Carbon Monoxide Mediated Hydrogen Release from PtCu Single-Atom Alloys: The Punctured Molecular Cork Effect

Pt-based materials are used extensively in heterogeneous catalytic processes, but they are notoriously susceptible to poisoning by CO. In contrast, highly dilute binary alloys formed of isolated Pt atoms in a Cu metal host, known as PtCu single-atom alloys (SAAs), are more resilient to CO poisoning during catalytic hydrogenation reactions. In this article, we describe how CO affects the adsorption and desorption of H 2 from a model PtCu(111) SAA surface and gain a microscopic understanding of these species’ interaction at the Pt atom active sites. By combining temperature-programmed desorption and scanning tunneling microscopy with first-principles kinetic Monte Carlo, we identify CO as a Pt site blocker that prevents the low temperature adsorption and desorption of H 2, the so-called molecular cork effect, first realized when examining PdCu SAAs. Intriguingly, for the case of PtCu, H 2 desorption occurs before CO release is detected. Furthermore, desorption experiments show a nonlinear relationship between CO coverage of the Pt sites and H 2 desorption peak temperature. When all the Pt atoms are saturated by CO, a very sharp H 2 desorption feature is observed 55 K above the regular desorption temperature of H 2 . Our simulations reveal that the origin of these effects is the fact that desorption of just one CO molecule from a Pt site facilitates the fast release of many molecules of H 2 . In fact, just 0.7% of the CO adsorbed at Pt sites has desorbed when the H 2 desorption peak maximum is reached. The release of H 2 from CO-corked PtCu SAA surfaces is analogous to the escape of gas from a pressurized container with a small puncture. Given that small changes in CO surface coverage lead to large changes in H 2 evolution energetics, the punctured molecular cork effect must be considered when modeling reaction mechanisms on similar alloy systems.