Article

Probing the surface adsorption and photocatalytic degradation of catechols on TiO2 by solid-state NMR spectroscopy.

Institute of Scientific and Industrial Research (SANKEN), Osaka University, Mihogaoka 8-1, Ibaraki, Osaka 567-0047, Japan.
Langmuir (Impact Factor: 4.19). 02/2006; 22(3):893-6. DOI: 10.1021/la051967p
Source: PubMed

ABSTRACT The local structure of the TiO2 surface modified with electron-donating bidentate ligands, such as catechols, has been investigated by solid-state NMR spectroscopy. The adsorption and degradation processes of catechols at the TiO2 surface were observed. The photocatalytic degradation mechanism of catechols at the TiO2 surface was interpreted in terms of the interfacial charge recombination reaction with conduction band electrons.

0 Bookmarks
 · 
35 Views
  • [Show abstract] [Hide abstract]
    ABSTRACT: This review covers the in situ molecular physicochemical characterization of bioadhesives at solid/liquid interfaces, with the aim of elucidating the adhesion strategies that lie at the root of marine biofouling. It focuses on three major foulers: mussels, algae and barnacles. The dispersal of these organisms, their colonization of surfaces, and ultimately their survival rely critically on the ability of the organisms’ larvae or spores to locate a favourable settlement site and undergo metamorphosis, thus initiating their sessile existence. Differences in the composition of adhesive secretions and the strategies employed for their temporary or permanent implementation exists between the larval and adult life stages. To date, only a few adhesive secretions from marine fouling organisms have been adequately described in terms of their chemical composition, and a survey revealed the presence of certain recurrent functional groups, specifically catechol, carboxylate, monoester-sulphate and -phosphate. This review will describe the binding modes of such functionalities to wet mineral/metal oxides surfaces. Such functionalities will be ranked based on their ability to bind to hydrophilic surfaces replacing surface-bound water (Langmuir adsorption constant) as well as other adsorbates (competitive adsorption). A plausible explanation for the propensity of the reviewed adhesive functionalities to bind to hydrous metal oxide surfaces will be given on the basis of the Hard and Soft Acids and Bases principle, Hofmeister effects and entropic considerations. From the in situ analysis of marine organism bioadhesives and adsorption studies of functionalities relevant to the bioadhesion process, insights can be gleaned for a knowledge-based innovation of antifouling strategies and the synthesis of strong, durable adhesive materials, which are suitable for implementation in wet environments.
    Advances in Colloid and Interface Science 03/2013; · 6.17 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: Titanium dioxide (TiO2), as an important semiconductor metal oxide, has been widely investigated in the field of photocatalysis. The properties of TiO2, including its light absorption, charge transport and surface adsorption, are closely related to its defect disorder, which in turn plays a significant role in the photocatalytic performance of TiO2. Among all the defects identified in TiO2, oxygen vacancy is one of the most important and is supposed to be the prevalent defect in many metal oxides, which has been widely investigated both by theoretical calculations and experimental characterizations. Here, we give a short review on the existing strategies for the synthesis of defective TiO2 with oxygen vacancies, and the defect related properties of TiO2 including structural, electronic, optical, dissociative adsorption and reductive properties, which are intimately related to the photocatalytic performance of TiO2. In particular, photocatalytic applications with regard to defective TiO2 are outlined. In addition, we offer some perspectives on the challenge and new direction for future research in this field. We hope that this tutorial minireview would provide some useful contribution to the future design and fabrication of defective semiconductor-based nanomaterials for diverse photocatalytic applications.
    Nanoscale 03/2013; · 6.23 Impact Factor
  • Source
    [Show abstract] [Hide abstract]
    ABSTRACT: The electronic structure and the optical response of free catechol, [Ti(cat)(3)](2-) complex, and catechol bound to TiO(2) nanoclusters have been analysed using time dependent density functional theory (TD-DFT) performing calculations both in real time and frequency domains. Both approaches lead to similar results providing the basis sets and functionals are similar. For all cases, the simulated spectra agree well with the experimental ones. For the adsorption systems, the spectra show a band at 4.7 eV associated to intramolecular catechol π→π* transitions, and low energy bands corresponding to transitions from catechol to the cluster with a tail that is red-shifted when the coupling between the dye and the cluster is more effective. Thus, dissociative adsorption modes provide longer tails than the molecular mode. Although the bidentate complex is more stable than the monodentate, the energy difference between both is smaller when the cluster size increases. Small cluster models reproduce the main features of the optical response, however, the (TiO(2))(15) cluster constitutes the minimal size to provide a complete picture. In this case, the conventional TD-DFT (frequency domain) calculations are highly demanding computationally, while real time TD-DFT is more efficient and the calculations become affordable.
    Physical Chemistry Chemical Physics 01/2011; 13(4):1506-14. · 3.83 Impact Factor