Low-temperature Activation and Catalytic Transformation of Methane to Non-CO2 Products

Franklin Tao, Ph.D., Professor of Chemistry and Chemical Engineering was elected a Fellow of the American Association for the Advancement of Science (AAAS) in 2017 and a recipient of the University Scholarly Achievement Award in 2019 while serving as a professor at the University of Kansas. He has published more than 210 research articles in the fields of catalysis for transformation of light hydrocarbons including methane, single-atom catalysis, catalytic conversion of biomass derivatives, electrochemical and photocatalytic transformations of small molecules, surface chemistry, catalyst structure dynamics, in situ/operando characterization techniques and methods, and instrumentation for studying materials and reactions under reaction and operational conditions. He has been a professor or visiting scientist at multiple academic institutions including University of Notre Dame and University of California, Berkeley.

• Preface xiAcknowledgments xv1 Why Do We Care About Methane? 11.1 Chemical Production 11.2 Energy Supply 21.3 Climate Change 51.4 Reconciling Shale- Gas Utilization and Environmental Issue 5References 62 Properties and Chemical Inertness of Methane 8References 103 Formation of Methane in Nature and by Anthropogenic Activity 113.1 Methane Formed in Rocks 113.2 Methane Hydrate Formed in Seabed 123.3 Bio- methanation 123.4 Methane Formed as a Byproduct in Industrial Processes 18References 194 Extraction of Methane for Chemical Production 21References 245 Methane Emission and Its Impact on Environment 265.1 Methane Emissions 265.2 Fundamentals on Methane-relevant Environmental Issue 27References 316 Brief of High- Temperature Catalytic and Noncatalytic Transformation of Methane 336.1 Steam Reforming of Methane 336.1.1 Brief of Activity of Transition Metals 346.1.2 Deactivation of Metal Catalysts 356.1.3 Catalyst of Singly Dispersed Sites 366.2 Reforming of Methane by Consumption of CO2 406.2.1 Brief of Dry Reforming on Transition Metal Single- Crystal Model Catalyst Ni(111) 416.2.2 Catalyst of Singly Dispersed Sites 436.3 Partial Oxidation of Methane 446.3.1 Brief of Catalytic Methane Partial Oxidation 446.3.2 Supported Ni Catalyst 456.3.3 Supported Co Catalyst 486.3.4 Supported Pt Catalyst 496.3.5 Supported Rh Catalyst 496.3.6 Supported Ru Catalyst 506.3.7 Supported Single- Atom Rh Catalyst 516.4 Methane Transformation Involving both Heterogeneous and Homogeneous Catalysis 526.5 Oxidative Coupling of Methane 546.6 Aromatization of Methane 606.6.1 Brief 606.6.2 Catalyst Preparation 616.6.3 Catalyst Structure 636.6.4 Formation of Active Phases 686.6.5 Carburization 696.6.6 Generally Agreed Reaction Intermediate 696.6.7 Facing Challenge and Promising Topic 706.7 Direct Activation of Methane on Single Sites of Fe to Synthesize Ethylene and Aromatics 716.8 Transformation of Methane to Form Hydrogen and Carbon 726.8.1 Noncatalytic Approaches 726.8.2 Catalysis by Supported Fe, Co or Ni 736.8.3 Catalysis by Melted Metal 736.8.4 Catalysis by Melted Alloy 736.9 Methane Oxidation to Formaldehyde 79References 827 Electrochemical Conversion of Chemical Energy of CH 4 to Electrical Energy at Intermediate Temperature 102References 1058 Brief of Thermodynamics of Transformation of Methane at Low Temperature 1078.1 Feasibility of Methane Conversion at Low Temperature through Oxidation 1078.2 Why Should We Pursue a Low- temperature CH4 Transformation Route? 1088.3 Significance of Catalyst Design for Compensating Slow Kinetics of Methane Conversion at Low Temperature 109Reference 1099 Activation of CH4 by Free- standing Cations (M+or Man+) of Single Atom or Cluster at Room Temperature and Its Significant Indication for CH4 Low-Temperature Activation 1109.1 Activity in Dehydrogenation of CH4 and Reaction with Other Hydrocarbons on Free- standing Cation of Single- atom M+ of the First- row (3d) Transition Metals and Its Indication for CH4 Low-Temperature Activation 1119.2 Activity in Dehydrogenation of CH4 on Free- standing Cation of Single- atom M+ of the Third- row (5d) Transition metals and Its Indication for CH4 Low-Temperature Activation 1129.3 Factors Leading to the Difference between High Activity of 5d Transition Metal Ion to CH4 Dehydrogenation and Nearly Inertness of 3d or 4d Metal Ion 1149.4 Activity in CH4 Dehydrogenation or C2H4 Formation on Free- standing Cluster [Ma]0 or Cluster Cation [Ma ]n+ and Its Indication to CH4 Low-Temperature Activation 116References 11810 Oxidization of CH4 by Free- standing MO+ Clusters at Room Temperature in Low- pressure CH4 12110.1 Brief 12110.2 Preparation of MO+ Clusters 12110.3 Experimental and Computational Approaches for Studying Reaction between MO+ Cluster and CH4 12210.4 Chemical Properties of MO+ and Their Indications for Activity in Oxidizing CH4 12310.5 Fundamental Understanding of the Evolution of the Activity of MO+ in Oxidizing CH4 and Its Indication for Catalytic Oxidation of CH4 12410.6 Fundamental Understanding of Product Selectivity for CH3OH in Oxidation of CH4 133References 13511 Catalytic Oxidation of Methane through Free- standing M+ in Gas Phase at Low Temperature 139 Reference 14112 Activation and Catalytic Oxidation of CH4 through M1 On Clusters Anchored on Open Support at Low Temperature 14212.1 Context 14212.2 Cations Doped on Open Surface of Transition Metal Oxide 14212.3 Cations on the Surface of Iridium Oxide Thin Film 148References 15213 Catalytic Transformation of Methane through Organometallic Approach at Low Temperature 15313.1 Pt- based Catalysts for Production of Methanol 15313.2 Pt- based Catalysts for the Production of Acetic Acid 15513.3 Pd- based Catalyst for Production of Methanol 15613.4 Pd- based Catalyst for the Production of Acetic Acid 15713.5 Rh- based Molecular Catalysts for the Production of Acetic Acid with the Participation of External CO 16013.6 Hg- based Catalysts for Production of Methanol 16213.7 Ru- based Catalysts for the Production of Methanol 16513.8 Peroxydisulphate for the Production of Acetic Acid without External CO 16613.9 Polyoxometalates for the Production of Methanol 16713.10 Ag- based Catalyst for Inserting CH2 16713.11 Au- based Catalyst for the Production of Methanol 16813.12 Ir- based Catalyst for Borylation of Methane 170References 17214 Solid Organic Catalysts for the Selective Low- temperature Oxidation of Methane to Methanol 175References 17915 Confinement Effect in Micropores of Microporous Aluminosilicate 18015.1 Origin of Confinement: Elevation of Energy of Molecular Orbitals and Reduction of Gap of HOMO and LUMO 18015.2 Relaxation of Atoms of the Concave Surface 18415.3 Quantification of the Confinement Effect 18615.4 Confinement- directed Catalytic Performance 187References 18816 Brief of Experimental Methods of Low- temperature Activation and Catalytic Conversion of CH4 through M– O Clusters Anchored in Zeolite 190References 19217 Oxidation of Methane by N2O through M– O Clusters Anchored in Zeolite in the Gas Phase at Low Temperature 19417.1 Early Studies of Partial Oxidation of Methane 19417.2 Fe-ZSM- 5 19617.3 Small Pore Metallozeolite 20017.4 A Comparison of Pore Size on Oxidation of Methane 20117.5 Isothermal Activation of Cu-ZSM-5, Partial Oxidation, and Gas Phase Extraction of Methanol 202References 20418 Oxidation of Methane through M– O Sites Anchored in Zeolite or AuPd Nanoparticles by H2O2 at Low Temperature 20718.1 Brief of the Difference between the Catalytic Oxidation of CH 4 with N 2 O at a Relatively High Temperature and that with H2O2 in Aqueous Solution at a Low Temperature 20718.2 Fe- S- 1 and Fe- ZSM- 5 20818.3 Pd- ZSM- 5 21218.4 AuPd Supported on ZSM- 5 217References 22019 Noncatalytic and Catalytic Oxidation of Methane with O2 through M–O Clusters Anchored in Zeolite in Liquid at Low Temperature 22219.1 Cu- ZSM- 5 22219.1.1 Identification of Reactive Oxygen Species for Oxidizing CH4 in Cu- ZSM- 5 through O2 Treatment 22219.1.2 Confirmed Reactivity of the Formed Oxygen Species in Oxidizing CH4 22519.1.3 Characterization of the Formed Oxygen Species with Resonance Raman Spectroscopy 22619.2 Cu- MOR 23019.2.1 Correlation between Pretreatment Condition and Structure of Active Copper Sites 23019.2.2 Formation of Momo(μ- oxo)di- copper Species in Cu- MOR through Activation at 450 °C in O2 23419.2.3 Formation of Copper Oxide Clusters Instead of Momo(μ- oxo)di- copper Species in Cu- MOR through Activation at 200 °C in O2 23819.2.4 How Activation Temperature of Cu- MOR in O2 in 350–550 °C Influence Activity or Reactivity of Cu- MOR 24019.3 Ni- ZSM- 5 24119.4 Zeolite with Small Pore Cu- SSZ- 13, Cu- SSZ- 16, and Cu- SSZ- 39 24519.5 Pore Size- dependence on Activity 24719.6 Catalytic Oxidation of Methane with O2 by Cu- zeolite 24819.7 Catalytic Coupling between O2or HOO· and CH3· in a Solution with Coexisting O2 and H2O2 252References 25620 Oxidation of CH4 and CO with O2 through M–O Clusters Anchored in Zeolite in Liquid at Low Temperature 259References 26721 Challenges and Prospect 26821.1 Challenge in Achieving High Selectivity for a Specific Product 26821.2 Challenge in Achieving High Conversion of CH4 26821.3 Challenge in Finding a New Reaction 26921.4 Challenge in Reproducible Preparation of Metallozeolite with Homogeneous Catalytic Sites 27021.5 Challenge in Characterizing the Actual Catalyst during Catalysis 27121.6 Challenge in the Fundamental Understanding of the Catalytic Mechanism 27221.7 Challenge in Transforming Low- concentration Methane of Waste Gas 272References 273Index 277