Catalysis for a Sustainable Environment

About the Editors xiii Preface xv Volume 1 1 Introduction 1 Armando J.L. Pombeiro, Manas Sutradhar, and Elisabete C.B.A. Alegria Structure of the Book 2 Final Remarks 4 Part I Carbon Dioxide Utilization 5 2 Transition from Fossil-C to Renewable-C (Biomass and CO2) Driven by Hybrid Catalysis 7 Michele Aresta and Angela Dibenedetto 2.1 Introduction 7 2.2 The Dimension of the Problem 8 2.3 Substitutes for Fossil-C 8 2.4 Hybrid Catalysis: A New World 11 2.5 Hybrid Catalysis and Biomass Valorization 13 2.6 Hybrid Catalysis and CO2 Conversion 16 2.6.1 CO2 as Building Block 16 2.6.2 CO2 Conversion to Value-added Chemical and Fuels via Hybrid Systems 17 2.7 Conclusions 21 References 21 3 Synthesis of Acetic Acid Using Carbon Dioxide 25 Philippe Kalck 3.1 Introduction 25 3.2 Synthesis of Methanol from CO2 and H2 26 3.3 Carbonylation of Methanol Using CO2 28 3.4 Carbonylation of Methane Using CO2 31 3.5 Miscellaneous Reactions, Particularly Biocatalysis 31 3.6 Conclusions 32 References 32 4 New Sustainable Chemicals and Materials Derived from CO2 and Bio-based Resources: A New Catalytic Challenge 35 Ana B. Paninho, Malgorzata E. Zakrzewska, Leticia R.C. Correa, Fátima Guedes da Silva, Luís C. Branco, and Ana V.M. Nunes 4.1 Introduction 35 4.2 Cyclic Carbonates from Bio-based Epoxides 37 4.2.1 Bio-based Epoxides Derived from Terpenes 39 4.2.2 Bio-based Vinylcyclohexene Oxide Derived from Butanediol 41 4.2.3 Bio-based Epichlorohydrin Derived from Glycerol 42 4.2.4 Epoxidized Vegetable Oils and Fatty Acids 42 4.3 Cyclic Carbonates Derived from Carbohydrates 44 4.4 Cyclic Carbonates Derived from Bio-based Diols 46 4.5 Conclusions 50 Acknowledgements 50 References 50 5 Sustainable Technologies in CO 2 Utilization: The Production of Synthetic Natural Gas 55 M. Carmen Bacariza, José M. Lopes, and Carlos Henriques 5.1 CO 2 Valorization Strategies 55 5.1.1 CO 2 to CO via Reverse Water-Gas Shift (RWGS) Reaction 56 5.1.2 CO2 to CH 4 56 5.1.3 Co2 to C X H Y 57 5.1.4 CO2 to CH 3 OH 58 5.1.5 CO2 to CH 3 OCH 3 58 5.1.6 CO2 to R-OH 59 5.1.7 CO2 to HCOOH, R-COOH, and R-CONH 2 60 5.1.8 Target Products Analysis Based on Thermodynamics 60 5.2 Power-to-Gas: Sabatier Reaction Suitability for Renewable Energy Storage 61 5.3 CO 2 Methanation Catalysts 63 5.4 Zeolites: Suitable Supports with Tunable Properties to Assess Catalysts’s Performance 64 5.5 Final Remarks 68 References 69 6 Catalysis for Sustainable Aviation Fuels: Focus on Fischer-Tropsch Catalysis 73 Denzil Moodley, Thys Botha, Renier Crous, Jana Potgieter, Jacobus Visagie, Ryan Walmsley, and Cathy Dwyer 6.1 Introduction 73 6.1.1 Sustainable Aviation Fuels (SAF) via Fischer-Tropsch-based Routes 73 6.1.2 Introduction to FT Chemistry 75 6.1.3 FT Catalysts for SAF Production 79 6.1.4 Reactor Technology for SAF Production Using FTS 81 6.2 State-of-the-art Cobalt Catalysts 82 6.2.1 Catalyst Preparation Routes for Cobalt-based Catalysts 85 6.2.1.1 Precipitation Methodology – a Short Summary 85 6.2.1.2 Preparation Methods Using Pre-shaped Supports 85 6.2.1.2.1 Support Modification 85 6.2.1.2.2 Cobalt Impregnation 85 6.2.1.2.3 Calcination 86 6.2.1.2.4 Reduction 88 6.2.2 Challenges for Catalysts Operating with High Carbon Efficiency: Water Tolerance 88 6.2.3 Strategies to Increase Water Tolerance and Selectivity for Cobalt Catalysts 90 6.2.3.1 Optimizing Physico-chemical Support Properties for Stability at High Water Partial Pressure 90 6.2.3.2 Stabilizing the Support by Surface Coating 91 6.2.3.3 Impact of Crystallite Size on Selectivity 91 6.2.3.4 Metal Support Interactions with Cobalt Crystallites of Varying Size 92 6.2.3.5 The Role of Reduction Promoters and Support Promoters in Optimizing Selectivity 94 6.2.3.6 Role of Pore Diameter in Selectivity 96 6.2.3.7 Effect of Activation Conditions on Selectivity 98 6.2.4 Regeneration of Cobalt PtL Catalysts- Moving Toward Materials Circularity 100 6.3 An Overview of Fe Catalysts: Direct Route for CO 2 Conversion 101 6.3.1 Introduction 101 6.3.2 Effect of Temperature 102 6.3.3 Effect of Pressure 103 6.3.4 Effect of H 2 :CO Ratio 104 6.3.5 Catalyst Development 104 6.3.6 Stability to Oxidation by Water 104 6.3.7 Sufficient Surface Area 105 6.3.8 Availability of Two Distinct Catalytically Active Sites/phases 105 6.3.9 Sufficient Alkalinity for Adsorption and Chain Growth 106 6.4 Future Perspectives 106 References 108 7 Sustainable Catalytic Conversion of CO 2 into Urea and Its Derivatives 117 Maurizio Peruzzini, Fabrizio Mani, and Francesco Barzagli 7.1 Introduction 117 7.2 Catalytic Synthesis of Urea 119 7.2.1 Urea from CO 2 Reductive Processes 120 7.2.1.1 Electrocatalysis 120 7.2.1.2 Photocatalysis 122 7.2.1.3 Magneto-catalysis 123 7.2.2 Urea from Ammonium Carbamate 124 7.3 Catalytic Synthesis of Urea Derivatives 127 7.4 Conclusions and Future Perspectives 133 Part II Transformation of Volatile Organic Compounds (VOCs) 139 8 Catalysis Abatement of No X /vocs Assisted by Ozone 141 Zhihua Wang and Fawei Lin 8.1 No X /voc Emission and Treatment Technologies 141 8.1.1 No X /voc Emissions 141 8.1.2 No X Treatment Technologies 142 8.1.2.1 Sncr 142 8.1.2.2 Scr 142 8.1.2.3 SCR Catalysts 142 8.1.2.4 Ozone-assisted Oxidation Technology 142 8.1.3 VOC Treatment Technologies 143 8.1.3.1 Adsorption 143 8.1.3.2 Regenerative Combustion 143 8.1.3.3 Catalytic Oxidation 144 8.1.3.4 Photocatalytic Oxidation 144 8.1.3.5 Plasma-assisted Catalytic Oxidation 144 8.2 NO Oxidation by Ozone 144 8.2.1 NO Homogeneous Oxidation by Ozone 145 8.2.1.1 Effect of O 3 /NO Ratio 145 8.2.1.2 Effect of Temperature 145 8.2.1.3 Effect of Residence Time 145 8.2.1.4 Process Parameter Optimization 146 8.2.2 Heterogeneous Catalytic Deep Oxidation 146 8.2.2.1 Catalytic NO Deep Oxidation by O 3 Alone 146 8.2.2.2 Catalytic NO Deep Oxidation by Combination of O 3 and H 2 O 148 8.3 Oxidation of VOCs by Ozone 150 8.3.1 Aromatics 150 8.3.1.1 Toluene 150 8.3.1.2 Benzene 153 8.3.2 Oxygenated VOCs 154 8.3.2.1 Formaldehyde 154 8.3.2.2 Acetone 154 8.3.2.3 Alcohols 155 8.3.3 Chlorinated VOCs 155 8.3.3.1 Chlorobenzene 155 8.3.3.2 Dichloromethane 155 8.3.3.3 Dioxins and Furans 156 8.3.4 Sulfur-containing VOCs 157 8.4 Conclusions 157 References 157 9 Catalytic Oxidation of VOCs to Value-added Compounds Under Mild Conditions 161 Elisabete C.B.A. Alegria, Manas Sutradhar, and Tannistha R. Barman 9.1 Introduction 161 9.2 Benzene 162 9.3 Toluene 167 9.4 Ethylbenzene 171 9.5 Xylene 172 9.6 Final Remarks 175 Acknowledgments 176 References 176 10 Catalytic Cyclohexane Oxyfunctionalization 181 Manas Sutradhar, Elisabete C.B.A. Alegria, M. Fátima C. Guedes da Silva, and Armando J.L. Pombeiro 10.1 Introduction 181 10.2 Transition Metal Catalysts for Cyclohexane Oxidation 182 10.2.1 Vanadium Catalysts 182 10.2.2 Iron Catalysts 186 10.2.3 Cobalt Catalysts 189 10.2.4 Copper Catalysts 191 10.2.5 Molybdenum Catalysts 198 10.2.6 Rhenium Catalysts 199 10.2.7 Gold Catalysts 200 10.3 Mechanisms 201 10.4 Final Comments 202 Acknowledgments 203 References 203 Part III Carbon-based Catalysis 207 11 Carbon-based Catalysts for Sustainable Chemical Processes 209 Katarzyna Morawa Eblagon, Raquel P. Rocha, M. Fernando R. Pereira, and José Luís Figueiredo 11.1 Introduction 209 11.1.1 Nanostructured Carbon Materials 209 11.1.2 Carbon Surface Chemistry 210 11.2 Metal-free Carbon Catalysts for Environmental Applications 212 11.2.1 Wet Air Oxidation and Ozonation with Carbon Catalysts 212 11.3 Carbon-based Catalysts for Sustainable Production of Chemicals and Fuels from Biomass 214 11.3.1 Carbon Materials as Catalysts and Supports 214 11.3.2 Cascade Valorization of Biomass with Multifunctional Catalysts 216 11.3.3 Carbon Catalysts Produced from Biomass 219 11.4 Summary and Outlook 220 Acknowledgments 221 References 221 12 Carbon-based Catalysts as a Sustainable and Metal-free Tool for Gas-phase Industrial Oxidation Processes 225 Giulia Tuci, Andrea Rossin, Matteo Pugliesi, Housseinou Ba, Cuong Duong-Viet, Yuefeng Liu, Cuong Pham-Huu, and Giuliano Giambastiani 12.1 Introduction 225 12.2 The H 2 S Selective Oxidation to Elemental Sulfur 226 12.3 Alkane Dehydrogenation 231 12.3.1 Alkane Dehydrogenation under Oxidative Environment: The ODH Process 231 12.3.2 Alkane Dehydrogenation under Steam- and Oxygen-free Conditions: The DDH Reaction 237 12.4 Conclusions 240 Acknowledgments 241 References 241 13 Hybrid Carbon-Metal Oxide Catalysts for Electrocatalysis, Biomass Valorization and, Wastewater Treatment: Cutting-Edge Solutions for a Sustainable World 247 Clara Pereira, Diana M. Fernandes, Andreia F. Peixoto, Marta Nunes, Bruno Jarrais, Iwona Kuźniarska-Biernacka, and Cristina Freire 13.1 Introduction 247 13.2 Hybrid Carbon-metal Oxide Electrocatalysts for Energy-related Applications 249 13.2.1 Oxygen Reduction Reaction (ORR) 249 13.2.2 Oxygen Evolution Reaction (OER) 254 13.2.3 Hydrogen Evolution Reaction (HER) 257 13.2.4 CO 2 Reduction Reaction (CO 2 RR) 259 13.3 Biomass Valorization over Hybrid Carbon-metal Oxide Based (Nano)catalysts 261 13.4 Advanced (Photo)catalytic Oxidation Processes for Wastewater Treatment 266 13.4.1 Heterogeneous Fenton Process 266 13.4.2 Heterogeneous photo-Fenton Process 271 13.4.3 Heterogeneous electro-Fenton Process 277 13.4.4 Photocatalytic Oxidation 281 13.5 Advanced Catalytic Reduction Processes for Wastewater Treatment 288 13.6 Conclusions and Future Perspectives 291 Acknowledgments 292 References 292 Volume 2 About the Editors xiii Preface xv Part IV Coordination, Inorganic, and Bioinspired Catalysis 299 14 Hydroformylation Catalysts for the Synthesis of Fine Chemicals 301 Mariette M. Pereira, Rui M.B. Carrilho, Fábio M.S. Rodrigues, Lucas D. Dias, and Mário J.F. Calvete 15 Synthesis of New Polyolefins by Incorporation of New Comonomers 323 Kotohiro Nomura and Suphitchaya Kitphaitun 16 Catalytic Depolymerization of Plastic Waste 339 Noel Angel Espinosa-Jalapa and Amit Kumar 17 Bioinspired Selective Catalytic C-H Oxygenation, Halogenation, and Azidation of Steroids 369 Konstantin P. Bryliakov 18 Catalysis by Pincer Compounds and Their Contribution to Environmental and Sustainable Processes 389 Hugo Valdés and David Morales-Morales 19 Heterometallic Complexes: Novel Catalysts for Sophisticated Chemical Synthesis 409 Franco Scalambra, Ismael Francisco Díaz-Ortega, and Antonio Romerosa 20 Metal-Organic Frameworks in Tandem Catalysis 429 Anirban Karmakar and Armando J.L. Pombeiro 21 (Tetracarboxylate)bridged-di-transition Metal Complexes and Factors Impacting Their Carbene Transfer Reactivity 445 LiPing Xu, Adrian Varela-Alvarez, and Djamaladdin G. Musaev 22 Sustainable Cu-based Methods for Valuable Organic Scaffolds 461 Argyro Dolla, Dimitrios Andreou, Ethan Essenfeld, Jonathan Farhi, Ioannis N. Lykakis, and George E. Kostakis 23 Environmental Catalysis by Gold Nanoparticles 481 Sónia Alexandra Correia Carabineiro 24 Platinum Complexes for Selective Oxidations in Water 515 Alessandro Scarso, Paolo Sgarbossa, Roberta Bertani, and Giorgio Strukul 25 The Role of Water in Reactions Catalyzed by Transition Metals 537 A.W. Augustyniak and A.M. Trzeciak 26 Using Speciation to Gain Insight into Sustainable Coupling Reactions and Their Catalysts 559 Skyler Markham, Debbie C. Crans, and Bruce Atwater 27 Hierarchical Zeolites for Environmentally Friendly Friedel Crafts Acylation Reactions 577 Ana P. Carvalho, Angela Martins, Filomena Martins, Nelson Nunes, and Rúben Elvas-Leitão Volume 3 About the Editors xiii Preface xv Part V Organocatalysis 609 28 Sustainable Drug Substance Processes Enabled by Catalysis: Case Studies from the Roche Pipeline 611 Kurt Püntener, Stefan Hildbrand, Helmut Stahr, Andreas Schuster, Hans Iding and Stephan Bachmann 29 Supported Chiral Organocatalysts for Accessing Fine Chemicals 639 Ana C. Amorim and Anthony J. Burke 30 Synthesis of Bio-based Aliphatic Polyesters from Plant Oils by Efficient Molecular Catalysis 659 Kotohiro Nomura and Nor Wahida Binti Awang 31 Modern Strategies for Electron Injection by Means of Organic Photocatalysts: Beyond Metallic Reagents 675 Takashi Koike 32 Visible Light as an Alternative Energy Source in Enantioselective Catalysis 687 Ana Maria Faisca Phillips and Armando J.L. Pombeiro Part VI Catalysis for the Purification of Water and Liquid Fuels 717 33 Heterogeneous Photocatalysis for Wastewater Treatment: A Major Step Towards Environmental Sustainability 719 Shima Rahim Pouran and Aziz Habibi-Yangjeh 34 Sustainable Homogeneous Catalytic Oxidative Processes for the Desulfurization of Fuels 743 Federica Sabuzi, Giuseppe Pomarico, Pierluca Galloni, and Valeria Conte 35 Heterogeneous Catalytic Desulfurization of Liquid Fuels: The Present and the Future 757 Rui G. Faria, Alexandre Viana, Carlos M. Granadeiro, Luís Cunha-Silva, and Salete S. Balula Part VII Hydrogen Formation, Storage, and Utilization 783 36 Paraformaldehyde: Opportunities as a C1-Building Block and H 2 Source for Sustainable Organic Synthesis 785 Ana Maria Faísca Phillips, Maximilian N. Kopylovich, Leandro Helgueira de Andrade, and Martin H.G. Prechtl 37 Hydrogen Storage and Recovery with the Use of Chemical Batteries 819 Henrietta Horváth, Gábor Papp, Ágnes Kathó, and Ferenc Joó 38 Low-cost Co and Ni MOFs/CPs as Electrocatalysts for Water Splitting Toward Clean Energy-Technology 847 Anup Paul, Biljana Šljukić, and Armando J.L. Pombeiro Index 871