Metal-Decorated C8 Quantum Dots as Lightweight Hydrogen Storage Materials: A Comprehensive DFT Study

Lightweight, efficient, and reversible hydrogen storage materials are critical for the advancement of hydrogen-based energy technologies. In this work, we present a comprehensive density functional theory (DFT) investigation of hydrogen storage in pristine and metal-decorated C8 carbon quantum dots (CQDs), representing ultrasmall, highly curved nanomaterials at the molecular–nanoscale interface. Lithium, magnesium, and titanium were investigated as representative decorating metals to tailor hydrogen adsorption strength and reversibility. The pristine C8 quantum dot is structurally stable but exhibits negligible hydrogen affinity (−0.062 eV per H2), rendering it unsuitable for practical storage applications. In contrast, metal decoration significantly enhances hydrogen adsorption while preserving molecular H2 physisorption, yielding optimal single-molecule adsorption energies of −0.172, −0.304, and −0.451 eV for Li-, Mg-, and Ti-CQDs, respectively. Sequential adsorption analysis indicates exceptionally high hydrogen uptakes of up to 18 H2 molecules for Li-CQD and 20 H2 molecules for both Mg- and Ti-CQDs, corresponding to very high theoretical gravimetric capacities. Energy decomposition and interaction region analyses demonstrate that hydrogen uptake proceeds via a cooperative physisorption mechanism driven by dispersion, electrostatic, and polarization interactions, strongly enhanced by quantum confinement and extreme curvature effects inherent to the CQD. Grand canonical thermodynamic modeling confirms fully reversible hydrogen storage under practical temperature and pressure conditions. Among the systems studied, Mg-CQD exhibits the most favorable balance between adsorption strength and desorption accessibility, delivering a remarkable reversible gravimetric hydrogen storage capacity of 21.7 wt%, significantly surpassing most metal-decorated graphene-, fullerene-, and carbon nanotube-based materials reported to date. These results establish metal-decorated C8 quantum dots as a new class of high-performance nanomaterials for reversible hydrogen storage and demonstrate the potential of ultrasmall carbon quantum dots to overcome the long-standing trade-off between hydrogen uptake and reversibility in nanostructured storage media.