Tailoring the d-band center of N-doped carbon nanotube arrays with Co4N nanoparticles and single-atom Co for a superior hydrogen evolution reaction

A 3D self-supported integrated electrode, consisting of heteroatomic nitrogen-doped carbon nanotube arrays on carbon cloth with confined ultrafine Co4N nanoparticles and a distribution of anchored single-atom Co, is fabricated via a cobalt-catalyzed growth strategy using dicyandiamide as the nitrogen and carbon source and a layered cobalt hydroxide-nitrate salt as the precursor. The abundance of exposed active sites, namely, the Co4N nanoparticles, single-atom Co, and heteroatomic N-doped carbon nanotubes, and multiple synergistic effects among these components provide suitable tailoring of the d-band center for facilitating vectorial electron transfer and efficient electrocatalysis. Benefiting from the merits of its structural features and electronic configuration, the prepared electrode exhibits robust performance toward the hydrogen evolution reaction with overpotentials of only 78 and 86 mV at 10 mA cm−2 in acidic and basic electrolytes, respectively. Density functional theory calculations and X-ray photoelectron spectroscopy valence band measurements reveal that the effective tailoring of the d-band center by Co4N nanoparticles plays a crucial role in optimizing the hydrogen adsorption free energy to a more thermoneutral value for efficient electrocatalysis. A carbon-based, environmentally friendly catalyst for enhancing the extraction of hydrogen from water has been synthesized by researchers in China. Separating water into its constituent atoms is a scalable method for producing hydrogen and therefore a source of clean energy. Platinum catalysts can enhance electrochemical splitting, but platinum is rare and expensive. Bo Cao from Inner Mongolia University, Hohhot, and co-workers have developed an alternative carbon nanotube-based catalyst that can be fabricated using a “green” process. Carbon nanotubes have been used previously, often in a powder form, from which it is difficult to make the electrodes required in practical applications. The researchers created three-dimensional electrodes on carbon cloth using arrays of nitrogen-doped carbon nanotubes containing cobalt nitride nanoparticles, and confirmed the excellent electrocatalytic properties of the material. A novel 3D self-supported integrated electrode of Co4N@CoSA/N-CNT/CC is designed for admirable HER electrocatalysis. Experiment and theory studies reveal that the suitable d-band center and electron-charge transfer optimized by Co4N nanoparticles and single-atom Co in the electrocatalyst contribute to an excellent performance. This electrode requires overpotentials of only 78 and 86 mV at 10 mA cm−2 in acidic and basic electrolytes, respectively. Notably, Co4N@CoSA/N-CNT/CC also exhibits superior long-term stability in acidic and alkaline medium, the decrease in current density after continuous electrocatalysis for 50 h are only 5% and 11%, respectively.