Unravelling the possibility of hydrogen storage on naphthalene dicarboxylate-based MOF linkers: a theoretical perspective

Abstract

Post-synthetic modification of organic linkers embedded in a metal–organic framework (MOF) is a favourable strategy to improve the storage of hydrogen through physisorption at ambient conditions. Density functional and domain-based local pair natural orbital coupled cluster calculations are conducted to evaluate the feasibility of hydrogen adsorption on open metal sites of a Napthalene Dicarboxylate-based linker. Both alkaline metal ions like Ca²⁺ and Mg²⁺ and transition metal ions like Zn²⁺ and Cd²⁺ are chosen for this study. DFT and DLPNO-CCSD(T) energies reveal that the Napthalene Dicarboxylate systems with open magnesium, zinc and cadmium sites are capable of reversible H₂ binding. However, the adsorption energy with calcium is rather low precluding build-up of H₂ on CaNDC coordination site. Furthermore, local energy decomposition analysis reveals charge transfer interaction is dominant in small ions like magnesium while exchange interaction of same spin electrons governs the complexation energy in transition metals like zinc and cadmium.

GRAPHICAL ABSTRACT

KEYWORDS:

• Hydrogen storage
• physisorption
• density functional theory
• local energy decomposition
• metal–organic framework

Acknowledgements

LR would like to acknowledge DST, India (DST/INSPIRE/04/2017/000446) and Start-up grant ICT-IOCB for financial support.

Disclosure statement

No potential conflict of interest was reported by the author(s).

ORCID

Lisa Roy http://orcid.org/0000-0003-4205-1626

Additional information

Funding

This work was supported by Department of Science and Technology, Ministry of Science and Technology: [Grant Number DST/INSPIRE/04/2017/000446].