Enhancement of Formic Acid Dehydrogenation Selectivity of Pd(111) Single Crystal Model Catalyst Surface via Brønsted Bases

The influence of ammonia (NH3) on the doubly deuterated formic acid (DCOOD, FA) dehydrogenation selectivity for a Pd(111) single crystal model catalyst surface was investigated under ultrahigh vacuum conditions using temperature-programmed desorption and temperature-programmed reaction spectroscopy techniques. NH3 adsorption on Pd(111) revealed reversible, molecular desorption without any significant decomposition products, while DCOOD adsorption on Pd(111) yielded D2, D2O, CO, and CO2 as a result of dehydration and dehydrogenation pathways. Functionalizing the Pd(111) surface with ammonia suppressed the FA dehydration and enhanced the dehydrogenation pathway. The boost in the FA dehydrogenation of Pd(111) in the presence of NH3 can be linked to the ease of FA deprotonation as well as the stabilization of the decomposition intermediate (i.e., formate) due to the presence of ammonium counterions on the surface. In addition, the presence of a H-bonded ammonia network on the Pd(111) surface increased the hyd...