Activating Hydrogen Evolution Reaction on Carbon Nanotube via Aryl Functionalisation: The Role of Hybrid sp2–sp3 Interface and Curvature

The hydrogen evolution reaction (HER) is a remarkable mechanism which yields the production of hydrogen through a process of water electrolysis. However, the evolution of hydrogen requires highly conductive and stable catalysts, such as the noble metal platinum (Pt). However, the problem lies in the limitations that this catalyst and others of its kind present. Due to limited availability, as well as the costs involved in acquiring such catalysts, researchers are challenged to manufacture catalysts that do not present these limitations. Carbon nanotubes (CNTs), which are nanomaterials, are known to have a wide range of applications. However, specifically, the pristine carbon nanotube is not suitable for the HER due to the binding free energy of its positive H-atoms. Hence, for the first time, we demonstrated the use of the proposed aryl-functionalised catalysts, i.e., Aryl-L@SWCNT (L = Br, CCH, Cl, CO2CH3, F, I, NO2, or t-butyl), along with the effect of the sp2–sp3 hybridised interface through the density functional theory (DFT). We performed calculations of single-walled carbon nanotubes with multiple aryl functional groups. By employing the DFT calculations, we proved that the curvature of the nanotubes along with the proposed aryl-functionalised catalysts had a noteworthy effect on the performance of the HER. Our study opens the door to investigating a promising group of catalysts for sustainable hydrogen production.