Metallic Phase-Free Zn-Al Mixed Oxide Dual Function Materials Enable High Co Selectivity in Reactive Carbon Capture From Dilute Streams

Scaling conventional carbon capture and utilization methods can be limited by cost and permitting issues associated with transportation of captured CO2. Reactive carbon capture (RCC), in which a single solid-phase dual function material (DFM) is used to both capture CO2 from dilute streams (e.g., flue gas) and catalytically convert the bound species to products in a single unit operation, has the potential to reduce energy and capital costs by over 50% relative to separate capture and conversion. To incentivize adoption, high-value products such as methanol and CO should be targeted. Appealingly, CO can be produced at atmospheric pressure, thereby lowering overall H2 demand; however, high reaction temperatures (> 600 degrees C) and the use of oxidizable transition metals, such as Ni, are often necessary to drive the reverse water-gas shift (RWGS) during reactive desorption of the bound CO2. The sensitivity of these transition metals to oxygen undercuts their utility in point source RCC. To further derisk RCC, it is essential to develop metallic-phase free DFMs that are insensitive to residual oxygen in flue gas and can achieve selective reactive desorption to CO at moderate pressures (< 400 degrees C). To this end, we have developed K-modified Zn-Al mixed oxides (K/ZnAlOx) to convert captured CO2 to CO with > 97% selectivity and yields up to 53% of captured CO2 at 400 degrees C. Complementary in situ spectroscopy studies revealed the role of K-modification in improving RCC performance of unmodified ZnAlOx. The top performing DFM was also subjected to extended RCC cycling with oxygen co-fed with CO2 during the capture test to assess durability under simulated flue gas.