Design and Applications of Hydroxyapatite-Based Catalysts

Doan Pham Minh is Associate Professor at IMT Mines Albi in France. Since 2020, he is Deputy Director of the RAPSODEE Research Center (UMR CNRS 5302). His current research focuses on the valorization of biomass, bio-waste, and industrial co-products into energy carriers, i.e. syngas, hydrogen, biomethane, biofuels, and useful materials, i.e. adsorbents, catalysts, and refractory ceramics applied in thermoconversion processes, catalytic processes and thermal energy storage.

• Preface xiii1 Introduction to Hydroxyapatite-based Materials in Heterogeneous Catalysis 1Doan Pham Minh1.1 Generality 11.2 Hydroxyapatite: A New Family of Catalytic Materials in the Heterogeneous Catalysis 41.2.1 Possible High Porous Volume and High Specific Surface Area 41.2.2 High Thermal Stability 41.2.3 Exceptional Ion Exchange Capacity 61.2.4 Tunable Acid-base Properties 71.2.5 High Affinity with Organic Compounds 81.2.6 Formulation of HA-based Materials 81.3 Opportunities and Challenges 11References 142 Synthesis and Characterization of Hydroxyapatite and Hydroxyapatite-Based Catalysts 19Yousra EL Jemli, Karima Abdelouahdi, Doan Pham Minh, Abdellatif Barakat, and Abderrahim Solhy2.1 Introduction 192.2 HA Synthesis and Characterization 202.2.1 HA Synthesis Routes 202.2.1.1 Coprecipitation Method 202.2.1.2 Sol–Gel Method 222.2.1.3 Emulsion Methods 242.2.1.4 Hydrolysis Methods 282.2.1.5 Hydrothermal Methods 302.2.1.6 Microwave (MW)-Assisted Methods 312.2.1.7 Ball-Milling Method 322.2.1.8 Sonochemical Method 342.2.1.9 Dry Methods 352.2.1.10 Other Methods 362.2.2 HA Structure 422.2.3 Physicochemical and Thermal Properties of HA 442.2.3.1 Thermal Stability 442.2.3.2 Solubility of HA 442.2.3.3 HA’s Surface Functional Groups 452.2.3.4 Non-stoichiometric Calcium-Deficient or Calcium-Rich Hydroxyapatites 462.2.4 Substitutions in the Structure of HA 472.2.5 Modification and Functionalization of the HA’s Surface 492.3 A Concise Overview on Synthesis and Characterization of HA-Based Catalysts 512.4 Summary and Conclusions 55References 553 Structure and Surface Study of Hydroxyapatite-Based Materials 73Guylène Costentin, Christophe Drouet, Fabrice Salles, and Stéphanie Sarda3.1 Introduction 733.2 Structure and Surface Properties of Hydroxyapatite: Overview 753.2.1 Apatite Structure and Model Studies 763.2.2 Specificities of Nonstoichiometric and/or Biomimetic Apatites 813.2.3 Relevance of Apatites in Catalysis 843.3 Advances in the Characterization of Structural and Surface Properties of Hydroxyapatite: Experimental and Computational Approaches 873.3.1 Structural and Compositional Characterization 873.3.2 Thermodynamic Properties and Thermal Stability 953.3.2.1 Overview of Apatites Thermodynamics 953.3.2.2 Thermal Behavior 983.3.3 Physicochemical and Interfacial Properties 1003.3.3.1 Solubility and Evolution in Solution 1003.3.3.2 Surface Charge 1023.3.3.3 Interfacial Tension 1033.3.4 Surface Reactivity 1063.3.4.1 Nature of Acid and Base Sites 1063.3.4.2 Influence of Substitution on Surface Reactivity 1093.3.4.3 Low Temperature Ion Immobilization and Adsorption Properties in Aqueous Media or Wet Conditions 1103.4 Conclusions 117References 1174 Hydroxyapatite-Based Catalysts: Influence of the Molar Ratio of Ca to P 141Zhen Ma4.1 Introduction 1414.2 Influence of Ca/P Ratio on the Performance of HA 1434.2.1 Relatively Simple Reactions 1434.2.2 More Complex Reactions 1474.3 Influence of Ca/P Ratio on the Performance of HA-Supported Catalysts 1524.3.1 Relatively Simple Reactions 1534.3.2 More Complex Reactions 1554.4 Concluding Remarks 156References 1585 Kinetics and Mechanisms of Selected Reactions over Hydroxyapatite-Based Catalysts 163U.P.M. Ashik, Nurulhuda Halim, Shusaku Asano, Shinji Kudo, and Jun-ichiro Hayashi5.1 Introduction 1635.2 Oxidative Coupling of Methane 1645.3 Partial Oxidation of Methane 1695.4 Acetone to Methyl Isobutyl Ketone 1735.5 Ethanol Coupling Reaction 1775.6 Ethanol to Gasoline 1805.7 Glycerol to Lactic Acid 1825.8 Benzene to Phenol 1835.9 Transesterification 1865.10 Conclusion 188References 1896 Aerobic Selective Oxidation of Alcohols and Alkanes over Hydroxyapatite-Based Catalysts 201Guylène Costentin and Franck Launay6.1 Introduction 2016.2 Liquid Phase Reactions: Selective Aerobic Oxidation of Alcohols 2026.2.1 Apatite-Based Catalysts Efficient in the Aerobic Oxidation of Alcohols 2036.2.2 Apatite/Ru(III) Catalysts 2046.2.3 Apatite/Pd(0) Catalysts 2116.3 Gas Phase Reactions 2146.3.1 Partial Oxidation of Methane 2146.3.2 Alkane Oxidative Dehydrogenation Reactions 2176.3.2.1 Catalytic Performance of the Metal-Modified Hydroxyapatite in the ODH Reactions 2186.3.2.2 Metal Ion Modifications 2196.3.2.3 Activation Site and Mechanism 2276.4 Conclusions and Perspectives 229References 2327 Selective Hydrogenation and Dehydrogenation Using Hydroxyapatite-Based Catalysts 241Vijay K. Velisoju, Hari Padmasri Aytam, and Venugopal Akula7.1 Introduction 2417.2 HA as Catalyst Support in Hydrogenation Reactions 2427.2.1 Hydrogenation of Biomass-Derived Compounds to Fuels and Fine Chemicals 2427.2.2 Hydrogenation of Olefins and Nitro Compounds 2457.2.3 Hydrogenation of Benzene, Phenol, and Diols 2477.2.4 Selective Catalytic Reduction of Nitric Oxide 2497.2.5 Higher Alcohol Synthesis by Simultaneous Dehydrogenation and Hydrogenation Reactions 2497.2.6 Hydrogenation of Carbon Dioxide 2527.2.6.1 CO2 Methanation 2537.2.6.2 CO2 Fisher–Tropsch (FT) Synthesis 2537.2.6.3 Alcohol Synthesis 2557.2.6.4 Water–Gas Shift and Reverse Water–Gas Shift 2557.2.7 Partial Conclusions 2577.3 HA as Support in Dehydrogenation Reactions 2577.4 Summary and Conclusions 262Acknowledgments 262References 2638 Reforming Processes Using Hydroxyapatite-Based Catalysts 269Zouhair Boukha, Rubén López-Fonseca, and Juan R. González-Velasco8.1 Introduction 2698.2 Overview on the Nature of the Interactions of HA with Transition Metal Catalysts 2718.3 HA-Supported Non-noble Metal Catalysts for Methane Reforming Reactions 2748.3.1 Suitability of the HA-Based Catalysts 2748.3.2 Effect of the Composition on the Performance of HA in the Reforming Reactions 2818.3.3 Bimetallic Catalysts 2848.4 Noble Metal Catalysts 2868.5 Reforming of Other Hydrocarbons 2878.6 Summary and Remarks 290Acknowledgments 291References 2919 Hydroxyapatite-Based Catalysts for the Production of Energetic Carriers 299Othmane Amadine, Karim Dânoun, Younes Essamlali, Said Sair, and Mohamed Zahouily9.1 Introduction 2999.2 Biodiesel Production 3009.2.1 Transesterification Reactions 3019.2.2 Esterification Reaction for Biodiesel Production 3079.2.3 Other Esterification Reactions 3089.3 Hydrogen Production 3129.3.1 Water–Gas Shift Reactions 3129.3.2 Borohydride Hydrolysis Reaction 3169.3.3 Ammonia Borane Hydrolysis Reaction 3189.4 Catalytic Production of High Value-Added Energy Additives 3199.4.1 n-Butanol and Its Derivative Chemicals 3209.4.2 Fuel Additives from Furfural 3249.4.3 Organic Carbonates Agents 3269.4.4 Energy Additives from Alcohols via Guerbet Reaction 3279.4.5 Other Value-Added Chemicals 3299.5 Conclusion 329References 33010 Hydroxyapatite-Based Catalysts in Organic Synthesis 345Michel Gruselle, Kaia Tõnsuaadu, Patrick Gredin, and Christophe Len10.1 Introduction 34510.2 Synthesis and Characterization of HA and HA-Based Catalysts 34610.2.1 Synthesis 34610.2.1.1 Stoichiometric and Nonstoichiometric Apatites 34610.2.1.2 Apatites as Catalyst Supports 34610.2.1.3 HA as Macro-ligands for Catalytic Moieties 34710.3 Apatites as Catalysts in C—C Bond Formation 34710.3.1 Cross-coupling Reactions 34710.3.2 Nucleophilic Carbon–Carbon Bond Forming Reactions 35010.3.3 Multicomponent Reaction 35210.4 Conclusions 361References 36411 Electrocatalysis and Photocatalysis Using Hydroxyapatite-Based Materials 373Eric Puzenat and Mathieu Prévot11.1 Photocatalysis with Hydroxyapatite-Based Materials 37311.1.1 Basic Photocatalysis Principles 37311.1.2 Hydroxyapatite Structure and Properties Implication in Photocatalysis 37611.1.3 Single-Phase HA for Photocatalysis 37711.1.4 Doped Photocatalytic HA 37811.1.5 Multiphasic HA-Containing Photocatalyst 37911.1.5.1 HA—TiO2 Biphasic Composites 38011.1.5.2 HA—TiO2 Multiphasic Composites 38111.1.5.3 Other Photocatalytic HA-Containing Composites 38111.1.6 Summary and Outlook 38211.2 Electrocatalysis with Hydroxyapatite-Based Materials 38311.2.1 Charge Transport Mechanism in Hydroxyapatites 38411.2.2 Electrocatalytic Sensors 38611.2.3 Fuel Cell Application 39611.2.4 Electrocatalytic Water Oxidation 40111.2.5 Summary and Outlook 403References 40412 Magnetic Structured Hydroxyapatites and Their Catalytic Applications 413Tasnim Munshi, Smriti Rawat, Ian J. Scowen, and Sarwat Iqbal12.1 Introduction 41312.2 Magnetic HA 41412.2.1 Synthesis Route of Magnetic HA 41512.3 Catalysis 42012.3.1 Magnetic HA Nanoparticles as Active Catalysts for Organic Reactions 42012.3.2 HA Analogs and Their Catalytic Applications 42512.3.3 HA Catalysts and Green Chemistry 42612.4 Summary and Conclusions 430References 43113 Materials from Eggshells and Animal Bones and Their Catalytic Applications 437Abarasi Hart and Elias Aliu13.1 Introduction 43713.2 Chemical Composition and Properties of Eggshell and Animal Bones 44113.3 Eggshell and Animal Bones Materials 44413.3.1 Calcium Carbonate/Oxide/Phosphate 44513.3.2 Calcium Supplement 44513.3.3 Biofilter (Adsorbent) Biomaterial 44613.3.4 Hydroxyapatite Material 44813.4 Catalytic Applications of Eggshell and Animal Bones 45113.4.1 Catalytic Material Preparation from Eggshells and Animal Bones 45113.4.2 Catalytic Applications of Catalyst Derived from Eggshell and Animal Bones 45413.4.2.1 Selective Catalytic Oxidation 45513.4.2.2 Gasification of Biomass for Hydrogen Production 45813.4.2.3 Reactive Carbon Dioxide Capture (Calcium Looping) 45913.4.2.4 Water–Gas Shift (WGS) Reaction 46013.4.2.5 Transesterification Reaction for Biodiesel Production 46113.4.2.6 Eggshell Membranes (ESM) in Fuel Cell Applications 46413.4.2.7 Catalytic Materials from Eggshells and Animal Bones in Organic Synthesis 46513.4.2.8 Other Catalytic Applications 46613.5 Conclusions 467References 46814 Natural Phosphates and Their Catalytic Applications 481Karima Abdelouahdi, Abderrahim Bouaid, Abdellatif Barakat, and Abderrahim Solhy14.1 Introduction 48114.2 Preparation and Characterization of Catalysts or Catalyst Supports from NP 48214.3 Organic Synthesis Using NP and NP-Supported Catalysts 48714.3.1 Condensation Reactions 48714.3.1.1 Knoevenagel Reaction 48714.3.1.2 Claisen–Schmidt Condensation 49114.3.1.3 Michael Addition 49414.3.2 Transesterification Reaction 49614.3.3 Friedel–Crafts Alkylation 49714.3.4 Suzuki–Miyaura Coupling Reaction 49914.3.5 Hydration of Nitriles 50114.3.6 Synthesis of α-Hydroxyphosphonates 50414.3.7 Multicomponent Reactions (MCRs) 50514.3.7.1 Biginelli Reaction 50514.3.7.2 Synthesis of α-Aminophosphonates 50614.3.8 Oxidation Reactions 50614.3.8.1 Oxidative Cleavage of Cycloalkanones 50614.3.8.2 Oxidation of Benzyl Alcohol 50914.3.8.3 Epoxidation of Electron-Deficient Alkenes 51014.3.9 Hydrogenation Reactions 51114.3.9.1 Selective Hydrogenation of Crotonaldehyde 51114.3.9.2 Reduction of Aromatic Nitro Compounds 51214.3.10 Reforming of Methane 51414.3.11 Photooxidation of VOC Model Compounds 51514.4 Conclusions 516References 516Index 533