Thermodynamic Screening of Metal-Substituted MOFs for Carbon Capture

TL;DR

This study computationally screens 36 metal-substituted MOFs to identify promising candidates for carbon capture based on their CO2 adsorption enthalpy, providing insights into electronic and structural factors influencing performance.

Contribution

It introduces a high-throughput vdW-DF computational screening method for metal-substituted MOFs, identifying candidates with optimal CO2 adsorption enthalpy for carbon capture.

Findings

13 compounds within the targeted enthalpy window 40-75 kJ/mol.

Partial charge on metal sites correlates with CO2 affinity.

vdW-DF calculations outperform other DFT functionals in accuracy.

Abstract

Metal-organic frameworks (MOFs) have emerged as promising materials for carbon capture applications due to their high CO2 capacities and tunable properties. Amongst the many possible MOFs, metal-substituted compounds based on M-DOBDC and M-HKUST-1 have demonstrated amongst the highest CO2 capacities at the low pressures typical of flue gasses. Here we explore the possibility for additional performance tuning of these compounds by computationally screening 36 metal-substituted variants (M = Be, Mg, Ca, Sr, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, W, Sn, and Pb) with respect to their CO2 adsorption enthalpy, $\Delta$H (T=300K). Supercell calculations based on van der Waals density functional theory (vdW-DF) yield enthalpies in good agreement with experimental measurements, out-performing semi-empirical (DFT-D2) and conventional (LDA and GGA) functionals. Our screening identifies 13 compounds having $\Delta$H values within the targeted thermodynamic window 40 $\leq$ $\Delta$H $\leq$ 75 kJ/mol: 8 are based on M-DODBC (M=Mg, Ca, Sr, Sc, Ti, V, Mo, and W), and 5 on M-HKUST-1 (M= Be, Mg, Ca, Sr and Sc). Variations in the electronic structure and the geometry of the structural building unit are examined and used to rationalize trends in CO2 affinity. In particular, the partial charge on the coordinatively unsaturated metal sites is found to correlate with $\Delta$H, suggesting that this property may be used as a simple performance descriptor. The ability to rapidly distinguish promising MOFs from those that are "thermodynamic dead-ends" will be helpful in guiding synthesis efforts towards promising compounds.