Reduction of Cofed Carbon Dioxide Modifies the Local Coordination Environment of Zeolite-Supported, Atomically Dispersed Chromium to Promote Ethane Dehydrogenation

The reduction of CO₂ is known to promote increased alkene yields from alkane dehydrogenations when the reactions are cocatalyzed. The mechanism of this promotion is not understood in the context of catalyst active-site environments because CO₂ is amphoteric, and even general aspects of the chemistry, including the significance of competing side reactions, differ significantly across catalysts. Atomically dispersed chromium cations stabilized in highly siliceous MFI zeolite are shown here to enable the study of the role of parallel CO₂ reduction during ethylene-selective ethane dehydrogenation. Based on infrared spectroscopy and X-ray absorption spectroscopy data interpreted through calculations using density functional theory (DFT), the synthesized catalyst contains atomically dispersed Cr cations stabilized by silanol nests in micropores. Reactor studies show that cofeeding CO₂ increases stable ethylene-selective ethane dehydrogenation rates over a wide range of partial pressures. Operando X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine-structure (EXAFS) spectra indicate that during reaction at 650 °C the Cr cations maintain a nominal 2+ charge and a total Cr-O coordination number of approximately 2. However, CO₂ reduction induces a change, correlated with the CO₂ partial pressure, in the population of two distinct Cr-O scattering paths. This indicates that the promotional effect of parallel CO₂ reduction can be attributed to a subtle change in Cr-O bond lengths in the local coordination environment of the active site. These insights are made possible by simultaneously fitting multiple EXAFS spectra recorded in different reaction conditions; this novel procedure is expected to be generally applicable for interpreting operando catalysis EXAFS data.