Water Enables Efficient CO₂ Capture from Natural Gas Flue Emissions in an Oxidation-Resistant Diamine-Appended Metal–Organic Framework

Supported by increasingly available reserves, natural gas is achieving greater adoption as a cleaner-burning alternative to coal in the power sector. As a result, carbon capture and sequestration from natural gas-fired power plants is an attractive strategy to mitigate global anthropogenic CO₂ emissions. However, the separation of CO₂ from other components in the flue streams of gas-fired power plants is particularly challenging due to the low CO₂ partial pressure (∼40 mbar), which necessitates that candidate separation materials bind CO₂ strongly at low partial pressures (≤4 mbar) to capture ≥90% of the emitted CO₂. High partial pressures of O₂ (120 mbar) and water (80 mbar) in these flue streams have also presented significant barriers to the deployment of new technologies for CO₂ capture from gas-fired power plants. Here, we demonstrate that functionalization of the metal-organic framework Mg₂(dobpdc) (dobpdc⁴⁻ = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) with the cyclic diamine 2-(aminomethyl)piperidine (2-ampd) produces an adsorbent that is capable of ≥90% CO₂ capture from a humid natural gas flue emission stream, as confirmed by breakthrough measurements. This material captures CO₂ by a cooperative mechanism that enables access to a large CO₂ cycling capacity with a small temperature swing (2.4 mmol CO₂/g with ΔT = 100 °C). Significantly, multicomponent adsorption experiments, infrared spectroscopy, magic angle spinning solid-state NMR spectroscopy, and van der Waals-corrected density functional theory studies suggest that water enhances CO₂ capture in 2-ampd-Mg₂(dobpdc) through hydrogen-bonding interactions with the carbamate groups of the ammonium carbamate chains formed upon CO₂ adsorption, thereby increasing the thermodynamic driving force for CO₂ binding. In light of the exceptional thermal and oxidative stability of 2-ampd-Mg₂(dobpdc), its high CO₂ adsorption capacity, and its high CO₂ capture rate from a simulated natural gas flue emission stream, this material is one of the most promising adsorbents to date for this important separation.