PNNL

Abstract

Both electrocatalytic hydrogenation (ECH) and thermal hydrogenation (TH) of phenol by Pt and Rh show a roll-over in rate with increasing temperature without changing the principal reaction pathways. The negative effect of temperature for aqueous-phase phenol H2 and electrocatalytic hydrogenation on Pt and Rh is deduced to be due to the unexpected buildup of dehydrogenated phenol adsorbates, which block active sites. Rates of ECH and TH increase similarly with increasing hydrogen chemical potential whether induced by applied potential or H2 pressure, both via increasing H coverage, and indirectly by removing site blockers, a very strong effect at high temperature. This enables unprecedented rates in the TH of phenol at these temperatures.