For Energy Harvesting and CO2 Conversion
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Comprehensive Study of Biocathode in Bio-electrochemical System (BES) for Energy Harvesting and CO2 Conversion Paniz Izadi A thesis presented for the degree of Doctor of Philosophy School of Engineering Newcastle University, UK February 2020 Abstract The focus of this thesis is studying the mixed community biocathode to solve the bottlenecks for the scale-up and commercialisation of Bio-electrochemical Systems (BESs). First, the utilisation of aerobic iron-oxidising bacteria enriched from natural environment and Fe2+ in Microbial fuel cell (MFC) equipped with gas diffusion electrodes was studied as an efficient alternative to Pt-based catalysts for MFCs with unlimited oxygen diffusion. Controlling the system pH during continuous operational mode, MFCs produced maximum power density of 0.251 mW cm-2, compared to 0.134 mW cm-2 for MFCs equipped with Pt catalyst (0.5 mg cm-2 Pt on carbon paper) indicating advantages of fully microorganism catalysed system, and importance of operational parameters in such systems. In microbial electrosynthesis (MES) converting CO2 to various organic compounds, optimisation of operational parameters, such as applied potential on the cathode, pH, and operational mode were investigated. The community analysis revealed different dominant communities on the electrode and in solution suggesting an electro-active biofilm was formed on the cathode. It also suggested the importance of cathodic potentials corresponding to - sufficient energy provided for MES and inorganic carbon sources (CO2 and HCO3 ) on biofilm formation and composition of bacterial community in biofilm responsible for MES, respectively. It was found that -1.0 V (Ag/AgCl) was required for MES, and CO2 was preferred inorganic carbon source for microorganisms for MES. Mechanisms of MES and chain elongation were studied. The hypothesis on hydrogen mediated electron transfer mechanism was confirmed from cyclic voltammetry showing a positive shift on hydrogen evolution onset potential with optimum conditions. The role of cathode on providing electrons was explored comparing the systems operated at open circuit potential (OCP) and applied potential. In addition, two different strategies of 1) impact of continuous operational mode and, 2) addition of external electron donors were investigated to promote chain elongation through acetate, triggering crucial parameters affecting production through MES. Acetate concentration reached the maximum of 6.8 g L-1 over fed-batch mode with a production rate of 660 ppm day-1 (maximum columbic efficiency~69%), while the highest acetate production rate in this study was reached over continuous operational mode (803 ppm day-1, maximum columbic efficiency~90%). Over longer operational time and providing extra electron donors, longer chain organic acids (Butyrate) and alcohols (Butanol and Hexanol) were produced, concluding MES is a promising technology alternative to petrochemical production. i ii Acknowledgments I would like to thank all those who helped me throughout my PhD. In first place, I owe my gratitude to my supervisory team, which gave me the opportunity to become the researcher I am today. I would like to thank Dr Eileen Yu for offering me the opportunity to conduct my research, being patient with me, supporting me from day 1 throughout all my PhD journey, and guiding me to the right research direction. I want to thank Professor Ian Head for his great amount of support, patience, guidance, thoughtfulness and encouragement. I am grateful that I have had this chance to discuss my findings in detail with him, receive his instructive feedback, and learn from his massive knowledge in microbial and environmental sciences, helping me to develop new valuable skills. Thank you both for inspiring and motivating me to improve. Thanks to my research group. Dr Jean-Marie Fontmorin for his great support in experimental designs, reviewing my reports and discussing my research findings. Dr Martin Spurr for precious discussions about my findings, helping me in interpreting my data and reviewing my thesis result chapters. Dr Alexiane Godain for kindly teaching me her great knowledge in biological processes and how to interpret and process community analysis data. I am very grateful to have you all as my friends and colleagues. Special thanks to the faculty of Science, Agriculture and Engineering Doctoral Training Award in Newcastle University (SAgE DTA) and School of Chemical Engineering for supporting me throughout my PhD, helped me to focus only on my research. I must also thank the technical workshop team in School of Chemical Engineering for constructing the reactors, the bio-imaging services in Medical School for the training in confocal microscopy, and the scanning electron microscopy (SEM) service for gold-coating the samples for SEM analysis. Lastly, I’d like to thank my parents and brother exclusively for always having faith in my abilities, supporting and encouraging me in all stages of my education. Your love, patience, support and understanding mean a lot to me. Many thanks to my best friend, Dr Rebeca Gonzalez-Cabaleiro for her guidance, kind support and being as if a family member during this exciting but tough journey. I look forward to seeing you all more often! iii iv Table of Contents Chapter 1. Introduction ........................................................................................................... 1 1.1 Background and context .............................................................................................. 1 1.2 Limitations, hypothesis, aim and objectives ............................................................... 2 1.3 Outline of chapters ...................................................................................................... 5 Chapter 2. Literature Review on Aerobic and Anaerobic Biocathodes .............................. 9 2.1 Principles of BES ........................................................................................................ 9 2.2 Applications of BES .................................................................................................. 11 2.3 Microbial Fuel Cell (MFC) ....................................................................................... 12 2.4 Microbial electrosynthesis (MES)............................................................................. 14 2.5 Role of bioanodes in MFCs....................................................................................... 16 2.5.1 Role of bioanode in electricity generation in MFCs ....................................... 16 2.5.2 Development of electro-active bioanode from mixed culture of bacteria in MFCs ........................................................................................................................ 17 2.6 Aerobic biocathode in BESs ..................................................................................... 19 2.6.1 Aerobic biocathodes and their effect on enhancing the performance of MFCs .................................................................................................................................. 19 2.6.2 Catalysing oxygen reduction reaction (ORR) using direct electron transfer between bacteria and cathode .................................................................................. 22 2.6.3 Catalysing oxygen reduction reaction (ORR) using the mediated electron transfer between bacteria and cathode ..................................................................... 23 2.7 CO2 reducing biocathode in BESs ............................................................................ 25 2.7.1 Anaerobic autotrophic bacteria ....................................................................... 25 2.7.2 Microbial electrosynthesis (MES) and conversion of CO2 to valuable organic chemicals using anaerobic biocathode ..................................................................... 29 2.7.3 Pure culture of acetogens as anaerobic biocathodes responsible for MES processes .................................................................................................................. 32 v 2.7.4 Acetogens responsible for MES processes in mixed culture anaerobic biocathode................................................................................................................ 33 2.7.5 Effect of cathodic potential on MES processes .............................................. 35 2.7.6 Effect of inorganic carbon source on MES processes .................................... 40 2.7.7 Role of biofilm at the cathode in MES processes........................................... 42 2.8 Production of long chain organic acids and alcohols ............................................... 46 2.8.1 Production of long chain organic chemicals from CO2 .................................. 46 2.8.2 Effect of different electron donors on production of long chain organic chemicals from CO2 ................................................................................................ 49 2.8.3 Production of long chain organic chemicals from CO2 through electro- fermentation ............................................................................................................. 51 2.9 Summary ................................................................................................................... 54 Chapter 3. Materials and Methods ....................................................................................... 57 3.1 Aerobic biocathode experiment ...............................................................................