Subsurface-Controlled CO2 Selectivity of PdZn Near-Surface Alloys in H2 Generation by Methanol Steam Reforming

More than skin deep: In spite of their identical 1:1 surface composition, the geometric and electronic structures of a multilayer and monolayer PdZn surface alloy are different, as are their catalytic selectivities. The CO2 selective multilayer alloy features surface ensembles of PdZn exhibiting a “Zn‐up/Pd‐down” corrugation (see picture). These act as “bifunctional” active sites both for water activation and for the conversion of methanol into CO2. On the monolayer alloy CO and not CO2 is produced.