Composition-Reactivity Correlations in Platinum-Cobalt Nanoporous Network as Catalyst for Hydrodeoxygenation of 5-Hydroxymethylfurfural

Identifying the influence of atomic order on the catalytic reactivity of bimetallic catalysts is essential for their rational design. However, the synthesis of atomically ordered nanostructures under mild conditions is not trivial, and in many cases a mixture of various compositions is formed. Here we show a simple and highly versatile approach for synthesis of Pt-Co bimetallic nanoporous network (BNN) and demonstrate the influence of preparation conditions on the BNN's atomic order and catalytic reactivity. High surface area Pt₃Co BNN was prepared by reduction of [Co(NH₃)₅Cl][PtCl₄] double complex salt crystals. The BNN phase was transformed from Pt₃Co to segregated Pt and Co domains once the reduction temperature of the double complex salt crystals was elevated. High selectivity toward hydrodeoxygenation of biomass-derived 5-hydroxymethylfurfural to 2,5-dimethylfuran was obtained while catalyzing the reaction with Pt₃Co BNN. The catalytic yield was deteriorated by more than an order of magnitude while catalyzing the reaction with BNN that was constructed of segregated Pt and Co domains. Spectroscopic analysis identified the presence of an oxidized Co species and a metallic Pt species in a close to 1:1 ratio on the Pt₃Co BNN surface as crucial factors in lowering the activation energy of the dehydration reaction.