Hydrogen Storage on Transition-Metal-Decorated Nitrogen-Modified Carbon Nanoribbons

Abstract

Recently synthesized carbon nanoribbons (CNRs) were investigated for hydrogen (H2) storage using first-principles density functional theory calculations. Pristine CNRs exhibited weak H2 adsorption; therefore, the host structure was modified by substituting carbon atoms at the C-H edges with 12 nitrogen atoms, followed by Mn and Y doping to enhance H2 binding. A maximum of five metal atoms could be accommodated on the 12N-CNRs. Electronic structure analysis revealed strong orbital hybridization between the metal atoms and the CNRs, while binding energy calculations confirmed the structural stability of the doped systems. Bader charge analysis further quantified the charge transfer between the metal atoms and the host structure. The average H2 adsorption energies were calculated to be -0.40 eV/H2 for the Mn-doped system and -0.25 eV/H2 for the Y-doped system, which are within the desirable range for reversible hydrogen storage. The maximum theoretical gravimetric storage capacities at 0 K reached 7.48 wt% for the Mn-doped system and 6.55 wt% for the Y-doped system. Under practical conditions of 30 atm and 298.15 K, the storage capacity of the Y-doped system decreased to 6.04 wt%, whereas the Mn-doped system maintained its full capacity of 7.48 wt%. Thermodynamic analysis indicated that H2 adsorption is favored at low temperatures and high pressures, while desorption becomes feasible at elevated temperatures and lower pressures. These results demonstrate that Mn- and Y-doped CNRs satisfy key U.S. Department of Energy requirements for reversible H2 storage and show promise as potential hydrogen storage materials under near-ambient conditions.