(704e) Two Dimensional Ferroelectric-Based Catalysts for Enhanced Carbon Dioxide Reduction

The electrochemical CO₂ reduction reaction (CO2RR), which can transform CO₂ to other C1 or multicarbon products, has been proposed as a route to combat global warming and produce value-added fuels; however, a lack of efficient catalysts limits its implementation. Here, we use DFT calculations to show that two dimensional ferroelectrics (2DFEs, monolayers having switchable spontaneous electric polarizations) can be used to overcome limiting scaling relationships and break the Sabatier principle, leading to enhanced CO2RR propensity. We first investigated the 2DFE MXene Y₂CO₂ and demonstrated that switching the polarization can (1) tune the binding strength of CO₂ or CO leading to preferential adsorption, and (2) alters the thermodynamically favored reaction pathway and product selectivity of CO₂ reduction to C1 products (methanol, formic acid, CO, methane) owing to differing stability of the *COOH versus *CHOO intermediates. Second, we show that heterostructures combining the catalytic properties of 2D-supported SACs and DACs with the switchable polarization of 2DFEs can exhibit higher efficiency and selectivity for CO2RR than existing catalysts. We investigated the CO2RR on SAC and DAC-doped graphene interfaced with the 2DFE In₂Se₃. In this case, the reduction of CO₂ to CO is greatly enhanced compared to the free-standing doped graphene layer regardless of the SAC/DAC coordination environment. Furthermore, the In₂Se₃ layer makes C-C coupling between two adsorbed species on the DAC-doped graphene significantly more favorable, potentially leading to enhanced production of C2 products like ethanol and ethylene. Finally, we show that these results stem from an asymmetry in the surface electron density between the poled up and poled down states of the 2DFE, allowing for the tuning of surface adsorption and intermediate stability. Overall, we demonstrate how the switchable properties of 2DFEs provides a unique route to overcome issues limiting CO2RR catalysis.