Nanostructured ZnO films for water treatment by photocatalysis

  • Anyela M. Ramirez Canon

Student thesis: Doctoral ThesisPhD


The development of nanostructured materials for environmental applications has received considerable attention in recent years. The properties of nanoparticles or nanostructured materials, such as large surface areas or high aspect ratios, translate into large improvements in the performance of existing devices and in the discovery of novel applications. On the other hand, photocatalysis is an attractive technology for the elimination of organic pollutants in water due to its simplicity, ease of implementation and reasonable cost compared to other advanced oxidation processes. A key disadvantage of many photocatalysts is their use in powder form which makes their recovery from treated water costly. In addition, incomplete removal can lead to accumulation over time with adverse effects to the environment. As a result significant effort has been placed in immobilizing photocatalytic materials on different substrates. The immobilization of photocatalyst results in a decrease in photocatalytic performance mainly due to reduction of surface area; therefore, research is now focusing on developing nanostructured materials which combine the attributes of nanotechnology and photocatalysis. In the present thesis, a systematic study of the relationship between properties of supported ZnO nanostructures and their photocatalytic activity was performed. Analysis was carried out by producing ZnO nanostructured films via anodization. The effects of voltage, temperature, reaction time and type of electrolyte on the morphology of ZnO nanostructures was studied. Results show that the type of electrolyte and its concentration determine the morphology and size of the nanostructures. Voltage, time and temperature affect the distribution and density of the nanostructures along the surface and affect the crystal size of the ZnO. The band gaps of the films were in the range of 3.27 and 3.50 eV. Although ZnO is a hydrophilic material, some of the films displayed hydrophobic and super-hydrophobic behaviour. The results obtained in this study and some data already published in the literature were correlated to the synthesis parameters, and were used to devise design guidelines to obtain ZnO films with specific nanostructures and macroscopic properties by controlling the anodization parameters. The photocatalytic activity of the ZnO nanostructured films (ZnO-NFs) were studied using three different photocatalytic reactors, (i) a thermo-stated batch reactor, (ii) a recirculating flat plate reactor, and (iii) a recirculating tubular annular reactor. Phenol and methyl orange (MO) were used as a model compounds. It was found that crystal size does not affect the photocatalytic performance of the films while morphology has an important impact on the degradation of phenol. The stability of the ZnO nanostructures was tested under different levels of oxygen, degradation of phenol occurred even at anoxic conditions following the Mars-van Krevelen mechanism. The formation of new nanostructures produced during the photocatalytic reaction was studied and a mechanism of formation was proposed. The study of the photocatalytic performance in the flat plate reactor showed that there was a mass transfer limitation in the process. ZnO nanostructures showed higher photocatalytic activity and morphology stability in the tubular annular reactor. Degradation of MO and phenol was produced in darkness by the nanostructures supported in Zn foil. It was also demonstrated that oxygen plasma post-treatment enhances the photocatalytic activity of the ZnO-NF by 36% while making the photocatalyst more stable for the photocatalytic degradation of phenol compared to those treated with heat. An electrical current was applied to the photocatalyst in the tubular annular reactor, which improved the degradation of phenol and participated in the formation of nanostructures in the Zn wire surface.
Date of Award18 Nov 2015
Original languageEnglish
Awarding Institution
  • University of Bath
SupervisorDavide Mattia (Supervisor)


  • ZnO
  • Nanostructures
  • Photocatalysis
  • water treatment

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