Effluent degradation followed hydrogen production using near-infrared sensitized nanocomposite of reduced nanographene oxide under visible light

Abstract

The purpose of this research work is to synthesize near-infrared dye-sensitized nanocomposites with core-shell nanostructures of titanium dioxide/reduced nanographene oxide (TiO₂/r-NGO) to be an effective photocatalyst for effluent degradation followed hydrogen generation under visible light irradiation. The generation of hydrogen using photocatalysts has been intensely researched for the effective utilization of hydrogen in a controlled way. The mechanistic pathway for both hydrogen generation and effluent degradation utilizes the electrons generated through photoexcitation during dye sensitization. For this reason, the squaraine dyes were synthesized by the C-H-direct arylation method and made the nanocomposites with self-assembled core/shell nanocomposites (r-NGOT), where TiO₂ serves as the core and r-NGO as the shell. Due to the lack of anchoring groups, VJ-Q was only adsorbed on the surface of r-NGOT through π-π stacking, which is confirmed by Fourier transformed-infrared spectroscopy, X-ray photoelectron spectroscopy, high resolution-transmission electron microscopy, and electron energy loss spectroscopy. The optical absorption spectra of VJ-Q/r-NGOT nanocomposites measured with diffuse reflectance UV/visible absorption spectroscopy covers the whole range of visible light wavelengths up to 800 nm. During the photocatalytic activity, VJ-Q/r-NGOT/Pt followed a ligand-to-metal-charge transfer (LMCT) type mechanism for the electron transfer to the core-shell nanostructure. This mechanistic pathway is utilized for the effluent dye degradation followed hydrogen generation through water splitting. The photocatalytic efficiency of the nanocomposite with adsorbed dye is superior to that of dye-TiO₂ due to the large surface area provided by r-NGO and the prevention of dye aggregation. The work is significant due to the limited research works that are carried under dye-sensitized nanocomposites that have been utilized for both dye degradation and hydrogen generation.

Keywords: C-H-arylated squaraine dye; Extended light absorption; Ligand-to-metal charge transfer; Photocatalytic degradation; Photochemical activity; π-π stacking.