Sustainable Catalysis

Rafael Luque is Ramon y Cajal Fellow at the University of Cordoba (UCO) in Spain. He studied chemistry at UCO and obtained his PhD in 2005. He then spent a postdoctoral placement in the Green Chemistry Centre of Excellence at the University of York, UK, with Prof. James Clark (2005-2008).He was also appointed as visiting professor and distinguished engineering fellow of the Department of Chemical and Biomolecular Engineering from the Hong Kong University of Science and Technology (HKUST) in 2013. Currently, he is visiting professor from the Xiamen University (China) and the Universidade Federal de Pelotas (Brazil). Prof. Luque has published over 260 research articles, filed 3 patent applications, and edited 8 books. His research is focused on (nano)materials science, heterogeneous (nano)catalysis, microwave and flow chemistry, biofuels and green chemical methods in synthetic organic chemistry. Frank Leung-Yuk Lam is a visiting assistant professor at the Department of Chemical and Biomolecular Engineering at the Hong Kong University of Science and Technology (HKUST) since 2012. He received his PhD at the HKUST in 2005 and then worked as a postdoctoral researcher in both University of Hong Kong and the HKUST. He has been a visiting assistant professor in the Department of Chemical Engineering in the Technion Israel Institute of Technology (TIIT) in Israel, doing research on functional materials for environment and teaching about environmental engineering. His research is focused on separation, air pollution control and wastewater treatment through adsorption and heterogeneous catalysis.

• 1 Introduction to Room-Temperature Catalysis 1Eduardo J. Garcia-Suarez and Anders Riisager1.1 Introduction 11.2 Room-Temperature Homogeneous Catalysts 21.2.1 Ionic-Liquid-Based Catalytic Systems at Room Temperature 21.2.2 Transition Metal Homogeneous Catalysts 61.2.2.1 Group 9-Based Homogeneous Catalysts (Co, Rh, Ir) 61.2.2.2 Group 10-Based Homogeneous Catalysts (Ni, Pd, Pt) 71.2.2.3 Group 11-Based Homogeneous Catalysts (Ag, Au) 101.3 Room-Temperature Heterogeneous Catalysts 101.3.1 Group 9-Based Heterogeneous Catalysts (Co, Rh, Ir) 111.3.2 Group 10-Based Heterogeneous Catalysts (Ni, Pd, Pt) 131.3.3 Group 11-Based Heterogeneous Catalysts (Cu, Pt, Au) 231.4 Conclusions and Perspectives 29References 312 Functionalized Ionic Liquid-based Catalytic Systems with Diversified Performance Enhancements 35Shiguo Zhang and Yanlong Gu2.1 Introduction 352.2 Functionalized ILs for Enhancing Catalytic Activity 362.3 Functionalized ILs for Improving Reaction Selectivity 382.4 Functionalized ILs for Facilitating Catalyst Recycling and Product Isolation 402.5 Functionalized ILs for Making Relay Catalysis 432.6 Cation and Anion Synergistic Catalysis in Ionic Liquids 452.7 Functionalized ILs for Aqueous Catalysis 462.8 Catalysis by Porous Poly-ILs 472.9 Functionalized IL-Based Carbon Material for Catalysis 492.10 Summary and Conclusions 54References 543 Heterogeneous Room Temperature Catalysis – Nanomaterials 59Liyu Chen and Yingwei Li3.1 Introduction 593.2 Solid-Acid-Based Nanomaterials 603.3 Grafted-Metal-Ions-Based Nanomaterial 653.4 Metal NPs-Based Nanomaterial 673.4.1 Metal NPs Stabilized by Ligands 673.4.2 Metal NPs@Polymers 683.4.3 Metal NPs@Metal Oxides 703.4.4 Metal NPs@Carbonaceous Support 723.4.5 Metal NPs@Siliceous Base Support 743.4.6 Metal NPs@MOF Nanocomposites 773.5 Metal Oxide NPs-Based Nanomaterial 823.6 Summary and Conclusions 83References 844 Biocatalysis at Room Temperature 89Ivaldo Itabaiana Jr and Rodrigo O. M. A. De Souza4.1 Introduction 894.2 Transaminases 904.2.1 General Features 904.2.2 Transaminase Applications at Room Temperature 904.3 Hydrolases 984.3.1 General Features 984.3.2 Application of Hydrolases at Room Temperature 1004.3.2.1 Lipases 1004.3.2.2 Aldol Additions 1014.3.2.3 Michael Addition 1024.3.2.4 Mannich Reaction 1024.3.2.5 C-Heteroatom and Heteroatom–Heteroatom Bond Formations 1034.3.2.6 Epoxidation 1034.3.2.7 Synthesis of Heterocycles 1044.3.2.8 Kinetic Resolutions 1054.3.3 Cutinases 1074.4 Laccases 1084.4.1 General Features 1084.4.2 Applications of Laccases 1104.5 Enzymes in Ionic Liquids 1154.5.1 General Features 115References 1255 Room Temperature Catalysis Enabled by Light 135Timothy Noël5.1 Introduction 1355.2 UV Photochemistry 1365.3 Visible Light Photoredox Catalysis 1395.4 Room Temperature Cross-Coupling Enabled by Light 1415.5 Photochemistry and Microreactor Technology –A Perfect Match? 1445.6 The Use of Photochemistry in Material Science 1465.7 Solar Fuels 1495.8 Conclusion 151References 1516 Mechanochemically Enhanced Organic Transformations 155Davin Tan and Tomislav Frišcic6.1 Introduction 1556.2 Mechanochemical Techniques and Mechanisms: Neat versus Liquid-Assisted Grinding (LAG) 1566.3 Oxidation and Reduction Using Mechanochemistry 1606.3.1 Direct Oxidation of Organic Substrates Using Oxone 1606.3.2 Mechanochemical Halogenations Aided by Oxone 1626.3.3 Reduction Reactions by Mechanochemistry 1636.4 Electrocyclic Reactions: Equilibrium and Templating in Mechanochemistry 1656.4.1 The Diels–Alder Reaction: Mechanochemical Equilibrium in Reversible C—C Bond Formation 1656.4.2 Photochemical [2+2] Cycloaddition during Grinding: Supramolecular Catalysis and Structure Templating 1676.5 Recent Advances in Metal-CatalyzedMechanochemical Reactions 1686.5.1 Copper-Catalyzed [2+3] Cycloaddition (Huisgen Coupling) 1686.5.2 Olefin Metathesis by Ball Milling 1696.5.3 Mechanochemical C—H Bond Activation 1706.5.4 Cyclopropanation of Alkenes Using Silver Foil as a Catalyst Source 1716.6 New Frontiers in Organic Synthesis Enabled by Mechanochemistry 1716.6.1 Synthesis of Active Pharmaceutical Ingredients (APIs) 1726.6.2 Reactivity Enabled or Facilitated by Mechanochemistry 1736.6.3 Trapping Unstable Reaction Intermediates 1756.7 Conclusion and Outlook 176Acknowledgments 176References 1767 Palladium-Catalyzed Cross-Coupling in Continuous Flow at Room andMild Temperature 183Christophe Len7.1 Introduction 1837.2 Suzuki Cross-Coupling in Continuous Flow 1847.3 Heck Cross-Coupling in Continuous Flow 1927.4 Murahashi Cross-Coupling in Continuous Flow 1997.5 Concluding Remarks 202References 2028 Catalysis for Environmental Applications 207Changseok Han, Endalkachew Sahle-Demessie, Afzal Shah, Saima Nawaz, Latif-ur-Rahman, Niall B.McGuinness, Suresh C. Pillai, Hyeok Choi, Dionysios, D. Dionysiou, andMallikarjuna N. Nadagouda8.1 Introduction 2078.2 Ferrate (FeO42−) forWater Treatment 2088.3 Magnetically Separable Ferrite forWater Treatment 2098.3.1 Magnetic Nanoparticles 2098.3.2 Magnetic Recovery of Materials Used forWater Treatment 2118.3.3 Ferrite Photocatalyst forWater Treatment 2128.4 UV, Solar, and Visible Light-Activated TiO2 Photocatalysts for Environmental Application 2128.5 Catalysis for Remediation of Contaminated Groundwater and Soils 2158.5.1 Catalytic Oxidative Pathways 2158.5.2 Catalytic Reductive Pathways 2178.5.3 Prospects and Limitations 2188.6 Novel Catalysis for Environmental Applications 2188.6.1 Graphene and Graphene Composites 2198.6.2 Perovskites and Perovskites Composites 2218.6.3 Graphitic Carbon Nitride (g-C3N4) and g-C3N4 Composites 2228.7 Summary and Conclusions 223Acknowledgments 224Disclaimer 224References 2249 Future Development in Room-Temperature Catalysis and Challenges in the Twenty-first Century 231Fannie P. Y. Lau, R. Luque, and Frank L. Y. LamCase Study 1: Magnetic Pd Catalysts for Benzyl Alcohol Oxidation to Benzaldehyde 237Yingying Li, Frank L.-Y. Lam, and Xijun Hu1.1 Introduction 2371.2 Pd/MagSBA Magnetic Catalyst for Selective Benzyl Alcohol Oxidation to Benzaldehyde 2391.2.1 Results and Discussion 2391.2.1.1 Characterization 2391.2.1.2 Effect of Reaction Temperature 2401.2.1.3 Effect of Pd Loading 2411.2.1.4 Recycling Test 2461.3 Summary and Conclusions 246References 247Case Study 2: Development of Hydrothermally Stable Functional Materials for Sustainable Conversion of Biomass to Furan Compounds 251Amrita Chatterjee, Xijun Hu, and Frank L.-Y. Lam2.1 Introduction 2512.2 Metal–Organic-Framework as a Potential Catalyst for Biomass Valorization 2542.3 Xylose Dehydration to Furfural Using Metal–Organic-Framework, MIL-101(Cr) 2552.3.1 Xylose Dehydration Catalyzed by Organosilane Coated MIL-101(Cr) 2552.3.2 Xylose to Furfural Transformation Catalyzed by Fly-Ash and MIL-101(Cr) Composite 2582.3.3 Xylose to Furfural Transformation Catalyzed by Tin Phosphate and MIL-101(Cr) Composite 2622.3.4 Role of Acid Sites, Textural Properties and Hydrothermal Stability of Catalyst in Xylose Dehydration Reaction 2642.4 Conclusion 267References 268Index 273