Nickel promotes selective ethylene epoxidation on silver.

Jalil, Anika; Happel, Elizabeth E; Cramer, Laura; Hunt, Adrian; Hoffman, Adam S; Waluyo, Iradwikanari; Montemore, Matthew M; Christopher, Phillip et al. · Science · 2025

basic_science · Level V

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Abstract

Over the last 80 years, chlorine (Cl) has been the primary promoter of the ethylene epoxidation reaction valued at ~40 billion USD per year, providing a ~25% selectivity increase over unpromoted silver (Ag) (~55%). Promoters such as cesium, rhenium, and molybdenum each add a few percent of selectivity enhancements to achieve 90% overall, but their codependence on Cl makes optimizing and understanding their function complex. We took a theory-guided, single-atom alloy approach to identify nickel (Ni) as a dopant in Ag that can facilitate selective oxidation by activating molecular oxygen (O<sub>2</sub>) without binding oxygen (O) too strongly. Surface science experiments confirmed the facile adsorption/desorption of O<sub>2</sub> on NiAg, as well as demonstrating that Ni serves to stabilize unselective nucleophilic oxygen. Supported Ag catalyst studies revealed that the addition of Ni in a 1:200 Ni to Ag atomic ratio provides a ~25% selectivity increase without the need for Cl co-flow and acts cooperatively with Cl, resulting in a further 10% initial increase in selectivity.