Amino-functionalized Pd-NH2/WOx(C) nanocatalysts with oxygen vacancy-rich for efficient formic acid dehydrogenation

Abstract

Formic acid (FA) is an attractive liquid hydrogen carrier, yet the development of heterogeneous catalysts that can efficiently release H2 from additive-free FA under mild conditions remains challenging. Herein, we report an amino-functionalized Pd-NH2/WOx(C) nanocatalyst rich in oxygen vacancies, which discloses an impressive initial turnover frequency of 5412 h-1 and a low activation energy of 25.2 kJ mol-1 without additives at room temperature, and maintains 100% selectivity and conversion in the fifth cycle reaction. Mechanistic investigations illustrate that the oxygen vacancies enhance the adsorption of HCOOH molecules and HCOO* intermediates, promote O−H bond activation, and facilitate C−H bond cleavage in the rate-determining step. This work provides new insights into a facile and controllable synthesis strategy of inexpensive and efficient catalysts for high efficiency dehydrogenation of liquid-phase hydrogen carrier