Highly Efficient Iridium-Iron-Molybdenum Catalysts Condensed on Boron Nitride for Biomass-Derived Diols' Hydrogenolysis to Secondary Monoalcohols

A trade-off of activity-selectivity exists in primary C-O hydrogenolysis of biomass-derived diols to secondary alcohols over bimetallic catalysts, especially the combination of noble metal and early transition metal in the metallic state and metal oxide state, respectively. Herein, the combination of high surface concentration of boron nitride (BN)-supported metals and the addition of Mo as third metal broke the trade-off. High yields (>50%) of secondary alcohols were obtained with robust productivity up to 25-fold based on Ir over Ir-Fe_0.13-Mo_0.08/BN (Ir = 20 wt %, Fe/Ir = 0.13, Mo/Ir = 0.08) than previously reported Ir-Fe catalysts. In contrast, simply increasing the loading amount of Ir-Fe catalysts or the addition of Mo species only enhanced the productivity by <2-4-fold. Various characterizations showed that large Ir loading enables the formation of condensed nanostructures (∼2 nm) on the BN support, which further alloy with Mo and Fe to form an face centred cubic (fcc)-type trimetallic alloy with surface enrichment of Fe. On the other hand, in Ir-Fe_0.25-Mo_0.08/BN with lower Ir (5 wt %) and lower Ir-based activity, the Mo species were rather bound on the support surface possibly as the MoB state. These structures were formed by simple impregnation and reduction with H₂ at the reaction temperature (453 K). The high activity of Ir-Fe_0.13-Mo_0.08/BN (20 wt % Ir) is derived from two aspects: (1) the formation of condensed nanostructures (∼2 nm) exposing more active sites and (2) alloying with Mo to modify the electronic state of Ir to enhance the H₂ activation ability, as shown by the decreased E_a (82-84 → 67 kJ mol^-1).