Dye-sensitized SnO2 electrodes with iodide and pseudohalide redox mediators

J Phys Chem B. 2005 Jan 20;109(2):937-43. doi: 10.1021/jp0461347.

Abstract

Dye-sensitized mesoporous nanocrystalline SnO2 electrodes and the pseudohalogen redox mediator (SeCN)2/SeCN- or (SCN)2/SCN- or the halogen redox mediator I3-/I- were implemented for regenerative solar cell studies. Adsorption isotherms of the sensitizers Ru(deeb)(bpy)2(PF6)2, Ru(deeb)2(dpp)(PF6)2, and Ru(deeb2(bpz)(PF6)2, where deeb is 4,4'-diethylester-2,2'-bipyridine, dpp is 2,3-dipyridyl pyrazine, and bpz is bipyrazine, binding to the SnO2 surface were well described by the Langmuir model from which the saturation coverage, Gamma0 = 1.7 x 10(-8) mol/cm2, and surface-adduct formation constant, Kad = 2 x 10(5) M(-1), were obtained. Following excited-state interfacial electron transfer, the oxidized sensitizers were reduced by donors present in the acetonitrile electrolyte as shown by transient absorption spectroscopy. With iodide as the donor, a rate constant k > 10(8) s(-1) was measured for sensitizer regeneration. In regenerative solar cells, it was found that the incident photon-to-current conversion efficiencies and open circuit voltages (Voc) were comparable for (SeCN)2/SeCN- and I3-/I- for all three sensitizers. The Voc varied linearly with the logarithm of the short circuit photocurrent densities (Jsc), with typical correlations of approximately 50-60 mV/decade. Capacitance measurements of the SnO2 electrode in the presence of I3-/I-, (SeCN)2/SeCN- or (SCN)2/SCN- are reported.

MeSH terms

  • Adsorption
  • Coloring Agents / chemistry*
  • Electrodes
  • Iodides / chemistry*
  • Organometallic Compounds / chemistry
  • Oxidation-Reduction
  • Porosity
  • Ruthenium / chemistry
  • Selenium Compounds / chemistry*
  • Sensitivity and Specificity
  • Thiocyanates / chemistry*
  • Time Factors
  • Tin Compounds / chemistry*

Substances

  • Coloring Agents
  • Iodides
  • Organometallic Compounds
  • Selenium Compounds
  • Thiocyanates
  • Tin Compounds
  • Ruthenium
  • stannic oxide
  • thiocyanate