Revealing the Surface Chemistry for CO₂ Hydrogenation on Cu/CeO_2–x Using Near-Ambient-Pressure X-ray Photoelectron Spectroscopy

Abstract

Catalytic reduction of CO2 to valuable products is an attractive route for CO2 recycling. CeO2-supported Cu catalysts have shown high activity and selectivity for the hydrogenation of CO2 to CO. To uncover the origin of their high performance, we prepared a practical and well-defined model of Cu/CeO2–x catalysts with Cu nanoparticles dispersed on a CeO2–x support. We studied the structure and catalytic activity of the practical catalyst and the evolution of the active phase and surface intermediates using near-ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS) over the model catalyst under CO2 hydrogenation conditions. For both model and practical catalysts, metallic copper and partially reduced ceria with oxygen vacancies were found to be active sites for the reduction of CO2 to CO. Over the model catalyst, partial covering of Cu by CeO2–x and diffusion of Cu into CeO2–x was observed, suggesting that a strong interaction between Cu and CeO2–x was favored during CO2 hydrogenation. The surface analysis results indicated that the CO2 hydrogenation proceeded through the following steps: activation of CO2 in the form of carbonate on the surface of CeO2–x , hydrogenation of carbonate to formate on the surface of Cu by the dissociated H2, and conversion of formate to CO. This work provides direct experimental evidence on the surface properties of Cu and ceria during the RWGS reaction and the activation and hydrogenation processes of CO2 over the Cu/CeO2–x surface for a high RWGS catalytic performance.

Support-Dependent Cu–In Bimetallic Catalysts for Tailoring the Activity of Reverse Water Gas Shift Reaction

“…In contrast, the In10/CeO 2 catalyst exhibited the worst RWGS activity and the highest apparent activation energy of 115 ± 4 kJ/mol compared to the Cu10/CeO 2 and Cu5In5/CeO 2 samples. This agrees with our previous results where both well-dispersed Cu and defective CeO 2 play important roles in CO 2 hydrogenation . As indicated by the RWGS activity of the In10/CeO 2 catalyst, H 2 dissociation is also possible on In 2 O 3 sites.…”

“…This agrees with our previous results where both welldispersed Cu and defective CeO 2 play important roles in CO 2 hydrogenation. 67 As indicated by the RWGS activity of the In10/CeO 2 catalyst, H 2 dissociation is also possible on In 2 O 3 sites. Nevertheless, it has been widely proposed that the CO 2 hydrogenation activity of In 2 O 3 -based catalysts is limited by the weak H 2 -spliting ability of In 2 O 3 .…”

Restructuring of titanium oxide overlayers over nickel nanoparticles during catalysis

“…This capability adds a parameter for catalyst optimization. These results could enable an understanding of the performance of a number of supported metals in reactions for sustainable technologies, such as biomass upgrading ( 20 ) and CO 2 valorization ( 21 , 22 ).…”

Exploring the Promotion of γ‐Al2O3 on Pd/CeO2‐Catalyzed Low‐Concentration Methane Oxidation Using Operando DRIFTS‐MS

“…The Ce 3d XPS spectra of 0.5Pd/10CeO 2 /γ‐Al 2 O 3 and 0.5Pd/CeO 2 are shown in Figure 6(a), where u and v were denoted as 3d 3/2 and 3d 5/2 spin‐coupled orbitals, respectively. v 0 , v ′, u 0 and u ′ represent Ce 3+ , v , v“ , v”′ , u , u“ , and u”′ represent Ce 4+ [32,33] . According to the literature, the ratio of Ce 3+ /(Ce 3+ +Ce 4+ ) was related to the number of oxygen vacancies, [34] with a larger ratio representing a larger number of oxygen vacancies.…”

“…v 0 , v', u 0 and u' represent Ce 3 + , v, v", v"', u, u", and u"' represent Ce 4 + . [32,33] According to the literature, the ratio of Ce 3 + /(Ce 3 + + Ce 4 + ) was related to the number of oxygen vacancies, [34] with a larger ratio representing a larger number of oxygen vacancies. The ratio of Ce 3 + /(Ce 3 + + Ce 4 + ) was calculated from the fitted peak areas [35,36] (Table 1), and had an order of 0.5Pd/10CeO 2 /γ-Al 2 O 3 > 0.5Pd/CeO 2 .…”