Efficient hydrogen production from formic acid dehydrogenation over ultrasmall PdIr nanoparticles on amine-functionalized yolk-shell mesoporous silica.

Developing heterogeneous catalysts with exceptional catalytic activity over formic acid (HCOOH, FA) dehydrogenation is imperative to employ FA as an effective hydrogen (H 2 ) carrier. In this work, ultrasmall (1.4 nm) and well-dispersed PdIr nanoparticles (NPs) immobilized on amine-functionalized yolk-shell mesoporous silica nanospheres (YSMSNs) with radially oriented mesoporous channels have been synthesized by a co-reduction strategy. The optimized catalyst Pd 4 Ir 1 /YSMSNs-NH 2 (Pd/Ir molar ratio = 4:1) exhibited a remarkable turnover frequency (TOF) of 5818 h -1 and remarkable stability at 50 °C with the addition of sodium formate (SF), resulting in complete FA conversion and H 2 selectivity, exceeding most of the solid heterogeneous catalysts in previous reports under similar circumstances. Kinetic isotope effect (KIE) exploration indicates the cleavage of the CH bond is regarded as the rate-determining step (RDS) during the FA dehydrogenation process. Such excellent catalytic properties arise from the ultrafine and well-dispersed PdIr NPs supported on the nanosphere support YSMSNs-NH 2 , the electronic synergistic effect of PdIr alloy NPs, and the strong metal-support interaction (MSI) effect between the introduced PdIr NPs and YSMSNs-NH 2 support. This work offers a new paradigm for exploiting the highly effective silica-supported Pd-based heterogeneous catalysts over the dehydrogenation of FA.