Reactive Separations of CO/CO<inf>2</inf> mixtures over Ru-Co Single Atom Alloys

Reactive separations of CO/CO2 mixtures are a promising pathway to lower the energy requirement of CO2 hydrogenation to chemicals and fuels, with applications in the U.S. Navy’s seawater-to-fuel process. With the CO/CO2 feedstock, a challenge is activating CO to produce heavier hydrocarbons while preventing CO2 methanation, requiring low-temperature Fischer-Tropsch synthesis (FTS) catalysts. In this work, we demonstrate that a Ru-Co single atom alloy (SAA) catalyst produces C5+ hydrocarbons at a rate of 11.7 μmol/s/g-cobalt (hexane basis) in a 50/50 CO/CO2 stream with ≤1% CO2 conversion. The reaction operates at a relatively low temperature (200 °C) and high gas hourly space velocity (GHSV: 84,000 mL/g/h) that is compatible with the upstream reverse water-gas shift reaction. Detailed experiments, catalyst characterizations, and density functional theory (DFT) calculations have been conducted to understand the active phase, the role of the Ru dopant, and catalyst restructuring that occurs at elevated temperatures (>200 °C). Ru dopants are found to promote the reduction of Co species, enabling catalytic activity for CO hydrogenation without pre-reduction, but may not enhance the FTS activity or desired C5+ hydrocarbon selectivity.