Promoting role of Ru species on Ir-Fe/BN catalyst in 1,2-diols hydrogenolysis to secondary alcohols

Abstract

Noble metal-based-bimetallic catalysts have been highly investigated and applied in wide applications including biomass transformation via regioselective C−O hydrogenolysis while further modification especially with noble metal is highly promising yet still under investigation. Herein, Ru was found as an effective modifier among the screened noble metals (Ru, Pt, Rh, Pd, Au, and Ag) for Ir-Fe/BN (Ir = 5 wt%, Fe/Ir = 0.25) catalyst in terminal C−O hydrogenolysis of 1,2-butanediol (1,2-BuD) to 2-butanol (2-BuOH). Only trace amount of Ru (up to 0.5 wt%) was effective in terms of high 2-BuOH selectivity (> 60%) and activity (about twice). Larger amount of Ru species (3 wt%) highly enhanced the activity but gave low selectivity to 2-BuOH with by-products of terminal C−C bond scission. Optimized catalyst (Ru(0.5)-Ir-Fe/BN) was reusable at least 4 times and gave moderate 2-BuOH yield (47%) in hydrogenolysis of 1,2-BuD. The promoting effect of Ru addition (0.5 wt%) to Ir-Fe/BN on hydrogenolysis of various alcohols was also confirmed. Combining catalytic tests with various characterizations, the promotion mechanism of Ru species in trimetallic catalysts was clarified. The Ru species in Ru(0.5)-Ir-Fe/BN form alloy with Ir and are enriched at the interface with BN surface, and direct interaction between Ru and Fe was not necessary in Ru-Ir-Fe alloy. The interface of Ir and Fe on the surface of Ir-Fe alloy may work as active sites for 1,2-diols to secondary alcohols via direct C−O hydrogenolysis, in which Ru-modified Ir activates H₂ to form hydride-like species. The activity of Ru species in C−C bond cleavage was highly suppressed due to the direct interaction with Ir species and less exposed to substrate. Larger loading amount of Ru species (3 wt%) led to the formation Ru-rich trimetallic alloy, which further works as active sites for C−C bond scission.