Facile synthesis of nitrogen-containing multiwalled carbon nanotubes as a worth metal-free electrocatalyst for hydrogen evolution reaction and semicarbazide oxidation

Abstract

Studies of metal-free carbon nanostructures prove effective in energy and environmental applications due to their molecular tunability and vast chemical space. Herein, we synthesize nitrogen-containing multi-walled carbon nanotubes (N-MWCNTs) via. acid-catalysed incorporation of 3, 4-diaminopyridine into multi-walled carbon nanotubes (MWCNTs), and demonstrating their efficacy in electrocatalytic hydrogen evolution reaction (HER) and semicarbazide (SCB) oxidation for energy and environmental waste management, respectively. Successful synthesis is further confirmed by analysis techniques, i.e. Fourier transform infrared (FTIR) spectral analysis shows the diminishing OH frequency around 3250 cm⁻¹ in MWCNTs after functionalization and the formation of an OC–NH bond in N-MWCNTs at 1710 cm⁻¹. X-ray diffraction (XRD) confirms the incorporation of N-species, while Raman spectroscopic analysis indicates an increase in the I_D/I_G ratio MWCNTs (∼1) to N-MWCNTs (∼1.25), suggesting more defective sites in the N-MWCNTs nanocomposite. X-ray photoelectron spectroscopy (XPS) reveals peaks at 399.38, 400.49, and 402.05 eV, attributed to pyridinic-N, aromatic amide-N, and protonated amine groups, respectively. N₂ adsorption-desorption studies shows a high Brunauer-Emmett-Teller (BET) surface area for N-MWCNTs (119.22 m²/g) compared to MWCNTs (74.94 m²/g). Linear sweep voltammetry (LSV) profiles demonstrate enhanced activity of N-MWCNTs for both HER and SCB oxidation at an ultralow potential of E = −0.55 V vs RHE at 10 mA/cm², with a lower Tafel slope of 108 mV.dec⁻¹. Moreover, the electrochemical sensing studies indicates on N-MWCNTs were demonstrating an efficient electron transfer to SCB with the lower detection limit of 0.004 μmol. This work provides carbon-based metal-free electrocatalysts for energy harvesting and environmental management.