Designing Undercoordinated Ni-Nx and Fe-Nx on Holey Graphene for Electrochemical CO2 Conversion to Syngas

In this study, we propose a top-down approach for the controlled preparation of undercoordinated Ni-N-x (Ni-hG) and Fe-N-x (Fe-hG) catalysts within a holey graphene framework, for the electrochemical CO2 reduction reaction (CO2RR) to synthesis gas (syngas). Through the heat treatment of commercial-grade nitrogendoped graphene, we prepared a defective holey graphene, which was then used as a platform to incorporate undercoordinated single atoms via carbon defect restoration, confirmed by a range of characterization techniques. We reveal that these Ni-hG and Fe-hG catalysts can be combined in any proportion to produce a desired syngas ratio (1-10) across a wide potential range (-0.6 to -1.1 V vs RHE), required commercially for the Fischer-Tropsch (F-T) synthesis of liquid fuels and chemicals. These findings are in agreement with our density functional theory calculations, which reveal that CO selectivity increases with a reduction in N coordination with Ni, while unsaturated Fe-N-x sites favor the hydrogen evolution reaction (HER). The potential of these catalysts for scale up is further demonstrated by the unchanged selectivity at elevated temperature and stability in a high-throughput gas diffusion electrolyzer, displaying a high-mass-normalized activity of 275 mA mg(-1) at a cell voltage of 2.5 V. Our results provide valuable insights into the implementation of a simple top-down approach for fabricating active undercoordinated single atom catalysts for decarbonized syngas generation.