Towards bridging thermo/electrocatalytic CO oxidation: from nanoparticles to single atoms

Proton exchange membrane fuel cells (PEMFCs), as a feasible alternative to replace the traditional fossil fuel-based energy converter, contribute significantly to the global sustainability agenda. At the PEMFC anode, given the high exchange current density, Pt/C is deemed the catalyst-of-choice to ensure that the hydrogen oxidation reaction (HOR) occurs at a sufficiently fast pace. The high performance of Pt/C, however, can only be achieved under the premise that high purity hydrogen is used. For instance, in the presence of trace level carbon monoxide, a typical contaminant during H₂ production, Pt is severely deactivated by CO surface blockage. Addressing the poisoning issue necessitates for either developing anti-poisoning electrocatalysts or using pre-purified H₂ obtained via a thermo-catalysis route. In other words, the CO poisoning issue can be addressed by either thermal-catalysis from the H₂ supply side or electrocatalysis at the user side, respectively. In spite of the distinction between thermo-catalysis and electro-catalysis, there are high similarities between the two routes. Essentially, a reduction in the kinetic barrier for the combination of CO to oxygen containing intermediates is required in both techniques. Therefore, bridging electrocatalysis and thermocatalysis might offer new insight into the development of cutting edge catalysts to solve the poisoning issue, which, however, stands as an underexplored frontier in catalysis science. This review provides a critical appraisal of the recent advancements in preferential CO oxidation (CO-PROX) thermocatalysts and anti-poisoning HOR electrocatalysts, aiming to bridge the gap in cognition between the two routes. First, we discuss the differences in thermal/electrocatalysis, CO oxidation mechanisms, and anti-CO poisoning strategies. Second, we comprehensively summarize the progress of supported and unsupported CO-tolerant catalysts based on the timeline of development (nanoparticles to clusters to single atoms), focusing on metal-support interactions and interface reactivity. Third, we elucidate the stability issue and theoretical understanding of CO-tolerant electrocatalysts, which are critical factors for the rational design of high-performance catalysts. Finally, we underscore the imminent challenges in bridging thermal/electrocatalytic CO oxidation, with theory, materials, and the mechanism as the three main weapons to gain a more in-depth understanding. We anticipate that this review will contribute to the cognition of both thermocatalysis and electrocatalysis.