Photoelectrochemical Studies on a Triad Electrode for Light-driven Water-splitting Open Access

Zhang, Naifei (2012)

Permanent URL:


A photoelectrochemical device is highly desirable for solar to chemical fuel (in our study H2 is the fuel) conversion. An essential component of such device is the photoanode which absorbs light and catalytically oxidizes water. Here we report a method of fabricating a photoanode by immobilizing a known homogeneous molecular water oxidation catalyst, [RuIV4O4(OH)2(H2O)4}(γ-SiW10O36)2]10-, onto a dye-sensitized nanostructured TiO2 photoelectrode by electrostatic interaction. The known sensitizers [Ru(bpy)2(4,4'-PO3H2bpy)]2+ (P2) and its modified version [Ru(5-crown-phen)2(dpb)]2+, dpb =4,4'-diphosphonic acid 2,2'bipyridine (C2P2) were both used. The polyoxometalate catalyst with different cations (inorganic and organic cations) was used. The effect of sensitizers and catalysts on photoelectrochemical properties were compared and discussed. An enhanced photocurrent is observed with the triad photoanode FTO/TiO2/P2/THpA-Ru4POM with an applied bias of 500mV and FTO/TiO2/C2P2/THpA-Ru4POM with no external bias. The bias-dependent behaviors of the photocurrent are in good agreement with calculated frontier orbitals.

Table of Contents

Table of Contents
List of Abbreviations...viii
List of Figures...ix
List of Schemes...x
Chapter 1 Introduction...1

1.1 General Introduction...2
1.2 Light-driven Water-splitting...3
1.3 Photoelectrochemical Cells...5
1.4 Sensitizers...9
1.4 POM WOCs...15

Chapter 2 Experimental Section: Preparation of Electrodes, Investigation of the Stability and Photoelecrochemical Performance...19

2.1 Material and Preparation...21

2.1.1 Preparation of TiO2 colloid and film...21
2.1.2 Sensitizers Used in This Work...21
2.1.3 WOCs Used in This Work...22

2.2 Electrode Assembly...23

2.2.1 Dyad Electrode...23
2.2.2 Triad Electrode...23

2.3 UV-Vis spectroscopic Measurements...24
2.4 Photoelectrochemical Measurements...25

Chapter 3 Results and Discussion...28

3.1 Electrode with P2 as Sensitizer...29

3.1.1 UV-Vis Spectra and Stability...30
3.1.2 Photoelectrochemical Measurements...33

3.2 Electrode with C2P2 as sensitizer...39

3.2.1 UV-Vis spectra and Stability...39
3.2.2 Photoelectrochemical Measurements...43

Chapter 4 Summary...48

About this Master's Thesis

Rights statement
  • Permission granted by the author to include this thesis or dissertation in this repository. All rights reserved by the author. Please contact the author for information regarding the reproduction and use of this thesis or dissertation.
  • English
Research field
Committee Chair / Thesis Advisor
Committee Members
Last modified

Primary PDF

Supplemental Files