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A series of ZnO/ZrO2 catalysts were synthesized by the precipitation method. The effect of different precipitation modes on the physicochemical properties of the ZnO/ZrO2 catalysts for CO2 hydrogenation to methanol was investigated. The catalysts were characterized by X-ray diffraction (XRD), N2 adsorption–desorption, transmission electron microscopy (TEM), temperature programmed desorption of CO2 (CO2-TPD), temperature programmed reduction of H2 (H2-TPR), and X-ray photoelectron spectroscopy (XPS). The results showed that the catalyst of ZnO/ZrO2 prepared by the concurrent precipitation method had more CO2 adsorption sites, resulting in its higher CO2 conversion. While the stepwise precipitation mode increased the surface oxygen content of ZnO/ZrO2, which enhanced the methanol selectivity. Overall, the ZnO/ZrO2 prepared by the concurrent precipitation mode exhibited a highly competitive efficacy for CO2 hydrogenation, giving a methanol selectivity of 81.4% with a CO2 conversion of 5.1% at 280 ℃ and 3 MPa, and the methanol yield reached 4.2%. The effect of different precipitation modes on the physicochemical properties of the ZnO/ZrO2 catalysts for CO2 hydrogenation to methanol was investigated, and the ZnO/ZrO2 prepared by the concurrent precipitation mode exhibited a highly competitive efficacy for CO2 hydrogenation. [ABSTRACT FROM AUTHOR]

A series of Cu-ZnO-ZrO2 (CCZ) catalysts were prepared by the solvothermal method with different solvothermal times (1 h, 3 h, 6 h, and 12 h). The physicochemical properties of these catalysts and the catalytic performance for CO2 hydrogenation to methanol were studied. The highest methanol yield was achieved when the solvothermal time was 6 h (CCZ-6). Furthermore, we found that the copper surface area (SCu) increases and then decreases with an increase in the solvothermal time and that there is a strong correlation between the methanol yield and the SCu. This research highlights the crucial influence of the solvothermal time on the structure and catalytic behavior of Cu-ZnO-ZrO2 catalysts, providing a valuable reference for the development of efficient catalysts. [ABSTRACT FROM AUTHOR]

Maintaining high conversion under the premise of high oxygenates selectivity in syngas conversion is important but a formidable challenge in Rh catalysis. Monometallic Rh catalysts provide poor oxygenate conversion efficiency, and efforts have been focused on constructing adjacent polymetallic sites; however, the one‐pass yields of C2+ oxygenates over the reported Rh‐based catalysts were mostly <20 %. In this study, we constructed a monometallic Rh catalyst encapsulated in UiO‐67 (Rh/UiO‐67) with enhanced proximity to dual‐site Rh1,2‐Rhn ensembles. Unexpectedly, this catalyst exhibited high efficacy for oxygenate synthesis from syngas, giving a high oxygenate selectivity of 72.0 % with a remarkable CO conversion of 50.4 %, and the one‐pass yield of C2+ oxygenates exceeded 25 %. The state‐of‐the‐art characterizations further revealed the spontaneous formation of an ensemble of Rh single atoms/dimers (Rh1,2) in the proximity of ultrasmall Rh clusters (Rhn) confined within the nanocavity of UiO‐67, providing adjacent Rh+‐Rh0 dual sites dynamically during the reaction that promote the relay of the undissociated CHO species to the CHx species. Thus, our results open a new route for designing highly efficient Rh catalysts for the conversion of syngas to oxygenates by precisely tuning the ensemble and proximity of the dual active sites in a confined space. [ABSTRACT FROM AUTHOR]

Maintaining high conversion under the premise of high oxygenates selectivity in syngas conversion is important but a formidable challenge in Rh catalysis. Monometallic Rh catalysts provide poor oxygenate conversion efficiency, and efforts have been focused on constructing adjacent polymetallic sites; however, the one-pass yields of C 2+ oxygenates over the reported Rh-based catalysts were mostly <20 %. In this study, we constructed a monometallic Rh catalyst encapsulated in UiO-67 (Rh/UiO-67) with enhanced proximity to dual-site Rh 1,2 -Rh n ensembles. Unexpectedly, this catalyst exhibited high efficacy for oxygenate synthesis from syngas, giving a high oxygenate selectivity of 72.0 % with a remarkable CO conversion of 50.4 %, and the one-pass yield of C 2+ oxygenates exceeded 25 %. The state-of-the-art characterizations further revealed the spontaneous formation of an ensemble of Rh single atoms/dimers (Rh 1,2 ) in the proximity of ultrasmall Rh clusters (Rh n ) confined within the nanocavity of UiO-67, providing adjacent Rh + -Rh 0 dual sites dynamically during the reaction that promote the relay of the undissociated CHO species to the CH x species. Thus, our results open a new route for designing highly efficient Rh catalysts for the conversion of syngas to oxygenates by precisely tuning the ensemble and proximity of the dual active sites in a confined space., (© 2024 Wiley-VCH GmbH.)