Structural Evolution and Dynamics of an In2O3 Catalyst for CO2 Hydrogenation to Methanol: An Operando XAS-XRD and in Situ TEM Study

Athanasia Tsoukalou, Paula M. Abdala, Dragos Stoian, Xing Huang, Marc Georg Willinger, Alexey Fedorov, Christoph R. Müller

Research output: Contribution to journalArticlepeer-review

236 Scopus citations

Abstract

We report an operando examination of a model nanocrystalline In2O3 catalyst for methanol synthesis via CO2 hydrogenation (300 °C, 20 bar) by combining X-ray absorption spectroscopy (XAS), X-ray powder diffraction (XRD), and in situ transmission electron microscopy (TEM). Three distinct catalytic regimes are identified during CO2 hydrogenation: activation, stable performance, and deactivation. The structural evolution of In2O3 nanoparticles (NPs) with time on stream (TOS) followed by XANES-EXAFS-XRD associates the activation stage with a minor decrease of the In-O coordination number and a partial reduction of In2O3 due to the formation of oxygen vacancy sites (i.e., In2O3-x). As the reaction proceeds, a reductive amorphization of In2O3 NPs takes place, characterized by decreasing In-O and In-In coordination numbers and intensities of the In2O3 Bragg peaks. A multivariate analysis of the XANES data confirms the formation of In2O3-x and, with TOS, metallic In. Notably, the appearance of molten In0 coincides with the onset of catalyst deactivation. This phase transition is also visualized by in situ TEM, acquired under reactive conditions at 800 mbar pressure. In situ TEM revealed an electron beam assisted transformation of In2O3 nanoparticles into a dynamic structure in which crystalline and amorphous phases coexist and continuously interconvert. The regeneration of the deactivated In0/In2O3-x catalyst by reoxidation was critically assessed revealing that the spent catalyst can be reoxidized only partially in a CO2 atmosphere or air yielding an average crystallite size of the resultant In2O3 that is approximately an order of magnitude larger than the initial one.

Original languageEnglish
Pages (from-to)13497-13505
Number of pages9
JournalJournal of the American Chemical Society
Volume141
Issue number34
DOIs
StatePublished - 28 Aug 2019
Externally publishedYes

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