A basic resin bearing −N(CH3)2 functional groups within its macroreticular structure performed as an efficient organic support for the active Pd nanoparticles (NPs) responsible for the production of high-quality H2 via formic acid (HCOOH) decomposition at convenient temperature. Physicochemical characterization as well as the kinetic isotope effect (KIE) revealed that not only the formation of small Pd NPs but also cooperative action by the −N(CH3)2 groups within the resins play crucial roles in achieving efficient catalytic performances. In addition to the advantages such as simple workup procedure, free of additives, and superior catalytic activity compared with the conventional inorganic supports, the present catalytic system can suppress unfavorable CO formation of <5 ppm, which makes it an ideal hydrogen vector in terms of potential industrial application for proton-exchange-membrane fuel cells. Moreover, the basic resin support also provides Pd–Ag nanocatalyst from an aqueous solution of mixture of PdCl2 and AgNO3. The catalytic activities in the H2 production from formic acid decomposition were strongly dependent on the presence of Ag atoms and were shown to perform significantly better than the pure Pd and Ag catalysts.

Highly dispersed PdCu alloy nanoparticles have been successfully prepared within a macroreticular basic resin bearing N(CH3 )2 functional groups. This previously unappreciated combination of alloy is first proven to be responsible for the efficient production of high-purity H2 from formic acid (HCOOH) dehydrogenation for chemical hydrogen storage. By the addition of Cu, the electronically promoted Pd sites show significantly higher catalytic activity as well as a better tolerance towards CO poisoning as compared to their monometallic Pd counterparts. Experimental and DFT calculation studies revealed not only the synergic alloying effect but also cooperative action by the N(CH3 )2 groups within the resin play crucial roles in achieving exceptional catalytic performances. In addition to the advantages such as, facile preparation method, free of additives, recyclable without leaching of active component, and suppression of unfavorable CO formation less than 3 ppm, the present catalytic system is cost-effective because of the superior catalytic activity compared with that of well-established precious PdAg or PdAu catalysts. The present catalytic system is particularly desirable for an ideal hydrogen vector in terms of potential industrial application for fuel cells.