Trimetallic CoAuPd alloy nanoparticles confined in mesoporous MIL-101 with low transition energy for enhanced hydrogen generation from formic acid

Abstract

Developing efficient and low-cost catalysts with excellent hydrogen generation from formic acid (FA) is highly desired but challenging. Herein, a uniform CoAuPd alloy nanoparticles (NPs) were successfully confined into MIL-101 by a surfactant-free co-reduction method. The elevated stability of Co0 in the protected alloy NPs makes its application in FA dehydrogenation successful. Significantly, the resulting Co0.3Au0.35Pd0.35/MIL-101 composites with the lower consumption of noble metals exhibit the 100% hydrogen selectivity, highest activity and excellent stability toward hydrogen generation from FA without any additive at room temperature. Theoretical results reveal that the enhanced hydrogen generation from FA can be ascribed to the synergistic effects between CoAuPd alloy NPs and MIL-101 frameworks with lowest transition energy between LUMO and HOMO and highest adsorption energy of FA, as compared to the bimetallic alloy NPs. Therefore, the present results open up new avenues for developing cost effective and high-performance catalysts for the generation of hydrogen from FA by using porous MOFs as hosts for non-noble metal based NPs.