Nguyen Van Duc Long is a Senior Fellow in the School of Chemical Engineering at the University of Adelaide. Volker Hessel is a Professor in the School of Chemical Engineering at the University of Adelaide. Annemie Bogaerts is a Professor in the Department of Chemistry at the University of Antwerp. Gabriele Centi is a Professor at the University of Messina. Evgeny Rebrov is a Professor in the School of Engineering at the University of Warwick.

• About the Editors xiiiList of Contributors xvPreface xxiPart I Fundamentals of Nitrogen Fixation 11 Fundamentals of Ammonia Production 3Kevin Rouwenhorst and Leon Lefferts1.1 Introduction to Nitrogen Fixation 31.2 The Haber-Bosch Process 41.3 Production Pathways to Ammonia 51.4 Novel Methods for Ammonia Synthesis 91.5 Applications of Ammonia 111.6 Conclusions 14References 142 Fundamentals of No X Production 21Filippo Buttignol, Alberto Garbujo, Raffaele Ostuni, Michal Bialkowski, and Pierdomenico Biasi2.1 Introduction 212.2 The Ostwald Process 222.2.1 Catalytic Oxidation of Ammonia 222.2.1.1 Reaction Mechanism and Kinetics 232.2.1.2 Reaction Engineering and Parameter Effect 242.2.1.3 Catalyst: Pt and New Development 252.2.2 NO Oxidation to NO 2 272.2.2.1 Reaction Mechanism and Kinetics 282.2.2.2 Process Implementation Exploiting the Catalytic Oxidation of NO 292.2.3 Nitrogen Oxides Absorption and HNO 3 Production 302.3 Type of Processes 322.3.1 Weak Nitric Acid 322.3.1.1 General Process Description 352.3.2 Concentrated Nitric Acid 352.4 Environmental Protection and Treatment of Exhaust Gases 372.4.1 Control of No X Emissions 382.4.2 Control of N 2 O Emissions 412.4.2.1 Primary Measures 412.4.2.2 Secondary Measures 422.4.2.3 Ternary Measures 422.5 Future Trends 462.6 Conclusions 47References 48Part II Plasma-Assisted Nitrogen Fixation 513 Introduction to Plasma Technology 53Anthony B. Murphy3.1 Fundamental Concepts 533.1.1 Types of Plasma 533.1.2 Scaling Parameters 543.2 Plasma Generation 583.3 Plasma Chemistry 623.3.1 Inelastic Collisions Between Electrons and Heavy Particles 623.3.2 Inelastic Collisions Between Heavy Particles 643.3.3 Equilibrium in Plasmas 663.4 Plasma Technology 683.4.1 Low-Pressure Plasma Applications 693.4.2 Non-equilibrium Atmospheric-Pressure Plasma Applications 703.4.3 Thermal Plasma Applications 743.5 Role of Plasma in Ammonia and No X Synthesis 773.6 Conclusions 79References 814 Plasma Reactors 85Evgeny Rebrov4.1 Introduction 854.2 Microwave and RF Plasma 874.2.1 Microwave Plasma Torch 874.2.2 Surfaguide-Type Discharge 904.2.3 RF Plasma Torch 924.3 Spark and High-frequency Pulsed Discharges 944.4 Gliding Arc 954.5 Propeller Arc 1004.6 Glow Discharge 1024.6.1 Triboelectric Nanogenerator 1034.7 Dielectric Barrier Discharge 1054.7.1 Micro-DBD Reactors 1054.7.2 DBD Reactors for N 2 /Water Plasma 1074.8 Conclusions and Outlook 109References 1115 Plasma-Assisted Ammonia Synthesis 119Mateo Ruiz-Martín, Adrián Megías-Sánchez, Servando Marín-Meana, Manuel Oliva-Ramírez, Agustín R. González-Elipe, and Ana Gómez-Ramírez5.1 Introduction 1195.2 Advanced Plasma Technologies for Ammonia Synthesis 1205.2.1 Ammonia Synthesis Reactions and Plasma Types 1215.2.1.1 MW Reactions 1225.2.1.2 RF Discharge Reactions 1225.2.1.3 Plasma-Electrochemistry 1235.2.1.4 Gliding Arc Reactions 1235.2.2 Effects of Plasma Reactor Operational Conditions 1245.2.2.1 Carrier Gas 1275.2.2.2 Gases Proportion 1275.2.2.3 Residence Time and Gas Flow Regime 1275.2.2.4 Driving Voltage and Frequency 1285.2.2.5 Barrier Materials and Catalysts 1285.3 Plasma-Catalysis of Ammonia: Seeking Synergies to Improving Energy Efficiency 1295.3.1 Plasma-Catalysis: A Brief Introduction 1295.3.2 Barrier Materials and Catalysts in Packed-Bed Plasma Reactors for NH 3 Synthesis 1315.3.2.1 Barrier Materials 1315.3.2.2 Catalyst: Active Phase and Support 1325.3.3 New Paradigms in Plasma-Catalysis for Ammonia Synthesis 1365.4 Conclusions 138References 1406 Plasma-assisted No X Synthesis 147Tianyu Li, Haoxuan Jiang, Rusen Zhou, Jing Sun, and Renwu Zhou6.1 Introduction 1476.2 The Mechanism of Plasma-Assisted Nitrogen Oxidation 1516.3 Nitrogen Oxidation Achieved by Different Types of Plasma 1566.4 Plasma–Water-Based Nitrogen Fixation 1636.5 Conclusion and Outlook 168References 170Part III Mechanisms of Nitrogen Fixation 1817 Ammonia Synthesis with Plasma Catalysis: Mechanisms 183Kevin Rouwenhorst and Leon Lefferts7.1 Introduction 1837.2 Methods to Study Mechanisms in Catalysis 1837.3 Experimental Kinetics: From Catalysis to Plasma Catalysis 1857.4 Beyond Equilibrium and Reverse Reactions 1877.5 Effect of Catalyst on Plasma 1897.6 Kinetics of Plasma-Catalytic Ammonia Synthesis 1907.7 Mechanism of Plasma-Catalytic Ammonia Synthesis 1917.7.1 Dominant Pathway: Catalytic Dissociation of Excited N 21917.7.2 Dominant Pathway: N 2 Dissociation in Plasma 1937.7.3 Surface Intermediate Species 1947.7.4 Other Mechanisms 1967.8 Energy Efficiency 1967.9 Conclusions 198References 1998 Mechanisms of Plasma-driven No X Synthesis 203Weitao Wang and Xin Tu8.1 Introduction 2038.2 No X Synthesis Without a Catalyst 2048.2.1 Plasma Physics Relevant to No X Formation 2048.2.2 Plasma Chemistry and Key Reaction Mechanisms 2088.2.2.1 Electrons Induced Reactions 2088.2.2.2 Formation and Loss Processes of NO and NO 2 2088.2.2.3 The Key Role of the Zeldovich Mechanism 2128.2.3 Factors Influencing Reaction Pathways 2138.2.3.1 Impact of Plasma Types 2138.2.3.2 Impact of Gas Composition 2158.2.3.3 Impact of Pressure 2178.2.3.4 Impact of Pulsed Discharge 2188.2.4 Mechanistic Insights from Experimental Studies 2218.3 Plasma-catalytic No X Synthesis 2238.4 Conclusion and Outlook 228References 230Part IV Environmental and Economic Viability 2379 Environmental Impact and Sustainability Aspects of Plasma-Based Nitrogen Fixation 239Nam Nghiep Tran, Nguyen Van Duc Long, Muhammad Yousaf Arshad, Jose Luis Osorio Tejada, and Volker Hessel9.1 Introduction 2399.2 Environmental Benefits of PANF 2419.2.1 Carbon Footprint Analysis 2439.2.2 Comparison with the HB Process 2449.2.3 Energy Efficiency and Consumption 2459.2.4 Reduction in GHG Emissions 2469.2.5 Integration with Renewable Energy Sources 2469.3 Circular Economy Considerations 2489.3.1 PANF Within the Circular Economy Model 2499.3.2 Resource Utilization and Waste Minimization 2499.3.3 Closed-Loop Systems and Recycling Opportunities 2509.3.4 Decentralization via Small-Scale Production 2529.4 Life Cycle Assessment 2539.4.1 LCA of PANF: Overview 2539.4.2 Benchmarking Against the HB Process 2549.4.3 Environmental Impact Analysis (Including CO 2 Emissions and Pollutants) 2559.5 Perspectives for Sustainable Plasma-Based Nitrogen Fixation 2599.6 Conclusion and Outlook 260References 26110 Industrial Applications and Economic Viability of Plasma-Based Nitrogen Fixation 271Magnus Nyvold and Rune Ingels10.1 Introduction 27110.2 Overview of The Reactive Nitrogen Industry 27410.3 Conventional Nitrogen Fixation 27510.3.1 Fossil-Based Ammonia Production 27610.3.2 Electricity-Based Ammonia Production 27810.3.3 Nitric Acid Production 27910.3.4 Overall Performance of Nitrate Production 28110.4 Plasma-Based Nitrate Production 28110.4.1 Stand-alone Nitric Acid Process 28310.4.2 Integrated Nitric Acid Process 28410.4.3 Nitrate Enrichment of Organic Substrates 28610.4.4 Other Avenues 28810.5 Economic Comparison 28910.6 Competitive Landscape 29310.7 Conclusion 294References 295Part V Advanced Processes of Nitrogen Fixation 29911 Microplasma for Nitrogen Fixation 301Liangliang Lin11.1 Introduction 30111.2 Microplasma Configurations for Nitrogen Fixation 30611.3 Microplasma-Based Process for Nitrogen Fixation 30911.3.1 No X 30911.3.2 Nh 3 31311.3.3 Nitride, Carbonitride, and Oxynitride Nanomaterials 31811.3.4 N-Doped Nanomaterials 32011.4 Challenges and Perspectives for Microplasma Nitrogen Fixation 32411.5 Conclusions 326Acknowledgments 326References 32712 Plasma–Liquid Interaction for Nitrogen Fixation 337Tianqi Zhang, Jungmi Hong, and Patrick Cullen12.1 Introduction 33712.2 Plasma Systems for Plasma–Liquid Discharges 33812.3 Mechanisms of Nitrogen Fixation in Plasma–Liquid Systems 34212.3.1 Physical Aspects of Plasma–Liquid Interactions 34212.3.1.1 Breakdown Mechanism of Plasma–Liquid Discharges 34212.3.1.2 Solvation of Plasma Species Through Plasma–Liquid Interface 34512.3.2 Chemical Aspect of Plasma–Liquid Interactions 34612.3.2.1 Effect of Water Content in Gas-Phase Plasma Discharge 34712.3.2.2 Production and Loss of Short-lived Species in Liquid 34812.3.2.3 Important Pathway of Long-lived Species Formation in Liquid 34912.3.3 Mass Transport Through the Plasma–Liquid Interface 35012.4 Key Challenges 35112.4.1 Diagnostics 35112.4.2 Modeling 35312.5 Conclusion 355References 35613 Plasma Electrochemistry for Nitrogen Fixation 363Susanta Bera, Dimitrios Zagoraios, and Mihalis N. Tsampas13.1 Introduction 36313.2 Motivation for Plasma-Enabled N 2 Oxidation Followed by Electrochemical Reduction 36513.3 Conventional and Plasma-enabled No X Feedstock 36713.4 Definition of Performance Metrics 36713.5 Electrochemical Conversion of No X to Nh 3 – Eno X Rr 36813.5.1 Electrochemical Conversion with No X in Liquid-phase Stream 37013.5.2 Electrochemical Conversion with No X in Gas-phase Or Catholyte-Free Stream 37313.5.3 Overview of the Eno X Rr Studies 37413.6 Plasma-enabled Electrochemical Studies for No X Conversion To Nh 3 – Pnor-eno X Rr 37513.6.1 Pnor-eno X Rr Integration Approaches 37713.6.1.1 Liquid-phase-based Pnor-eno X Rr 37713.6.1.2 Gas-phase-based Pnor-eno X Rr 37813.6.2 Alternative Plasma Electrochemical Systems 37813.6.3 Experimental Pnor-eno X Rr Studies 37913.6.3.1 Gas-phase No X Generation 37913.6.3.2 Liquid-phase No X Generation 38013.6.4 Overview of Pnor-eno X Rr Systems 38113.7 Implementation at Industrial Level 38313.8 Key Challenges and Future Outlook 38313.8.1 Electrochemical Systems 38313.8.2 Operational Considerations 38413.8.3 Product Separation 38413.8.4 Scalability and Process Integration 38513.9 Conclusions 385References 38614 Analytical Techniques for Plasma Catalysis 393Christopher Hardacre, Sarayute Chansai, and Shanshan Xu14.1 Optical Spectroscopy 39314.1.1 Introduction 39314.1.2 Experimental Setup 39614.1.3 OES Spectrum and Interpretation for Ammonia Synthesis 39714.1.4 OES Analysis and Proposed Reaction Mechanism for Ammonia Synthesis 40014.1.5 OES Analysis for Plasma Dynamics 40114.1.6 TDLAS Analysis for Plasma Dynamics and Kinetics 40514.2 Infrared Spectroscopy 40614.2.1 Introduction 40614.2.2 In situ Plasma-IR/DRIFTS Cell Designs and Setups 40814.2.3 In-plasma in Situ Drifts Analysis for No X Reduction 41114.2.4 Post Plasma in situ IR Analysis for Ammonia Synthesis 41114.3 Summary 413References 41615 Perspectives in Plasma-Based Nitrogen Fixation for Fertilizer Applications 423Yury Gorbanev and Annemie Bogaerts15.1 Nitrogen Compounds Used for Soil Fertilization 42315.2 Fertilizer Production: Haber-Bosch-Ostwald Process and Plasma for Nitrogen Fixation 42515.3 Metrics of Various Pathways of Plasma-Based Nitrogen Fixation 42915.4 Perspectives of NH 4 NO 3 Production by Plasma-Based Nitrogen Fixation 43415.4.1 Pathway Through NH 3 Synthesis: Plasma Reduction Followed by Oxidation 43415.4.2 Pathway Through Both Nh 3 and No X Synthesis: Combined Plasma Reduction and Plasma Oxidation 43515.4.3 Pathway Through No X Synthesis: Plasma Oxidation Followed by Reduction 43615.5 Plasma-Based Nitrogen Fixation for Reduction of NH 3 Emissions and Simultaneous Fertilizer Production 43815.6 Conclusion and Outlook: Challenges and Perspectives of Plasma-Based Nitrogen Fixation 439References 441Index 451