Metal-Nanoparticle-Catalyzed Hydrogen Generation from Formic Acid.

To meet the ever-increasing energy demand, the development of effective, renewable, and environmentally friendly sources of alternative energy is imperative. Hydrogen (H2) is a renewable, clean energy carrier, which exhibits a threefold energy density compared to gasoline; H2 is considered one of the most promising alternative energy carriers for enabling a secure, clean energy future. However, the realization of a hydrogen economy is restricted by several unresolved issues. Particularly, one of the most difficult challenges is the development of a safe, efficient hydrogen storage and delivery system. To this end, hydrogen storage techniques based on liquid-phase chemical hydrogen storage materials have become an attractive choice. Formic acid (FA) with a high volumetric capacity of 53 g H2/L demonstrates promise as a safe, convenient liquid hydrogen carrier. However, generating H2 from FA in a controlled manner at ambient temperature is still challenging, which primarily depends on the catalyst used. Hence, for practical purposes, it is imperative to develop high-performance heterogeneous catalysts for the dehydrogenation of FA. Ultrasmall metal NPs with a high surface-to-volume ratio and "clean" surface, and hence a high density of active sites exposed to reactants, are of significance for heterogeneous catalysis. However, the size of these "clean" ultrasmall metal NPs inevitably increase, and these particles undergo aggregation during synthesis and catalysis because of their high surface energy. The immobilization of metal NPs into appropriate support materials affords considerable advantages for catalytic applications, which not only offers spatial confinement to control the nucleation and growth of particles, but also prevents them from aggregation; hence, catalytic performance is significantly enhanced. In addition, the functionalization of the support with electron-rich groups is beneficial to the formation of intermediates for FA dehydrogenation, which in turn promotes the catalytic performance. In this Account, studies of hydrogen generation from FA using heterogeneous catalysts were reviewed, mainly focusing on the results reported by our group. By varying support materials (metal-organic frameworks, silica, graphene, and porous carbons) and synthetic strategies, a wide range of highly active metal NP catalysts for efficient H2 generation from FA under mild conditions were developed. In addition, the design and synthetic strategies were described, by which the size and composition of the NPs, as well as the well-defined NPs-support interactions, can be controlled for the enhancement of catalytic performance for the FA dehydrogenation. Furthermore, the performance of the prepared catalysts for the effective release of H2 from FA for the purpose of liquid-phase chemical hydrogen storage was discussed. Finally, the challenges, expected improvements, and future opportunities in this research area were summarized.