Experimental and computational studies of formic acid dehydrogenation over PdAu: influence of ensemble and ligand effects on catalysis

Abstract

The critical role of the ligand effect and ensemble effect in enhancing formic acid (FA) dehydrogenation over PdAu catalysts was highlighted by both experimental and theoretical studies. FA dehydrogenation energy was calculated by DFT on PdAu model catalysts of different surface atomic arrangements. The Pd₃Au₁ surface exhibited the lowest reaction energy and kinetic barrier for FA dehydrogenation among four different PdAu surfaces. The Pd trimer played a critical role in stabilizing reaction intermediates. The experimental FA dehydrogenation activity of three different PdAu catalysts supported the theoretical results. In addition, the electronic interaction between the surface and subsurface layers also proved to contribute to the improved catalytic activity of PdAu catalysts via modification of Pd d states.