Surface Fe clusters promote syngas reaction to oxygenates on Rh catalysts modified by atomic layer deposition

[Display omitted] •Fe2O3 atomic layer deposition occurs selectively on and near Rh nanoparticles.•Fe2O3 surface promoter atoms enhance alcohol-forming active sites on Rh.•Catalyst promoter improves the activity, selectivity, and stability. Converting syngas to higher oxygenates is a promising strategy for sustainably producing fuels and chemicals used every day. Rh-based catalysts promoted with metal oxides have long been of interest for oxygenate synthesis, but the role of promoters and the structure of the catalyst during reaction are often not well understood. In this work, we characterize a Rh/SiO2 catalyst modified by Fe2O3 deposited by atomic layer deposition (ALD). We show that Fe2O3 deposits selectively on the Rh nanoparticles and enhances both the turnover frequency and the oxygenate selectivity of the catalysts. A maximum 29% selectivity towards higher oxygenates is achieved with just 1 cycle of Fe2O3 ALD, and we relate the trends in selectivity to the changing availability of surface sites that drive higher alcohol (e.g., ethanol and propanol) formation. Further, we show that the ALD promoter mitigates catalyst sintering, improving the stability of these materials. In-situ X-ray absorption spectroscopy experiments reveal that the Fe2O3 undergoes reduction during the catalyst pretreatment and forms Fe clusters on the surface of the Rh that migrate but remain stable under syngas reaction conditions. We find that modification of the Rh with these surface Fe species is key to the enhanced alcohol production observed in these materials.