ZnO(core)/TiO2(shell) composites: influence of TiO2 microstructure, N-doping and decoration with Au nanoparticles on photocatalytic and photoelectrochemical activity

Efficient use of renewable energies is one of the most difficult technological challenges facing humanity. Among all renewable energy sources, the sunlight is considered as the most abundant and accessible one. To convert it into usable and controllable form, the modern technology relies on generation of electron-hole pairs in semiconductors upon light absorption. The obtained separated charge carriers possess extra energy brought by the converted sunlight which can be further utilized in various ways. Currently, the most common approach consists in its direct transformation into electricity in p-n junctions. Alternatively, the electrons and holes can be used to perform chemical reactions. The electrons can be transferred to reduce various organic compounds or inorganic species, while simultaneously the holes can play the role of oxidizer by subtracting the electrons from the other substances. Through these reactions it would be possible to accumulate the solar energy in chemical species allowing thus to alleviate the intermittence of the sunlight. Unfortunately, the existing materials do not easily cross the laboratory level to realize this approach on industrial scale. That is why the development of new semiconductor photocatalysts, which harvest and convert efficiently the visible part of solar spectrum, is of paramount importance. For many years the most often studied photocatalytic materials have been ZnO and TiO2. However, it has been recently shown that composites based on ZnO and TiO2 possess even more promising properties than many other semiconductors in various photocatalytic applications. Despite many works reporting high photoactivity of these composites in different applications, the detailed information about the structure–properties correlation is lacking. In order to fill this gap we decided to focus our attention to study the influence of microstructure of ZnO/TiO2 composites on their properties in photocatalytic degradation of organic pollutants, and in application in half-reaction of ‘solar fuel’ generation, namely photoassisted water electro-oxidation. To realize such study the composites should satisfy the requirements of a high surface area and good electric conductivity. We chose therefore the design based on ZnO nanorods supported on ITO (Indium Tin Oxide)-coated glass electrode. The ZnO nanorods (NRs) were then covered with a layer of TiO2 under different deposition conditions. The composition and microstructure of the obtained ZnO(core)/TiO2(shell) composites were modified in the aim to elucidate how these parameters influence their photocatalytic activity. Consequently, the efforts were made to impart visible light activity to the elaborated ZnO/TiO2 composites by modifying titanium dioxide layers with nitrogen and decoration with Au nanoparticles. The thesis consists of three parts: Bibliography, Experimental and Results and Discussion. First part of the present PhD thesis, Bibliography, is dedicated to the analysis of literature concerning fundamental properties of semiconductor materials, solid/electrolyte interface as well as principles of photocatalysis and photoelectrochemical water oxidation. Also, the photocatalytic properties of ZnO and TiO2, and those of their composites are reviewed in this section. Furthermore, methods for improvement visible-light absorption are also described, i.e. N-doping and surface plasmonic effects due to the noble metal nanoparticles (Au NPs) deposited on semiconductors. The second part, Experimental, covers the preparation procedures and characterization techniques used in the work. First, the details are given for electrochemical seeding of ITO support, hydrothermal growth of ZnO nanorods, sol-gel deposition of TiO2 (and N-doped TiO2), and photodeposition of Au NPs. Second, the characterization techniques used in realization of this project are described: SEM (Scanning Electron Microscopy), HAADF-STEM and HR-TEM (High Angle Annular Dark Field Scanning Electron Transmission Microscopy and High Resolution Transmission Electron Microscopy), XRD (X-ray Diffraction Analysis), XPS (X-ray Photoelectron Spectroscopy), EDS ‘or EDX’ (Energy Dispersive Spectroscopy) analyses connected with electron microscopy techniques, UV-vis Spectroscopy and DRS (Diffuse Reflectance UV-vis Spectroscopy, TGA-DSC (Thermogravimetry Differential Scanning Calorimetry Analysis), TOC (Total Organic Carbon) analysis, RT-PL (Room Temperature Photoluminescence Spectroscopy), electrochemical techniques including: LSV (Linear Sweep Voltammetry), CV (Cyclic Voltammetry), chronoamperometry, chronopotentiometry, as well as the set-ups elaborated by the author for the purpose of photocatalytic and photoelectrochemical measurements. The main results of the PhD thesis are presented in the third part, Results and Discussion, consisting of four chapters. In the first chapter (Chapter 4.1), the results of the studies on electrochemical seeding of ITO-electrode in Zn(CH3COO)2 solution are presented. The length and width of ZnO nanorods grown by hydrothermal method from Zn(NO3)2 aqueous solution on Zn/ZnO-seeded ITO substrate were shown to depend strongly on initial Zn2+ concentration and the synthesis duration. The arrays of well-separated ZnO ‘obelisk-like’ nanorods of width varied from 100 nm at tips to ~ 300 nm at bottom and average length of 1.9 µm were prepared under optimized conditions, and used as starting point for further fabrication of (core)ZnO/TiO2(shell) composites. In the second chapter (Chapter 4.2), a simple and low-cost sol-gel method was developed in order to form TiO2 thin layers on ZnO nanorods by hydrolysis of titanium(IV) butoxide. The results of studies lead to elaboration of two most distinctive variants of sol-gel procedure that allow to deposit TiO2 layers of controlled thicknesses and different morphology (rugged or compact). The rugged TiO2 layers were obtained after 6 hours of one step sol-gel synthesis followed by calcination of the sample at 450 oC, ensuring formation of anatase-TiO2, whereas the uniform coating of 25 nm – 40 nm thickness was obtained via three successive 30 min-synthesis with the intermediate calcination of the sample after each deposition cycle. The composite containing the rugged TiO2 layer was shown to possess significantly higher activity in model pollutant (methylene blue, MB) degradation and in photoassisted H2O electro-oxidation under 400 nm monochromatic light irradiation. This improved photoactivity was correlated with the composite microstructure and attributed to a higher porosity and better accessibility of ZnO/TiO2 interface region through the rugged TiO2 layer by the reagents. The TiO2 (shell) layers of similar morphology were also prepared by atomic layer (ALD) and chemical vapor deposition (CVD) techniques and it was shown that the composites fabricated by us with the use of simple sol-gel procedure yield comparable (or even higher) photoactivity. Finally, it was confirmed by total organic carbon (TOC) analysis that the ZnO/TiO2 composites elaborated in this work are also active in decomposition of the pollutants in a dumb hill leachate solution (waste water) under 400 nm monochromatic irradiation. In Chapter 4.3 it is shown that the ZnO/TiO2 interface plays a key role in enhancement of photodecomposition of MB under 400 nm illumination. The increase of photocatalytic activity was attributed to the shift of absorption edge of ZnO/TiO2 towards visible light in comparison to that of the ZnO(core)-etched TiO2. Further enhancement of photocatalytic activity of ZnO/TiO2 was achieved through its additional calcination at 450 °C for 3 h. This simple treatment brings 40% increase in the rate of MB decomposition and a two-fold rise of the photocurrent in H2O oxidation. Measurements of open circuit potential (VOC) showed that the improved properties of additionally calcined ZnO/TiO2 composites stem from the decrease of electron-hole recombination rate. STEM (Scanning Transmission Electron Microscopy) studies showed that the additional calcination resulted in formation of voids at the ZnO/TiO2 interface. EDX (Energy Dispersive X-ray) analysis and XPS (X-ray Photoelectron Spectroscopy) results proved that formation of voids is accompanied by the outward diffusion of Zn ions into TiO2 layer and allowed to conclude about the existence of the Kirkendall effect at ZnO/TiO2 interface. Occurrence of this effect observed for the first time at unusually moderate temperature (450 °C) was shown and attributed to a highly defective nature of the surface layer of the ZnO nanorods. In the last chapter (Chapter 4.4), the composites consisting of ITO-supported ZnO nanorods covered with nitrogen-doped titanium dioxide, TiO2(N), shell were decorated with gold nanoparticles (Au NPs) in order to improve their photocatalytic activity under visible light. The photocatalytic properties of ZnO/TiO2/Au and ZnO/TiO2(N)/Au ternary composites were studied under illumination with Xe lamp equipped with a 400 nm cut-off filter. It was found that low Au NPs loading (0.37% at.) resulted in 60% enhancement of photocatalytic decolorization of MB under visible light with respect to the Au-free sample owing to plasmonic effects. Also, a simultaneous N-doping and Au NPs-decoration allows to multiply by three the photocurrent in photoelectrochemical water oxidation at the potential of 0.8 V vs. Ag/AgCl. It was also demonstrated that the Au-decorated composites possess a strong electrocatalytic activity in reduction O2 to active oxygen species (via formation of O2⦁– radicals) under a small negative bias (–0.25 V vs. Ag/AgCl) in dark. Illumination of the polarized sample with visible light was shown to enhance this process resulting in rapid decomposition a model pollutant (MB) even in the presence of Na2SO4. This approach allows to completely overcome a problem of inhibition of the photocatalytic process by dissolved inorganic salts on non-polarized catalysts, thus meeting the aim of promising material for photoelectrocatalytic remediation of waste water, often containing a significant amount of inorganic ions.