Intermetallic synergy in platinum–cobalt electrocatalysts for selective C–O bond cleavage

Catalysts with tailored structures are crucial to determine the selectivity of chemical reactions. However, the design of catalyst structures for the selective cleavage of hydroxylic C–O(H) bonds while retaining etheric C–O(R) bonds remains a challenge and needs to be comprehensively explored. Here we report a series of mesoporous-carbon-supported platinum–cobalt (Pt–Co) bimetallic electrocatalysts in which different intermetallic interactions between Pt and Co species result in different hydrodeoxygenation and hydrogenation routes. Notably, Pt nanoparticles decorated with Co single atoms afford the selective cleavage of the C–O(H) bond in guaiacol and other lignin derivatives adjacent to an etheric C–O(R) bond with ether selectivities of >72.1%, and also work extensively for various other substrates with different substituents. This work highlights that a thorough understanding of the structure–performance relationship is crucial to rationally design and construct suitable catalysts with tailored sites for desired catalytic reactions. Being able to selectively derive desired compounds from biomass feedstock is very challenging. Now the selectivity of Pt–Co catalysts for the electroreduction of guaiacol and other lignin-derived substrates is shown to depend on the Co speciation and preferential C–OH cleavage can be obtained, retaining the C–OR group.