How Absorbed Hydrogen Affects the Catalytic Activity of Transition Metals

Heterogeneous catalysis is commonly governed by surface active sites. Yet, areas just below the surface can also influence catalytic activity, for instance, when fragmentation products of catalytic feeds penetrate into catalysts. In particular, H absorbed below the surface is required for certain hydrogenation reactions on metals. Herein, we show that a sufficient concentration of subsurface hydrogen, Hsub, may either significantly increase or decrease the bond energy and the reactivity of the adsorbed hydrogen, Had, depending on the metal. We predict a representative reaction, ethyl hydrogenation, to speed up on Pd and Pt, but to slow down on Ni and Rh in the presence of Hsub, especially on metal nanoparticles. The identified effects of subsurface H on surface reactivity are indispensable for an atomistic understanding of hydrogenation processes on transition metals and interactions of hydrogen with metals in general. Understanding hydrogenation on transition metals: Subsurface hydrogen, Hsub, is shown to significantly influence the stability and the reactivity of the adsorbed hydrogen in two different ways. Calculations on a representative reaction, ethyl hydrogenation, show that it is accelerated on Pd and Pt, but slowed down on Ni and Rh in the presence of Hsub.