Controlled Formation of Dimers and Spatially Isolated Atoms in Bimetallic Au-Ru Catalysts via Carbon-Host Functionalization

The introduction of a foreign metal atom in the coordination environment of single-atom catalysts constitutes an exciting frontier of active-site engineering, generating bimetallic low-nuclearity catalysts often exhibiting unique catalytic synergies. To date, the exploration of their full scope is thwarted by (i) the lack of synthetic techniques with control over intermetallic coordination, and (ii) the challenging characterization of these materials. Herein, carbon-host functionalization is presented as a strategy to selectively generate Au-Ru dimers and isolated sites by simple incipient wetness impregnation, as corroborated by careful X-ray absorption spectroscopy analysis. The distinct catalytic fingerprints are unveiled via the hydrogen evolution reaction, employed as a probe for proton adsorption properties. Intriguingly, the virtually inactive Au atoms enhance the reaction kinetics of their Ru counterparts already when spatially isolated, by shifting the proton adsorption free energy closer to neutrality. Remarkably, the effect is magnified by a factor of 2 in dimers. These results exemplify the relevance of controlling intermetallic coordination for the rational design of bimetallic low-nuclearity catalysts.

Automated summary

The introduction of foreign metal atoms in the coordination environment of single-atom catalysts has become an exciting frontier in active-site engineering. By functionalizing carbon hosts, Au-Ru dimers and isolated sites can be selectively generated. The distinct catalytic fingerprints of these materials have been revealed through hydrogen evolution reaction, which also showed that inactive Au atoms can enhance the reaction kinetics of Ru counterparts even when spatially isolated.