Catalysis for a Sustainable Environment

Armando Pombeiro is Full Professor Jubilado at Instituto Superior Técnico, Universidade de Lisboa, member of the Academy of Sciences of Lisbon, of the European Academy of Sciences (EURASC) and of the Academia Europaea. His research addresses activation of small molecules with industrial, environmental or biological significance.Manas Sutradhar is an Assistant Professor at the Universidade Lusófona, Lisbon and an integrated researcher at the Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Portugal.Elisabete C.B.A. Alegria is Adjunct Professor at the Chemical Engineering Department of Instituto Superior de Engenharia de Lisboa (ISEL) from Polytechnic Institute of Lisbon.

• About the Editors xiiiPreface xvVolume 11 Introduction 1Armando J.L. Pombeiro, Manas Sutradhar, and Elisabete C.B.A. AlegriaStructure of the Book 2Final Remarks 4Part I Carbon Dioxide Utilization 52 Transition from Fossil-C to Renewable-C (Biomass and CO2) Driven by Hybrid Catalysis 7Michele Aresta and Angela Dibenedetto2.1 Introduction 72.2 The Dimension of the Problem 82.3 Substitutes for Fossil-C 82.4 Hybrid Catalysis: A New World 112.5 Hybrid Catalysis and Biomass Valorization 132.6 Hybrid Catalysis and CO2 Conversion 162.6.1 CO2 as Building Block 162.6.2 CO2 Conversion to Value-added Chemical and Fuels via Hybrid Systems 172.7 Conclusions 21References 213 Synthesis of Acetic Acid Using Carbon Dioxide 25Philippe Kalck3.1 Introduction 253.2 Synthesis of Methanol from CO2 and H2 263.3 Carbonylation of Methanol Using CO2 283.4 Carbonylation of Methane Using CO2 313.5 Miscellaneous Reactions, Particularly Biocatalysis 313.6 Conclusions 32References 324 New Sustainable Chemicals and Materials Derived from CO2 and Bio-based Resources: A New Catalytic Challenge 35Ana B. Paninho, Malgorzata E. Zakrzewska, Leticia R.C. Correa, Fátima Guedes da Silva, Luís C. Branco, and Ana V.M. Nunes4.1 Introduction 354.2 Cyclic Carbonates from Bio-based Epoxides 374.2.1 Bio-based Epoxides Derived from Terpenes 394.2.2 Bio-based Vinylcyclohexene Oxide Derived from Butanediol 414.2.3 Bio-based Epichlorohydrin Derived from Glycerol 424.2.4 Epoxidized Vegetable Oils and Fatty Acids 424.3 Cyclic Carbonates Derived from Carbohydrates 444.4 Cyclic Carbonates Derived from Bio-based Diols 464.5 Conclusions 50Acknowledgements 50References 505 Sustainable Technologies in CO 2 Utilization: The Production of Synthetic Natural Gas 55M. Carmen Bacariza, José M. Lopes, and Carlos Henriques5.1 CO 2 Valorization Strategies 555.1.1 CO 2 to CO via Reverse Water-Gas Shift (RWGS) Reaction 565.1.2 CO2 to CH 4 565.1.3 Co2 to C X H Y 575.1.4 CO2 to CH 3 OH 585.1.5 CO2 to CH 3 OCH 3 585.1.6 CO2 to R-OH 595.1.7 CO2 to HCOOH, R-COOH, and R-CONH 2 605.1.8 Target Products Analysis Based on Thermodynamics 605.2 Power-to-Gas: Sabatier Reaction Suitability for Renewable Energy Storage 615.3 CO 2 Methanation Catalysts 635.4 Zeolites: Suitable Supports with Tunable Properties to Assess Catalysts’s Performance 645.5 Final Remarks 68References 696 Catalysis for Sustainable Aviation Fuels: Focus on Fischer-Tropsch Catalysis 73Denzil Moodley, Thys Botha, Renier Crous, Jana Potgieter, Jacobus Visagie, Ryan Walmsley, and Cathy Dwyer6.1 Introduction 736.1.1 Sustainable Aviation Fuels (SAF) via Fischer-Tropsch-based Routes 736.1.2 Introduction to FT Chemistry 756.1.3 FT Catalysts for SAF Production 796.1.4 Reactor Technology for SAF Production Using FTS 816.2 State-of-the-art Cobalt Catalysts 826.2.1 Catalyst Preparation Routes for Cobalt-based Catalysts 856.2.1.1 Precipitation Methodology – a Short Summary 856.2.1.2 Preparation Methods Using Pre-shaped Supports 856.2.1.2.1 Support Modification 856.2.1.2.2 Cobalt Impregnation 856.2.1.2.3 Calcination 866.2.1.2.4 Reduction 886.2.2 Challenges for Catalysts Operating with High Carbon Efficiency: Water Tolerance 886.2.3 Strategies to Increase Water Tolerance and Selectivity for Cobalt Catalysts 906.2.3.1 Optimizing Physico-chemical Support Properties for Stability at High Water Partial Pressure 906.2.3.2 Stabilizing the Support by Surface Coating 916.2.3.3 Impact of Crystallite Size on Selectivity 916.2.3.4 Metal Support Interactions with Cobalt Crystallites of Varying Size 926.2.3.5 The Role of Reduction Promoters and Support Promoters in Optimizing Selectivity 946.2.3.6 Role of Pore Diameter in Selectivity 966.2.3.7 Effect of Activation Conditions on Selectivity 986.2.4 Regeneration of Cobalt PtL Catalysts- Moving Toward Materials Circularity 1006.3 An Overview of Fe Catalysts: Direct Route for CO 2 Conversion 1016.3.1 Introduction 1016.3.2 Effect of Temperature 1026.3.3 Effect of Pressure 1036.3.4 Effect of H 2 :CO Ratio 1046.3.5 Catalyst Development 1046.3.6 Stability to Oxidation by Water 1046.3.7 Sufficient Surface Area 1056.3.8 Availability of Two Distinct Catalytically Active Sites/phases 1056.3.9 Sufficient Alkalinity for Adsorption and Chain Growth 1066.4 Future Perspectives 106References 1087 Sustainable Catalytic Conversion of CO 2 into Urea and Its Derivatives 117Maurizio Peruzzini, Fabrizio Mani, and Francesco Barzagli7.1 Introduction 1177.2 Catalytic Synthesis of Urea 1197.2.1 Urea from CO 2 Reductive Processes 1207.2.1.1 Electrocatalysis 1207.2.1.2 Photocatalysis 1227.2.1.3 Magneto-catalysis 1237.2.2 Urea from Ammonium Carbamate 1247.3 Catalytic Synthesis of Urea Derivatives 1277.4 Conclusions and Future Perspectives 133Part II Transformation of Volatile Organic Compounds (VOCs) 1398 Catalysis Abatement of No X /vocs Assisted by Ozone 141Zhihua Wang and Fawei Lin8.1 No X /voc Emission and Treatment Technologies 1418.1.1 No X /voc Emissions 1418.1.2 No X Treatment Technologies 1428.1.2.1 Sncr 1428.1.2.2 Scr 1428.1.2.3 SCR Catalysts 1428.1.2.4 Ozone-assisted Oxidation Technology 1428.1.3 VOC Treatment Technologies 1438.1.3.1 Adsorption 1438.1.3.2 Regenerative Combustion 1438.1.3.3 Catalytic Oxidation 1448.1.3.4 Photocatalytic Oxidation 1448.1.3.5 Plasma-assisted Catalytic Oxidation 1448.2 NO Oxidation by Ozone 1448.2.1 NO Homogeneous Oxidation by Ozone 1458.2.1.1 Effect of O 3 /NO Ratio 1458.2.1.2 Effect of Temperature 1458.2.1.3 Effect of Residence Time 1458.2.1.4 Process Parameter Optimization 1468.2.2 Heterogeneous Catalytic Deep Oxidation 1468.2.2.1 Catalytic NO Deep Oxidation by O 3 Alone 1468.2.2.2 Catalytic NO Deep Oxidation by Combination of O 3 and H 2 O 1488.3 Oxidation of VOCs by Ozone 1508.3.1 Aromatics 1508.3.1.1 Toluene 1508.3.1.2 Benzene 1538.3.2 Oxygenated VOCs 1548.3.2.1 Formaldehyde 1548.3.2.2 Acetone 1548.3.2.3 Alcohols 1558.3.3 Chlorinated VOCs 1558.3.3.1 Chlorobenzene 1558.3.3.2 Dichloromethane 1558.3.3.3 Dioxins and Furans 1568.3.4 Sulfur-containing VOCs 1578.4 Conclusions 157References 1579 Catalytic Oxidation of VOCs to Value-added Compounds Under Mild Conditions 161Elisabete C.B.A. Alegria, Manas Sutradhar, and Tannistha R. Barman9.1 Introduction 1619.2 Benzene 1629.3 Toluene 1679.4 Ethylbenzene 1719.5 Xylene 1729.6 Final Remarks 175Acknowledgments 176References 17610 Catalytic Cyclohexane Oxyfunctionalization 181Manas Sutradhar, Elisabete C.B.A. Alegria, M. Fátima C. Guedes da Silva, and Armando J.L. Pombeiro10.1 Introduction 18110.2 Transition Metal Catalysts for Cyclohexane Oxidation 18210.2.1 Vanadium Catalysts 18210.2.2 Iron Catalysts 18610.2.3 Cobalt Catalysts 18910.2.4 Copper Catalysts 19110.2.5 Molybdenum Catalysts 19810.2.6 Rhenium Catalysts 19910.2.7 Gold Catalysts 20010.3 Mechanisms 20110.4 Final Comments 202Acknowledgments 203References 203Part III Carbon-based Catalysis 20711 Carbon-based Catalysts for Sustainable Chemical Processes 209Katarzyna Morawa Eblagon, Raquel P. Rocha, M. Fernando R. Pereira, and José Luís Figueiredo11.1 Introduction 20911.1.1 Nanostructured Carbon Materials 20911.1.2 Carbon Surface Chemistry 21011.2 Metal-free Carbon Catalysts for Environmental Applications 21211.2.1 Wet Air Oxidation and Ozonation with Carbon Catalysts 21211.3 Carbon-based Catalysts for Sustainable Production of Chemicals and Fuels from Biomass 21411.3.1 Carbon Materials as Catalysts and Supports 21411.3.2 Cascade Valorization of Biomass with Multifunctional Catalysts 21611.3.3 Carbon Catalysts Produced from Biomass 21911.4 Summary and Outlook 220Acknowledgments 221References 22112 Carbon-based Catalysts as a Sustainable and Metal-free Tool for Gas-phase Industrial Oxidation Processes 225Giulia Tuci, Andrea Rossin, Matteo Pugliesi, Housseinou Ba, Cuong Duong-Viet, Yuefeng Liu, Cuong Pham-Huu, and Giuliano Giambastiani12.1 Introduction 22512.2 The H 2 S Selective Oxidation to Elemental Sulfur 22612.3 Alkane Dehydrogenation 23112.3.1 Alkane Dehydrogenation under Oxidative Environment: The ODH Process 23112.3.2 Alkane Dehydrogenation under Steam- and Oxygen-free Conditions: The DDH Reaction 23712.4 Conclusions 240Acknowledgments 241References 24113 Hybrid Carbon-Metal Oxide Catalysts for Electrocatalysis, Biomass Valorization and, Wastewater Treatment: Cutting-Edge Solutions for a Sustainable World 247Clara Pereira, Diana M. Fernandes, Andreia F. Peixoto, Marta Nunes, Bruno Jarrais, Iwona Kuźniarska-Biernacka, and Cristina Freire13.1 Introduction 24713.2 Hybrid Carbon-metal Oxide Electrocatalysts for Energy-related Applications 24913.2.1 Oxygen Reduction Reaction (ORR) 24913.2.2 Oxygen Evolution Reaction (OER) 25413.2.3 Hydrogen Evolution Reaction (HER) 25713.2.4 CO 2 Reduction Reaction (CO 2 RR) 25913.3 Biomass Valorization over Hybrid Carbon-metal Oxide Based (Nano)catalysts 26113.4 Advanced (Photo)catalytic Oxidation Processes for Wastewater Treatment 26613.4.1 Heterogeneous Fenton Process 26613.4.2 Heterogeneous photo-Fenton Process 27113.4.3 Heterogeneous electro-Fenton Process 27713.4.4 Photocatalytic Oxidation 28113.5 Advanced Catalytic Reduction Processes for Wastewater Treatment 28813.6 Conclusions and Future Perspectives 291Acknowledgments 292References 292Volume 2About the Editors xiiiPreface xvPart IV Coordination, Inorganic, and Bioinspired Catalysis 29914 Hydroformylation Catalysts for the Synthesis of Fine Chemicals 301Mariette M. Pereira, Rui M.B. Carrilho, Fábio M.S. Rodrigues, Lucas D. Dias, and Mário J.F. Calvete15 Synthesis of New Polyolefins by Incorporation of New Comonomers 323Kotohiro Nomura and Suphitchaya Kitphaitun16 Catalytic Depolymerization of Plastic Waste 339Noel Angel Espinosa-Jalapa and Amit Kumar17 Bioinspired Selective Catalytic C-H Oxygenation, Halogenation, and Azidation of Steroids 369Konstantin P. Bryliakov18 Catalysis by Pincer Compounds and Their Contribution to Environmental and Sustainable Processes 389Hugo Valdés and David Morales-Morales19 Heterometallic Complexes: Novel Catalysts for Sophisticated Chemical Synthesis 409Franco Scalambra, Ismael Francisco Díaz-Ortega, and Antonio Romerosa20 Metal-Organic Frameworks in Tandem Catalysis 429Anirban Karmakar and Armando J.L. Pombeiro21 (Tetracarboxylate)bridged-di-transition Metal Complexes and Factors Impacting Their Carbene Transfer Reactivity 445LiPing Xu, Adrian Varela-Alvarez, and Djamaladdin G. Musaev22 Sustainable Cu-based Methods for Valuable Organic Scaffolds 461Argyro Dolla, Dimitrios Andreou, Ethan Essenfeld, Jonathan Farhi, Ioannis N. Lykakis, and George E. Kostakis23 Environmental Catalysis by Gold Nanoparticles 481Sónia Alexandra Correia Carabineiro24 Platinum Complexes for Selective Oxidations in Water 515Alessandro Scarso, Paolo Sgarbossa, Roberta Bertani, and Giorgio Strukul25 The Role of Water in Reactions Catalyzed by Transition Metals 537A.W. Augustyniak and A.M. Trzeciak26 Using Speciation to Gain Insight into Sustainable Coupling Reactions and Their Catalysts 559Skyler Markham, Debbie C. Crans, and Bruce Atwater27 Hierarchical Zeolites for Environmentally Friendly Friedel Crafts Acylation Reactions 577Ana P. Carvalho, Angela Martins, Filomena Martins, Nelson Nunes, and Rúben Elvas-LeitãoVolume 3About the Editors xiiiPreface xvPart V Organocatalysis 60928 Sustainable Drug Substance Processes Enabled by Catalysis: Case Studies from the Roche Pipeline 611Kurt Püntener, Stefan Hildbrand, Helmut Stahr, Andreas Schuster, Hans Iding and Stephan Bachmann29 Supported Chiral Organocatalysts for Accessing Fine Chemicals 639Ana C. Amorim and Anthony J. Burke30 Synthesis of Bio-based Aliphatic Polyesters from Plant Oils by Efficient Molecular Catalysis 659Kotohiro Nomura and Nor Wahida Binti Awang31 Modern Strategies for Electron Injection by Means of Organic Photocatalysts: Beyond Metallic Reagents 675Takashi Koike32 Visible Light as an Alternative Energy Source in Enantioselective Catalysis 687Ana Maria Faisca Phillips and Armando J.L. PombeiroPart VI Catalysis for the Purification of Water and Liquid Fuels 71733 Heterogeneous Photocatalysis for Wastewater Treatment: A Major Step Towards Environmental Sustainability 719Shima Rahim Pouran and Aziz Habibi-Yangjeh34 Sustainable Homogeneous Catalytic Oxidative Processes for the Desulfurization of Fuels 743Federica Sabuzi, Giuseppe Pomarico, Pierluca Galloni, and Valeria Conte35 Heterogeneous Catalytic Desulfurization of Liquid Fuels: The Present and the Future 757Rui G. Faria, Alexandre Viana, Carlos M. Granadeiro, Luís Cunha-Silva, and Salete S. BalulaPart VII Hydrogen Formation, Storage, and Utilization 78336 Paraformaldehyde: Opportunities as a C1-Building Block and H 2 Source for Sustainable Organic Synthesis 785Ana Maria Faísca Phillips, Maximilian N. Kopylovich, Leandro Helgueira de Andrade, and Martin H.G. Prechtl37 Hydrogen Storage and Recovery with the Use of Chemical Batteries 819Henrietta Horváth, Gábor Papp, Ágnes Kathó, and Ferenc Joó38 Low-cost Co and Ni MOFs/CPs as Electrocatalysts for Water Splitting Toward Clean Energy-Technology 847Anup Paul, Biljana Šljukić, and Armando J.L. PombeiroIndex 871