NMR studies of adsorption and diffusion in porous carbonaceous materials

TL;DR

This paper reviews how NMR spectroscopy and modelling techniques are used to study adsorption and diffusion in porous carbon materials, providing insights into their structure and behavior for various applications.

Contribution

It offers a comprehensive overview of recent methodological advances and applications of NMR and modelling in understanding porous carbon materials.

Findings

NMR can distinguish in-pore from ex-pore species based on chemical shifts.

Theoretical models help interpret NMR data on adsorption phenomena.

Combined experiments and simulations reveal detailed adsorbate behavior.

Abstract

Porous carbonaceous materials have many important industrial applications including energy storage, water purification, and adsorption of volatile organic compounds. Most of their applications rely upon the adsorption of molecules or ions within the interior pore volume of the carbon particles. Understanding the behaviour and properties of adsorbate species on the molecular level is therefore key for optimising porous carbon materials, but this is very challenging owing to the complexity of the disordered carbon structure and the presence of multiple phases in the system. In recent years, NMR spectroscopy has emerged as one of the few experimental techniques that can resolve adsorbed species from those outside the pore network. Adsorbed, or "in-pore" species give rise to resonances that appear at lower chemical shifts compared to their free (or "ex-pore") counterparts. This shielding effect arises primarily due to ring currents in the carbon structure in the presence of a magnetic field, such that the observed chemical shift differences upon adsorption are nucleus-independent to a first approximation. Theoretical modelling has played an important role in rationalising and explaining these experimental observations. Together, experiments and simulations have enabled a large amount of information to be gained on the adsorption and diffusion of adsorbed species, as well as on the structural and magnetic properties of the porous carbon adsorbent. Here, we review the methodological developments and applications of NMR spectroscopy and related modelling in this field, and provide perspectives on possible future applications and research directions.