CO2 Reduction by Hydrogen Pre‐Reduced Acceptor‐Doped Ceria

The reactivity of H2 pre‐reduced acceptor‐doped ceria materials Gd0.10Ce0.90O2‐δ (GDC10) and Sm0.15Ce0.85O2‐δ (SDC15) was tested with respect to the reduction of CO2 to CO in the context of the reverse water‐gas shift reaction. It was demonstrated that not only oxygen vacancies, but also dissolved hydrogen is a reactive species for the reduction of CO2. Dissolved hydrogen must be considered upon discussion of the mechanism of the reverse water‐gas shift reaction on ceria‐derived materials apart from oxygen vacancies and formates. The reduction of CO2 is preceded by the formation of carbonate species of different thermal stability and reactivity. The stability of these carbonates was directly demonstrated by in situ infrared spectroscopy and revealed the largely reversible nature of CO2 ad‐ and desorption. In comparison to pre‐reduced samples, decreased carbonate coverage is obtained after oxidative treatments of GDC10 and SDC15. No significant effect of the sample treatment (O2 oxidation or H2 reduction) on the surface carbonate stability was noticed. Mono‐dentate carbonates and carboxylates appear to be more easily formed on pre‐reduced (i. e. defective) samples. Ce4+ reduction to Ce3+ (by H2) and re‐oxidation to Ce4+ (by CO2) on GDC10/SDC15 were directly monitored by infrared spectroscopic analysis of a distinct, IR‐active electronic transition of Ce3+. These results show the complex interplay of oxygen vacancy/dissolved hydrogen reactivity and surface chemical aspects in acceptor‐doped ceria materials. Reducing CO2: We show that pre‐reduced acceptor‐doped ceria is capable of CO2 adsorption and reduction to CO. Dissolved hydrogen shows only limited reactivity for the reduction of CO2, but both oxygen vacancies and stored hydrogen participate in the CO2 reduction. CO2 adsorption on ceria leads to various carbonate species with different reactivity, whereby highly stable polydentate carbonates were observed at temperatures as high as 1000 °C.