Development of catalytic microreactors by plasma processes and sol-gel processes Xi Rao To cite this version: Xi Rao. Development of catalytic microreactors by plasma processes and sol-gel processes. Analytical chemistry. Université Pierre et Marie Curie - Paris VI, 2016. English. NNT : 2016PA066145. tel- 01592658 HAL Id: tel-01592658 https://tel.archives-ouvertes.fr/tel-01592658 Submitted on 25 Sep 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. Université Pierre et Marie Curie Ecole doctorale 391 : Sciences Mécaniques, Acoustique, Electronique et Robotique de Paris IRCP, UMR 8247 (CNRS-Chimie ParisTech) Equipe Procédés, Plasmas, Microsystèmes Développement de microréacteurs catalytiques par procédés plasma et procédés sol-gel Par RAO Xi Thèse de doctorat en : Chimie - Génie des Procédés Dirigée par TATOULIAN Michaël Présentée et soutenue publiquement le 24 Mai 2016 Devant un jury composé de : Mme. PONCIN-EPAILLARD Fabienne Directeur de recherche CNRS Rapporteur Université du Maine M. LEONARD Didier Professeur des Universités Rapporteur Institut des Sciences Analytiques M. DA COSTA Patrick Professeur des Universités Examinateur UPMC Sorbonne Universités M. ABOU-HASSAN Ali Maître des Conférences, HDR Examinateur UPMC Sorbonne Universités M. GUYON Cédric Maître des Conférences Examinateur Chimie ParisTech, PSL M. CHU Chenglin Professeur des Universités Examinateur Southeast University (China) M. TATOULIAN Michaël Professeur des Universités Directeur de thèse Chimie ParisTech, PSL Acknowledgments PhD dissertation of UPMC Acknowledgments The work leading to the completion of this PhD thesis was performed in the Procédés, Plasmas, Microsystèmes (2PM) team in Chimie ParisTech in Paris, France. It would not have been possible to write this doctoral thesis without the support of many people in both my private and professional life, to only some of whom it is possible to give particular mention here. Firstly, I would like foremost to express my sincere gratitude to my supervisor and director of the 2PM team, Prof. Michael Tatoulian, for his guidance, tolerance, and insight scientific support during this project over these years. His superior knowledge extended all the way my vision as a rookie researcher, and his kind patience has allowed me to wander and attempt goals in various directions. Also, I am deeply grateful to my co-supervisors Dr. Ali Abou-Hassan and Dr. Stéphanie Ognier, for a number of highly enlightening conversations on my project and for the endless hours they have spent correcting my papers and dissertation. Their extensive knowledge, serious scientific attitude, and rigorous approach have always been inspiring. I am particularly indebted to Dr. Cédric Guyon who also supervised my research. His good advice, support and friendship always conveyed me the message that nothing is difficult. Especially, thanks for his involvement in the intensive corrections of my dissertation. Moreover, I would like to extend my thanks to the other members of the committee, Mme. Fabienne Poncin-Epaillard, Prof. Didier Leonard, Prof. Patrick Da Costa and Prof. Chenglin Chu for their precious time to read my thesis and the valuable advice on this work. Thanks to all the 2PM members who provided me professional knowledge, personal support and true friendship for the last 4 years. I want to thank every member of our research group, Simeon Cavadias, Fatiha Abdennebi, Guillaume Schelcher, 1 Acknowledgments PhD dissertation of UPMC Erick Martinez, Ines Hauner, Mengxue Zhang, Magdalena Nizio, Olivier Lesage, Bradley Da Silva. Especially, I would particularly like to thank Mengxue as she provided me so much kind help at the end of my Ph.D. Also, I would like to thank the other kind people that helped me in this lab, Frederic Rousseau, Alexandre Ma, Daniel Morvan, Rafik Benrabbah, Abhay Kumar Jaiswal, Dhia Ben Salem, Houssam Fakhouri, Isabelle Mabille, Willy Morscheidt, Bruno Pelat, Maxime Cloutier and so on. Finally, I would like to thank my family. My parents and my grandparents, I could never achieve this goal without your unconditional love and warmest support in life. Thank you for teaching me things that cannot be learned at school. 2 Contents PhD dissertation of UPMC Contents Acknowledgments .................................................................................................................... 1 Abstract of the thesis ............................................................................................................... 7 Chapter I: Bibliography ....................................................................................................... 11 1.1 Introduction .................................................................................................................. 11 1.2 General introduction of microfluidic systems ........................................................... 11 1.2.1 The development of microsystems ................................................................... 11 1.2.2 Microfluidic systems for chemical engineering ............................................... 12 1.2.3 Materials for microreactors fabrication ............................................................ 14 1.2.4 Fabrication methods ......................................................................................... 16 1.2.5 Other components of a microfluidic system ..................................................... 17 1.2.6 Sealing of a microreactor .................................................................................. 19 1.3 Plasma surface modifications of microchannels ........................................................ 20 1.3.1 Definition of a plasma ...................................................................................... 20 1.3.2 Applications of plasma ..................................................................................... 21 1.3.3 Plasma enhanced chemical vapor deposition (PECVD) ................................... 22 1.3.4 Influence of the parameters during PECVD process ........................................ 24 1.3.5 Amino functionalization by PECVD method ................................................... 31 1.4 Catalysts and their immobilization ............................................................................ 32 1.4.1 Gold nanoparticles (AuNPs) as catalysts .......................................................... 32 1.4.2 Zeolite as a support material ............................................................................. 33 1.4.3 Synthesis of AuNPs .......................................................................................... 35 1.4.4 Immobilization of AuNPs ................................................................................. 37 1.4.5 Deposition zeolite and gold@zeolite on substrate surface ............................... 38 1.5 Application: oxidation in microreactors .................................................................... 39 1.5.1 Liquid phase oxidation of benzyl alcohol and its products .............................. 39 1.5.2 Influence of reaction conditions ....................................................................... 40 1.5.3 Recent studies of using microsystem for benzyl alcohol oxidation .................. 43 1.6 Objectives of this work ................................................................................................ 44 1.7 Outline ........................................................................................................................... 45 Chapter II Characterization methods ................................................................................. 47 3 Contents PhD dissertation of UPMC 2.1 Contact angle measurement ....................................................................................... 47 2.2 Fourier Transform infrared spectroscopy (FTIR) ................................................... 48 2.3 X-ray Photoelectron Spectroscopy (XPS).................................................................. 50 2.4 Spectroscopic ellipsometer .......................................................................................... 52 2.5 Field-emission scanning electron microscopy (FESEM) .......................................... 54 2.6 Transmission electron microscopy (TEM) ................................................................ 56 2.7 Zeta potential ............................................................................................................... 57 2.8 X-ray diffraction (XRD).............................................................................................. 59 2.9 Ultraviolet-visible spectroscopy (UV-Vis) ................................................................. 61 2.10 High performance liquid chromatography (HPLC) .............................................. 64 Chapter III Deposition of amine groups by means of APTES PECVD process .............. 67 3.1 Abstract ......................................................................................................................... 67