FREE ELECTRONIC LIBRARY - Abstract, dissertation, book

Pages:   || 2 | 3 | 4 | 5 |   ...   | 22 |

«Inauguraldissertation zur Erlangung der Würde eines Doktors der Philosophie vorgelegt der Philosophisch-Naturwissenschaftlichen Fakultät der ...»

-- [ Page 1 ] --

Copper(I) polypyridine complexes: the

sensitizers of the future for dye-sensitized

solar cells (DSSCs)



Erlangung der Würde eines Doktors der Philosophie

vorgelegt der

Philosophisch-Naturwissenschaftlichen Fakultät

der Universität Basel


Ana Hernández Redondo

aus Oñate, Spanien

Basel, 2009

Genehmigt von der Philosophisch-Naturwissenschaftlichen Fakultät auf Antrag


Prof. Dr. Edwin C. Constable Prof. Dr. Wolfgang P. Meier

Basel, den 26. 05. 2009 Prof. Dr. Eberhard Parlow Dekan Originaldokument gespeichert auf dem Dokumentenserver der Universität Basel edoc.unibas.ch Dieses Werk ist unter dem Vertrag „Creative Commons Namensnennung-Keine kommerzielle Nutzung-Keine Bearbeitung 2.5 Schweiz“ lizenziert. Die vollständige Lizenz kann unter creativecommons.org/licences/by-nc-nd/2.5/ch eingesehen werden.

Namensnennung-Keine kommerzielle Nutzung-Keine Bearbeitung 2.5 Schweiz

Sie dürfen:

das Werk vervielfältigen, verbreiten und öffentlich zugänglich machen

Zu den folgenden Bedingungen:

Namensnennung. Sie müssen den Namen des Autors/Rechteinhabers in der von ihm festgelegten Weise nennen (wodurch aber nicht der Eindruck entstehen darf, Sie oder die Nutzung des Werkes durch Sie würden entlohnt).

Keine kommerzielle Nutzung. Dieses Werk darf nicht für kommerzielle Zwecke verwendet werden.

Keine Bearbeitung. Dieses Werk darf nicht bearbeitet oder in anderer Weise verändert werden.

Im Falle einer Verbreitung müssen Sie anderen die Lizenzbedingungen, unter welche dieses Werk fällt, • mitteilen. Am Einfachsten ist es, einen Link auf diese Seite einzubinden.

Jede der vorgenannten Bedingungen kann aufgehoben werden, sofern Sie die Einwilligung des • Rechteinhabers dazu erhalten.

Diese Lizenz lässt die Urheberpersönlichkeitsrechte unberührt.

• Die gesetzlichen Schranken des Urheberrechts bleiben hiervon unberührt.

Die Commons Deed ist eine Zusammenfassung des Lizenzvertrags in allgemeinverständlicher Sprache:



Die Commons Deed ist kein Lizenzvertrag. Sie ist lediglich ein Referenztext, der den zugrundeliegenden Lizenzvertrag übersichtlich und in allgemeinverständlicher Sprache wiedergibt. Die Deed selbst entfaltet keine juristische Wirkung und erscheint im eigentlichen Lizenzvertrag nicht. Creative Commons ist keine Rechtsanwaltsgesellschaft und leistet keine Rechtsberatung. Die Weitergabe und Verlinkung des Commons Deeds führt zu keinem Mandatsverhältnis.

Quelle: http://creativecommons.org/licenses/by-nc-nd/2.5/ch/ Datum: 3.4.2009 A mis padres, Mateo y Pilar.

To my parents, Mateo and Pilar.

Acknowledgements First of all, I would like to thank my supervisors Prof. Dr. Edwin C. Constable and Prof. Dr.

Catherine E. Housecroft for helping, advising and supporting me during the last three years.

Since the very beginning they encouraged me to work and transmitted me their passion for chemistry, for what I am very grateful. Ed, as the direct supervisor of my project, has led me through the PhD giving me a lot of freedom, and I would say that he has also vibrated with the amazing and to some point unexpected results that we have had. Catherine has always been there for anything that I have needed during the time I was working in the laboratory, and also while I was writing at home. I really appreciate her patience any time I would “skype” her with a question and her invaluable corrections.

I also want to thank Prof. Wolfgang P. Meier and Prof. Dr. Michael Grätzel for being the coreferee and external expert on my PhD-defense.

Prof. Michael Grätzel also has to be acknowledged together with Dr. Md. Khaja Nazeeruddin and Dr. Takeru Bessho for the measurements that were performed in their laboratories, at the EPFL in Lausanne. The results obtained with my copper compounds in collaboration with them allowed us to publish our work very successfully and attracted the attention of the scientific community.

Next, I would also like to say thank you to all the past and present members of the Constable/Housecroft group. During my PhD, I have always feel comfortable working in the laboratory and in the practical courses with the students, and have always find help to any problems/doubts that I could have. Not to forget the good times spent in the kitchen and the good friendships that I have started here. I am not going to mention all these people by name because I am afraid I could forget someone, but thank you to you all!!! I am also very grateful for those that have run MALDI, ESI and NMR experiments for me, and of course to Stefan Graber, who has always repaired any computer problem that I could have (and I can have lots of them in a short time!) and has been patient enough to explain me anything I should know about them.

–  –  –

Thank you to Beatrice Erismann for doing all the paperwork that I could have never done on my own and for being a good friend. Markus Hauri has also been helpful with anything I needed during this time. Apart from them, I also want to acknowledge all the people that work in the faculty that have help me in one or another way, sometimes in unexpected ways.

I would also like to acknowledge the financial support of the Schweizerischer Nationalfonds zur Förderung der Wissenschaftlichen Forschung, Universität Basel and the Schweizerische Chemische Gesellschaft. With this support I have been able to carry out my own research as well as travel to various national and international conferences in order to present my results and I am very grateful for this opportunity.

I also want to say thank you to all my friends in Spain and in Switzerland for supporting me during this time. I have you all in my heart.

My family has always been there for me, especially my parents and my brother, for anything I needed, since the very beginning, before I could even think of doing a PhD. My parents have always encouraged me to learn, to study, to improve and to go ahead, and nothing that I can write here could express to what extent I am grateful. You have made me what I am. Now you are also doctors!

Mi familia siempre ha estado ahí para mi, especialmente mis padres y mi hermano. Para cualquier cosa que pudiera necesitar, desde el principio, antes incluso de que se me pasara por la cabeza la idea de hacer un doctorado. Mis padres siempre me han animado a aprender, a estudiar, a mejorar y a seguir adelante, y nada de lo que pueda escribir aqui puede expresar hasta qué punto les estoy agradecida por ello. Me habeis hecho lo que soy. Y ahora vosotros también sois doctores!

ii And last but not least, I want to thank Jorge for his love and help before, during and hopefully after (!) my PhD studies. I still remember my first days here, when I was lost and didn’t know what to do; he supported and helped me “see the light”. You always see the good things in me and help me see them. Before and especially after my operation, you have been the best partner I could have ever dreamed of, and hope you will keep being it now that we have a common, and I would say, the most important project of our lives coming.

–  –  –

I Introduction

I. 1 Different parts of the dye-sensitized solar cell (DSSC)

I. 1. 1 Semiconductor

I. 1. 2 Dye

I. 1. 3 Electrolyte

I. 1. 4 Conducting substrate

I. 2 Ruthenium(II)- vs. copper(I)-polypyridyl complexes for sensitizer applications........ 28 II 2,2´-Bipyridine ligands

II. 1 Synthesis and characterization of ligands

II. 2 Crystal structures of 2,2´-bipyridine ligands

II. 2. 1 (1E,5E)-1,6-Diphenylhexa-1,5-diene-3,4-dione

II. 2. 2 (1E,5E)-1,6-Di(furan-2-yl)hexa-1,5-diene-3,4-dione

II. 2. 3 6,6´-Dimethyl-4,4´-diphenyl-2,2´-bipyridine (L1)

II. 2. 4 4,4´,6,6´-Tetraphenyl-2,2´-bipyridine (L2)

II. 2. 5 Dimethyl 4,4´-(6,6´-dimethyl-2,2´-bipyridine-4,4’-diyl)dibenzoate (L3)............ 66 II. 2. 6 4,4´-Di(furan-2-yl)-6,6´-dimethyl-2,2´-bipyridine (L9)

II. 2. 7 6,6´-Dimethyl-2,2´-bipyridine-4,4´-dicarboxylic acid (H2L10)

II. 2. 8 Dimethyl 6,6´-dimethyl-2,2´-bipyridine-4,4´-dicarboxylate (L11)

II. 2. 9 4,4´-Di(furan-2-yl)-6,6´-diphenyl-2,2´-bipyridine (L16)

II. 2. 10 [H3L17][CF3COO]·2CF3COOH

II. 2. 11 Dimethyl 6,6´-diphenyl-2,2´-bipyridine-4,4´-dicarboxylate (L18).................. 79 II. 2. 12 Tetraethyl 6,6´-dimethyl-2,2´-bipyridine-4,4´-diyldiphosphonate (L23)......... 81 III 2,2´:6´,2´´-Terpyridine ligands

III. 1 Synthesis and characterization of 2,2´:6´,2´´-terpyridine ligands

IV Copper(I) complexes

IV. 1 Synthesis and characterization of copper(I) complexes

IV. 2 Crystal structures of copper(I) 2,2´-bipyridine complexes

IV. 2. 1 [Cu(L1)2][PF6]·2CHCl3

IV. 2. 2 2{[Cu(L2)2][PF6]}·Et2O

IV. 2. 3 2{[Cu(L5)2][PF6]}·2Et2O·CHCl3

IV. 2. 4 4[Cu(H2L8)(HL8)]·3H2O

IV. 2. 5 [Cu(L9)2][PF6]

IV. 2. 6 [Cu(L11)2][PF6]

IV. 2. 7 Na3[Cu(L17)2]

IV. 2. 8 [Cu(L18)2][PF6]

IV. 2. 9 Na3[Cu(H2L24)2]·15O

V Building dye sensitized solar cells (DSSCs)

V. 1 Characteristic parameters of DSSCs

V. 2 Preparation of dye-coated nanocrystalline TiO2 electrodes

V. 3 DSSCs with homoleptic copper(I) complexes as sensitizers

V. 4 DSSCs with heteroleptic copper(I) complexes as sensitizers

VI Experimental part

VII Crystallographic data

VIII Bibliography

IX Curriculum Vitae


–  –  –

General experimental H, C and P spectra were recorded at room temperature on Bruker AM250 (250 MHz), Bruker DRX400 (400 MHz), Bruker Avance DRX500 (500 MHz) and DRX600 (600 MHz) spectrometers. Chemical shifts for 1H and 13C are relative to residual solvent peaks with TMS δ 0 ppm. 31P spectra are referenced with respect to 85% aqueous H3PO4 (δ 0 ppm).

Infrared spectra were recorded on a Shimadzu FTIR-8400S spectrophotometer with solid samples on a Golden Gate diamond ATR accessory.

Electron impact (EI), electrospray ionization (ESI), and MALDI-TOF mass spectra were recorded using Finnigan MAT95 and MAT LCQ and PerSeptive Biosystems Voyager mass spectrometers, respectively.

Electronic absorption spectra were recorded on a Varian-Cary 5000 spectrophotometer.

Electrochemical measurements were performed with an Eco Chemie Autolab PGSTAT 20 system using glassy carbon working and platinum auxiliary electrodes with a silver wire as pseudo-reference electrode. Solvents (see experimental section) were purified and 0.1M [nBu4N][PF6] was used as supporting electrolyte. Ferrocene (Fc) was added at the end of each experiment as an internal reference. For Na3[Cu(L17)2], the supporting electrolyte was 0.1M NaClO4 and measurements were made relative to Ag/AgCl, then corrected to be with respect to Fc/Fc+.

Photoelectrochemical measurements at the University of Basel were performed with a CHI-900B potentiostat connected to the cells. The light source was a 300 W halogen lamp (ELH, General electrics) with a UV-filter to block light with wavelengths under 400 nm. The solar cells were mounted at a distance where the light intensity was 100 mW/cm2 (measured with an optical power meter head, Thorlabs), the equivalent of one sun at air mass 1.5. Masking tape was added around the cells to prevent reflected light disturbing the measurement.

The elemental analyses were performed with a Leco CHN-900 microanalyser by W. Kirsch.

–  –  –

Now, more than ever before, energy is what makes our world continuously work. World energy annual consumption is ca. 4.7 x 1020 J and is expected to grow about 2% each year for the next 25 years [1]. The World’s conventional energy supplies (oil, natural gas and coal) have a finite lifetime as our major source of energy, and current forecasts suggest that alternatives must make a major contribution in the near future, also because mankind cannot afford to continue to progress by relying on sources of energy that release greenhouse gases. Though nuclear power was once regarded as a solution for increasing energy demand and the depletion of fossil fuels, concerns about the storage of nuclear waste led scientists to explore alternative and renewable sources of energy.

Most renewable energy options must rely on a net input of energy into the Earth and since the Sun is our only external energy source, using its energy, which is clean and infinite, is the main objective of all alternative energy strategies. It is remarkable that a mere 10 minutes of solar irradiation onto the Earth’s surface is equal to the total annual human energy consumption [2].

However, nowadays renewable sources comprise about 13% of all energy production and photovoltaics (PV) (from photons to electrons) only account for no more than 0.04%, and, most probably, only in 2030 will that figure reach 1% [3]. Solar PV energy costs are not yet competitive and continued PV growth is mainly based on government support, as is easily perceived by analyzing three major consumers: Germany, Japan and the USA. Nevertheless, PV solar cells are clearly very elegant and attractive devices for producing energy: cells are free from chemical and noise pollution; their power output is flexible; production can be done in situ, it is not dependent on the electrical grid, which makes them uniquely portable; they do not rely on reserves located abroad in geopolitically unstable countries and, of course, their source of energy, the Sun, as already said, is free and inexhaustible for the next few million years.

The first modern PV solar cells, silicon (Si) p/n, were developed by Chapin et al. at Bell Laboratories in 1954 [4], and a few years later they were already used in space exploration.

Pages:   || 2 | 3 | 4 | 5 |   ...   | 22 |

Similar works:

«Vocal Characteristics, Speech, and Behavior of Telephone Interviewers by Jessica Susan Broome A dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy (Survey Methodology) in The University of Michigan Doctoral Committee: Professor Frederick G. Conrad, Chair Professor Norbert Schwarz Research Scientist Steven G. Heeringa Professor Susan E. Brennan, State University of New York at Stony Brook Acknowledgments This work would not have been possible...»

«EINE THEORIE DER KAUSALITÄT Wolfgang Spohn Habilitationsschrift eingereicht bei der Fakultät für Philosophie, Wissenschaftstheorie und Statistik der Ludwig-Maximilians-Universität in München im Oktober 1983 INHALTSVERZEICHNIS Vorbemerkung TEIL I: PRÄLIMINARIEN 1 Aspekte der Kausalität. Ein Problemüberblick 2 Einige Explikationen des Ursachenbegriffs 2.1 Die klassische Regularitätstheorie 2.2 Die verbesserte Regularitätstheorie 2.3 Der kontrafaktische Ansatz 2.4 Das probabilistische...»

«DEVELOPMENT OF QUATERNARY AMMONIUM BASED ELECTROLYTES FOR RECHARGEABLE BATTERIES AND FUEL CELLS A Dissertation Presented to The Academic Faculty By Christopher M. Lang In Partial Fulfillment Of the Requirements for the Degree Doctor of Philosophy in Chemical Engineering Georgia Institute of Technology December 2006 Development Of Quaternary Ammonium Based Electrolytes For Rechargeable Batteries And Fuel Cells Approved By: Dr. Paul A. Kohl, Advisor Dr. Lawrence A. Bottomley School of Chemical &...»

«UNCOVERING THE FUNCTIONAL EFFECTS OF BIOMOLECULAR MUTATIONS THROUGH COMPUTER SIMULATIONS Peter Huwe A DISSERTATION in Biochemistry and Molecular Biophysics Presented to the Faculties of the University of Pennsylvania in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy Supervisor of Dissertation Graduate Group Chairperson _ Ravi Radhakrishnan, Ph.D. Kathryn M. Ferguson, Ph.D. Associate Professor of Bioengineering Associate Professor of Physiology Dissertation...»

«To my Parents, Rosa Estela and Heleno To my brothers, Ivan, Cesar and Karina To my wife and “complice en la vida” Roshelly To my people, “Los Latinoamericanos”, wherever they are Hugo Alberto Guti´ rrez-Jurado e New Mexico Institute of Mining and Technology December, 2011 A HOLISTIC EXPLANATION OF THE ECOHYDROLOGIC AND GEOMORPHIC PROPERTIES FOR A SEMIARID BASIN WITH CONTRASTING ECOSYSTEMS by Hugo Alberto Guti´ rrez-Jurado e Submitted in Partial Fulfillment of the Requirements for the...»

«Comportement du ballast sous l'action du bourrage et du trafic ferroviaire THÈSE NO 4697 (2010) PRÉSENTÉE LE 4 JUIN 2010 À LA FACULTÉ ENVIRONNEMENT NATUREL, ARCHITECTURAL ET CONSTRUIT LABORATOIRE DES VOIES DE CIRCULATION PROGRAMME DOCTORAL EN STRUCTURES ÉCOLE POLYTECHNIQUE FÉDÉRALE DE LAUSANNE POUR L'OBTENTION DU GRADE DE DOCTEUR ÈS SCIENCES PAR Chiara PADERNO acceptée sur proposition du jury: Prof. F. Golay, président du jury Prof. A.-G. Dumont, directeur de thèse Prof. E....»

«Electoral Systems and the Proportionality-Concentration Trade-off Promises and Pitfalls of Mixed Designs Dissertation zur Erlangung des Doktorgrades der Philosophischen Fakultät der Christian-Albrechts-Universität zu Kiel vorgelegt von Johannes Raabe Kiel 26.05.2015 Erstgutachter: Prof. Dr. Eric Linhart Zweitgutachter: Prof. Dr. Christian Martin Tag der mündlichen Prüfung: 13.11.2015 Durch den zweiten Prodekan Prof. Dr. John Peterson zum Druck genehmigt: 19.11.2015 Danksagung Diese...»

«Fanon’s Children: The Black Panther Party and the Rise of the Crips and Bloods in Los Angeles By George Percy Barganier III A dissertation submitted in partial satisfaction of the Requirements for the degree of Doctor of Philosophy In Education in the Graduate Division of the University of California, Berkeley Committee in charge: Professor Daniel Perlstein, Chair Professor Jabari Mahiri Professor Stephen Small Spring 2011 Abstract Fanon’s Children: The Black Panther Party and the Rise of...»

«The Emerging Idea o f Humanitarian Intervention 15001800 Cam illa B oisen A dissertation submitted at the School o f European Studies, Cardiff University, in candidature for the degree o f Doctor o f Philosophy, Cardiff University UMI Number: U585274 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be...»

«FROM AMELIORATION TO TRANSFORMATION IN HUMAN SERVICES: TOWARDS CRITICAL PRACTICE By Scot D. Evans Dissertation Submitted to the Faculty of the Graduate School of Vanderbilt University in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY in Community Research and Action December, 2005 Nashville, Tennessee Approved: Isaac Prilleltensky, Chair Douglas Perkins Paul Speer Bill Barkley Daniel Cornfield For Hannah. As you grow older, may you encounter a more just and...»

«DEVELOPMENT AND ADVANCED CHARACTERIZATION OF NOVEL CHEMICALLY AMPLIFIED RESISTS FOR NEXT GENERATION LITHOGRAPHY A Dissertation Presented to The Academic Faculty by Cheng-Tsung Lee In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the School of Chemical and Biomolecular Engineering Georgia Institute of Technology December 2008 COPYRIGHT 2008 BY CHENG-TSUNG LEE DEVELOPMENT AND ADVANCED CHARACTERIZATION OF NOVEL CHEMICALLY AMPLIFIED RESISTS FOR NEXT GENERATION...»

«Tritangents to Spherical Curves A Dissertation presented by Yury Arkady Sobolev to The Graduate School in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy in Mathematics Stony Brook University August 2015 Stony Brook University The Graduate School Yury Arkady Sobolev We, the dissertation committee for the above candidate for the Doctor of Philosophy degree, hereby recommend acceptance of this dissertation Oleg Viro Dissertation Advisor Professor, Department of...»

<<  HOME   |    CONTACTS
2016 www.abstract.xlibx.info - Free e-library - Abstract, dissertation, book

Materials of this site are available for review, all rights belong to their respective owners.
If you do not agree with the fact that your material is placed on this site, please, email us, we will within 1-2 business days delete him.