Functional Nanostructured Membranes Functional Nanostructured Membranes edited by Enrico Drioli Lidietta Giorno Annarosa Gugliuzza Published by Pan Stanford Publishing Pte. Ltd. Penthouse Level, Suntec Tower 3 8 Temasek Boulevard Singapore 038988 Email: [email protected] Web: www.panstanford.com British Library Cataloguing-in-Publication Data A catalogue record for this book is available from the British Library. Functional Nanostructured Membranes All rights reserved. This book, or parts thereof, may not be reproduced in any form Copyright © 2019 by Pan Stanford Publishing Pte. Ltd. or by any means, electronic or mechanical, including photocopying, recording or any information storage and retrieval system now known or to be invented, without written permission from the publisher. For photocopying of material in this volume, please pay a copying fee through the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, USA. In this case permission to photocopy is not required from the publisher. ISBN 978-981-4774-79-6 (Hardcover) ISBN 978-1-351-13511-5 (eBook) Contents Preface 1. An Intro duction to Nanostructured Membranes for xv Advanced Applications in Strategic Fields 1 Enrico Drioli, Lidietta Giorno, and Annarosa Gugliuzza 1.1 Nanosized Materials and Nanostructured Membrane Concepts 1 1.2 Viewpoint on Membrane Processes 5 1.3 Perspectives of Nanostructured Membranes 2. Nanostriunc Ltuifree dS cMieenmcebsr anes for Selective Separations: 8 Modeling and Simulations 13 Elena Tocci, Carmen Rizzuto, Johannes Carolus Jansen, and Enrico Drioli 2.1 Introduction 13 2.2 Polymers of Intrinsic Microporosity 15 2.2.1 PIM-PI, Ethanoanthracene (EA), and Tröger’s Base–Based PIMs 21 2.2.2 Crosslinked PIMs 22 2.2.3 Mixed Matrix Membranes 24 2.3 Simulation Methods 25 2.3.1 Ab initio 26 2.3.2 Atomistic 27 2.3.2.1 Monte Carlo simulations 28 2.3.2.2 Molecular dynamics 28 2.3.3 Physical Structure and Properties 29 2.3.4 Thermodynamics and Transport in Polymeric Membranes 31 2.3.5 Transition-State Theory 32 2.3.6 Diffusivity 33 2.4 Modeling of Polymers of Intrinsic Microporosity 34 2.4.1 Physical Structure and Properties 35 vi Contents 2.4.1.1 Torsion angle analysis 35 2.4.1.2 WAXD and packing ability of PIMs 37 2.4.1.3 Cavity size distribution 39 2.4.1.4 Surface area 42 2.4.1.5 Fractional free volume and fractional accessible volume 43 2.4.2 Thermodynamics and Transport Properties 46 2.4.2.1 Adsorption of different gases and solubility coefficient 46 2.4.2.2 Modeling of diffusion coefficients 52 3. 2Fa.5b ricatCioonn colfu Osirodne raendd M Peicrrsop- eacntdiv Nesa noporous 55 Membranes 83 Maria Luisa Perrotta and Annarosa Gugliuzza 3.1 Introduction 84 3.2 Lithographic Techniques 86 3.2.1 Nanoimprint Lithography and Related Subcategories 87 3.3 Phase Separation and Micro-Molding Combined Techniques 92 3.4 Micro- and Nanostructured Arrays by Colloidal Template Techniques 97 3.5 Self-Assembly of Nano-patterned Polymeric Architectures 102 3.6 Breath Figure for Bio-inspired High-Defined Membranes 106 3.6.1 Potential Controlling Mechanisms 107 3.6.2 Polymers Chemistry 109 3.6.3 Nature of Solvents 111 3.6.4 Temperature Effect 112 3.6.5 Surface Free Tension 112 3.6.6 Potential Applications of Honeycomb Structures 114 3.7 Future Prospects and Concluding Remarks 118 Contents vii 4. Nanostructured Ion-Exchange Membranes 131 Enrica Fontananova and Enrico Drioli 4.1 Introduction to Ion-Exchange Membranes 132 4.2 Role of Physical and Chemical Microenvironment on IEM Transport Properties 136 4.3 Nanostructured Polymeric IEMs 144 4.4 Nanostructured Mixed Matrix IEMs 148 5. 4N.a5n ostrCuoctnucrleuds iZoeno lite Membranes: Synthesis and 152 Applications 161 Catia Algieri, Angelo Garofalo, and Enrico Drioli 5.1 Introduction 162 5.2 Preparation of Nanostructured Zeolite Membranes 164 5.3 Characterization of Nanostructured Zeolite Membranes 169 5.4 Scale-Up of MFI Zeolite Membranes 171 5.5 MFI Zeolite Membranes: Application in Desalination Process 173 5.6 Zeolite Membranes in Catalytic Process 176 6. 5Tw.7o -DimFuentusrioen Pael rMspaetectriiavles afonrd M Coenmcblurasnioens 118923 Annarosa Gugliuzza, Antonio Politano, and Enrico Drioli 6.1 Introduction 194 6.2 Methods for Exfoliation of 2D Materials 195 6.3 The Graphene Era: Status and Prospect 197 6.4 2D Materials “Beyond Graphene” 199 6.5 The Advent of 2D Materials in Membrane Technology 202 6.5.1 Ion Filtering 202 6.5.2 Gas Separation 210 6.5.3 Energy Power and Storage 211 6.6 Conclusion and Outlook 213 viii Contents 7. Nanostructured Material Membranes for Gas Separation 225 Paola Bernardo 7.1 Introduction 226 7.2 Nanostructured Materials 229 7.2.1 Polymers of Intrinsic Microporosity 231 7.2.1.1 Chemical modification of PIM-1 235 7.2.1.2 Novel PIM structures 237 7.2.1.3 Free volume in PIMs 240 7.2.1.4 PIM-PIs 241 7.2.1.5 Shift in the state of the art by ladder and semi-ladder polymers 243 7.2.1.6 Mixed matrix membranes 244 7.2.1.7 Physical aging 246 8. 7N.a3n o-BaCsoendc Cluastiaolynt ic Membrane Reactors for 247 Hydrogen Production 259 Adele Brunetti and Giuseppe Barbieri 8.1 Introduction 260 8.2 Membrane Reactors 263 8.2.1 Configuration and Utilization 263 8.3 Membranes for MR 268 8.3.1 Pd Alloy 269 8.3.2 Ceramic 271 8.3.3 Zeolite 272 8.3.4 Carbon 272 8.3.5 Perovskites and MIEC 273 8.3.6 Composite 274 8.4 Membrane Reactors: Applications 274 8.4.1 Steam Reforming 276 8.4.1.1 Autothermal reforming 278 8.4.2 Water Gas Shift 279 8.5 CO Clean-Up 284 Contents ix 9. Nanostructured Functional Membranes for Self-Cleaning Separations 297 Abaynesh Yihdego Gebreyohannes, Annarosa Gugliuzza, and Lidietta Giorno 9.1 Introduction 298 9.2 Self-Cleaning Related Wetting 300 9.2.1 Wetting Concepts 301 9.2.2 Responsive Materials–Induced Surface Cleaning via Wetting 303 9.2.2.1 Temperature and pH stimulation 304 9.2.2.2 Light irradiation 304 9.2.2.3 Mechanical stress and solvent annealing 305 9.3 Inorganic–Organic Nanocomposite Membranes 306 9.3.1 TiO2-Loaded Self-Cleaning Membrane 307 9.3.2 Nano-silica Fabricated with Silver Nanoparticle Antifouling Membranes 309 9.3.3 Carbon Nanotubes–Coated Self-Cleaning Membranes 310 9.4 Biomimetic and Bio-inspired Self-Cleaning Membranes 311 9.4.1 Enzyme-Loaded Self-Cleaning Membranes 312 9.4.2 Bio-hybrid Magnetic-Responsive Membranes 313 9.4.3 Polyoxometalates-Loaded 10. Innovative CoatinSge lMf-Celmeabnrainnge sM feomr Wbraatneer sT reatment 331279 Alberto Figoli, Claudia Ursino, and Francesco Galiano 10.1 Introduction 330 10.2 Solution Coating 331 10.2.1 Dip Coating 331 10.2.2 Spin and Spray Coating 333 10.2.3 Casting Coating 333 10.3 Polymerization Reactions 334 10.3.1 Interfacial Polymerization 334