would like to thank Wolfgang Caliebe and Vadim Murzin for the expert advice on the beamline operation during the experiments.
Funding
The funding was provided by Horizon 2020 Framework Programme (Grant No. 730872) and Javna Agencija za Raziskovalno Dejavnost RS (Grant Nos. P1-0112, P1-0175, P2-152).
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Pori, M., Arčon, I., Dasireddy, V.D.B.C. et al. Photo-Chemically-Deposited and Industrial Cu/ZnO/Al2O3 Catalyst Material Surface Structures During CO2 Hydrogenation to Methanol: EXAFS, XANES and XPS Analyses of Phases After Oxidation, Reduction, and Reaction. Catal Lett 151, 3114–3134 (2021). https://doi.org/10.1007/s10562-021-03556-1
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DOI: https://doi.org/10.1007/s10562-021-03556-1