Lee, Won Jong Hwang, Yeon Jin Kim, Joohoon Jeong, Hyangsoo Yoon, Chang Won 2024-01-19T20:02:31Z 2024-01-19T20:02:31Z 2021-09-02 2019-05-16 1439-4235 https://pubs.kist.re.kr/handle/201004/119986 Formic acid (HCOOH, FA) has long been considered as a promising hydrogen-storage material due to its efficient hydrogen release under mild conditions. In this work, FA decomposes to generate CO2 and H-2 selectively in the presence of aqueous Pd2+ complex solutions at 333K. Pd(NO3)(2) was the most effective in generating H-2 among various Pd2+ complexes explored. Pd2+ complexes were insitu reduced to Pd-0 species by the mixture of FA and sodium formate (SF) during the course of the reaction. Since C-H activation reaction of Pd2+-bound formate is occurred for both Pd2+ reduction and H-2/CO2 gas generation, FA decomposition pathways using several Pd2+ species were explored using density functional theory (DFT) calculations. Rotation of formate bound to Pd2+, -hydride elimination, and subsequent CO2 and H-2 elimination by formic acid were examined, providing different energies for rate determining step depending on the ligand electronics and geometries coordinated to the Pd2+ complexes. Finally, Pd2+ reduction toward Pd-0 pathways were explored computationally either by generated H-2 or reductive elimination of CO2 and H-2 gas. English WILEY-V C H VERLAG GMBH IRON-CATALYZED DEHYDROGENATION HYDROGEN GENERATION EFFICIENT CATALYST CARBON-DIOXIDE NANOPARTICLES LIGAND FUEL Pd2+-Initiated Formic Acid Decomposition: Plausible Pathways for C-H Activation of Formate Article 10.1002/cphc.201801088 1 CHEMPHYSCHEM, v.20, no.10, pp.1382 - 1391 CHEMPHYSCHEM 20 10 1382 1391 scie scopus 000472446600021 2-s2.0-85060972082 Chemistry, Physical Physics, Atomic, Molecular & Chemical Chemistry Physics Article IRON-CATALYZED DEHYDROGENATION HYDROGEN GENERATION EFFICIENT CATALYST CARBON-DIOXIDE NANOPARTICLES LIGAND FUEL decomposition pathway density functional theory formic acid hydrogen storage palladium