The Role of Density Functional Theory Methods in the Prediction of Nanostructured Gas-Adsorbent Materials

TL;DR

This review critically examines the application of density functional theory (DFT) in predicting nanostructured gas-adsorbent materials, highlighting its strengths, limitations, and best practices for improved material design.

Contribution

It provides a comprehensive analysis of DFT performance in modeling GAM, discusses unresolved controversies, and proposes best practices for future research in hydrogen storage and carbon capture.

Findings

DFT has been crucial in GAM design but has limitations in accuracy.

Benchmark studies often do not generalize well to real materials.

Effective approaches can improve DFT predictions for gas-adsorption phenomena.

Abstract

With the advent of new synthesis and large-scale production technologies, nanostructured gas-adsorbent materials (GAM) like carbon nanocomposites and metal-organic frameworks are becoming increasingly more influential in our everyday lives. First-principles methods based on density functional theory (DFT) have been pivotal in establishing the rational design of GAM, a factor which has tremendously boosted their development. However, DFT methods are not perfect and due to the stringent accuracy thresholds demanded in modelling of GAM (i.e., exact binding energies to within ~0.01 eV) these techniques may provide erroneous conclusions in some challenging situations. Examples of problematic circumstances include gas-adsorption processes in which both electronic long-range exchange and nonlocal correlations are important, and systems where many-body energy and Coulomb screening effects cannot be disregarded. In this critical review, we analyse recent efforts done in the assessment of the performance of DFT methods in the prediction and understanding of GAM. Our inquiry is constrained to the areas of hydrogen storage and carbon capture and sequestration, for which we expose a number of unresolved modelling controversies and define a set of best practice simulation principles. Also, we identify the subtle problems found in the generalization of DFT benchmark studies performed in model cluster systems to real materials, and discuss effective approaches to circumvent them. The increasing awareness of the strengths and imperfections of DFT methods in the simulation of gas-adsorption phenomena should lead in the medium term to more precise, and hence even more fruitful, ab initio engineering of GAM.