Development of electrode architectures for miniaturized biofuel cells Aleksandar Karajic To cite this version: Aleksandar Karajic. Development of electrode architectures for miniaturized biofuel cells. Chemical Physics [physics.chem-ph]. Université de Bordeaux, 2015. English. NNT : 2015BORD0305. tel- 01424143 HAL Id: tel-01424143 https://tel.archives-ouvertes.fr/tel-01424143 Submitted on 2 Jan 2017 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. THÈSE PRÉSENTÉE A L’UNIVERSITÉ DE BORDEAUX ÉCOLE DOCTORALE DES SCIENCES CHIMIQUES Par Aleksandar Karajić POUR OBTENIR LE GRADE DE DOCTEUR SPÉCIALITÉ : Chimie-Physique Development of electrode architectures for miniaturized biofuel cells Directeurs de thèse : Prof. Alexander Kuhn et Dr. Nicolas Mano Soutenue le : 15.12.2015. Devant la commission d’examen formée de : M. BARTLETT N. Philip Professeur, Université de Southampton Rapporteur M. WALCARIUS Alain Directeur de recherche, CNRS, Nancy Rapporteur M. MIHI Agustín Chercheur, Université de Rovira i Virgili Tarragona Examinateur M. RAVAINE Serge Professeur, Université de Bordeaux Examinateur M. KUHN Alexander Professeur, INP - Bordeaux Directeur de thèse M. MANO Nicolas Directeur de recherche, CNRS, Bordeaux Co- directeur de thèse Acknowledgements This work has been done in the laboratories of Institute of Molecular Sciences (ISM) and Research Center Paule Pascal (CRPP) at the University of Bordeaux. First of all I would like to take this opportunity to acknowledge all members of the jury for their acceptance to evaluate my thesis and for their useful comments and suggestions, particularly to Prof. Philip Bartlett from the University of Southampton and Dr. Alan Walcarius from CNRS/University of Loraine for accepting the invitation as reviewers of this manuscript and for their useful comments and corrections. I would like to express my big gratitude to both of my supervisors, Prof. Alexander Kuhn (ISM) and Dr. Nicolas Mano (CRPP) for guiding me during the last three years through complex fields of electrochemistry, material science and bioelectrochemistry and for sharing their great experience and knowledge with me. Thank you for providing me guidance at key moments in my work while also allowing me to work independently. Merci beaucoup et/und Danke schön! This work has been financially supported by AMADEus-LabEx project (University of Bordeaux) on what I am very grateful. Also, I would like to acknowledge the Institute of molecular sciences (ISM/Bordeaux) and National Polytechnic Institute of Bordeaux (INP/Bordeaux). Thank you all! I am very grateful to my colleagues from NSYSA group for their support and a lot of nice moments that we spent together. Many thanks to Dr. Suresh Vajrala, Dr. Léa Messager, Dr. Aileen Justies, Dr. Salem Ben Amor, Dr. Florent Pinaut, Dr. Catherine Adam, Dr. Jérome Roche, Hannah Nas, Antoine Richieu, Alessandra Zanut, Dr. Sudarat Yadnum, Dr. Churalat Wattanakit, Oranit Phuakkong, Supakit Tiewchareon, Thittaya Yutthalekham, Dr. Damien Quinton, Dr. Pascal Massé, Dr. Vasilica Lates, Dr. Marlène Rouhet, Beatriz Diez Buitrago, Saioa Basauri Cadarso, Eugenio Gianessi, Li Haidong, Iuliia Malytska, Hélène Labie, Pauline Lefrancois, Gibran Hernandez Moreno, Dr. Milena Milutinovic-Dumont, Dr. Zahra Fatah Ali, Pierre Bouillac, Jovana Jovanovic, Damla Keskin and Dr. Habatmu Henock. However, I would like to express my special gratitude to Dr. Anne de Poulpiquet, Dr. Stéphane Reculusa and Dr. Emmanuel Suraniti for everything that they have done for me. Thank you for the honest friendship, your support and professional help. I will always remember it. Merci a tous! Many thanks to Prof. Jochen Lang and Dr. Eileen Pedraza from the Institute of Chemistry and Biology of Membranes and Nano-objects (University of Bordeaux) for the collaboration in the field of coupling electrochemistry with electrophysiology of pancreatic beta cells. Thank you Eileen for plenty of nice conversations that we had during the experiments and for helping me to improve my English skills. Also, I would like to knowledge Prof. Philippe Barthélémy and Dr. Deepak Jain from the Institute of Health and Medical Care (INSERM) from the University of Bordeaux for their collaboration on the project about low molecular weight hydrogel for bio-electrode interfaces. I would especially like to acknowledge permanent members of NSYSA group for the fruitful academic discussions that we had during the lab seminars. Thank you Dr. Bertrand Goudeau, Dr. Dodzi Zigah, Dr. Laurent Bouffier, Dr. Neso Sojic, Dr. Stéphane Arbault, Dr. Valérie Ravaine, Dr. Adeline Perro-Marre, Patrick Garrigue and Véronique Lapeyre. For the administrative support, I would like to acknowledge to our secretary Aline Simon-Lalande. I would like to thank the CRPP team for the collaboration in the area of biofuel cells and for a great time that we have spent together, especially during the last few months of my PhD project. Many thanks to Dr. Marine Cadet, Magdalena Murawska, Dr. Jad Rouhana, Dr. Lise Edembe and Sébastien Gounel. Najiskrenije se zahvaljujem svojoj porodici na razumevanju, ljubavi i podršci koju su mi pružili ne samo tokom izrade i pisanja ove teze vec tokom celokupnog dosadašnjeg života. Hvala! Posebnu zahvalnost dugujem profesoru Draganu Manojloviću i svojoj bivoj mentorki profesorki Snežani Nikolić-Mandić sa Hemijskog fakulteta na Univerzitetu u Beogradu na znanju i iskustvu koje su mi preneli tokom osnovnih i master studija kao i na nesebičnoj podršci. Zahvaljujem koleginici dr Milica Sentić na iskrenom prijateljstvu, podršci i nesvakidašnjim situacijama kroz koje smo zajedno prošli tokom prethodne četiri godine. Veliko ti hvala na svemu!!! Posebno se zahvaljujem Siniši Mitroviću, Stefanu Mijatoviću, Diane Michalon i Mariam Hovhannisyan na iskrenom prijateljstvu i mnoštvu lepih trenutaka koje smo zajedno proveli. Hvala vam! Abstract The increasing demand for miniaturized and eventually implantable electrochemical tools such as biosensors, biofuel cells and batteries has led to the development of new technologies to overcome existing problems related to large dimensions, low current densities, and insufficient power output of such devices. In the present work we describe new approaches for the fabrication of miniaturized, macroporous and coaxial electrode architectures that could find their practical application for the fabrication of the systems mentioned above. Furthermore, we have demonstrated the functionality of macroporous electrodes with respect to the design of miniaturized glucose/oxygen biofuel cells. Preliminary results regarding the design of a new type of whole-cell based glucose biosensors are also presented. The first part of this work is focusing on different strategies for the fabrication of colloidal crystals (Chapter 1) that can be used for the synthesis of macroporous electrodes (Chapter2) by following the so-called hard template approach. The synthesis of macroporous electrodes is based on the potentiostatic electrodeposition of conductive materials (such as metals in the present work) into a silica based colloidal template that has been synthesized by the Langmuir- Blodgett procedure. This method has been used for the design and fabrication of miniaturized coaxial and macroporous two electrode-electrochemical cells by following two different and complementary procedures: 1. The first fabrication procedure is based on the electrodeposition of alternating gold-nickel-gold metal layers, subsequent etching of the intermediate nickel layer and a structural stabilization; 2. The second alternative and complementary strategy for the fabrication of coaxial and macroporous double electrochemical cells relies on assembling the final architecture from two independently prepared and electrochemically addressable cylindrical macroporous electrodes. The main difference between these two approaches is the range of inter-electrode distances (from tens of micrometers (first approach) to hundreds of micrometers that can be achieved by second fabrication procedure). Also, we demonstrate the electrochemical functionality of both electrode architectures by cyclo-voltammetric investigation of the oxygen reduction reaction that takes place at the surface of both electrodes. The biggest advantage of the presented strategies is the possibility to fine tune the electrode thickness (and therefore active surface areas), the spatial separation between inner and outer electrode (the volume of electrolyte that can be stored between them) and the pore size (by changing the diameter of silica colloidal particles). In the following segment (Chapter 3), we demonstrate the possibility to use macroporous electrodes for the fabrication of an enzymatic biocathode. The macroporous gold substrates were chosen as promising candidates to improve the electrochemical performances (current and power output) of an enzymatic glucose/oxygen biofuel cells due to their high active surface area. Cyclic-voltammetry has been used for electrodeposition of Os-redox polymer and a Bilirubin oxidase (BOD)/Os-redox polymer