p>Formic acid acts as a portable hydrogen storage medium, but the ability of formic acid for providing hydrogen on demand relies heavily on dehydrogenation catalysts capable of promoting dehydrogenation reaction efficiently without any undesired carbon monoxide formation via the pathway of formic acid dehydration. In this article, the use of Pd nanoparticles decorated with boron doped pores in carbon support matrix (Pd/BPC) as a structure-tuned catalyst for low temperature formic acid dehydrogenation has been investigated. Specifically, the key research question of this paper addresses whether Pd/BPC shows superior catalytic performance due to pore retention, enhancement in Pd-support interaction, or coupling effect of both. In order to answer such research question, the Pd/BPC catalysts have been evaluated based on final gas evolution amount, specific rate, pore-retention factor, anchoring ratio determined from adsorption energy, surface evidence for mixed valent Pd, and cycleability. Optimal Pd/BPC catalyst shows a BET specific surface area of 530.1 m2 g−1, pore volume of 3.03 cm3 g−1, representative pore diameter of 26.3 nm, boron content of 1.3 wt.%, palladium content of 3.0 wt.% and Pd nanoparticle size of approximately 3.6 nm. At 50 °C, this optimal catalyst generates around 105 mL of \(H_2/CO_2\) gas mixture during 90 minutes’ period, corresponding to 38.9 mL g min−−1 gas generation capacity. It corresponds to approximately 2.9 times of Pd/PC and 3.9 times of commercial Pd/C. The BET surface area of the pores and the original carbon remain 79.9%, pore volume remains 86.1%, and representative pore diameter remains 96.3% of the respective original counterparts, leading to a combined pore retention factor of 0.663. Meanwhile, anchoring ratio of Pd increases from 1.00 for pure graphene to 1.04 for nitrogenated graphene to 2.34 for B-graphene. The enhanced activity cannot be simply attributed to the increase in surface area.
