The high catalytic activity of Pt is accompanied by a high affinity for CO, making it extremely susceptible to poisoning. Such CO poisoning limits the use of proton exchange membrane fuel cells. In this work, using global minima search techniques and exhaustive electronic structure characterization, the dopant concentration is pinpointed as a crucial factor to improve the CO tolerance of Pt catalysts. By investigating the PtGe nanoclusters of different sizes and compositions, we found that, for those clusters with roughly the same amount of Pt and Ge, the binding to CO is weakened significantly. The uniqueness of the PtGe equimolar clusters is traced down to the electronic effects. The strong covalency and electrostatic stabilization arising from the advantageous Pt–Ge mixing make the equimolar clusters highly resistant toward CO poisoning and therefore more durable. Importantly, the novel catalysts not only are more resistant to deactivation but also remain catalytically active toward hydrogen oxidation. Representative clusters are additionally deposited on graphene with a pentagon–octagon–pentagon (5-8-5) reconstructed divacancy. The remarkable results of free-standing clusters hold true for surface mounted clusters, in which the interaction with CO is dramatically weakened for those compounds with a Pt:Ge ratio of 1:1. Our results demonstrate that Ge can be a promising alloying agent to mitigate the deactivation of Pt and that the dopant concentration is a critical factor in the design of advanced catalysts.
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2022
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