University of Kentucky UKnowledge Theses and Dissertations--Chemistry Chemistry 2017 SEMICONDUCTOR PHOTOCATALYSIS: MECHANISMS, PHOTOCATALYTIC PERFORMANCES AND LIFETIME OF REDOX CARRIERS Ruixin Zhou University of Kentucky, [email protected] Author ORCID Identifier: https://orcid.org/0000-0002-2405-4893 Digital Object Identifier: https://doi.org/10.13023/ETD.2017.394 Right click to open a feedback form in a new tab to let us know how this document benefits ou.y Recommended Citation Zhou, Ruixin, "SEMICONDUCTOR PHOTOCATALYSIS: MECHANISMS, PHOTOCATALYTIC PERFORMANCES AND LIFETIME OF REDOX CARRIERS" (2017). Theses and Dissertations--Chemistry. 85. https://uknowledge.uky.edu/chemistry_etds/85 This Doctoral Dissertation is brought to you for free and open access by the Chemistry at UKnowledge. It has been accepted for inclusion in Theses and Dissertations--Chemistry by an authorized administrator of UKnowledge. For more information, please contact [email protected]. STUDENT AGREEMENT: I represent that my thesis or dissertation and abstract are my original work. Proper attribution has been given to all outside sources. I understand that I am solely responsible for obtaining any needed copyright permissions. I have obtained needed written permission statement(s) from the owner(s) of each third-party copyrighted matter to be included in my work, allowing electronic distribution (if such use is not permitted by the fair use doctrine) which will be submitted to UKnowledge as Additional File. I hereby grant to The University of Kentucky and its agents the irrevocable, non-exclusive, and royalty-free license to archive and make accessible my work in whole or in part in all forms of media, now or hereafter known. I agree that the document mentioned above may be made available immediately for worldwide access unless an embargo applies. I retain all other ownership rights to the copyright of my work. I also retain the right to use in future works (such as articles or books) all or part of my work. I understand that I am free to register the copyright to my work. REVIEW, APPROVAL AND ACCEPTANCE The document mentioned above has been reviewed and accepted by the student’s advisor, on behalf of the advisory committee, and by the Director of Graduate Studies (DGS), on behalf of the program; we verify that this is the final, approved version of the student’s thesis including all changes required by the advisory committee. The undersigned agree to abide by the statements above. Ruixin Zhou, Student Dr. Marcelo I. Guzman, Major Professor Dr. Mark A. Lovell, Director of Graduate Studies SEMICONDUCTOR PHOTOCATALYSIS: MECHANISMS, PHOTOCATALYTIC PERFORMANCES AND LIFETIME OF REDOX CARRIERS DISSERTATION A dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy in the College of Arts and Sciences at the University of Kentucky By Ruixin Zhou Lexington, Kentucky Director: Dr. Marcelo Guzman, Associate Professor of Chemistry Lexington, Kentucky 2017 Copyright © Ruixin Zhou 2017 ABSTRACT OF DISSERTATION SEMICONDUCTOR PHOTOCATALYSIS: MECHANISMS, PHOTOCATALYTIC PERFORMANCES AND LIFETIME OF REDOX CARRIERS Photocatalytic reactions mediated by semiconductors such as ZnS, TiO2, ZnO, etc. can harvest solar energy into chemical bonds, a process with important prebiotic and environmental chemistry applications. The recycling of CO2 into organic molecules (e.g., formate, methane, and methanol) facilitated by irradiated semiconductors such as colloidal ZnS nanoparticles has been demonstrated. ZnS can also drive prebiotic reactions from the reductive tricarboxylic acid (rTCA) cycle such as the reduction of fumarate to succinate. However, the mechanism of photoreduction by ZnS of the previous reaction has not been understood. Thus, this thesis reports the mechanisms for heterogeneous photocatalytic reductions on ZnS for two model reactions in water with sulfide hole scavenger. First the reduction of CO2 is carried out under variable wavelength of irradiation and proposed to proceed thorough five steps resulting in the exclusive formation of formate. Second the reduction of the double bond of fumaric acid to succinic acid is reported in detail and compared to the previous conversion of CO2 to formic acid. Both reactions are carried out under variable wavelength of irradiation and proposed to proceed thorough one electron transfer at a time. In addition, a new method to measure the bandgap of colloidal ZnS suspended in water is established. Furthermore, the time scales of electron transfer and oxidizing hole loss during irradiation of ZnS for both reactions are reported and interpreted in terms of the Butler-Volmer equation. The sunlight promoted production of succinate introduced above, provides a connection of this prebiotic chemistry work to explore if central metabolites of the rTCA cycle can catalyze the synthesis of clay minerals. Clay minerals are strong adsorbents that can retain water and polar organic molecules, which facilitate the polymerization of biomolecules and conversion of fatty acid micelles into vesicles under prebiotic conditions relevant to the early Earth. While typical clay formation requires high temperatures and pressures, this process is hypothesized herein to be accelerated by central metabolites. A series of synthesis are designed to last only 20 hours to study the crystallization of sauconite, an Al- and Zn-rich model clay, at low temperature and ambient pressure in the presence of succinate as a catalyst. Succinate promotes the formation of the trioctahedral 2:1 layer silicate at ≥ 75 °C, 6.5 ≤ pH ≤ 14, [succinate] ≥ 0.01 M. Cryogenic and conventional transmission electron microscopies, X-ray diffraction, diffuse reflectance Fourier transformed infrared spectroscopy, and measurements of total surface area and cation exchange capacity are used to study the time evolution during the synthesis of sauconite. While the studies with ZnS presented above advanced the fundamental understanding of photocatalysis with single semiconductors, the environmental applications of this material appear limited. A common limitation to photocatalysis with single semiconductors is the rapid recombination of photogenerated electron-hole pairs, which reduces significantly the efficiency of the process that in the case of ZnS also suffers from photocorrosion in the presence of air. In order to overcome the fast charge recombination and the limited visible-light absorption of semiconductor photocatalysts, an effective strategy is developed in this work by combining two semiconductors into a nanocomposite. This nanocomposite is solvothermally synthesized creating octahedral cuprous oxide covered with titanium dioxide nanoparticles (Cu2O/TiO2). The nanocomposite exhibits unique surface modifications that provide a heterojunction with a direct Z-scheme for optimal CO2 reduction. The band structure of the nanocomposite is characterized by diffused reflectance UV-visible spectroscopy, X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy. The photoreduction of CO2(g) to CO(g) on the nanocomposite is investigated in the presence water vapor as the hole scavenger that generates the quantifiable hydroxyl radical (HO•). The quantum efficiency of CO production under irradiation at λ ≥ 305 nm with the nanocomposite is 2- • times larger than for pure Cu2O. The detection of HO and XPS analysis contrasting the stability of Cu2O/TiO2 vs Cu2O during irradiation prove that TiO2 prevents the photocorrosion of Cu2O. Overall, the studies of photocatalytic reductions on single component semiconductors reveal new knowledge needed for developing future photocatalytic application for fuel production, wastewater treatment, reducing air pollution, and driving important prebiotic chemistry reactions. Furthermore, the design of a photocatalyst operating under a Z- scheme mechanism provides a new proof of concept for the design of systems that mimic photosynthesis. Finally, this work also demonstrates how molecules obtained by mineral mediated photochemistry can catalyze clay formation; highlighting the important role that photochemistry may have played for the origin of life on the early Earth and other rocky planets. KEYWORDS: semiconductor, photocatalysis, CO2 photoreduction, rTCA cycle, sauconite, heterojunction. Student’s signature: Ruixin Zhou Date: August 31, 2017 SEMICONDUCTOR PHOTOCATALYSIS: MECHANISMS, PHOTOCATALYTIC PERFORMANCES AND LIFETIME OF REDOX CARRIERS By Ruixin Zhou Dr. Marcelo I. Guzman Director of Dissertation Dr. Mark A. Lovell Director of Graduate Studies 08/31/17 ACKNOWLEDGEMENTS First, I would like to express my sincere gratitude to my advisor Dr. Marcelo I. Guzman for the continuous support of my Ph.D study and related research, for his patience, motivation, and immense knowledge. I am very lucky to have chosen Dr. Guzman as my research adviser. With his help, I have had access to a lot of opportunities to learn how to use new instruments, present our work at national and international conferences, collaborate with other famous scientists, and share our work through press media releases. Besides my advisor, I would like to thank the rest of my thesis committee: Dr. Dong- Sheng Yang, Dr. John Selegue and Dr. Christopher J. Matocha, for their useful comments and encouragement, but also for the wonderful enquiring process during meetings and exams that guided me and helped me to understand my research better. Many people helped me through this wonderful journey of graduate school life.