Single-atom catalyst for high-performance methanol oxidation

It is still challenging to engineer single-atom catalysts for electrocatalytic methanol oxidation. Here, the authors design Pt single atom supported on RuO2 for highly active methanol oxidation in contrast to the inert Pt single atom supported on carbon. Single-atom catalysts have been widely investigated for several electrocatalytic reactions except electrochemical alcohol oxidation. Herein, we synthesize atomically dispersed platinum on ruthenium oxide (Pt-1/RuO2) using a simple impregnation-adsorption method. We find that Pt-1/RuO2 has good electrocatalytic activity towards methanol oxidation in an alkaline media with a mass activity that is 15.3-times higher than that of commercial Pt/C (6766 vs. 441 mA mg(Pt)(-1)). In contrast, single atom Pt on carbon black is inert. Further, the mass activity of Pt-1/RuO2 is superior to that of most Pt-based catalysts previously developed. Moreover, Pt-1/RuO2 has a high tolerance towards CO poisoning, resulting in excellent catalytic stability. Ab initio simulations and experiments reveal that the presence of Pt-O-3f (3-fold coordinatively bonded O)-Ru-cus (coordinatively unsaturated Ru) bonds with the undercoordinated bridging O in Pt-1/RuO2 favors the electrochemical dehydrogenation of methanol with lower energy barriers and onset potential than those encountered for Pt-C and Pt-Ru.

Automated summary

In this study, Pt single atom supported on RuO2 exhibits highly active methanol oxidation compared to Pt single atom supported on carbon. The newly synthesized Pt-1/RuO2 catalyst shows significantly improved mass activity for methanol oxidation in alkaline media, surpassing most previously developed Pt-based catalysts. Additionally, Pt-1/RuO2 demonstrates high tolerance to CO poisoning and excellent catalytic stability, with the presence of unique Pt-O-3f-Ru-cus bonds contributing to lower energy barriers for the electrochemical dehydrogenation of methanol.