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Dissertation Photoelectrochemical DISSERTATION PHOTOELECTROCHEMICAL CELLS EMPLOYING MOLECULAR LIGHT-HARVESTING MATERIALS FOR THE CAPTURE AND CONVERSION OF SOLAR ENERGY Submitted by Joel Thomas Kirner Department of Chemistry In partial fulfillment of the requirements For the Degree of Doctor of Philosophy Colorado State University Fort Collins, Colorado Spring 2017 Doctoral Committee: Advisor: Richard G. Finke Melissa Reynolds Alan Van Orden Walajabad Sampath Copyright by Joel Thomas Kirner 2017 All Rights Reserved ABSTRACT PHOTOELECTROCHEMICAL CELLS EMPLOYING MOLECULAR LIGHT-HARVESTING MATERIALS FOR THE CAPTURE AND CONVERSION OF SOLAR ENERGY Solar light has the potential to be a substantial contributor to global renewable energy production. The diffuse nature of solar energy requires that commercially viable devices used to capture, convert, and store that energy be inexpensive relative to other energy-producing technologies. Towards this end, photoelectrochemical cells have been the subject of study for several decades. Particularly interesting to chemists, molecular light-harvesting materials can be employed in photoelectrochemical cells. For example, a dye-sensitized solar cell (DSSC) is a type of photoelectrochemical cell designed to capture solar energy and convert it to electricity. Alternatively, molecular light-harvesting materials have also been employed in water-splitting photoelectrolysis cells (PECs), which capture solar energy and store it in the form of chemical bonds such as H2 and O2. The work presented in this dissertation falls into two major projects. The first involves fundamental studies of water-oxidizing PECs employing a novel perylene diimide molecule as the light-harvesting unit. Background is provided in Chapter II, composed of a comprehensive literature review of water-oxidizing PEC systems that employ light-harvesting materials composed of earth-abundant elements. Chapter III describes preliminary studies of a water- oxidizing PEC composed of a perylene diimide organic thin-film (OTF) and cobalt oxide catalyst, the first of its kind in the literature. Characterization of this novel device provided knowledge of the efficiency-limiting processes that would need to be addressed in order to ii improve device performance. Subsequently, Chapter IV describes preliminary studies of the same perylene diimide molecule in an alternative, literature-precedented, dye-sensitized photoelectrolysis cell (DS-PEC) architecture aimed at improving the efficiency-limiting processes of the first OTF-PEC. Characterization of this DS-PEC architecture reveals that the efficiency-limiting processes of the OTF-PEC were indeed improved. However, deposition of the cobalt oxide catalyst onto the DS-PEC did not successfully result in water oxidation. Alternative catalyst-deposition strategies from the literature are described as direction for future studies. The second project of this dissertation involves the study of novel high-redox-potential organometallic cobalt complexes as redox mediators in DSSCs, and is presented in Chapter V. Therein, it was found that the use of electron-withdrawing functional groups on cobalt- coordinating ligands not only increased the redox potential, but also increased the lability of the ligands. The resulting complex instability caused performance-limiting electron-recombination reactions in assembled DSSCs. These results point future researchers towards the study of higher-chelating ligands for enhanced stability in high-potential cobalt complexes. iii ACKNOWLEDGEMENTS I would like to thank my research co-advisors, Prof. Richard Finke and Prof. C. Michael Elliott, for their scientific tutelage throughout graduate school. I would not be the chemist I am today without their guidance. I acknowledge my supporting group of colleagues, classmates, and friends who have helped to make this phase of life an adventure, not monotony. Last, but certainly not least, I would like to thank my wife Anna for her patience and support through the long years of graduate school. iv TABLE OF CONTENTS ABSTRACT .................................................................................................................................... ii ACKNOWLEDGEMENTS ........................................................................................................... iv I. INTRODUCTION ........................................................................................................................1 II. WATER-OXIDATION PHOTOANODES USING ORGANIC LIGHT-HARVESTING MATERIALS: A REVIEW .......................................................................................................4 Overview ....................................................................................................................................4 Introduction ................................................................................................................................4 Performance Metrics ................................................................................................................17 Water Oxidizing Organic Thin-Film Photoelectrolysis Cells (OTF-PECs) ............................20 Water Oxidizing Dye-Sensitized Photoelectrolysis Cells (DS-PECs).....................................41 Summary and Outlook .............................................................................................................68 REFERENCES ..............................................................................................................................75 III. VISIBLE-LIGHT-ASSISTED PHOTOELECTROCHEMICAL WATER OXIDATION BY THIN FILMS OF A PHOSPHONATE-FUNCTIONALIZED PERYLENE DIIMIDE PLUS COBALT OXIDE COCATALYST ........................................................................................93 Overview ..................................................................................................................................93 Introduction ..............................................................................................................................94 Results and Discussion ............................................................................................................96 Conclusions ............................................................................................................................112 Experimental Section .............................................................................................................114 REFERENCES ............................................................................................................................123 IV. SENSITIZATION OF NANOCRYSTALLINE METAL OXIDES WITH A PHOSPHONATE-FUNCTIONALIZED PERYLENE DIIMIDE: A PHOTOELECTROCHEMICAL ANODE EN ROUTE TO WATER-OXIDATION CATALYSIS .........................................................................................................................127 Overview ................................................................................................................................127 Introduction ............................................................................................................................128 Experimental Section .............................................................................................................131 Results and Discussion ..........................................................................................................135 Conclusions ............................................................................................................................157 REFERENCES ............................................................................................................................159 v V. ARE HIGH-POTENTIAL COBALT TRIS(BIPYRIDYL) COMPLEXES SUFFICIENTLY STABLE TO BE EFFICIENT MEDIATORS IN DYE-SENSITIZED SOLAR CELLS? SYNTHESIS, CHARACTERIZATION, AND STABILITY TESTS ..................................167 Overview ................................................................................................................................167 Introduction ............................................................................................................................168 Experimental Section .............................................................................................................170 Results and Discussion ..........................................................................................................178 Conclusions ............................................................................................................................201 REFERENCES ............................................................................................................................203 VI. SUMMARY ...........................................................................................................................208 APPENDIX I. SUPPORTING INFORMATION FOR CHAPTER III .......................................212 APPENDIX II. SUPPORTING INFORMATION FOR CHAPTER IV .....................................224 APPENDIX III. SUPPORTING INFORMATION FOR CHAPTER V .....................................280 LIST OF ABBREVIATIONS ......................................................................................................309 vi I. INTRODUCTION This dissertation follows a “journal’s format” where each chapter is a manuscript that has been prepared for, submitted for, or accepted for publication in a peer-reviewed scientific journal. Therefore, each chapter follows the formatting
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