Hydrogen adsorption in metal-organic frameworks: the role of nuclear quantum effects

TL;DR

This study investigates how nuclear quantum effects influence hydrogen adsorption in various metal-organic frameworks using advanced density-functional theory methods, revealing significant quantum and many-particle effects.

Contribution

It introduces a validated quantum density-functional approach to accurately model hydrogen adsorption in MOFs, considering nuclear quantum effects explicitly.

Findings

Quantum effects significantly impact hydrogen adsorption predictions.

GC-QLDFT results align well with experimental data.

Quantum and many-particle effects become more pronounced at low temperatures and high pressures.

Abstract

The role of nuclear quantum effects on the adsorption of molecular hydrogen in metal-organic frameworks (MOFs) has been investigated on grounds of Grand-Canonical Quantized Liquid Density-Functional Theory (GC-QLDFT) calculations. For this purpose, we have carefully validated classical H2 -host interaction potentials that are obtained by fitting Born-Oppenheimer ab initio reference data. The hydrogen adsorption has first been assessed classically using Liquid Density-Functional Theory (LDFT) and the Grand-Canonical Monte Carlo (GCMC) methods. The results have been compared against the semi-classical treatment of quantum effects by applying the Feynman-Hibbs correction to the Born-Oppenheimer-derived potentials, and by explicit treatment within the Grand-Canonical Quantized Liquid Density-Functional Theory (GC-QLDFT). The results are compared with experimental data and indicate pronounced quantum and possibly many-particle effects. After validation calculations have been carried out for IRMOF-1 (MOF-5), GC-QLDFT is applied to study the adsorption of H2 in a series of MOFs, including IRMOF-4, -6, -8, -9, -10, -12, -14, -16, -18 and MOF-177. Finally, we discuss the evolution of the H2 quantum fluid with increasing pressure and lowering temperature.