Solid Base Catalysts

Dr. Ravi Tomar is a SERB-TARE fellow at the Department of Chemical Engineering, Indian Institute of Technology (IIT), Delhi and also working an Assistant Professor, Department of Chemistry, SRM Institute of Science and Technology, Delhi-NCR Campus, Ghaziabad, Uttar Pradesh. Also serve as Adjunct Researcher, Isfahan University of Technology, Esteghlal Square, Isfahan, Islamic Republic of Iran. His current research focus is on the synthesis of various materials, and ionic liquids and on the exploration of their applications in the various fields. Prof. K. K. Pant is currently serving as the Director at IIT Roorkee (on deputation), following his previous role as the Dean of Faculty at IIT Delhi. He holds the esteemed position of Petrotech (FIPI) Chair Professor and also serves as Adjunct Faculty at the University of Saskatchewan in Canada, Joint Faculty at CRDT IIT Delhi, and Honorary Faculty at the University of Queensland in Australia. Renowned as one of India’s leading academicians, Prof. Pant focuses on cutting-edge and futuristic technologies of national and international importance. His research encompasses catalysis and reaction engineering, with specific expertise in coal to methanol conversion, e-waste and plastic management, hydrogen generation, CO2 capture and conversion, biomass valorization, among others. Prof. Ramesh Chandra is currently the Vice-Chancellor at Maharaja Surajmal Brij University, he served as Head of the Department of Chemistry at University of Delhi, Delhi. Prof. Ramesh Chandra is a distinguished scientist; Fellow of the Royal Society of Chemistry, London and an outstanding researcher in the field of Biomedical Sciences. He is a Professor of Chemistry at University of Delhi since April 1993 and Founder Director of Dr. B. R. Ambedkar Center for Biomedical Research, University of Delhi. He has been Vice-Chancellor, Bundelkhand University, Jhansi for six years (1999–2005) as well as the President of the Indian Chemical Society (2004–2006).

• Preface xiii1 Introduction to Solid Base Catalyst 1Indu Sindhu, Ravi Tomar, and Anshul Singh1.1 Introduction 11.2 History and Main Facts on Solid Base Catalysts 21.3 Literary Perspective of Solid Base Catalyst 31.4 Solid Basic Sites 41.5 Types of Solid Base Catalysts 51.5.1 Metal Oxides 51.5.1.1 Alkaline Earth Oxides 51.5.1.2 Zirconium Oxides 61.5.1.3 Rare Earth Oxides 71.5.1.4 Titanium Oxides 91.5.1.5 Zinc Oxide 91.5.1.6 Alumina 101.5.1.7 Mixed Oxides 101.5.1.8 Alkali Metal-Loaded Metal Oxides 101.5.2 Zeolites 111.5.3 Mesoporous Materials 131.5.4 Clay Minerals (Hydrotalcite) 131.5.5 Oxynitride 141.5.6 Calcined Metal Phosphates 141.6 Why Solid Base Catalysts Have Fascinated the Scientific Community? 161.7 Advantages and Disadvantages of Solid Base Catalysts Over Inorganic/Organic Bases 171.8 Role of Solid Base Catalysts in Green Chemistry 181.9 Future Prospects for Solid Base Catalysts 201.10 Conclusion 20References 212 Synthesis of Solid Base Catalysts 27Chetna Kumari, Nishu Dhanda, Nirmala Kumari Jangid, and Sudesh Kumar2.1 Introduction 272.2 K2O/Al2O3–CaO 272.2.1 Preparation of K2O/Al2O3–CaO 282.2.1.1 Preparation of Al2O3–CaO Mixed Oxides Basic Support 282.2.1.2 Potassium Nitrate Loading with Calcined Mixed Oxides Basic Support 282.2.2 Catalytic Activity of K2O/Al2O3–CaO in the Knoevenagel Condensation Process for the Preparation of Benzylidene Barbituric and Benzylidenemalononitrile Derivatives 282.2.3 Catalytic Activity of K2O/Al2O3–CaO for the Preparation of Pyrano[2,3-d]pyrimidinone Derivatives 292.3 Solid Base Fly Ash 302.3.1 Synthesis 302.3.2 Catalytic Activity of SBFA 302.3.3 Condensation Between Benzaldehyde and Cyclohexanone 312.3.4 Catalyst Regeneration 312.4 Calcined Water Sludge 312.4.1 Catalyst Preparation 322.5 Oxides of Rare Earth 322.5.1 Preparation 322.6 Titanium Dioxide 332.6.1 Preparation 332.7 Zinc Oxide 342.7.1 Preparation 342.8 Alkaline Earth Oxides 342.8.1 Preparation 352.8.1.1 Conventional Method for MgO Catalyst 352.8.1.2 Effects of Starting Magnesium Salt 352.8.1.3 Preparation of MgO by Sol–Gel Method 362.8.1.4 Preparation of Mesoporous MgO 362.8.1.5 Catalytic Activity for Claisen–Schmidt Reaction 372.9 Hydrotalcite 382.9.1 Synthesis of Hydrotalcite 382.9.1.1 Coprecipitation Method 382.9.1.2 Sol–Gel Method 392.9.1.3 Michael Addition 392.10 Comparison of Different Solid Base Catalysts 392.11 Conclusion 42Conflicts of Interest 42Acknowledgment 42References 423 Advanced Characterization Techniques for Solid Base Catalysts: An Overview 51Neelam Sharma, Suman Swami, Sakshi Pathak, Aruna, and Rahul Shrivastava3.1 Introduction 513.2 Traditional Characterization Techniques for Solid Base Catalyst 553.2.1 Titration Method 553.2.2 IR Analysis 563.2.3 Scanning Electron Microscopes 583.3 Advanced Characterization Techniques for Solid Base Catalyst 593.3.1 Fourier Transform Infrared Spectroscopy (FT-IR) 593.3.2 Field Emission Scanning Electron Microscopes (FE-SEM) 623.3.3 Transmission Electron Microscope (TEM) 663.3.4 X-ray Diffraction (XRD) Analysis 683.3.5 Thermogravimetric Analysis (TGA) 733.3.6 Brunauer–Emmett–Teller BET Surface Area Pore Diameter Analysis [Gas Interaction and Surface Area Measurement: (Brunauer–Emmett–Teller (BET), Barrett–Joyner–Halenda (BJH) N 2 Adsorption–Desorption Isotherms)] 783.3.7 X-Ray Photoelectron Spectroscopy (XPS) 833.3.8 X-Ray Fluorescence (XRF) 853.4 Protocol for Characterization of Catalyst 873.4.1 Sample Preparation 873.4.1.1 XRD 873.4.1.2 FT-IR 883.4.1.3 FE-SEM 883.4.1.4 TEM 883.4.1.5 BET 893.4.1.6 TGA 893.5 Characterization of Some Basic Sites of Solid Base Catalyst with Suitable Example 893.6 Conclusion 91Acknowledgment 92References 924 Advanced Solid Catalysis for Biomass Conversion into High Value-Added Chemicals 97Urja, Amanpreet Kaur Jassal4.1 Introduction 974.2 Advanced Solid Catalysis 994.2.1 Types of Solid Catalysts 1004.2.2 Methods for the Synthesis of Solid Catalysts 1034.3 Biomass, Its Composition, and Properties 1054.4 Biomass Conversion into High Value-Added Chemicals 1074.5 Utilization of Solid Catalysts for Biomass Conversion into High Value-Added Chemicals 1114.6 Electrocatalytic Conversion of Biomass into High Value-Added Chemicals 1134.7 Challenges in Design of Solid Catalysts for Biomass Conversion into High Value-Added Chemicals 1164.8 Advantages of High Value-Added Chemicals 1184.9 Summary and Future Prospectus 119Acknowledgments 119References 1195 Applications of Solid Basic Catalysts for Organic Synthesis 129Aditi Tiwari, Anirudh Singh Bhathiwal, and Anjaneyulu Bendi5.1 Introduction 1295.2 Solid-Based Catalyst for Organic Synthesis 1315.2.1 Metal Oxides 1315.2.2 Zeolites 1345.2.3 Clays 1365.2.4 Solid-Supported Basic Catalysts 1375.3 Conclusion 144List of Abbreviations 144Consent for Publication 144Conflict of Interest 145Acknowledgment 145References 1456 Multicomponent Reactions for Eco-compatible Heterocyclic Synthesis Over Solid Base Catalysts 153Amanpreet Singh and Jasdeep Kaur6.1 Introduction 1536.2 Multicomponent Reactions (MCRs) 1546.2.1 The Biginelli Multicomponent Reaction 1556.2.2 The Hantzsch Multicomponent Reaction 1566.2.3 The Mannich Multicomponent Reaction 1566.2.4 The Passerini Multicomponent Reaction 1566.2.5 The Ugi Multicomponent Reaction 1566.2.6 The Gewald Multicomponent Reaction 1566.3 Solid Base Catalysts for Organic Reactions 1566.4 Characterization Techniques for Solid Base Catalysts 1586.5 Heterocycle Synthesis Using Solid Base-Catalyzed MCRs 1596.6 Conclusion and Future Trends 165Acknowledgment 165References 1657 Industrial Applications of Solid Base Catalysis 169Navdeep Kaur and Nibedita Banik7.1 Introduction to Solid Base Catalysis 1697.1.1 Definition and Characteristics of Solid Base Catalysts 1697.1.2 Importance in Industrial Catalysis 1717.1.3 Comparison with Solid Acid Catalysts 1717.2 Biodiesel Production 1717.2.1 Transesterification Reactions 1747.2.2 Catalysts and Mechanisms 1757.2.3 Industrial-scale Biodiesel Production 1767.3 Hydrogenation and Dehydrogenation Reactions 1787.3.1 Role of Solid Base Catalysts 1787.3.2 Case Studies: Hydrogenation of Oils and Dehydrogenation of Hydrocarbons 1797.3.3 Catalytic Mechanisms 1817.4 Bimolecular Reactions 1827.4.1 Dialkyl Carbonate Synthesis 1837.4.2 Catalyst Selection and Reaction Pathways 1837.4.3 Applications and Industrial Scale-Up 1847.5 Methanol and DME Synthesis 1857.5.1 Importance of Methanol and DME 1857.5.2 Catalysts and Reaction Conditions 1877.5.3 Technological Advancements 1877.6 Transesterification of Esters 1887.6.1 Role in Chemical and Petrochemical Industries 1887.6.1.1 Producing Biodiesel 1897.6.1.2 Specialized Chemical Production 1897.6.1.3 Procedures for Polymerization 1897.6.1.4 Engineering Reactions and Catalysis 1897.6.1.5 Resource Efficiency and Waste Reduction 1907.6.2 Catalysts for Transesterification 1907.7 Alkylation and Isomerization Reactions 1907.7.1 Solid Base Catalysis in Petrochemical Processes 1907.7.2 Environmental and Economic Implications 1937.7.2.1 Economic Implications 1947.8 Environmental Applications 1957.8.1 Sulfur Removal from Flue Gas 1957.8.2 Nox Reduction in Catalytic Converters 1967.8.3 Waste Remediation and Pollution Control 1967.9 Dehydration Reactions 1977.9.1 Dehydration of Alcohols to Olefins 1977.9.2 Dehydration of Alkanes 1997.9.3 Industrial Significance and Process Optimization 2007.10 Sulfur Removal in Fuel Refining 2007.10.1 Hydrodesulfurization (HDS) Catalysts 2017.10.2 Sulfur Removal Mechanisms 2027.10.3 Impact on Clean Fuel Production 2027.11 Processing Methods 2027.11.1 Impregnation Method 2037.11.2 Precipitation and Coprecipitation Method 2037.11.3 Sol–Gel Method 2047.11.4 Hydrothermal Process 2067.11.5 Vapor Phase Deposition Method 2077.12 Use of Solid Base Catalyst in Various Industries 2087.12.1 Biodiesel Production (Refer to Section 2) 2097.12.2 Petrochemical Industries (Refer to Section 6.1) 2097.12.3 Environmental Applications (Refer to Section 8) 2107.12.4 Catalytic Cracking in Refining 2107.12.5 Biomass Conversion 2107.12.6 Water Treatment 2107.12.7 Catalytic Decomposition of Ammonia 2127.12.8 Aldol Condensation and Knoevenagel Reactions 2127.12.9 Hydrogenation Reactions (Refer to Section 3) 2127.13 Socioeconomic Impact of Using Solid Base Catalyst 2137.14 Challenges and Future Prospects 2147.14.1 Current Challenges in Solid Base Catalysis 2147.14.2 Emerging Technologies and Materials 2157.14.3 Prospects for Sustainable Industrial Catalysis 2167.15 Conclusion 2167.15.1 Summary of Key Points 2167.15.2 Outlook for Continued Research and Development 217References 2188 Silica-Supported Heterogenous Catalysts: Application in the Synthesis of Tetrazoles 233Suman Swami, Neelam Sharma, and Rahul Shrivastava8.1 Introduction 2338.1.1 General Synthetic Protocol for Tetrazoles 2348.2 Silica-Supported Heterogenous Catalysts for Tetrazole Synthesis 2368.2.1 Generalized Reaction Mechanism of Silica-Supported Heterogenous-Catalyzed Tetrazole Synthesis 2528.2.1.1 Via [3 + 2] Cycloaddition 2538.2.1.2 Via One-Pot Multicomponent Reaction of Amine, Triethyl Orthoformate, and Azide 2548.3 Future Perspective of Silica-Supported Catalysts in Tetrazole Synthesis 2558.4 Conclusion 256Acknowledgment 256References 2579 Theoretical Insights on Reduction of CO2 Using Functionalized Ionic Liquid at Gold Surface 259Shanmugasundaram Kamalakannan, Muthuramalingam Prakash, and Majdi Hochlaf9.1 Introduction to Heterogeneous Catalysts for CO2 RR Applications 2599.2 Computational Methodology 2619.3 Characterization of Functionalized Ionic Liquids Interacting with CO2 2629.3.1 Studies of CO2 Interacting with ILs in Gas Phase 2629.3.2 Geometries and Energetics of CO2 Interacting with Solid–Liquid Interface 2649.4 CO2 Catalytic Activation at IL@Au(111) Liquid–Solid Interface Model 2659.4.1 CO2 interacting with [EMIm-Z]+[DCA]−@Au(111) Interface 2659.4.2 CO2 Interacting with [EMIm-Z]+[SCN]−@Au(111) Interface 2679.5 Charge Transfer and Charge Density Analyses at the Interface 2689.5.1 Charge Redistribution Between CO2 and Interfacial Medium 2689.5.2 Interfacial Charge Transfer Analysis of CO2 @Interface 2689.5.3 Electronic Structure Analysis of CO2 at the IL@Au(111) Interface 2709.6 Application: Conversion of CO2 into HCOOH 2729.7 Conclusion 272References 27410 Mixed Metal Oxides as Solid Base Catalysts: Fundamentals and Their Catalytic Performance 279Naveen Kumar, Sauraj, and Naveen Chandra Joshi10.1 Introduction 27910.2 Why Mixed Metal Oxides (MMOs)? 28010.3 Mixed Metal Oxides (MMOs) 28110.4 Synthesis Aspect of MMO Catalysts 28210.5 Characterization Techniques for MMO Catalysts 28510.6 Catalytic Applications of MMO Catalysts 28910.6.1 Applications in Industrially Important Reactions 29010.6.2 Applications in Organic Synthesis 29710.6.3 Applications in Green Chemistry 29910.6.4 Applications in Environmental Catalysis 30310.7 Challenges and Future Scope of Mixed Metal Oxides 30410.8 Conclusion 305References 30611 Recent Advances in Conversion of Carbon Dioxide into Value-Added Product over the Solid Base Catalyst 317Rajan Singh and Kamal K. Pant11.1 Introduction 31711.2 CO2 Hydrogenation to Methane 31911.2.1 Thermodynamics of CO2 Hydrogenation to Methane 31911.2.2 Catalyst for Methane Synthesis 32011.2.3 Proposed Reaction Pathways for CO2 Hydrogenation to Methane 32111.3 CO2 Hydrogenation to Methanol 32311.3.1 Thermodynamics of CO2 Hydrogenation to Methanol 32311.3.2 Catalytic System for CO2 Hydrogenation to Methanol 32411.3.3 Reaction Pathways for Methanol Synthesis 32811.3.3.1 HCOO Pathway 32911.3.3.2 COOH Pathways 33111.3.3.3 RWGS+ CO Hydrogenation Pathways 33111.4 CO2 Hydrogenation to Dimethyl Ether 33211.4.1 Thermodynamics of Single-Step DME Synthesis 33211.4.2 Catalysts for Single-Step DME Synthesis by CO2 Hydrogenation 33311.4.3 Mechanism of CO2 Hydrogenation to DME 33711.5 CO2 Hydrogenation to Light Olefins 33711.5.1 Catalysts for Light Olefin Synthesis by CO2 Hydrogenation 33811.5.1.1 Reverse Water–Gas Shift (RWGS)-Mediated Pathway 33811.5.1.2 Methanol-Mediated Pathways 34011.5.2 Mechanism of CO2 Hydrogenation to Olefins 34111.6 Conclusions and Future Prospects 343References 344Index 351