ZnO nanorods covered with a TiO2 layer: simple sol–gel preparation, and optical, photocatalytic and photoelectrochemical properties
In this work, composite core–shell ZnO/TiO2 materials were fabricated by deposition of TiO2 layers via a sol–gel method onto ZnO nanorods hydrothermally grown on an ITO electrode. Two approaches to the sol–gel procedure resulted in strongly different morphologies and thicknesses of the deposited TiO2 layer, as shown in electron microscopy studies. The decrease of the optical band gap energies of the ZnO/TiO2 composites by about 0.2–0.3 eV with respect to the TiO2 nanoparticles and ZnO nanorods was determined from UV-Vis diffuse reflectance spectra. The photocatalytic activities of the systems were determined by investigation of the decolorization of Methylene Blue (MB) in aqueous solution, …
Enhancement of visible light photoelectrocatalytic activity of ZnO(core)/TiO2(shell) composite by N-doping and decorating with Au0 nanoparticles
Abstract The composites consisting of ITO-supported ZnO nanorods covered with TiO2 shell were doped with nitrogen and decorated with gold nanoparticles in order to improve their photocatalytic activity under visible light. N-doped TiO2 (TiO2(N)) was prepared under mild conditions through a simple sol-gel synthesis in the presence of NH4Cl. Such procedure results in formation of a highly porous shell of TiO2(N) on the ZnO nanorods. The gold nanoparticles (AuNPs) of the size 7–25 nm were grafted onto the surface of TiO2 as well as TiO2(N) by a photodeposition method from aqueous solution of [AuCl(4-x)(OH)x]− precursor at pH 6.7. The composition and microstructure of the prepared samples were …
Memory effects in functionalized conducting polymer films: titanocene derivatized polypyrrole in contact with THF solutions
Abstract Films with a polypyrrole matrix and pendant titanocene dichloride centers, p(Tc3Py), have been obtained by potentiostatic electropolymerization of the titanocene-pyrrolyl derivative, Tc3Py=Tc(CH 2 ) 3 NC 4 H 4 (Tc=Cl 2 TiCpCp′, Cp=C 5 H 5 , Cp′=C 5 H 4 ), in acetonitrile (AN) solutions on a Pt surface. The redox activity has been studied after the transfer of the film-coated electrode into the monomer-free solution of the same electrolyte, TBAPF 6 , in THF. Contrary to the case of AN or dichloromethane solutions, one can achieve a stable redox activity of the immobilized Tc centers in THF solutions during a series of cycles. A parallel between the redox properties of the Tc complex…
Influence of chloride anions on the electrodeposition and electroactivity of the polymer matrix in polypyrrole, poly( N -methylpyrrole) and polypyrrole derivatives functionalized by titanocene centers, in dry non-aqueous solutions
We report electrochemical studies on the influence of a small concentration of chloride ions on the electroactivity of the polymer matrix of polypyrrole (PPy), poly(N-methylpyrrole) [p(N-MePy)] and a poly(titanocene-propyl-pyrrole) derivative, p(Tc3Py) [Tc(CH2)3NC4H4; Tc=CpCp′TiCl2; Cp=C5H5; Cp′=C5H4] in acetonitrile (AN), tetrahydrofuran (THF) and N,N-dimethylformamide (DMF). The polymer films were obtained on Pt disc electrodes from AN solutions of the monomers containing 0.1 M tetrabutylammonium hexafluorophosphate (TBAPF6) as the supporting electrolyte and then transferred to the corresponding monomer-free solution. Studies in Cl−-containing solutions have shown that the p(Tc3Py) matrix…
Mechanism of redox transformation of titanocene dichloride centers immobilized inside a polypyrrole matrix—EQCM and XPS evidences
Abstract We report electrochemical quartz crystal microbalance (EQCM) results for electrodeposition of titanocene derivatized polypyrrole p(Tc3Py) films and redox transformation of polypyrrole matrix and titanocene centers immobilized in the film. Films of p(Tc3Py), Tc3Py = Tc(CH 2 ) 3 NC 4 H 4 (Tc = Cl 2 TiCpCp′, Cp = C 5 H 5 , Cp′ = C 5 H 4 ) were obtained from acetonitrile solutions of monomer on a Pt disc or thin Au layer evaporated on 10 MHz quartz crystals. Polymerization efficiency, derived from the slope of the change of resonant frequency as a function of the deposition charge ranged from 54% to 75%. A gradual loss of redox activity of Tc centers during consecutive redox cycles of …
Improvement of photocatalytic and photoelectrochemical activity of ZnO/TiO2 core/shell system through additional calcination: Insight into the mechanism
Abstract ZnO/TiO2 composites were prepared by sol-gel deposition of TiO2 on ZnO nanorods hydrothermally grown on electrically conductive indium tin oxide substrate (ITO). It has been shown that the ZnO/TiO2 interface plays a key role in enhancement of photodecomposition of methylene blue (MB) used as a model test pollutant, under monochromatic light irradiation (400 nm). The increase of photocatalytic activity was attributed to the shift of absorption edge of ZnO/TiO2 towards visible light in comparison with bare TiO2. Further enhancement of photocatalytic activity of ZnO/TiO2 was achieved through its additional calcination at 450 °C for 3 h. This treatment brings 40% increase in the rate o…
Atomic force microscopy study of conducting polymer films near electrode's edge or grown on microband electrode
Abstract Polypyrrole (PPy) films of different thicknesses (within the range from 200 nm to 2.5 μm) were electrodeposited on two types of inhomogeneous substrates, single band and double-band Pt electrodes. Topographic images of the polymer layers were obtained by means of ex situ large-scale AFM technique to demonstrate how the propagation rates of the film growth above the electrode (in the normal direction to the electrode surface) and along the insulating surface surrounding the single- or double-band electrodes (in the horizontal direction) change with the deposition charge. It is proved that variations in the film thickness over the double band electrodes and progressive changes of the…
Electrosynthesis and properties of poly(3,4-ethylenedioxythiophene) films functionalized with titanocene dichloride complex
Synthesis of a titanocene dichloride derivative functionalized with 3,4-etylenedioxythiophene group, Tc1EDOT (Cl 2TiCpC5H4(CH2) (3,4ethylenedioxythiophene)) has been described. Redox behavior of the monomer in tetrahydrofuran (THF), dichloromethane (DCM) and acetonitrile (AN) at different scan rates has been discussed in terms of different ability of these solvents to coordination with the reduced titanocene (Tc) complex and the solvation of Cl − anions. Electrooxidation of Tc1EDOT to get a conducting polymer film with immobilized titanocene dichloride centers and electrochemical properties of its polymer matrix in background acetonitrile solution have been compared with those of non-substi…