Electrode accessibility and mass transport through periodic nanoporous silica thin films determined by electrochemical methods

Ta-Chen Wei, Purdue University

Abstract

Ordered nanoporous silica films have attracted great interest for their potential use to template nanowires for photovoltaics and thermoelectrics. However, it is crucial to develop films such that electrode under the nanoporous film is accessible to solution species via facile mass transport through welldefined pores. In this thesis, the electrode accessibility and the effective species diffusivity were quantitatively determined for nearly all the known nanoporous silica film structures formed by evaporation induced self-assembly upon dipcoating or spin-coating. Grazing-angle of incidence small-angle X-ray scattering (GISAXS) was used to verify the nanoscale structure of the films and insure that all films were highly ordered and oriented. Electrochemical impedance spectroscopy (EIS) was then used to assess the transport properties. A model has been developed that separates the electrode/film kinetics and the film transport properties from the film/solution interface and bulk solution effects. Accounting for this, the accessible area of the nanoporous film coated FTO electrode (1-&thetas;) is obtained from the high frequency data, while the effective diffusivity of the ferrocene dimethanol (DFDM) redox couple is obtained from intermediate frequencies. It was found that the degree of order and orientation in the film, in addition to the symmetry/topology is a dominant factor that determines these two key parameters. The EIS data show that the (211) oriented double gyroid, (110) oriented distorted body center cubic, and (211) distorted primitive cubic silica films have significant accessibility (larger than 26% of geometric area). However, the double-gyroid films showed the highest diffusivity by over an order of magnitude. Both the (10) oriented 2D hexagonal and (111) oriented rhombohedral films were found to be highly blocking with only small accessibility due to microporosity. The impedance data were also collected to study the stability of the nanoporous silica films in aqueous solutions as a function of pH. The distorted primitive cubic film showed much faster degradation in pH 7 solution when compared to a blocking film such as the 2D hexagonal. However silica films maintained their structure at pH 2 for at least 12 hours.

Degree

Ph.D.

Advisors

Hillhouse, Purdue University.

Subject Area

Chemical engineering

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