High-throughput computational screening of functionalized MOFs for energy-efficient CO2 capture: Balancing selective CO2 adsorption performance and energy inputs

The rational design of high-performance CO2 adsorbents remains a critical challenge in addressing global carbon emissions, with metal-organic frameworks (MOFs) emerging as promising candidates due to their tunable pore environments. However, the lack of systematic guidelines for functional group selection has hindered their practical implementation in carbon capture applications. Here, this gap was addressed by developing a comprehensive design framework through high-throughput computational screening. Through construction of a topology-directed database of 4797, integrating 10 metal centers with 144 functionalized ligands (18 ligands modified by –NH2, –NO2, –CH3, –CF3, –SH2, –SO2, –OH, and –OLi) across 36 topologies, the fundamental structure–property relationships governing CO2 capture performance was established. Multi-metric evaluation reveals that –NO2, –SO2, and –OLi dramatically enhance CO2 selectivity over CH4/N2 via selectivity (Sads), working capacity (ΔN), adsorbent performance score (APS), sorbent selection parameter (Ssp), and renewability R. Specially, ΔN rises from 2.34 (pristine) to 5.91–7.94 mmol g−1 and Sads surges from 24.94/40.36 to 121.11/176.87 (–NO2), 149.94/215.54 (–SO2), and 58.64/267.44 (–OLi). Besides, the critical trade-off between adsorption strength and renewability demonstrates that enhanced performance comes at the cost of reduced renewability, where stronger CO2 affinity (isosteric heat of −29.15, −29.96, and −30.09 for –NO2, –SO2, and –OLi) compromises renewability (R reduced by ∼50 %). To resolve this trade-off, a novel energy efficiency (η) metric was introduced, which holistically evaluates both adsorption performance (Sads, ΔN, APS, Ssp, and R) and energy inputs (desorption heat, pressure-swing energy, net loss). This leads to the identification of –SO2 as the optimal functional group that balances exceptional CO2 capture (η = 6.17/12.78 for CO2 over CH4/N2), surpassing the second higher of 4.74/8.80 in –CF3 and 0.99/2.18 in non-functionalized counterparts. Adopting high-throughput computational screening methods, this work provides both fundamental insights into host–guest interactions in functionalized MOFs and a practical framework for designing next-generation adsorbents, bridging the gap between materials discovery and process engineering considerations in carbon capture technologies.