The role of chlorine promoters in mediating particle size effects in silver-catalyzed ethylene epoxidation

Measured chlorine coverages over Ag/α-Al2O3 catalysts with varying Ag weight loadings (1.3–35 wt%) and different Ag particle size distributions when parsed in terms of Cl coverages over particles of varying size constituted in the distribution reveal that Ag particles of size below ∼ 30 nm are covered in more than 1 monolayer (ML) of chlorine in presence of 3.5 ppm C2H5Cl. These assessments of Cl coverages were made possible by correlating the cumulative Cl coverage to the lognormal surface area distribution of 22 Ag/α-Al2O3 samples using a single exponential decay function. Fully chlorided small Ag particles exhibit low rates of epoxidation and only large Ag particles which exhibit sub-monolayer Cl coverages catalyze ethylene epoxidation with high ethylene oxide (EO) rates and selectivity. The Ag particle size dependence of Cl coverages plausibly explains why ≥ 100 nm Ag particles are typical in promoted Ag/α-Al2O3 ethylene epoxidation catalysts.