Electrocatalytic activity of metal encapsulated, doped, and engineered fullerene-based nanostructured materials towards hydrogen evolution reaction

The utilization of nanostructured materials as efficient catalyst for several processes has increased tremendously, and carbon-based nanostructured materials encompassing fullerene and its derivatives have been observed to possess enhanced catalytic activity when engineered with doping or decorated with metals, thus making them one of the most promising nanocage catalyst for hydrogen evolution reaction (HER) during electro-catalysis. Prompted by these, and the reported electrochemical, electronic and stability advantage, an attempt is put forward herein to inspect the metal encapsulated, doped, and decorated dependent HER activity of C(24) engineered nanostructured materials as effective electro-catalyst for HER. Density functional theory (DFT) calculations have been utilized to evaluate the catalytic hydrogen evolution reaction activity of four proposed bare systems: fullerene (C(24)), calcium encapsulated fullerene (Ca(enc)C(24)), nickel-doped calcium encapsulated fullerene (Ni(dop)Ca(enc)C(24)), and silver decorated nickel-doped calcium encapsulated (Ag(dec)Ni(dop)Ca(enc)C(24)) engineered nanostructured materials at the TPSSh/GenECP/6-311+G(d,p)/LanL2DZ level of theory. The obtained results divulged that, a potential decrease in energy gap (E(gap)) occurred in the bare systems, while a sparing increase was observed upon adsorption of hydrogen onto the surfaces, these surfaces where also observed to maintain the least E(H–L) gap while the Ag(dec)Ni(dop)Ca(enc)C(24) surface exhibited an increased electrocatalytic activity when compared to others. The results also showed that the electronic properties of the systems evinced a correspondent result with their electrochemical properties, the Ag-decorated surface also exhibited a proficient adsorption energy [Formula: see text] and Gibb’s free energy (ΔG(H)) value. The engineered Ag-decorated and Ni-doped systems were found to possess both good surface stability and excellent electro-catalytic property for HER activities.