Mechanistic insights into the catalytic methanol steam reforming performance of Cu/ZrO2 catalysts by in situ and operando studies
| Autor: | Parastoo Delir Kheyrollahi Nezhad, Stefan Vanicek, Maximilian Watschinger, Lukas Schlicker, Christoph Thurner, Lei Zhang, Albert Gili, Bernhard Klötzer, Aleksander Gurlo, Eva-Maria Köck, Andrew Doran, Nicholas Köwitsch, Kevin Ploner, Thomas Götsch, Marc Armbrüster, Simon Penner, Wolfgang Wallisch |
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| Rok vydání: | 2020 |
| Předmět: |
Phase boundary
010405 organic chemistry Formaldehyde chemistry.chemical_element 010402 general chemistry 01 natural sciences Copper Catalysis 0104 chemical sciences Steam reforming chemistry.chemical_compound chemistry Chemical engineering Methanol Physical and Theoretical Chemistry Selectivity Monoclinic crystal system |
| Zdroj: | Journal of Catalysis. 391:497-512 |
| ISSN: | 0021-9517 |
| Popis: | We assessed the catalytic properties of the Cu/ZrO2 interface in methanol and formaldehyde steam reforming (MSR and FSR) on powder catalysts by using a comparative approach with respect to the influence of the ZrO2 polymorph support structure (monoclinic (m-)ZrO2 vs. tetragonal (t-)ZrO2), its synthesis routine and the choice of the precursor material on the CO2 selectivity. Our studies reveal that ZrO2 exhibits a pronounced versatility as a support material and its catalytic properties depend most strongly on its surface properties governed by its synthesis, especially by the choice of the Zr precursor. The way of combining the support with copper introduces an additional layer of complexity, but its influence on the MSR performance is limited to a modification of the conditions provided by the ZrO2 support. Exploiting the comparative approach regarding the Cu-ZrO2 catalysts in FSR and MSR – including the pure support materials – in combination with in situ Fourier transform infrared (FT-IR) spectroscopy shows that the CO observed in MSR on Cu/m-ZrO2 can be attributed to a spillover of formaldehyde to the support. Side reactions of m-ZrO2 are suppressed at lower temperatures due to its lack of highly reactive sites, resulting in a CO2-selective MSR performance. In Cu/t-ZrO2, however, the amount of CO is higher and a combination of a formaldehyde spillover to the support and a Cu-ZrO2 phase boundary yielding CO leads to the lower CO2 selectivity of these samples. An elevated number of defects and reactive Lewis acidic and Bronsted basic centers of t-ZrO2 explains this increased activity towards side reactions in contrast to Cu/m-ZrO2 catalysts. |
| Databáze: | OpenAIRE |
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