CO₂ from carbonate-based capture solutions requires a substantial energy input. Replacing this step with (bi)carbonate electrolysis has been commonly proposed as an efficient alternative that coproduces CO/syngas. Here, we assess the feasibility of directly integrating air contactors with (bi)carbonate electrolyzers by leveraging process, multiphysics, microkinetic, and technoeconomic models. We show that the copresence of CO₃^2- with HCO₃^- in the contactor effluent greatly diminishes the electrolyzer performance and eventually results in a reduced CO₂ capture fraction to ≤1%. Additionally, we estimate suitable effluents for (bi)carbonate electrolysis to require 5-14 times larger contactors than conventionally needed contactors, leading to unfavorable process economics. Notably, we show that the regeneration of the capture solvent inside (bi)carbonate electrolyzers is insufficient for CO₂ recapture. Thus, we suggest process modifications that would allow this route to be operationally feasible. Overall, this work sheds light on the practical operation of integrated direct air capture with (bi)carbonate electrolysis.

Renewably driven, electrochemical conversion of carbon dioxide into value-added products is expected to be a critical tool in global decarbonization. However, theoretical studies based on the computational hydrogen electrode largely ignore the nonlinear effects of the applied potential on the calculated results, leading to inaccurate predictions of catalytic behavior or mechanistic pathways. Here, we use grand canonical density functional theory (GC-DFT) to model electrochemical CO2 reduction (CO2R) over metal- and nitrogen-doped graphene catalysts (MNCs) and explicitly include the effects of the applied potential. We used GC-DFT to compute the CO2 to CO reaction intermediate energies at -0.3, -0.7, and -1.2 VSHE catalyzed by MNCs each doped with 1 of the 10 3d block metals coordinated by four pyridinic nitrogen atoms. Our results predict that Sc-, Ti-, Co-, Cu-, and Zn-N4Cs effectively catalyze CO2R at moderate to large reducing potentials (-0.7 to -1.2 VSHE). ZnN4C is a particularly promising electrocatalyst for CO2R to CO both at low and moderate applied potentials based on our thermodynamic analysis. Our findings also explain the observed pH independence of CO production over FeN4C and predict that the rate-determining step of CO2R over FeN4C is not *CO2- formation but rather *CO desorption. Additionally, the GC-DFT-computed density of states analysis illustrates how the electronic states of MNCs and adsorbates change non-uniformly with applied potential, resulting in a significantly increased *CO2- stability relative to other intermediates and demonstrating that the formation of the adsorbed *CO2- anion is critical to CO2R activation. This work demonstrates how GC-DFT paves the way for physically realistic and accurate theoretical simulations of reacting electrochemical systems.