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Development of Bismuth Oxyhalide Photocatalysts for Environmental and Industrial Applications Robert Arthur University of Maine, [email protected]

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Development of Bismuth Oxyhalide Photocatalysts for Environmental and Industrial Applications Robert Arthur University of Maine, Robert.Arthur@Maine.Edu The University of Maine DigitalCommons@UMaine Electronic Theses and Dissertations Fogler Library Spring 5-11-2019 Development of Bismuth Oxyhalide Photocatalysts for Environmental and Industrial Applications Robert Arthur University of Maine, [email protected] Follow this and additional works at: https://digitalcommons.library.umaine.edu/etd Part of the Analytical Chemistry Commons, Environmental Chemistry Commons, and the Inorganic Chemistry Commons Recommended Citation Arthur, Robert, "Development of Bismuth Oxyhalide Photocatalysts for Environmental and Industrial Applications" (2019). Electronic Theses and Dissertations. 2961. https://digitalcommons.library.umaine.edu/etd/2961 This Open-Access Thesis is brought to you for free and open access by DigitalCommons@UMaine. It has been accepted for inclusion in Electronic Theses and Dissertations by an authorized administrator of DigitalCommons@UMaine. For more information, please contact [email protected]. DEVELOPMENT OF BISMUTH OXYHALIDE PHOTOCATALYSTS FOR ENVIRONMENTAL AND INDUSTRIAL APPLICATIONS By Robert Brent Arthur B.Sc., College of Charleston, 2013 A DISSERTATION Submitted in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy (in Chemistry) The Graduate School The University of Maine May 2019 Advisory Committee: Dr. Howard Patterson, Professor of Chemistry, Co-advisor Dr. Elizabeth Stemmler, Professor of Chemistry, Bowdoin College, Co-advisor Dr. Scott Collins, Professor of Chemistry, Co-advisor Dr. Alice Bruce, Professor of Chemistry Dr. Matthew Brichacek, Assistant Professor of Chemistry Dr. Carl Tripp, Professor of Chemistry DEVELOPMENT OF BISMUTH OXYHALIDE PHOTOCATALYSTS FOR ENVIRONMENTAL AND INDUSTRIAL APPLICATIONS By Robert B. Arthur Co-advisors: Dr. Howard H. Patterson, Dr. Elizabeth A. Stemmler, and Dr. Scott D. Collins An Abstract of the Dissertation Presented in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy (in Chemistry) May 2019 Heterogeneous semiconductor photocatalysis, of interest for water splitting and environmental remediation applications, uses light to drive reactions. Metal oxide and sulfide semiconductors have been previously studied but have limitations that include large band gap energies and high rates of recombination. Bismuth oxyhalides (BiOX) are an emerging class of photocatalysts with tunable band gaps and low rates of recombination due to their unique crystal structures. Studies of BiOX photocatalytic activity have largely focused on removal of azo dyes from aqueous solutions, with little attention paid to degradation byproducts. Furthermore, these catalysts have not been explored as a means to conduct organic transformations including C-C bond formation. In this work, BiOX solids were evaluated for the photocatalytic degradation of the persistent organic pollutants atrazine and ibuprofen. Work with atrazine, degraded with BiOCl • •- and Cu-BiOCl under 254 nm light conditions was explored for OH radical, O2 and electron hole contributions to the reaction pathway. The reaction rates and products generated by the photocatalytic degradation of ibuprofen using BiOCl were characterized and a degradation mechanism was proposed. The photocatalytic degradation studies suggest the high reactivity of electron holes in the valence band of BiOCl play an important role in the observed degradation efficiency. Finally, BiOI photocatalysts were evaluated for their potential to drive coupling reactions under visible light irradiation. It was found that coupling products of cyclohexyl halides and toluene are achieved in high yield, but cyclohexane dehydrodimerization reactions proceeded with low yields. DEDICATION Dedicated to My parents, John and Cathy Arthur For their love, support and encouragement. ii ACKNOWLEDGEMENTS First, I would like express my gratitude to my advisor, Dr. Howard Patterson, for his guidance and support. Special thanks to Aaron Nicholas, Matthew Moyet, Patrick Breeding, Jesse Bonin, Luke Ardill, Ryan Warner, and Justin Hamilton for their contributions to this work. I have thoroughly enjoyed working with all of you. I would like to thank Dr. Elizabeth Stemmler, for her mentorship, support, and use of the LC- MS/MS facilities at Bowdoin College. Beth’s expertise in analytical chemistry was instrumental in creating the scientist I am today. I would like to thank the members of my advisory committee, Dr. Elizabeth Stemmler, Dr. Scott Collins, Dr. Matthew Brichacek, Dr. Alice Bruce, and Dr. Carl Tripp for their advice and suggestions throughout my Ph.D. work. This dissertation could not have been completed without the help of Dave LaBrecque. I would also like to thank Dr. George Bernhardt for his assistance in acquiring XRD and SEM data. Thank you to all of my friends at the University of Maine, especially Kyle Veillette, Ealin Patel, Nayeem Ibnul, Peter Strand, and Zach Connarty-Marin for making this experience great. Finally, I would like to thank my family. My parents, John and Cathy Arthur, have supported me throughout my education and always believed in my ability to succeed. iii TABLE OF CONTENTS DEDICATION …………………………………………………………………………………... ii ACKNOWLEDGEMENTS …………………………………………………………………….. iii LIST OF TABLES ……………………………………………………………………………. xiii LIST OF FIGURES …………………………………………………………………………… xvi CHAPTER 1. INTRODUCTION ……………………………………………………………….. 1 1.1.Motivation ……………………………………………………………………………….. 1 1.1.1. Environmental …………………………………………………………………… 1 1.1.2. Industrial ………………………………………………………………………… 2 1.2. Introduction to Photocatalysis ………………………………………………………….. 3 1.3. Heterogeneous Semiconductor Photocatalysis …………………………………………. 4 1.3.1. Application in Environmental Remediation …………………………………….. 5 1.3.2. Application in C-C Coupling Reactions ………………………………………… 6 1.4. Bismuth Oxyhalides …………………………………………………………………….. 8 1.4.1. Applications of BiOX Photocatalysts ………………………………………….. 11 1.4.1.1. Environmental Applications of BiOX Photocatalysts …………………. 11 1.4.1.2. Industrial Applications of BiOX Photocatalysts …..…………………… 13 1.5. Thesis Objectives and Organization …………………………………………………... 14 1.6. References ……………………………………………………………………………... 16 iv CHAPTER 2. THE ROLE OF COPPER (II) IONS IN Cu-BiOCl FOR THE PHOTOCATALYTIC DEGRADATION OF ATRAZINE …………………… 40 2.1 Introduction …………………………………………………………………………….. 40 2.2 Experimental …………………………………………………………………………… 42 2.2.1 Materials and Sample Preparation ……………………………………………... 42 2.2.2 Catalyst Characterization ………………………………………………………. 43 2.2.3 Dark Adsorption and Photocatalytic Activity ………………………………….. 44 2.2.4 Fourier Transform Infrared Spectroscopy ……………………………………... 45 2.3 Results and Discussion ………………………………………………………………… 45 2.3.1 Catalyst Characterization ………………………………………………………. 45 2.3.1.1 X-Ray Diffraction ……………………………………………………… 45 2.3.1.2 Scanning Electron Microscopy-Electron Dispersive Spectroscopy …… 46 2.3.1.3 UV-Vis Diffuse Reflectance Spectroscopy ……………………………. 50 2.3.1.4 Photoluminescence Spectroscopy ……………………………………… 51 2.3.2 Adsorption and Photocatalytic Activity ………………………………………... 52 2.3.3 Radical Scavenging Experiments ……………………………………………… 53 2.3.4 Proposed Mechanism …………………………………………………………... 56 2.3.5 Fourier Transform Infrared Spectroscopy ……………………………………... 58 2.4 Conclusion ……………………………………………………………………………... 59 2.5 References ……………………………………………………………………………… 60 v CHAPTER 3. PHOTOCATALYTIC DEGRADATION OF IBUPROFEN OVER BiOCl NANOSHEETS WITH IDENTIFICATION OF INTERMEDIATES ………… 64 3.1 Introduction …………………………………………………………………………….. 64 3.2 Experimental …………………………………………………………………………… 67 3.2.1 Materials and Sample Preparation ……………………………………………... 67 3.2.2 Catalyst Characterization ………………………………………………………. 67 3.2.3 Photocatalytic Degradation of IBP and IBAP …………………………………. 68 3.2.4 HPLC Analysis ………………………………………………………………… 69 3.2.5 LC-MS/MS Analysis …………………………………………………………... 69 3.3 Results and Discussion ………………………………………………………………… 70 3.3.1 Catalyst Characterization ………………………………………………………. 70 3.3.2 Dark Adsorption of IBP to BiOCl ……………………………………………... 71 3.3.3 IBPE and IBAP are the Primary IBP Photocatalytic Degradation Products for BiOCl ……………………………………………………………………..... 72 3.3.4 Photocatalytic Degradation of IBAP is an Important Pathway for the Formation of Secondary Photocatalytic Products for BiOCl …………………... 79 3.3.5 Summary of Products and Mechanistic Insights for the Photodegradation of IBP and IBAP with BiOCl ………………………………………………….. 83 3.4 Conclusion ……………………………………………………………………………... 86 3.5 References …………………………………………………………………………….... 86 vi CHAPTER 4. DEVELOPMENT OF BiOX PHOTOCATALYSTS FOR INDUSTRIAL APPLICATIONS ………………………………………………………………. 94 4.1 Introduction …………………………………………………………………………….. 94 4.2 Materials and Methods …………………………………………………………………. 96 4.2.1 Synthesis of Catalysts ………………………………………………………….. 96 4.2.1.1 BiOI ………………………………………………………………………… 96 4.2.1.2 Metal Doping ………………………………………………………………. 97 4.2.1.3 Insertion of BiOI into Zeolite Support ……………………………………... 97 4.2.2 Characterization of Catalysts …………………………………………………... 98 4.2.2.1 Infrared Spectroscopy ……………………………………………………… 98 4.2.2.2 Diffuse Reflectance Spectroscopy …………………………………………. 99 4.2.3 General Reaction Setup ……………………………………………………….. 100 4.2.3.1 Photocatalytic Dehydrodimerization of Cyclohexane ……………………. 100 4.2.3.2 Visible-light Photoinitiated Iodination of Cyclohexane ………………….. 101 4.2.3.3 Photocatalytic Coupling Reactions with Cyclohexyl Halides ……………. 101 4.2.4 Analysis of Reaction Products ………………………………………………... 101 4.3 Results and Discussion ……………………………………………………………….. 103
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