Since the discovery of graphene, two-dimensional nanomaterials including Transition metal dichalcogenides (TMDCs), Hexagonal Boron Nitride (hBN), non-layered compounds, black phosphorous, and Xenes with large lateral dimensions, have emerged as promising candidates for heterogenous electrocatalysis owing to their exceptional physical, chemical, and electronic properties. The tremendous opportunities of using 2D nanomaterials in electrochemical CO2 reduction arises from their unique properties and vast number of applications. Covering the fundamentals, properties, and applications, all aspects of 2D nanomaterial composites within carbon dioxide conversion are discussed. The industrial scale-up and new challenges that exist in the field of electrochemical reduction of carbon dioxide will also be presented. With chapters written by internationally recognized researchers, this state-of-the-art overview will serve the growing interest amongst academic and industrial researchers in understanding 2D nanomaterials composites, their hidden interfaces and nanoscale dispersion of the metal oxide with nanocomposites for specific uses in carbon dioxide conversion to chemicals for fuel applications. This book will be of interest to graduate students and researchers in materials science, energy, and environmental science, as well as those in industry.
Author(s): Kishor Kumar Sadasivuni, Karthik Kannan, Aboubakr M. Abdullah, Bijandra Kumar
Publisher: Royal Society of Chemistry
Year: 2022
Language: English
Pages: 466
City: London
Cover
2D Nanomaterials for CO2 Conversion into Chemicals and Fuels
Preface
Acknowledgements
Contents
Chapter 1 - A Fundamental Approach Towards Carbon Dioxide Conversion to Chemicals and Fuels: Current Trends for CO2 Utilization Technologies
1.1 Introduction
1.2 CO2 Mitigation
1.2.1 Electrochemical Reduction of CO2
1.2.2 CO2 Adsorption on Electrocatalyst Surface
1.2.3 Confines and Current Approaches
1.2.4 Design of Electrocatalyst for Enhanced Electrocatalytic Reduction of CO2
1.3 Photocatalytic CO2 Reduction
1.3.1 Confines and Current Approaches
1.3.2 Design of Photocatalyst
1.4 Thermo Catalytic Conversion of CO2
1.4.1 Synthesis of CO Through Reverse Water Gas Shift Reaction
1.4.2 CH3OH Synthesis
1.4.3 CO2 Methanation
1.5 Biological Mitigation of CO2
1.5.1 d-Ribulose-1,5-biphosphate Carboxylase/Oxygenase Enzyme
1.5.2 Dehydrogenase Enzymes
1.5.3 CO Dehydrogenase Enzyme
1.5.4 Formate Dehydrogenase Enzyme
1.5.5 Formaldehyde Dehydrogenase Enzyme
1.5.6 Alcohol Dehydrogenase
1.6 Conclusion
Acknowledgements
References
Chapter 2 - Synthesis and Characterization of Two Dimensional Materials
2.1 Introduction
2.2 Different Types of 2-D Materials
2.2.1 Graphene
2.2.2 Transition Metal Chalcogenides
2.2.3 Topological Materials
2.2.4 Black Phosphorous
2.2.5 Hexagonal Boron Nitride
2.3 Synthesis Method of 2-D Materials
2.3.1 Top-down Techniques
2.3.1.1 Mechanical Exfoliation
2.3.1.1.1
Micromechanical Cleavage.In this method, mechanical force is applied using the Scotch Tape method to synthesize single or multi-...
2.3.1.1.2
Ball Milling-based Exfoliation.The ball milling exfoliation technique is based on the shear force and compression forces that a...
2.3.1.2 Solution Processing Techniques
2.3.1.2.1
Liquid-phase Exfoliation Method.Liquid-phase exfoliation (LPE) is the highly preferred method to attain huge scale and well-o...
Mechanical Force Assisted LPE. The parent materials are exfoliated into ultrathin NSs on a huge scale with high yield using mech...
Oxidation-1396983920assisted LPE (Modified Hummers1397969777 Method). This is a much better method for the synthesis of graphene...
Selective Etching-1396983920assisted LPE. Generally, this is used for the synthesis of M-1396983920Xenes 2-1396983920D nanosheet...
2.3.1.2.2
Ion Intercalation.The ultrathin 2-D nanomaterials are synthesized from the ion intercalation method in which Na+, Li+, K+, and ...
2.3.2 Bottom-up Approach
2.3.2.1 Chemical Vapor Deposition
2.3.2.2 Pulse Laser Deposition/Physical Vapor Deposition
2.3.2.3 Wet-chemical Synthesis
2.3.2.3.1
Hydro/solvothermal Synthesis.This is used to synthesis various types of 2-D materials such as metal oxides NSs, TMDCs NSs.130 I...
2.4 Material Characterizations
2.4.1 Scanning Electron Microscopy
2.4.2 Transmission Electron Microscopy
2.4.3 Atomic Force Microscopy
2.4.4 Raman Spectroscopy
2.4.5 Energy Dispersive X-ray Analysis
2.4.6 X-ray Diffraction Spectroscopy
2.5 Concluding Remarks
List of Abbreviations
Acknowledgements
References
Chapter 3 - Synthesis of Two-dimensional Hybrid Materials, Unique Properties, and Challenges
3.1 Introduction
3.2 CO2 Reduction in the Presence of Hybrid Nanomaterials through Electrocatalysis Process
3.3 CO2 Reduction in the Presence of Hybrid Nanomaterials through the Photocatalysis Process
3.4 Graphene Oxides (GOs)
3.5 Two-dimensional Transitional Metal Dichalcogenides
3.5.1 Synthesis of TMDs through the Different Process
3.5.1.1 Exfoliation Method of Layered Solids
3.5.1.2 Chemical Vapor Deposition Growth
3.5.1.3 Wet Chemical Approaches
3.5.1.4 Biological Synthesis
3.5.2 Properties of TMDs
3.5.2.1 Magnetic and Electronic Properties of Pristine TMDs
3.5.2.2 Stability
3.5.2.3 Crystal Structure
3.5.2.4 Plasmonic Properties
3.5.3 Applications
3.5.3.1 Catalysis
3.5.3.2 Electrocatalysis
3.5.3.3 Heterogeneous Catalysis
3.5.3.4 Solar Cells
3.5.3.5 Surface Enriched Raman Scattering
3.5.3.6 Bioimaging
3.5.3.7 2D Hybrid TMDs
3.5.4 Classification of 2D TMD Hybrid Nanomaterials for Generation of Energy
3.5.4.1 2D TMD-based Inorganic Hybrids
3.5.4.1.1
2D TMD/Metal Chalcogenide Nanohybrids.2D TMDs have chemically dangling/inert 2D basal (bond free) planes held together by mild v...
3.5.4.1.2
2D TMD/Transition Metal Oxides.Because of their environmental friendliness, low cost, and good catalytic activity, transition me...
3.5.4.1.3
2D TMD and Noble Metal Nanohybrids.Different noteworthy noble metals like Pt, Pd, Ag, and Au are appealing due to their wide ran...
3.5.4.2 2D TMD-based Organic Hybrids
3.5.4.2.1
2D TMD/Carbonaceous Materials.Due to their lightweight, low toxicity, higher value of electrical conductivities, and improved fa...
3.5.4.2.2
2D TMD/Conductive Polymers.Because of their high electrical conductivity, cost effectiveness, simple process, biodegradability, ...
3.6 Metal Carbides/Carbonitrides (MXenes)
3.6.1 Synthesis
3.6.2 Properties
3.6.3 Applications
3.7 Graphene and Metal Oxides Hybrid
3.7.1 2D Stable MAX Supported Multiheterojunction Protonated Graphitic Carbon Nitride (pg-C3N4)/Ti3AlC2/TiO2 Photocatalyst (Z-S...
3.7.2 2D/2D/0D TiO2/C3N4/Ti3C2 Composite MXene Photocatalyst (S-Scheme)
3.7.3 Mesoporous TiO2's Hierarchical Structure on 3D Graphene along with MoS2
3.7.4 Graphene-wrapped Pt/TiO2 Photocatalysts
3.7.5 Surface Modified Heterojunction Photocatalysts of TiO2/rGO/CeO2
3.8 Molecular Catalysts/Carbon Materials Nanohybrids
3.9 Metal Phthalocyanine Complexes
3.10 2D Hybrid Nanomaterials as Electrocatalysts
3.10.1 Modified Rhenium(i)-Pyrene Diimine Complex
3.10.2 Molecular Rhenium on Colloid Carbon (Imprinted) Catalyst
3.10.3 Heterogenized Pyridine-Substituted Cobalt(ii) Phthalocyanine
3.10.4 Crystalline Copper(ii) Phthalocyanine Catalysts
3.10.5 Mn-Complex Catalyst Electrode Supported by Nanocarbon Support and K+ Cations
3.10.6 Carbon Cloth Electrodes with Immobilized Molecular Wires
3.10.7 A Redox-innocent Metal Center in a Heterogenized ZnPorphyrin Complex
3.10.8 Cobalt Phthalocyanine/Graphene Catalyst Incorporating Steric Modification
3.10.9 Hybrid Co Quaterpyridine Complex/Carbon Nanotube Catalytic Material
3.10.10 Covalently Grafted Cobalt Porphyrin on Carbon Nanotube
3.10.11 Electrochemically Replaced Metal Phthalocyanine, e-MPc (M = Ni, Co)
3.10.12 Iron Porphyrin
3.10.13 Pyridine-functionalized Carbon Nanotubes with Cobalt Phthalocyanine
3.10.14 Re(tBu-bpy)(CO)3Cl Maintained on Multiwalled Carbon Nanotubes
3.10.15 Cobalt Phthalocyanine/Carbon Nanotube Nanohybrid Structures
3.10.16 Metal Phthalocyanines
3.10.17 Copper-complex Catalytic Material (Copper(ii) Phthalocyanine)
3.10.18 Active Cobalt Phthalocyanine
3.10.19 Metal Catalysts with Organic Ligands that have been Functionalized
3.11 MOFs and their Composites
3.11.1 Copper(Cu)-Based MOFs and their Composites
3.11.1.1 Copper Rubeanate-Metal–Organic Framework
3.11.1.2 Cu3(BTC)2 (BTC = 1,3,5-Benzene Tricarboxylic)
3.11.1.3 CuSIM NU-1000 Thin Film
3.11.1.4 HKUST-1 (C18H6Cu3O12, Cu3(BTC)2·H2O, btc = Benzene-1,3,5-Tricarboxylate)
3.11.1.5 Ru(iii) Doped HKUST-1
3.11.1.6 Cu3(BTC)2 (Cu-MOF)
3.11.1.7 HKUST-1/CAU-17 Blends
3.11.1.8 Cu2O@Cu3(BTC)2
3.11.1.9 Cu2(CuTCPP) Nanosheet
3.11.1.10 CuII/ade-MOF Nanosheets
3.11.1.11 Cu Matrix Reinforced SiC–Graphite Hybrid
3.11.2 Fe-Based Metal–Organic Frameworks and their Composites
3.11.2.1 Fe_MOF-525
3.11.2.2 ZIF-8 with Ammonium Ferric Citrate, C-AFC©ZIF-8
3.11.2.3 PCN-222(Fe)/C
3.11.2.4 MOF-1992/CB
3.11.3 Co-Based Metal–Organic Frameworks and their Composites
3.11.3.1 Al2(OH)2TCPP-Co
3.11.3.2 Co-PMOFs
3.11.3.3 TPY-MOL-CoPP
3.11.3.4 CoCp2@MOF-545-Co
3.11.3.5 TCPP(Co)/Zr-BTB-PSABA
3.11.4 Zn-Based Metal–Organic Frameworks and their Composites
3.11.5 Noble-metal-based Metal–Organic Frameworks and their Composites
3.12 Other Inorganic and Organic Hybrid Nanomaterials
3.12.1 Covalent Organic Frameworks Hybrids
3.12.2 Hybrids based on Metal Sulfide
3.12.3 Hybrids based on g-C3N4
3.13 Conclusion
Acknowledgements
References
Chapter 4 - CO2 Conversion to Chemicals and Fuel Cells Using Renewable Energy Sources
4.1 Introduction
4.2 Renewable Energy and CO2 Conversion
4.3 Fuel Cells: Basic Principle and Current Applications
4.4 Solar-driven CO2 Conversion
4.5 Classifications of Solar-driven CO2 Conversion Approaches
4.5.1 Photosynthetic and Photocatalytic Approach
4.5.1.1 Limitations and Enhancement Techniques
4.5.2 Photoelectrochemical Approach
4.5.2.1 Challenges of CO2 Photoelectroreduction
4.5.3 Photovoltaic Plus Electrochemical or Photoelectrochemical (PV+EC) Approach
4.5.3.1 Challenges of (PV+EC) Approach
4.5.4 Photothermal Approach
4.5.4.1 Challenges in the Photothermal Approach
4.5.5 Bio-photosynthetic Approach
4.5.5.1 Challenges in Bio-photosynthetic Approach
4.5.6 Microbial-photoelectrochemical Approach
4.5.6.1 Limitations and Enhancement Techniques
4.6 Conclusion
List of Abbreviations
Acknowledgements
References
Chapter 5 - Two-dimensional Metal Oxide Nanomaterials for Electrochemical Conversion of CO2 Into Energy-rich Chemicals
5.1 Introduction
5.2 Overview of 2D Materials
5.3 CO2 Reduction: What Catalysts Are Used, What Is the State of the Art
5.4 The Electrochemical Pathway
5.5 The Experimental Setup for Electrocatalysis
5.6 Processes Occurring in the Electrode–electrolyte System
5.7 Synthesis of Metal Oxides
5.7.1 Top-down Methods
5.7.1.1 Conventional Solid-state Synthesis
5.7.1.2 Exfoliation of 2D Metal Oxides
5.7.1.3 Layered Host for Exfoliation
5.7.1.4 Cation Exchange-assisted Liquid Exfoliation
5.7.1.5 Mechanical Force-assisted Liquid Exfoliation
5.7.2 Bottom-up Methods
5.7.2.1 Chemical Vapor Deposition (CVD)
5.7.2.2 Atomic Layer Deposition
5.7.2.3 Electrostatic Self-assembly
5.7.2.4 Langmuir–Blodgett (LB) Deposition
5.8 Applications to CO2 Reduction Including Electrochemical Studies: Theoretical and Experimental Studies
5.8.1 CO2 Reduction Over 2D Metal Oxides: Theoretical Perspective
5.8.2 CO2 Reduction Over 2D Metal Oxides: Experimental Studies
5.9 Conclusions and Perspectives
References
Chapter 6 - Two-dimensional Based Hybrid Materials for CO2-to-fuels Electrochemical Conversion CO2 Process
6.1 Introduction
6.2 Parameters in CO2 Electroreduction
6.3 2D Hybrid Materials for Electroreduction of CO2
6.4 Conclusions
Acknowledgement
References
Chapter 7 - Two-dimensional Nanomaterials Design and Reactor Engineering of Different Methods for CO2 Electrochemical Conversion Process
7.1 Introduction
7.2 Fundamentals of CO2 Electrochemical Conversion
7.2.1 Reaction Overpotential
7.2.2 Faradic Efficiency
7.2.3 Turnover Frequency
7.2.4 Tafel Slope
7.2.5 Other Parameters
7.3 2D Nanocatalysts for CO2RR
7.4 2D Metal for CO2 Electrochemical Conversion
7.5 Transition Metal Dichalcogenides for CO2 Electrochemical Conversion
7.6 2D MXene for CO2 Electrochemical Conversion
7.7 2D Metal/Metal Oxides for CO2 Electrochemical Conversion
7.8 2D Doped Nanomaterials for CO2 Electrochemical Conversion
7.9 Metal Organic Framework for CO2 Electrochemical Conversion
7.10 Electrolyzer
7.10.1 H-Cell Electrolyzer
7.10.2 Flow Cell Electrolyzer
7.10.2.1 Liquid Phase Electrolyzers
7.10.2.2 Gas Phase Electrolyzers
7.10.2.3 Solid Phase Electrolyzers
7.10.2.4 Gas Diffusion Electrode
7.11 Conclusion
Acknowledgements
References
Chapter 8 - Photoelectrochemical CO2 Conversion Through the Utilization of Non-oxide Two-dimensional Nanomaterials
8.1 Introduction
8.2 The Most Employed Non-oxide 2D Nanomaterials for CO2 Reduction
8.2.1 Transition-metal Dichalcogenide Catalysts
8.2.2 Nitride-based Materials
8.2.3 g-carbon Nitride Catalysts
8.2.4 Metal–Organic Framework Catalysts
8.3 Conclusion
Acknowledgements
References
Chapter 9 - Photocatalytic Conversion of CO2 Into Energy-rich Chemicals by Two-dimensional Nanomaterials
9.1 Introduction
9.2 Process of Photocatalytic Conversion of CO2
9.3 2D Nanomaterials for Photocatalytic Conversion of CO2 into Energy-rich Chemicals
9.3.1 2D Graphitic Carbon Nitride-based Nanomaterials
9.3.2 2D Graphene-based Nanomaterials
9.3.3 2D Metal Chalcogenide-based Nanomaterials
9.3.4 2D Metal Oxide-based Nanomaterials
9.3.5 2D Metal Oxyhalide-based Nanomaterials
9.4 Concluding Remarks
Acknowledgements
Declaration
References
Chapter 10 - Two-dimensional Based Hybrid Materials for Photocatalytic Conversion of CO2 Into Hydrocarbon Fuels
10.1 Introduction
10.2 Challenges and Opportunities of Carbon Dioxide
10.3 2D Hybrid Materials and Their Photocatalytic Applications
10.3.1 Photocatalytic Application of 2D Hybrid Materials
10.3.2 Hydrogen Evolution
10.3.3 Degradation of Pollutants
10.3.4 Photoelectrochemical Catalysis
10.3.5 CO2 Reduction
10.4 Photocatalytic CO2 Reduction: Principles
10.5 Preparation Methods of Photocatalytic 2D Hybrid Material
10.5.1 Graphene-based Photocatalysts
10.5.2 Graphitic Carbon Nitride-based (g-C3N4) Photocatalysts
10.5.3 Transition Metal-oxides (TMO) and Transition Metal-chalcogenides (TMC) Based Photocatalysts
10.6 2D Hybrid Materials for Photocatalystic Co2 Conversion into Hydrocarbon Fuels
10.6.1 CO2 Reduction into Hydrocarbon Fuels Through the Photoelectrochemical Approach
10.6.1.1 Nanosized 2D Hybrid Material for CO2 Reduction
10.6.1.1.1
0D/2D Nanomaterial for Photocatalytic CO2 Reduction.The 0D/2D nanomaterial created photocatalysts are produced by spreading nano...
10.6.1.1.2
1D/2D Nanomaterial for Photocatalytic CO2 Reduction.1D nanomaterials such as rods, wires, fibers, tubes etc., possess high aspec...
10.6.1.1.3
2D/2D Nanomaterial for Photocatalytic CO2 Reduction.The 2D/2D nanomaterial holds a larger face-to-face contact area than 0D/2D...
10.7 State-of-the-art Theoretical Approach to Studying Photocatalytic CO2 Conversion on 2D Hybrid Materials
10.8 Conclusions
List of Abbreviation
Acknowledgements
References
Chapter 11 - Catalytic Thermal Conversion of CO2 to Fuels Using Two-dimensional Nanomaterials
11.1 Introduction
11.2 CO2 Hydrogenation Reaction
11.2.1 Graphene Family
11.2.2 Layered Double Hydroxides
11.2.3 Metal Nanosheets
11.3 Dry Reforming of Methane Over 2D Materials
11.3.1 MXenes
11.3.2 Siloxene
11.3.3 Boron Nitride Nanosheet
11.4 CO2 for Fischer–Tropsch Synthesis
11.4.1 Fe Species Supported on Layered-double-hydroxide Nanosheets
11.4.2 Fe Species Supported on Graphene Oxide
11.4.3 Fe Species Supported on Carbon Nanotube
11.5 CO2 to High-value Carbon Materials
11.5.1 Graphene
11.5.2 Carbon Nanotubes and Others
11.6 Current Status and Future Outlook of CO2 to Fuels Using 2D Nanomaterials
11.7 Concluding Remarks
Acknowledgements
References
Chapter 12 - Oxidative Dehydrogenation of Ethane to Ethylene Over Two-dimensional Nanomaterial Catalysts Using CO2
12.1 Introduction
12.1.1 Ethylene – Importance, Utilization, Demand, and Feedstocks
12.1.2 Conventional Ethylene Production Technology – Steam, Thermal, Catalytic Cracking
12.2 Oxidative Dehydrogenation of Ethane
12.2.1 Role of Oxidant in the ODHE; O2, N2O, CO2
12.2.2 Reactivity and Selectivity of Catalyst – Active Site, Mechanism, Promoters
12.3 Traditional ODH Catalyst Upgrading
12.3.1 Transition-metal Oxides
12.3.2 Rare Earth Metal Oxides
12.3.3 Other Catalysts
12.4 Future Perspective on Catalytic ODH Reactions
12.5 Conclusion
Acknowledgements
References
Chapter 13 - A Comparative Study of 0D, 1D, and 2D Nanocatalysts Towards CO2 Conversion
13.1 Introduction
13.1.1 Principles of CO2 Reduction
13.2 Recent Progress on Nanoparticle Design and the Rise of Two-dimensional Materials
13.3 Important Improvements in Chemical Transformation of Carbon Dioxide
13.3.1 Catalytic Reduction of CO2
13.3.2 Photocatalytic Reduction of CO2
13.3.3 Electrocatalytic Reduction of CO2
13.3.4 Photoelectrocatalytic Reduction of CO2
13.3.5 Thermocatalytic Conversion
13.3.6 Biochemical Reduction
13.3.7 Reforming
13.3.8 Mineralization
13.4 Synthesis for Conventional Selective Conversions of CO2 Using Nano Dimensional Catalyst to Reusable Low Carbon-based Produc...
13.4.1 0D Nanomaterials
13.4.2 1D Nanomaterials
13.4.3 2D Nanomaterials
13.4.3.1 0D/2D Nanomaterials
13.4.3.2 1D/2D Nanomaterials
13.4.3.3 2D/2D Nanomaterials
13.5 Conclusion
13.6 Future Challenges and Perspectives
Acknowledgment
References
Chapter 14 - CO2 Capture and Conversion Using Different Renewable Sources
14.1 Introduction
14.2 CO2 Capture Techniques
14.3 Conversion of CO2 into Chemicals and Useful Products
14.3.1 Photoelectrochemical Method
14.3.2 Thermal Catalytic Method
14.3.3 Electrocatalytic Method
14.3.4 Biochemical Method
14.3.5 Radiolysis Method
14.4 Conclusions and Future Perspectives
Acknowledgement
References
Chapter 15 - CO2 Capture by Functionalized Two-dimensional Nanomaterials
15.1 Introduction
15.2 Different Types of 2D Nanomaterials for CO2 Capture
15.3 Metal-based 2D Nanomaterials for CO2 Capture
15.3.1 MoS2 Based 2D Nanomaterials
15.3.2 Composites of MoS2 Nanosheets
15.4 Carbon-based 2D Nanomaterials for CO2 Capture
15.4.1 g-C3N4 Nanosheets
15.4.1.1 Composites of g-C3N4 Nanosheets
15.4.2 Graphene Nanosheets
15.4.2.1 Composites of Graphene-based Nanosheets
15.5 Conclusion and Future Outlook
Acknowledgement
References
Chapter 16 - Conversion of CO2 into Energy-dense Chemicals and the Commercialization Using Two-dimensional Nanomaterials as Catalysts
16.1 Introduction
16.1.1 eCO2RR Principles
16.1.1.1 Solvent Selection
16.1.1.2 Selection of Electrolytes
16.2 Two-dimensional Nanomaterials and eCO2RR
16.2.1 Transition Metals as eCO2RR Catalysts
16.2.2 Dichalcogenide Metals as eCO2RR Catalysts
16.2.3 Graphene Basis as eCO2RR Catalysts
16.2.4 New eCO2RR Catalysts
16.2.5 Current Trends in Industry Based on eCO2RR
16.3 Reverse Microbial Fuel Cells for eCO2RR
16.4 Conclusion
References
Subject Index
