Interfacial engineering Pb skin-layer at Rh surface to promote ethanol electrooxidation into CO2 in alkaline media

Rh is recently regarded as the promising electrocatalyst for ethanol oxidation into CO 2 due to its high activity of splitting C–C bond, whereas the further oxidation of as-generated C1 species (CO and CH x ) is pretty sluggish at Rh surface. To solve this, here the oxophile Pb skin-layer is inhabited at Rh nanoparticles to obtain the Pb@Rh core-shell structure with controllable Pb coverage ( θ Pb ), expecting to tune the surface reactivity of ethanol oxidation reaction (EOR) according to the Langmuir-Hinshelwood Mechanism as well as the strain effect. Fortunately, the as-obtained Pb@Rh/C catalysts indeed significantly enhance the catalysis performance of EOR, the optimal mass activity is ca. 1450 mA mg -1 metal when θ Pb is ca. 0.53 (Pb 0.53 @Rh), being ca. 13 times higher than pristine Rh catalyst. Meanwhile, as much as ca. 57% of the initial EOR current remains even after a 20,000-s durability measurement. And the apparent C1 pathway faraday efficiency (CO 2 selectivity) is also estimated to be ca. 21% at Pb 0.53 @Rh surface. This work can provide a simple and promising protocol to tune the surface reactivity by interfacial engineering manipulation. Pb@Rh core-shell structure were rationally designed to obtain upmost EOR mass activity of 1450 mA mg-1 catalyst and as high as 21% CO 2 selectivity. • Manipulating Pb skin-layer at Rh surface through the simple immersion-reduction strategy. • As-generated Pb@Rh core-shell interfaces leading to the bifunctional effect. • EOR mass activity at Pb@Rh showing upmost ca. 13-times enhancement than pristine Rh. • EOR activity still remaining 57% even after 20,000 s measurement. • Apparent C1 pathway faraday efficiency being as high as 21%.