Abstract
This review critically examines recent Density Functional Theory (DFT) studies on hydrogen storage in Metal-Organic Frameworks (MOFs). We focus on how DFT provides fundamental insights into the electronic-level interactions governing hydrogen uptake. The analysis reveals that MOFs can be rationally designed for enhanced hydrogen storage capacity by tuning their structural and electronic properties. DFT has found several key techniques, including changing pore size and linker chemistry, substituting or functionalizing frameworks with light metals such as Li and Sc, and introducing open metal sites. The article discusses how DFT simulations accurately anticipated optimal binding energies for H2 physisorption and highlighted the importance of backdonation from metal d-orbitals to hydrogen σ∗ orbitals in strengthening interactions. Furthermore, we show that DFT-guided material design results in anticipated capacities that meet or surpass DOE requirements for onboard hydrogen storage. This work underscores the indispensable role of DFT as a predictive tool, enabling the efficient screening and development of MOF materials with superior performance for the future hydrogen economy.