Photocatalytic Degradation of Pharmaceuticals in Aqueous Solutions and Development of New ...

319 Pages·2012·34.22 MB·English

Photocatalytic Degradation of Pharmaceuticals in
Aqueous Solutions and Development of New Dye
Sensitised Photocatalytic Materials.

Sharon Murphy (B.Sc.)

A thesis submitted for the degree of
Doctor of Philosophy

Supervised by
Dr. Kieran Nolan
School of Chemical Sciences

Dublin City University January 2012
Declaration
I hereby certify that this material, which I now submit for assessment on the programme of
study leading to the award of Doctor of Philosophy is entirely my own work, that I have
exercised reasonable care to ensure that the work is original, and does not to the best of my
knowledge breach any law of copyright, and has not been taken from the work of others save
and to the extent that such work has been cited and acknowledged within the text of my work.
Signed: ____________
ID No.: 53537102
Date: _______

I
Dedicated to the best Mum ever xxx

II
“What we have learned from others becomes our own reflection.”
Ralph Waldo Emerson

“You must be the change you want to see in the world”
Gandhi

III
Acknowledgements
Firstly, massive thanks are due to my supervisor Dr. Kieran Nolan. Kieran has been committed
to my work at every stage, and changed my way of thinking about problems (of any kind) and
ways of solving them. I really could not have completed this work without his vast knowledge,
experience, wisdom, and immense positivity!

I would also like to thank my examiners Dr. Blánaid White and Dr. Leon Barron for their advice
regarding corrections which I feel improved not only the thesis, but will also assist me greatly in
my future endeavours! Sincere thanks are extended to the amazing NCSR technicians Maurice
Burke and Stephen Fuller. Thanks also to all staff of the school of chemical sciences including
all of the amazing technicians whom are the glue that holds the place together!

Thanks to all my colleagues in X249: especially Kieran, Declan, Brian and the previous
members of our group Emma and Sonia who offered me much help, advice and alcohol when it
was needed. Thanks to all my past visiting students (apprentices!): Juliana, Diego, Anais, David
and Carla. Thanks also to Debbie, Áine, Donnick, Christopher, Melody, Kim, Mary, Ana,
Ubaldo, Denis and Nadia for being great friends and for the many needed laughs throughout this
experience! Thanks also to Rosemarie for the endless support, and amazing experiences we
have shared for the last 8 years. You have been the greatest friend and I don’t think you realise
how much you have influenced my life in such a positive way, so thank you so much. Nora,
thanks so much for everything: the amazing coffees, the nights out, the chats, the shopping trips
and for the many laughs we have had over the years together. Thanks for always being there for
me too.

Thanks so much to my dad for the calls, and the support. It was so nice to confide in a family
member who was also trying to write a thesis. Thanks also so much for supplying me with a
laptop to finish this work and for being there always. I love my family so much and could not
have come this far without their support not only throughout this process but throughout my
life. Mum and Tom thanks for believing in me, always thinking of me and helping me in every
way you could. Thanks to my sisters Tamara and Thea and my brother Tom Jr. I have really
enjoyed seeing you all grow up and spending time with you (it was such a welcome distraction
to this PhD). You are such great people and I love you all so so much. I owe a significant
amount of gratitude to Jamie. He has been a best friend, colleague, housemate and partner
throughout this whole experience. Not only has he mastered all these roles but also achieved a
PhD while being there for me with mine. Thank you for all your advice, love, respect,
challenges, laughs etc. (I could write another thesis here…) so just thank you for everything.
IV
Table of Contents
Page

Declaration……….……….………………………………………..…………………….……….I
Dedication…….………….………………………………………..……………………….…….II
Acknowledgements….…..……………………….………………………………………..……IV
Table of Contents……….…………..……………………………………………………………V
List of Conferences Attended, Poster Presentations and Papers Published/In preparation….....IX
Abbreviations/ Acronyms/ Symbols……..….…………..………………………….…………..XI
Abstract……………………………………………………………………………….……....XIV

Chapter 1 - Literature Review……………………………………………………………...….1
1.0 Introduction: Pharmaceuticals in the Environment…………………………………….…….2
1.1 Current and Potential Methods for Removal of Pharmaceuticals…………….……...............4
1.2 Advanced Oxidation Processes (AOPs)……….………....……………………..……………6
1.3 Heterogeneous Photocatalysis………………….……………………………...…………....11
1.4 Titanium Dioxide…………………………………………………………………………....16
1.5 Optimising the Photocatalytic Process………………….…………………………….…….23
1.6 Literature Concerning the Pharmaceuticals Targets in this Work.……….…..…..................26
1.7. Project Proposal…………………….................…………………………..………………..29
1.8 Thesis Outline..………………………………………………………………………..…….30
Chapter 2 - Experimental……………………………………………………………..……....32
2.1 General………………………………………………………………………….…………..33
2.2 Chromatographic Methods……………………………………………………….................34
2.3: Chapter 3: Photolytic and Photocatalytic Degradation Studies with Famotidine, Tamsulosin
and Solifenacin……………………………………………………………………………..…...35
2.4: Chapter 4: Intermediate Analysis and Elucidation of Degradation Mechanism for
Famotidine, Tamsulosin and Solifenacin……………………….................................................41
2.5: Chapter 5: Development and Characterisation of Visible Light Sensitised Photocatalytic
Materials and Evaluation of their Photocatalytic Activity with
Famotidine…………………………………….………………………………………...............42
Chapter 3 - Photolytic and Photocatalytic Degradation Studies of Famotidine, Tamsulosin
and Solifenacin with TiO …………………………………………………………………….51
2
3.1 Introduction………………………….……………………….……………….….…………52
3.2 Results and Discussion………………………………………………………………….......54
Heterogeneous Photocatalysis Part I: Famotidine………………………………………………54
3.2.1 UV-vis Studies…………………………………………………………………...54
V
3.2.2 Quartz Glassware: Photolysis Studies……………………………………………55
3.2.3 Quartz Glassware: Photocatalysis Studies ………………………………………56
3.2.4 Alternative Reactor Studies………………………………………………………57
3.2.5 Pyrex Glassware: Photolysis Studies…………………………………………….58
3.2.6 HPLC Analysis of Photolysis Studies……………………………………………58
3.2.7 Famotidine Heterogeneous Photocatalysis: Pyrex...……………………………..59
3.2.8 Famotidine Heterogeneous Photocatalysis: TiO Optimisation………………….60
2
3.2.9 Famotidine pH Adjustment Studies ……………………………………………..63
3.2.10 Famotidine Hydrogen Peroxide Addition: P-25 TiO …………………………..70
2
3.2.11 Adsorption Studies: Glassware and TiO ……………………………………….76
2
3.2.12 Famotidine Concentration Variation Studies…………………………………...78
3.2.13 Famotidine Heterogeneous Photocatalytic Degradation Conclusions………….79
Heterogeneous Photocatalysis Part II: Tamsulosin……………………………………………..79
3.2.14 UV-vis Studies………………………………………………………………….79
3.2.15 Quartz Glassware: Photolysis Studies……………………………..……………80
3.2.16 Quartz Glassware: Photocatalysis Studies……………………………………...81
3.2.17 Pyrex Glassware: Photolysis Studies…………………………………………...82
3.2.18 HPLC Analysis of Photolysis Studies…………………………………………..83
3.2.19 Tamsulosin Heterogeneous Photocatalysis: Pyrex……………………………...83
3.2.20 Tamsulosin Heterogeneous Photocatalysis: TiO Optimisation……………...…84
2
3.2.21 Tamsulosin pH Adjustment Studies…………………………………………….86
3.2.22 Tamsulosin Hydrogen Peroxide Addition: P-25 TiO …………………….…….88
2
3.2.23 Adsorption Studies: Glassware ………..……………………………………….93
3.2.24 Tamsulosin Concentration Variation Studies…………………………………...93
3.2.25 Tamsulosin Heterogeneous Photocatalytic Degradation Conclusions………….93
Heterogeneous Photocatalysis Part III: Solifenacin…………………………………………….94
3.2.26 UV-vis Studies………………………………………………………………….94
3.2.27 Quartz Glassware: Photolysis Studies…………………………………………..95
3.2.28 Quartz Glassware: Photocatalysis Studies……………………………………...96
3.2.29 Pyrex Glassware: Photolysis Studies…………………………………………...97
3.2.30 HPLC Analysis of Photolysis Studies…………………………………………..98
3.2.31 Solifenacin Heterogeneous Photocatalysis: Pyrex……………………………...98
3.2.32 Solifenacin Heterogeneous Photocatalysis: TiO Optimisation….……………100
2
3.2.33 Solifenacin pH Adjustment Studies…………………………………………...102
3.2.34 Solifenacin Hydrogen Peroxide Addition: P-25 TiO ……………………...….103
2
3.2.35 Adsorption Studies: Glassware………………………………………………..105
3.2.36 Solifenacin Concentration Variation Studies………………………………….107
VI
3.2.37 Solifenacin Heterogeneous Photocatalytic Degradation Conclusions…...……107
Chapter 4 - Intermediate Analysis and Elucidation of Degradation Mechanisms for
Famotidine, Tamsulosin and Solifenacin …………………………………………………..109
4.1 Introduction……………...……………….…………………………..……………….…...110
4.2 Results and Discussion………………….…………………………………………….…...110
4.2.1 LC-MS/MS Method Transfer and Re-optimisation………………………….…110
4.2.2 Molecular Oxidation Analysis………………………………………………..…113
4.2.3 Direct Infusion Mass Spectrometry Studies: Famotidine…………………….....114
4.2.4 Follow-Up Direct Infusion Mass Spectrometry Studies: Famotidine..…………119
4.2.5 LC-MS/MS Studies and Intermediate Analysis: Famotidine………………..….122
4.2.6 Ions which could not be Elucidated…………………………………………..…137
4.2.7 Famotidine Proposed Intermediates Structures Conclusions………………...…141
4.2.8 Direct Infusion Mass Spectrometry Studies: Tamsulosin………………………144
4.2.9 Follow-Up Direct Infusion Mass Spectrometry Studies: Tamsulosin………..…147
4.2.10 LC-MS/MS Studies and Intermediate Analysis: Tamsulosin…………………148
4.2.11 Ions which could not be Elucidated……………………………………………172
4.2.12 Tamsulosin Proposed Intermediates Structures…………………………..……176
4.2.13 Direct Infusion Mass Spectrometry Studies: Solifenacin…………………...…179
4.2.14 Follow-Up Direct Infusion Mass Spectrometry Studies: Solifenacin…………182
4.2.15 LC-MS/MS Studies and Intermediate Analysis: Solifenacin……………….…183
4.2.16 Ions which could not be Elucidated…………………………………………....211
4.2.17 Solifenacin Proposed Intermediates Structures……………………………..…213
4.2.18 Control Experiments………………………………………………………..…216
4.2.19 LC-MS/MS Analysis of the Optimised TiO /UV/H O Process………………216
2 2 2
4.2.20 Intermediate Studies Conclusions…………………………………………..…217
Chapter 5 - Development and Characterisation of Visible Light Sensitised Photocatalytic
Materials and Evaluation of their Photocatalytic Activity with Famotidine
………………………………………………………………………………………………....218
5.1 Introduction……..……………………………………………..……....……………….….219
5.2 Results and Discussion………...….……………………………….…..……………….….220
5.2.1 Synthesis of TCPP-TiO …………………………………………………….…..220
2
5.2.2 Characterisation of TCPP-TiO ………………………………………………....221
2
5.2.3 Examination of the Photocatalytic Efficiency of TCPP-TiO in Famotidine
2
Degradation with Visible Light.……………………………………………………....225
5.2.4 Synthesis of Zn-Hexadecafluorophthalocyanine-TiO ……………………….....236
2
5.2.5 Characterisation……………………………………………………….……...…237
VII
5.2.6 Examination of the Photocatalytic Efficiency of ZnHFphthalocyanine-TiO in
2
Famotidine Degradation with Visible Light. …………………………………………239
5.2.7 Preparation of 1,4-(tetrabenzaldehyde)phthalocyanine-TiO …………………...241
2
5.2.8 Characterisation…………………………………………………………………242
5.2.9 Examination of the Photocatalytic Efficiency of β-(tetrabenzaldehyde)-
phthalocyanine-TiO in Famotidine Degradation with Visible Light. ……………….245
2
5.2.10 Synthesis of Acetylacetonate linker (3-[4-benzoic acid] pentane-2,4-dione)....246
5.2.11 Immobilisation onto TiO …………………………….……………………….246
2
5.2.12 Synthesis of TDI-TiO …………………………………………………………246
2
5.2.13 Characterisation of TDI-TiO ………………………………………………….247
2
5.2.14 Synthesis of APS-TiO ……………………………………………………..….248
2
5.2.15 Characterisation of APS-TiO …………………………………………………248
2
5.2.16 Visible Light Sensitised Photocatalyst Development Conclusions…………....251
Chapter 6 - Thesis Conclusions and Future Work……………………………………..…..253
References…….….….………….………………………………………………………….....258
Appendices……….……….…………..…..……………………………………………..…….A1

VIII
List of Conferences attended, Poster presentations and Papers Published/In
preparation
(Presenters starred)

International Conferences
Oxidation Technologies for Water and Wastewater Treatment AOP5 (5th IWA Specialist
Conference / 10th IOA-EA3G-Conference) (Attendance Only) 30th March- 3rd April 2009 Berlin,
Germany.

S. Murphy*, M. Oelgemöller, J. Tobin, A. Morrissey, K. Nolan "Photocatalytic Degradation of
Pharmaceuticals in Aqueous Solutions” Journées Européennes de la Photocatalyse (JEP) 22-
23rd September 2009, Bordeaux, France.

S. Murphy*, M. Oelgemöller, J. Tobin, A. Morrissey, K. Nolan "Photocatalytic Degradation of
Pharmaceuticals in Aqueous Solutions” CECP, 7-11th February 2010 Bad Hofgastein, Austria.

Local Conferences
M. Cullen*, A. Deegan*, C. Lacey, S. Murphy*, A. Morrissey, M. Oelgemoeller, J. Tobin
“Pharmaceuticals in the Aquatic Environment” ENVIRON (DkIT) 1- 3rd February 2008,
Dundalk, Ireland.

K. Joyce*, S. Murphy*, M. Oelgemöller “Green Photochemistry: From the Synthesis of Fine
Chemicals to Water Treatment with Sunlight” EPA conference, Royal Hospital Kilmainham,
6th-7th February 2008, Dublin, Ireland.

S. Murphy, A. Deegan, M. Cullen, C. Lacey, A. Morrissey, M. Oelgemöller*, J. Tobin “Green
Photochemistry” Detection and Sustainable Degradation of Pharmaceuticals” Challenge of
Sustainability Conference, 20th June 2008, Dundalk (DkIT), Ireland.

S. Murphy*, M. Oelgemöller, J. Tobin, A. Morrissey, K. Nolan "Photocatalytic Degradation of
Pharmaceuticals in Aqueous Solutions” ENVIRON (WIT) 15-17th January 2009, Waterford,
Ireland.

S. Murphy*, M. Oelgemöller, J. Tobin, A. Morrissey, K. Nolan "Photocatalytic Degradation of
Pharmaceuticals in Aqueous Solutions” SCI Green Chemistry Helix, DCU April 2010.

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