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Optimal amounts of CO2 are added to syngas to boost the methanol synthesis rate on Cu-ZnO-Al2O3 in the industrial process. The reason for CO2 promotion is not sufficiently understood at the particle level due to the catalyst complexity and the high demands of characterization under true reaction conditions. Herein, we applied operando synchrotron X-ray powder diffraction and modulated-excitation infrared spectroscopy on a commercial catalyst to gain insights into its morphology and surface chemistry. These studies unveiled that Cu and ZnO agglomerate and ZnO particles flatten under CO/H2 and/or CO2/H2. Under the optimal CO/CO2/H2 mixture, sintering is prevented and ZnO crystals adopt an elongated shape due to the minimal presence of the H2O byproduct, enhancing the water-gas shift activity and thus the methanol production. Our results provide a rationale to the CO2 promotion emphasizing the importance of advanced analytical methods to establish structure-performance relations in heterogeneous catalysis. [ABSTRACT FROM AUTHOR]

Methanol synthesis by CO2 hydrogenation is attractive in view of avoiding the environmental implications associated with the production of the traditional syngas feedstock and mitigating global warming. However, there still is a lack of efficient catalysts for such alternative processes. Herein, we unveil the high activity, 100 % selectivity, and remarkable stability for 1000 h on stream of In2O3 supported on ZrO2 under industrially relevant conditions. This strongly contrasts to the benchmark Cu-ZnO-Al2O3 catalyst, which is unselective and experiences rapid deactivation. In-depth characterization of the In2O3-based materials points towards a mechanism rooted in the creation and annihilation of oxygen vacancies as active sites, whose amount can be modulated in situ by co-feeding CO and boosted through electronic interactions with the zirconia carrier. These results constitute a promising basis for the design of a prospective technology for sustainable methanol production. [ABSTRACT FROM AUTHOR]

It takes two to tango The production of the energy carrier and platform chemical methanol by CO2 hydrogenation is expected to become a key step in a sustainable economy but the realization of this process requires high‐performance catalysts. In their Communication on page 6261 ff., J. Pérez‐Ramírez and co‐workers demonstrate that the synergistic interaction of In2O3 and a ZrO2 carrier leads to a highly stable material that provides methanol in high space time yields and with almost 100 % selectivity. [ABSTRACT FROM AUTHOR]