Titanium dioxide is a widely-investigated semiconductor photocatalyst due to its wide availability and low cost. Although it has been successfully used in the photocatalytic treatment of various organics in wastewater, it remains a challenge to modify its structure to achieve enhanced catalytic properties at a wider light spectrum. Doping with transition metals was seen to narrow its optical band gap yet synthesis routes have been largely limited to the use of high-end equipment. Herein we demonstrate the use of a simpler one-pot approach to synthesize nanoporous arrays of silver-doped titanium dioxide nanotubes (Ag-TiNTs) by double anodization of titanium sheets. The synthesized Ag-TiNTs have an average inner diameter of 58.68 nm and a wall thickness of 16.46 nm. ATR-FTIR spectroscopy revealed its characteristic peaks attributed to O-Ti-O bonds. Silver doping increased the lattice volume and crystallite size of anatase with a corresponding decrease in the degree of crystallinity due to the introduction of impurity Ag atoms in its tetragonal structure. Silver was homogeneously distributed across the nanotube surface at an average loading of 1.41 at. %. The synthesized Ag-TiNTs were shown to have a superior photoelectrocatalytic activity in degrading C.I. Basic Blue 9 under UV illumination with a pseudo-first-order kinetic rate of 1.0253 x 10-2 min-1. Most importantly, the Ag-TiNTs are photoelectrocatalytically-active even at a low Ag loading.

Humic acid - functionalized silver nanoparticles (HA-AgNPs) were successfully synthesized and used to detect Cu (II) ions in aqueous solutions. The HA-AgNPs was shown to have an average hydrodynamic diameter of 101.4 nm and a polydispersity index of 0.447. The absorbance spectra of HA-AgNPs showed the characteristic local surface plasmon resonance (LSPR) peak of AgNPs at 408.3 nm. Addition of Cu (II) in the HA-AgNPs led to their agglomeration as evidenced by the change in their surface morphology and their corresponding optical absorbance spectra. The synthesized HA-AgNPs showed a strong linear response for Cu (II) concentrations in the range of 0.00 – 1.25 mM with a limit of detection (LoD) of 4.4428 ± 0.1091 mg L-1, a limit of quantification (LoQ) of 14.8094 ± 0.3636 mg L-1, and a limit of blank (LoB) of 0.1214 ± 0.0065 mg L-1. Statistical analysis showed that this calibration curve could be used to quantify Cu (II) concentrations within a 95% confidence level. Furthermore, HA-AgNPs was found to be selective for Cu (II) detection based on the selectivity study against common metal ions found in drinking water. This shows that the synthesized HA-AgNPs can be used as an environment-friendly colorimetric nanosensor for rapid and point-of-need quantification of Cu (II) ions in aqueous media.

Highly-organized one-dimensional arrays of copper-doped titanium dioxide nanotubes (Cu-TiNTs) were synthesized in a one-pot approach by double anodization of titanium sheets. Field-emission scanning electron microscopy showed that Cu-TiNTs have an average inner diameter of 52.13 nm, a wall thickness of 14.28 nm, and a tube length of 0.6401 μm. Fourier-transform infrared spectroscopy confirmed the presence of characteristic O-Ti-O bond of TiO2. X-ray fluorescence spectroscopy confirmed copper-doping with an average dopant loading of 0.0248%. Even at this low dopant loading, Cu-TiNTs were shown to be photo-active in degrading Acid Orange 52 (AO 52) under UV light illumination. The kinetic profiles of AO 52 photoelectrochemical degradation were best described by the pseudo-first-order kinetic model (R2 ≥ 0.991) with kinetic constants 9.42 x 10-3 min-1 for Cu-TiNTs as compared to 6.04 x 10-3 min-1 for pristine TiNTs. Overall, doping pristine TiNTs with Cu was shown to enhance its photoelectrocatalytic properties in degrading textile dyes such as AO 52.

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