On the Correlation between Group III‐A Elements Doping and Structure Performance of Cu/ZnO/ZrO2 Catalysts System for CO2 Hydrogenation to Methanol

• Published in: ChemCatChem Vol. 16; no. 20
• Main Authors: Shrivastaw, Vivek Kumar, Kaishyop, Jyotishman, Khan, Tuhin Suvra, Khurana, Deepak, Singh, Gaje, Paul, Subham, Chowdhury, Biswajit, Bordoloi, Ankur
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 21-10-2024
• Subjects: Adsorption; Basicity; Carbon dioxide; Catalysts; Catalytic activity; Chemical synthesis; Chemisorption; CO2 Hydrogenation; Copper; Density functional theory; Doping; Gallium; Hydrogenation; in-situ DRIFT study; Methanol; Oxygen vacancy; Self-assembly; Surface basicity; Theoretical studies; Zinc oxide; Zirconium dioxide
• ISSN: 1867-3880; 1867-3899
• DOI: 10.1002/cctc.202400534

A set of Cu/ZnO/ZrO2 catalysts doped with Group‐IIIA elements (M=B, Al, Ga & In) were synthesized via a facile single‐step evaporation‐induced self‐assembly (EISA) method to tune up the catalyst basicity and modulate the structure to improve the methanol yield in CO2 hydrogenation reaction. To understand the catalyst‘s textural properties and catalytic activity, prepared catalysts were exposed to several in‐situ/ex‐situ characterization techniques like Physisorption & Chemisorption studies, XRD, XPS, TEM, and in‐situ DRIFT. The addition of group IIIA elements has a significant impact on the CO2 conversion and Methanol selectivity via tailoring the important textural properties such as metallic surface area of Cu, reducibility of catalysts, particle size, controlled oxygen vacancy, and basicity of catalyst surface. CZZ doped with Al appeared to be the best catalyst, in this study. The modified Cu‐ZnO interface via density functional theory (DFT) calculations also indicated that the CO2 adsorption energy is found to be highest for CZZAl, which is concomitant with CO2‐TPD analysis results. The lowest to highest CO2 adsorption energy order over the catalyst set follows CZZIn<CZZB<CZZGa<CZZO<CZZAl. Moreover, the surface model of Cu/ZnO after doping each element was also studied to elucidate the elemental promotional effect on CO2 adsorption.
Cu/ZnO/ZrO2 catalysts doped with Group‐IIIA elements (B, Al, Ga, In) were synthesized via EISA to enhance methanol yield in CO2 hydrogenation. Characterization techniques (Physisorption, Chemisorption, XRD, XPS, TEM, in‐situ DRIFT) revealed that IIIA elements improve CO2 conversion and methanol selectivity by altering textural properties. Al‐doped CZZ showed the best performance, with DFT confirming the highest CO2 adsorption energy for CZZAl.