Influence of Cs Loading on Pt/m-ZrO2 Water–Gas Shift Catalysts

Certain alkali metals (Na, K) at targeted loadings have been shown in recent decades to significantly promote the LT-WGS reaction. This occurs at alkali doping levels where a redshift in the C-H band of formate occurs, indicating electronic weakening of the bond. The C-H bond breaking of formate is the proposed rate-limiting step of the formate associative mechanism, lending support to the occurrence of this mechanism in H2-rich environments of the LT-WGS stage of fuel processors. Continuing in this vein of research, 2%Pt/m-ZrO2 was promoted with various levels of Cs in order to explore its influence on the rate of formate intermediate decomposition, as well as that of LT-WGS in a fixed bed reactor. In situ DRIFTS experiments revealed that Cs promoter loadings of 3.87% to 7.22% resulted in significant acceleration of the forward formate decomposition in steam at 130 °C. Of all of the alkali metals tested to date, the redshift in the formate ν(CH) band with the incorporation of Cs was the greatest. XANES difference experiments at the Pt L2 and L3 edges indicated that the electronic effect was not likely due to an enrichment of electronic density on Pt. CO2 TPD experiments revealed that, unlike Na and K promoters, Cs behaves more like Rb in that the decomposition of the second intermediate in LT-WGS, carbonate species, is hindered due to (1) increased basicity of Cs, (2) the tendency of Cs to cover Pt sites that facilitate CO2 decomposition, and (3) the tendency of Cs to increase Pt particle size as shown by EXAFS results, resulting in fewer Pt sites that facilitate CO2 decomposition. As such, the LT-WGS rate was hindered overall and the rate-limiting step shifted to carbonate decomposition (CO2 removal). Like its Rb counterpart, low levels of added Cs (e.g., 0.72%Cs) were found to improve the stability of the catalyst relative to the unpromoted catalyst; the stability comparison was made at similar CO conversion level as well as similar space velocity.

Enhanced Carbon Dioxide Decomposition Using Activated SrFeO3−δ

Today, climate change caused by global warming has become a worldwide problem with increasing greenhouse gas (GHG) emissions. Carbon capture and storage technologies have been developed to capture carbon dioxide (CO2); however, CO2 storage and utilization technologies are relatively less developed. In this light, we have reported efficient CO2 decomposition results using a nonperovskite metal oxide, SrFeCo0.5Ox, in a continuous-flow system. In this study, we report enhanced efficiency, reliability under isothermal conditions, and catalytic reproducibility through cyclic tests using SrFeO3−δ. This ferrite needs an activation process, and 3.5 vol% H2/N2 was used in this experiment. Activated oxygen-deficient SrFeO3−δ can decompose CO2 into carbon monoxide (CO) and carbon (C). Although SrFeO3−δ is a well-known material in different fields, no studies have reported its use in CO2 decomposition applications. The efficiency of CO2 decomposition using SrFeO3−δ reached ≥90%, and decomposition (≥80%) lasted for approximately 170 min. We also describe isothermal and cyclic experimental data for realizing commercial applications. We expect that these results will contribute to the mitigation of GHG emissions.