Morphological control of mesoporosity and nanoparticles within Co3O4-CuO electrospun nanofibers: quantum confinement and visible light photocatalysis performance

Abstract

The one-dimensional (1D) mesoporous and interconnected nanoparticles (NPs) enriched composite Co3O4-CuO nanofibers (NFs) in the ratio Co:Cu = 1/4 (Co3O4-CuO NFs) composite have been synthesized by electrospinning and calcination of mixed polymeric template. Not merely the mesoporous composite Co3O4-CuO NFs but also single mesoporous Co3O4 NFs and CuO NFs have been produced for comparison. The choice of mixed polymer templates such as polyvinylpyrrolidone (PVP) and polyethylene glycol (PEG) for electrospinning is responsible for the formation of 1D mesoporous NFs. The HR-TEM result showed evolution of interconnected nanoparticles (NPs) and creation of mesoporosity in all electrospun NFs. The quantum confinement is due to NPs within NFs and has been proved by the surface-enhanced Raman scattering (SERS) study and the UV-vis-NRI diffuse reflectance spectra (DRS). The high intense photoluminescence (PL) spectra showing blue shift of all NFs also confirmed the quantum confinement phenomena. The lowering of PL spectrum after mixing of CuO in Co3O4 nanofibers framework (Co3O4-CuO NFs) proved CuO as an efficient visible light response low cost cocatalyst/charge separator. The red shifting of the band gap in composite Co3O4-CuO NFs is due to the internal charge transfer between Co2+ to Co3+ and Cu2+, proved by UV-vis absorption spectroscopy. Creation of oxygen vacancies by mixing of CuO and Co3O4 also prevents the electron-hole recombination and enhances the photocatalytic activity in composite Co3O4-CuO NFs. The photocurrent density, Mott-Schottky (MS), and electrochemical impedance spectroscopy (EIS) studies of all NFs favor the high photocatalytic performance. The mesoporous composite Co3O4-CuO NFs exhibits high photocatalytic activity toward phenolic compounds degradation as compared to the other two NFs (Co3O4 NFs and CuO NFs). The kinetic study of phenolic compounds followed first order rate equation. The high photocatalytic activity of composite Co3O4-CuO NFs is attributed to the formation of mesoporosity and interconnected NPs within NFs framework, quantum confinement, extended light absorption property, internal charge transfer, and effective photogenerated charge separations.