Hydrogen production by catalytic decomposition of formic acid in solution is a key reaction for hydrogen storage and palladium is one of the most efficient catalysts. We explain form first-principles calculations why the presence of an anionic promoter renders palladium more active and more selective for formic acid dehydrogenation. The promotion effect is already present when the anion is modeled by a negatively charged surface. This promotional effect is related to the modulation of the electric field at the catalyst surface and to the electrostatic interaction between this electric field and the surface dipole moment. The reaction intermediates induce different surface dipoles and  their energies are hence differently affected by the interaction with the field generated by the promoter. As a result, both the reaction kinetics and selectivity are markedly improved. This opens the door to a rational design of catalytic systems using promoters.

Understanding the role of anionic dopants on Pd for hydrogen production from formic acid

253rd National Meeting (2017)

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