Sustainable Inorganic Chemistry E-Book
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- Herausgeber: John Wiley & Sons
- Kategorie: Wissenschaft und neue Technologien
- Serie: EIC Books
- Sprache: Englisch
The Earth's natural resources are finite and easily compromised by contamination from industrial chemicals and byproducts from the degradation of consumer products. The growing field of green and sustainable chemistry seeks to address this through the development of products and processes that are environmentally benign while remaining economically viable. Inorganic chemistry plays a critical role in this endeavor in areas such as resource extraction and isolation, renewable energy, catalytic processes, waste minimization and avoidance, and renewable industrial feedstocks.
Sustainable Inorganic Chemistry presents a comprehensive overview of the many new developments taking place in this rapidly expanding field, in articles that discuss fundamental concepts alongside cutting-edge developments and applications. The volume includes educational reviews from leading scientists on a broad range of topics including: inorganic resources, sustainable synthetic methods, alternative reaction conditions, heterogeneous catalysis, photocatalysis, sustainable nanomaterials, renewable and clean fuels, water treatment and remediation, waste valorization and life cycle sustainability assessment.
The content from this book will be added online to the Encyclopedia of Inorganic and Bioinorganic Chemistry.
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Seitenzahl: 1659
Veröffentlichungsjahr: 2016
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Table of Contents
Cover
EIBC Books
Title Page
Copyright
Encyclopedia of Inorganic and Bioinorganic Chemistry
Contributors
Series Preface
Volume Preface
Recovery of Gold from Incinerated Sewage Sludge
1 Overview
2 Introduction
3 Experimental Procedure
4 Results and Discussion
5 Conclusions
6 Acknowledgments
7 Abbreviations and Acronyms
8 References
Rare Earth Recycling from NdFeB
1 Introduction
2 Present Situation of NdFeB Magnet Recycling
3 Preprocessing
4 Rare Earths Recovery
5 Conclusions
6 Acknowledgements
7 Related Articles
8 Abbreviations and Acronyms
9 References
Life Cycle Sustainability Assessments
1 Overview
2 Introduction
3 State-of-the-Art LCSA Methods
4 Environmental Dimension of Sustainability/Life Cycle Assessment
5 Economic Dimension of Sustainability/Life Cycle Costing
6 Social Dimension of Sustainability/Social Life Cycle Assessment
7 Application of LCSA Framework to the Case of Palm Oil System
8 Palm Oil Biodiesel Life Cycle and its Sustainability Indicators
9 Integrated Assessment and Modeling Framework
10 Conclusions
11 Acknowledgments
12 Glossary
13 Related Articles
14 Abbreviations and Acronyms
15 References
Trends in Food and Agricultural Waste Valorization
1 Introduction
2 Food Waste Valorization
3 Agricultural and Agro-Industrial Waste Valorization
4 Winery Waste Valorization
5 Dairy Waste Valorization
6 Bakery Waste Valorization
7 Conclusions and Outlook
8 Acknowledgments
9 Related Articles
10 Abbreviations and Acronyms
11 References
Toxicity Assessment of Molecular Rhenium(VII) Epoxidation Catalysts
1 Introduction
2 Studies of the Toxicity of MTO and MTO-Lewis Base Complexes
3 Toxicity Studies of Perrhenate Salts
4 Conclusions
5 Acknowledgments
6 Related Articles
7 Abbreviations and Acronyms
8 References
Challenges in Green Analytical Chemistry
1 Overview
2 Green Analytical Chemistry in the Inorganic Field
3 Evaluation of Method Greenness
4 From Off-Line to Noninvasive Inorganic Analysis
5 Inorganic Waste Treatment
6 Inorganic Materials as Analytical Tools
7 Future Trends in Inorganic Green Analysis
8 Acknowledgments
9 Glossary
10 Related Articles
11 Abbreviations and Acronyms
12 References
Mobile Apps for Green Chemistry
1 Overview
2 Introduction
3 Green Solvents and Lab Solvents
4 Green Lab Notebook
5 Conclusions
6 Acknowledgments
7 Abbreviations and Acronyms
8 References
Renewable Plant-Based Raw Materials for Industry
1 Overview
2 Introduction
3 Renewable versus Fossil Resources
4 General Classification of Renewable Plant-Based Raw Materials (PRM)
5 Plant-Based Materials as Renewable Feedstock
6 Industrial Applications of Plant-Based Renewable Raw Materials
7 Disadvantages
8 Conclusions
9 Acknowledgments
10 Glossary
11 Related Articles
12 Abbreviations and Acronyms
13 References
14 Further Reading
Sustainable Synthesis of Fine Chemicals from Aliphatic Nitro Compounds
1 Overview
2 Introduction
3 One-Pot Synthetic Processes
4 Synthetic Processes Under Aqueous Medium
5 Synthetic Processes Under Solvent-Free Conditions
6 Conclusions
7 Related Articles
8 Abbreviations and Acronyms
9 References
Sustainable Production of Glycerol
1 Introduction
2 Bioglycerol: A Sustainable Resource?
3 The Glycerol Market
4 Direct and Indirect Uses
5 Perspectives and Conclusions
6 Acknowledgments
7 Related Articles
8 Abbreviations and Acronyms
9 References
Production of Biopropylene Using Biomass-Derived Sources
1 Overview
2 Introduction
3 Biopropylene: Production Processes Based on Renewable Resources
4 Novel Biopropylene Catalytic Production Processes
5 Conclusions
6 Glossary
7 Related Articles
8 Abbreviations and Acronyms
9 References
10 Further Reading
Methylethers from Alcohols and Dimethyl Carbonate
1 Overview
2 Introduction
3 Results and Discussion
4 Conclusions
5 Acknowledgments
6 Related Articles
7 Abbreviations and Acronyms
8 References
9 Further Reading
Sustainable Surfactants Based on Amino Acids
1 Overview
2 Introduction
3 Amino Acids
4 Single Chain Amino Acid Based Surfactants
5 Arginine Diacyl-Glycero Conjugates
6 Lysine-Bisglycerol Conjugates
7 Gemini Surfactants from Amino Acids
8 Polydispersed Lipopeptides from a Mixture of Amino Acids
9 Lipoamino Acid Surfactants Mixtures from the Protein Fraction of Process Wastewater
10 Conclusions
11 Acknowledgments
12 Related Article
13 Abbreviations and Acronyms
14 References
Sustainable Biosurfactants
1 Overview
2 Introduction
3 Classification of Biosurfactants
4 Biosurfactants Production
5 Characterization of Biosurfactants
6 Properties of Biosurfactants
7 Industrial Applications of Biosurfactants
8 Disadvantages Associated with Biosurfactants
9 Conclusions
10 Acknowledgement
11 Glossary
12 Related Articles
13 Abbreviations and Acronyms
14 References
15 Further Reading
Solvent Systems for Sustainable Chemistry
1 Overview
2 Introduction
3 Bio-Derived Solvents
4 Water as a Solvent
5 Supercritical Carbon Dioxide, Tuneable, and Switchable Solvent Systems
6 Ionic Liquids
7 Mechanochemistry and Solvent-Free Approaches
8 Conclusions
9 Glossary
10 Related Articles
11 Abbreviations and Acronyms
12 References
Fluorous Hydrocarbon Oxidation
1 Overview
2 Introduction
3 Fluorous Media
4 Fluorous Catalysts
5 Conclusions
6 Glossary
7 Related Article
8 Abbreviations and Acronyms
9 References
10 Further Reading
Ionic Liquids: Industrial Applications
1 Overview
2 Introduction
3 Synthesis of ILs
4 Properties of IL
5 Industrial Applications of IL
6 Conclusions
7 Glossary
8 Related Articles
9 Abbreviations and Acronyms
10 References
Ionic Liquids: Enzymatic Hydrolysis of Lignocellulose
1 Overview
2 Introduction
3 From Lignocellulose to Biofuels and Chemicals via the Sugar Platform Pathway
4 Ionic Liquids in Lignocellulose Processing and Pretreatment
5 One-pot Saccharification in IL Solutions
6 ILs in Biorefineries—Can it Become Economically Feasible?
7 Conclusions
8 Acknowledgments
9 Glossary
10 Related Articles
11 Abbreviations and Acronyms
12 References
13 Further Reading
Ionic Liquids: Applications by Computational Design
1 Introduction
2 Methods
3 Case Study 1: Design of Ionic Liquid for Ibuprofen Dissolution
4 Case Study 2: Design of Ionic Liquids with High Electrical Conductivity
5 Related Articles
6 Abbreviations and Acronyms
7 References
Ionic Liquids: Recycling
1 Introduction
2 Major Ionic Liquid Recycling Techniques
3 Conclusions
4 Acknowledgments
5 Abbreviations and Acronyms
6 References
Ionic Liquids: Bacterial Degradation in Wastewater Treatment Plants
1 Introduction
2 Toxicity Tests
3 Toxicity of Ionic Liquids
4 Biodegradability Tests
5 Biodegradability of Ionic Liquids
6 Ionic Liquids Management in Wastewater Treatment Plant (WWTP)
7 Conclusions
8 Related Articles
9 Abbreviations and Acronyms
10 References
Water Treatment by Electrocoagulation
1 Overview
2 Introduction
3 Colloids and Coagulation
4 Electrocoagulation (EC)
5 Conclusions
6 Glossary
7 Related Articles
8 Abbreviations and Acronyms
9 References
Sustainable Water Remediation
1 Overview
2 Introduction
3 Reasons and Problems Related to Wastewater
4 Remediation of Contaminated Water
5 Conclusion
6 Acknowledgement
7 Glossary
8 Related Articles
9 Abbreviations and Acronyms
10 References
11 Further Reading
Dimethylcarbonate for the Catalytic Upgrading of Amines and Bio-Based Derivatives
1 Overview
2 Introduction
3 Selective Reactions of Dimethyl Carbonate with Amines
4 Selective Reactions of Dimethyl Carbonate with Bio-Based Derivatives
5 Related Articles
6 Abbreviations and Acronyms
7 References
Sustainable Syntheses with Microwave Irradiation
1 Overview
2 Introduction
3 Microwave Effects
4 Microwave Reactors
5 Microwaves in Laboratory: Hazards and Safety Measures
6 Microwave-Assisted Synthesis
7 Conclusion
8 Glossary
9 Related Articles
10 Abbreviations and Acronyms
11 References
12 Further Reading
Radical Reactions, β-Cyclodextrin and Chitosan and Aqueous Media: From Fundamental Reactions to Potential Applications
1 Introduction
2 The Cyclodextrin Reaction Media
3 Chitosan as a Viable Alternative
4
β
-Cyclodextrin-Based Molecular Reactors for Free Radical Chemistry in Aqueous Media and Chain Reactions
5 Radical Cyclizations in
β
-Cyclodextrins in Aqueous Media Under Photolytic Conditions
6 Mn(OAc)
3
Radical Cyclizations in
β
-Cyclodextrin
7 Cu(OAc)
2
Radical Cyclizations in
β
-Cyclodextrins
8
β
-Cyclodextrins as Molecular Batch Reactors
9 “Teabag” Methodology and Radical Reactions: Screening the Scope and Flexibility
10 Biomaterial Applications
11 Shear Bond Strengths
12 Bioadhesion In Vitro Model
13 Modulus of Elasticity
14 Conclusions and Future Directions
15 References
Catalytic Epoxidation of Organics from Vegetable Sources
1 Overview
2 Introduction
3 Epoxidation of Unsaturated Oils, Fats, and Fatty Acid Derivatives
4 Epoxidation of Terpenes
5 Conclusions
6 Acknowledgments
7 Glossary
8 Related Articles
9 Abbreviations and Acronyms
10 References
Catalytic Cyclic Carbonate Synthesis with Sustainable Metals
1 Overview
2 Introduction
3 Potassium Catalysts
4 Aluminum Catalysts
5 Iron Catalysts
6 Summary
7 Related Articles
8 Abbreviations and Acronyms
9 References
Solid Catalysts for Epoxidation with Dilute Hydrogen Peroxide
1 Overview
2 Introduction
3 The Peroxy–Hydroperoxy Mechanism
4 The Oxo Mechanism
5 The Hydroperoxide Anion Mechanism
6 Conclusions
7 Glossary
8 Related Article
9 Abbreviations and Acronyms
10 References
11 Further Reading
TiO2-Based Heterogeneous Catalysis for Photocatalytic Hydrogen Generation and Photodegradation
1 Introduction
2 Electronic Structure Engineering
3 Structural Design
4 Conclusions and Outlook
5 Related Articles
6 Abbreviations and Acronyms
7 References
Photocatalytic Production of Hydrogen with Earth-Abundant Metal Catalysts
1 Overview
2 Introduction
3 Organic Model Compounds of Photosynthesis Reaction Center
4 Incorporation of Organic Photocatalysts and Earth-Abundant Metal Catalyst on Al
2
O
3
–SiO
2
5 Hydrogen-Evolution Catalyst Composed of Earth-Abundant Metals
6 Conclusion and Perspective
7 Acknowledgments
8 Related Articles
9 Abbreviations and Acronyms
10 References
Multifunctional MOF-Based Photocatalysis
1 Overview
2 Introduction
3 Multifunctional MOFs in Photocatalysis
4 Concluding Remarks
5 Acknowledgments
6 Glossary
7 Related Articles
8 Abbreviations and Acronyms
9 References
Sustainable Nanomaterials
1 Overview
2 Introduction
3 History of Nanomaterials
4 Classification of Nanomaterials
5 Methodology Used in the Fabrications of Nanomaterials
6 Structural Characterization of Nanomaterials
7 Physical and Chemical Characteristics of Nanomaterials
8 Applications of Nanomaterials
9 Limitations
10 Conclusions
11 Acknowledgments
12 Glossary
13 Related Articles
14 Abbreviations and Acronyms
15 References
16 Further Reading
Sustainable Synthesis of Metal Oxide Nanostructures
1 Introduction to Nanoscience
2 Classification of Nanomaterials
3 Importance and Application of Metal Oxide Nanomaterials
4 Metal Oxide and their Morphology
5 Nanomaterials and Metal Oxide Nanostructure—Methods and their Synthesis
6 Gas Phase Methods
7 Liquid Phase Methods
8 Solid Phase Mechanical Processes
9 Nonconventional Methods in Nanoparticles Synthesis
10 Synthesis and Properties of Metal Oxide Nanoparticles
11 Structure–Activity Relationship for Metal Oxide Nanoparticles
12 Zeta Potential for Metal Oxide Nanoparticles
13 Conclusion
14 Related Articles
15 Abbreviations and Acronyms
16 References
Micellar Nanoreactors
1 Overview
2 Introduction
3 Application of Traditional Surfactants in Catalysis
4 Metal-Mediated Micellar Catalysis: Yield Enhancement
5 Metal-Mediated Micellar Catalysis: Product Selectivity
6 Substrate Selectivity
7 Designer Surfactants
8 Metallosurfactant Conjugates
9 Summary and Future Perspectives
10 Acknowledgments
11 Abbreviations and Acronyms
12 References
Index
Abbreviations and Acronyms used in this Volume
End User License Agreement
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Guide
Cover
Table of Contents
Begin Reading
List of Illustrations
Recovery of Gold from Incinerated Sewage Sludge
Figure 1 A proposed dry recovery process of gold from secondary resources
Figure 2 Procedure of quantitative analyses of gold and coexisting elements. (Reprinted with permission from Kakumazaki, J.; Kato, T.; Sugawara, K. Recovery of Gold from Incinerated Sewage Sludge Ash by Chlorination. ACS Sustainable Chem. Eng., 2014, 2, 2297–2300 © (2014) American Chemical Society)
Figure 3 Thermodynamic equilibrium calculation for (a) Au–Cl
2
and (b) Au–C–Cl
2
systems
Figure 4 Release behavior of gold from ash during heating in a chlorine gas stream (Type I experiment). (Reprinted with permission from Kakumazaki, J.; Kato, T.; Sugawara, K. Recovery of Gold from Incinerated Sewage Sludge Ash by Chlorination. ACS Sustainable Chem. Eng., 2014, 2, 2297–2300 © (2014) American Chemical Society)
Figure 5 Distribution of gold during heating in a chlorine gas stream (Type I experiment). (Reprinted with permission from Kakumazaki, J.; Kato, T.; Sugawara, K. Recovery of Gold from Incinerated Sewage Sludge Ash by Chlorination. ACS Sustainable Chem. Eng., 2014, 2, 2297–2300 © (2014) American Chemical Society)
Figure 6 Distribution of gold during heating in nitrogen and chlorine gases stream (Type II experiment). (Reprinted with permission from Kakumazaki, J.; Kato, T.; Sugawara, K. Recovery of Gold from Incinerated Sewage Sludge Ash by Chlorination. ACS Sustainable Chem. Eng., 2014, 2, 2297–2300 © (2014) American Chemical Society)
Figure 7 Distribution of gold during heating in a nitrogen gas stream (Type III experiment). (Reprinted with permission from Kakumazaki, J.; Kato, T.; Sugawara, K. Recovery of Gold from Incinerated Sewage Sludge Ash by Chlorination. ACS Sustainable Chem. Eng., 2014, 2, 2297–2300 © (2014) American Chemical Society)
Figure 8 Thermodynamic equilibrium calculation for Au–S system
Figure 9 XRD pattern of solid carbon. (Reprinted with permission from Kakumazaki, J.; Kato, T.; Sugawara, K. Recovery of Gold from Incinerated Sewage Sludge Ash by Chlorination. ACS Sustainable Chem. Eng., 2014, 2, 2297–2300 © (2014) American Chemical Society)
Figure 10 SEM-EDX image of solid carbon
Rare Earth Recycling from NdFeB
Figure 1 Potential–pH diagram of Fe–Nd–H
2
O system calculated by FactSage
Figure 2 Schematic of liquid membrane system for rare earth extraction
Life Cycle Sustainability Assessments
Figure 1 Life cycle sustainability dashboard. (Reproduced with permission from M. Finkbeiner, E. Schau, A. Lehmann, and M. Traverso, Sustainability, 2010, 2(10), 3309–3322)
Figure 2 Life cycle sustainability triangle. (Reproduced with permission from M. Finkbeiner, E. Schau, A. Lehmann, and M. Traverso, Sustainability, 2010, 2(10), 3309–3322)
Figure 3 CALCAS framework. (Reproduced with permission from Ref. 17 © A. Zamagni)
Figure 4 Halog and Manik's AISMF LCSA. (Reproduced from Ref. 6 © Halog A, Manik Y, 2011)
Figure 5 PROSUITE methodology. (Reproduced with permission from K. Blok, M. Huijbregts, L. Roes,
et al.
, 2013 © PROSUITE methodology)
Figure 6 LCA framework. (ISO 14040-2006 Figure 1 - Reproduced with permission from SAI Global Ltd under Licence 1510-c117)
Figure 7 Process flow diagram of palm oil biodiesel life cycle. (Adapted from Ref. 48 © Y. Manik, 2013)
Figure 8 The integrative assessment and modeling framework (a modified/simplified version of Halog and Manik integrated framework. (Adapted from Ref. 6 © Halog A, Manik Y, 2011)
Figure 9 Life cycle GHG emissions. (Reproduced with permission from Ref. 47 © Wiley, 2012)
Figure 10 Stakeholders and key social impacts in the palm oil biodiesel value chain
Figure 11 Energy return of energy invested (EROI). (Adapted from Ref. 48 © Y. Manik, 2013)
Figure 12 Causal loop diagram of palm oil biodiesel life cycle
Figure 13 MCDA matrix
Figure 14 Schematic diagram of sustainable palm oil biodiesel decision hierarchy
Trends in Food and Agricultural Waste Valorization
Figure 1 Total world proven crude oil reserves, 2013. (Reprinted with permission from Ref. 1 © OPEC, 2014)
Figure 2 OPEC Reference Basket price assumptions in the Reference Case. (Reprinted with permission from Ref. 2 © OPEC, 2014)
Figure 3 The integrated biorefinery as a mixed feedstock source of chemicals, energy, fuels, and materials. (Reproduced from Ref. 7 © Annual Reviews, 2012)
Figure 4 Components derived from food waste and their applications. (Reproduced from Ref. 18 © 2012 with permission of The Royal Society of Chemistry)
Figure 5 Basic steps ethanol production from lignocellulosic feedstocks. (Reproduced with permission from Ref. 35 ©McGraw-Hill Education, 2008)
Figure 6 Schematic representation of bakery waste valorization to polymers, chemicals, and biofuels
Toxicity Assessment of Molecular Rhenium(VII) Epoxidation Catalysts
Figure 1 Structures of the investigated compounds (test set 1)
Figure 2 Structures of the various MTO-based complexes and selected Lewis bases used for cytotoxicity screening (test set 2): (
5
) (4,4-dimethyl-2,2-bipyridine)-methyltrioxorhenium (MTO-bipy), (
6
) 4,4-dimethyl-2,2-bipyridine (BiPy), (
7
) (((4-chlorophenyl)imino)methyl)-phenol-methyltrioxorhenium (MTO-ClPh), (
8
) (((4-chlorophenyl)imino)-methyl)phenol (ClPh), (
9
) (1,2-cyclohexanediylbis[(E)-nitrilomethylidyne]-bis[4-bromophenol])-methyltrioxorhenium (MTO-BrPh), (
10
) 1,2-cyclo-hexanediylbis[(E)-nitrilomethylidyne]bis[4-bromophenol] (BrPh), (
11
) (pyrazole)-methyltrioxorhenium (MTO-Pz), (
12
) (4-cyanopyridine)-methyltrioxorhenium (MTO-CNPy), (
13
) (1,10-phenanthroline)-methyltrioxorhenium (MTO-Phen)
Figure 3 Illustration of the ammonium- and imidazolium perrhenates used in the study: [NBu
4
][ReO
4
] (
1
), [BnBnIm][ReO
4
] (
2
), [MeHDecIm][ReO
4
] (
3
), and [MeBnFIm][ReO
4
] (
4
) (Bn = benzyl, Me = methyl, HDec = hexadecyl, Bn
F
= 2,3,4,5,6-pentafluorobenzyl, and Im = imidazolium). (Reproduced from Ref. 64 with permission from the Centre National de la Recherche Scientifique (CNRS) and The Royal Society of Chemistry)
Figure 4 Hydrolysis kinetic (a) and hydrolysis rate (b) of MTO in different biological test media and incubated under the given test conditions. (S. Steudte, H. Bui Thi Thu, V. Korinth, J. Arning, A. Białk-Bielińska, U. Bottin-Weber, M. Cokoja, A. Hahlbrock, V. Fetz, R. Stauber, B. Jastorff, C. Hartmann, R. W. Fischer, F. E. Kühn, S. Stolte, Green Chem. 2015, 17(2), 1136–1144 - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC)
Figure 5 MTO treatment but not ammonium perrhenate is genotoxic and affects cell viability. (a/b/c) MTO but not ammonium perrhenate treatment results in enhanced phosphorylation of histone H2AX, indicative of DNA-damage. (a) Whole cell extracts of HeLa cells were analyzed by western blotting using an anti-γ-H2AX- or GAPDH-specific antibody. Cells were treated with MTO or ammonium perrhenate for 48 h. GAPDH served as a load control. Molecular weight is indicated. (b) The number of γ-H2AX-foci per cell was analyzed using high content microscopy. HeLa cells were treated with MTO or ammonium perrhenate for 8 h. γ-H2AX-foci were visualized using immunofluorescent staining. (c) Representative micrographs of γ-H2AX-foci are shown. Bar, 10 µm. (d) The impact of MTO-exposure on cell vitality was assessed using the alamarBlue® assay. * =
P
-value < 0.05; ** =
P
-value < 0.01; *** =
P
-value < 0.005. MTO treatment is genotoxic and affects cell viability. (S. Steudte, H. Bui Thi Thu, V. Korinth, J. Arning, A. Białk-Bielińska, U. Bottin-Weber, M. Cokoja, A. Hahlbrock, V. Fetz, R. Stauber, B. Jastorff, C. Hartmann, R. W. Fischer, F. E. Kühn, S. Stolte, Green Chem. 2015, 17(2), 1136–1144 - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC)
Figure 6 Correlation between toxicity (log(EC
50
)) and lipophilicity (log(
k
0
)) for all test compounds and different species. (Reproduced from Ref. 64 with permission from the Centre National de la Recherche Scientifique (CNRS) and The Royal Society of Chemistry)
Challenges in Green Analytical Chemistry
Figure 1 Ways for greening the analytical methods in the inorganic field
Figure 2 Pictograms used to evaluate the greenness of analytical methods
Figure 3 Inorganic analysis as a function of the state and nature of samples
Figure 4 Steps and risks involved by the use of different analytical approaches to solve the problems
Figure 5 Degradation processes for the treatment of analytical wastes
Mobile Apps for Green Chemistry
Figure 1 Green Solvents main view
Figure 2 Green Solvents—Detail view of Benzene
Figure 3 Green Solvents—Detail view of Sulfolane
Figure 4 Lab Solvents Main screen
Figure 5 Detail view—Benzene
Figure 6 Lab Solvents results of benzofuran search
Figure 7 Lab Solvents Indicator symbols
Figure 8 Green Lab Notebook
Renewable Plant-Based Raw Materials for Industry
Figure 1 Plant based products and their industrial applications
Sustainable Synthesis of Fine Chemicals from Aliphatic Nitro Compounds
Scheme 1 One-pot synthesis of 1,3-dinitroalkanes
4
Scheme 2 One-pot synthesis of 1,2-diketones
9
under MW and neat conditions
Scheme 3 One-pot synthesis of allylrethrones
14
vs
multisteps sequences
Scheme 4 One-pot synthesis of nitrocyclopropanes
18
Scheme 5 One-pot diastereoselective synthesis of bicyclo[3.3.1]nonanes
20
Scheme 6 Mechanism of the one-pot preparation of bicyclo[3.3.1]nonanes
20
Scheme 7 One-pot synthesis of
bis
-bicyclo[3.3.1]nonanes
22
Scheme 8 Two one-pot processes from nitromethane to
bis
-bicyclo[3.3.1]nonanes
22
Scheme 9 One-pot synthesis of acethophenone and benzoate derivatives
27
from 1,3-dinitroalkanes
4
Scheme 10 Direct conversion of primary haloderivatives
28
to nitroderivatives
29
under aqueous medium
Scheme 11 Direct conversion of α,ω-dihaloderivatives
30
to α,ω-dinitroderivatives
31
under aqueous medium
Scheme 12 Nitroaldol reaction under aqueous medium
Scheme 13 Conjugate addition of nitroalkanes
5
to electron-poor alkenes
34
(Michael reaction) under aqueous medium
Scheme 14 One-pot Synthesis of a variety of 1,4-difunctionalized derivatives
37-40
via Michael reaction of nitroalkanes
29
under aqueous medium
Scheme 15 One-pot synthesis of γ-nitroalkanols
37
under aqueous medium
Scheme 16 One-pot synthesis of γ-hydroxyketones
38
under aqueous medium
Scheme 17 One-pot synthesis of 1,4-diketones
39
under aqueous medium
Scheme 18 One-pot synthesis of 1,4-diols
40
under aqueous medium
Figure 1 PS-BEMP (2-
tert
-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine supported on polystyrene)
Scheme 19 Michael reaction of nitroalkanes catalized by PS-BEMP under solvent-free conditions
Scheme 20 Nitroaldol and Michael reaction of nitroalkanes
5
catalyzed by Isolute® Si-Carbonate under neat conditions
Scheme 21 One-flask sequence of both nitroaldol reaction and Micahel reaction catalized by Isolute® Si-Carbonate under neat conditions
Scheme 22 One-pot synthesis of cycloexanols derivatives
50
from 1,3-dinitroalkenes
4
under neat conditions
Scheme 23 Formation of C,C double bond by Michael reaction of nitroalkanes to electron-poor alkenes
51
having two electron withdrawing groups in α- and β-positions
Scheme 24 Chemoselective formation of C,C single or double bond by Michael reaction of nitroalkanes
51
under heterogeneous (KF/basic Al
2
O
3
) and neat conditions
Sustainable Production of Glycerol
Figure 1 The transesterification reaction of triglycerides with methanol. Glycerol is the inevitable by-product. (Reproduced from Ref. 1 with permission from the Royal Society of Chemistry)
Figure 2 The world's biggest biodiesel-producing countries according to their production volume in 2014. (Reproduced with permission from Ref. 13 © REN21 Secretariat, 2015)
Figure 3 Price of 80% crude glycerol in Europe (2004–2008, in $/t). (Data taken from Ref. 23)
Production of Biopropylene Using Biomass-Derived Sources
Figure 1 Chemical products from propylene
Figure 2 Propylene uses
Figure 3 Propylene global production per region. (Adapted from Ref. 2)
Figure 4 Propylene production technologies
Figure 5 Propylene production processes based on biomass feedstocks. (Adapted from Ref. 11)
Figure 6 Process flow diagram of metathesis reaction to propylene. (Adapted from Ref. 14)
Figure 7 Reactions taking place during hydroprocessing of a triglyceride
Figure 8 Rapeseed oil cracking steps under typical FCC conditions: LCO, light cycle oil; LHCO, light heavy cycle oil.
20
(Reprinted from Applied Catalysis B: Environmental, Vol. 72, X. Dupain, D.J. Costa, C.J. Schaverien, M. Makkee, and J.A. Moulijn, Cracking of a rapeseed vegetable oil under realistic FCC conditions, 44–61, Copyright (2007), with permission from Elsevier)
Figure 9 Product distribution versus glycerol conversion over a Fe-Mo/C catalyst (H
2
pressure: 80 bar, Temperature: 300 °C), PG: 1,2-propanediol. (Reproduced from Ref. 24. © 2015 with permission of The Royal Society of Chemistry)
Figure 10 C2, propylene, and propane yields obtained for different oxygenates as feed, under H
2
300 °C. (Reproduced with permission from Ref. 26. © John Wiley & Sons)
Figure 11 Hydrodeoxygenation of acetone involving vacancy creation and regeneration. (Reproduced from Ref. 27. © 2013 with permission of The Royal Society of Chemistry)
Figure 12 Glycerol two-step conversion to propylene. (Reproduced with permission from Ref. 29. © John Wiley & Sons.)
Methylethers from Alcohols and Dimethyl Carbonate
Scheme 1 DMC as methylating (eq. 1) and carboxymethylating (eq. 2) agent
Scheme 2 Methylation of 1-octanol to form methyl octyl ether (MOE)
Scheme 3 Methylation of alcohols via DMC chemistry
Scheme 4 Two-step reaction mechanism in the methylation of an alcohol by DMC
Figure 1 Dialkyl carbonates
1–6
selected for investigating the decarboxylation reaction
Scheme 5 Competitive processes involved in the decarboxylation of alkyl methylcarbonates: (a) decarboxylation of methylcarbonates; (b)
dismutation
via transesterification (trace of methanol, owing to the presence of a small amount of water, or other Bronsted acids catalyze the reaction); (c) decarboxylation of the dialkyl carbonates
Scheme 6 Dismutation of methyl alkyl carbonates. Owing to the presence of acidic hydroxyls on the surface of the catalyst, transesterification reactions occur: methanol and alcohol are released, which, in turn, produce, through a series of equilibria reactions, DMC and the symmetrical dialkyl carbonate
Figure 2 Applications of isosorbide
Figure 3 Carboxymethyl and methyl derivatives of isosorbide
Scheme 7 Synthesis of dimethyl isosorbide
Figure 4 View of isosorbide molecule
Sustainable Surfactants Based on Amino Acids
Figure 1 General structure of amino acids. R is the amino acid side chain
Figure 2 Different type of amino acid and hydrophobic alkyl chain linkages. (a) Ester derivatives. (b) Acyl derivatives. (c) Alkyl derivatives. (d) Amide derivatives
Figure 3 Chemical structure of single chain arginine based surfactants. (a) R = −CH
3
,
n
= 8 CAM,
n
= 10 LAM,
n
= 12 MAM,
n
= 14 PAM. (b)
n
= 9 ACA,
n
= 11 ALA,
n
= 13 AMA. (c)
n
= 7 AOE,
n
= 9 ACE,
N
= 11 ALE
Figure 4 Chemical structures with
n
= 11. (a) Lysine lauroyl ester. (b) Lysine lauroyl amide
Figure 5
N
α
-palmitoyl-lysine surfactants with two lysine residues on the polar head
Figure 6 Structure of
N
ϵ
-acyl lysine esters. R
1
and R
2
are always methyl groups. For DMLL, R
3
is hydrogen and
n
= 10. For DMPL R
3
is hydrogen and
n
= 14. For TMLL R
3
is a methyl group and
n
= 10. For TMPLR
3
is a methyl group and
n
= 14
Figure 7 Chemical structures. (a)
N
α
-lauroyl methyl ester. (b)
N
ϵ
-acyl lysine methyl ester. In LKM
n
= 10, in MKM
n
= 12 and in PKM
n
= 14
Figure 8 (a) Structure of a phospholipid, DPPC
n
= 13. (b) Structure of XXR compounds. 88R
n
= 5, 1010R
n
= 7, 1212R
n
= 9, 1414R
n
= 11. (c) Structure of XXRAc compounds. 1212RAc
n
= 9, 1414RAc
n
= 11
Figure 9 Schematic structure of the
N
ϵ
,
N
ϵ′
-bis(η-acyloxypropyl)-
L
-lysine methyl ester salts,
n
= 10 or
n
= 12
Figure 10 Chemical structure of
N
α
,
N
α′
-bis(
N
-dodecyl
N
,
N
-dimethylglycine) cystine dimethyl ester dihydrochloride.
n
= 10
Figure 11 General formula for cationic gemini surfactants C
n
(LA)
2
compounds.
n
= 2, 3, 4, 6, 9, or 10
Figure 12 Cationic gemini surfactants from lysine
Sustainable Biosurfactants
Figure 1 Glycolipid
Figure 2 Rhamnolipids
Figure 3 Trehalose lipids
Figure 4 Sophorolipids
Figure 5 Lipopeptides and lipoproteins
Figure 6 Fatty acids biosurfactants
Figure 7 Phospholipids biosurfactants
Figure 8 Neutral lipids biosurfactants
Figure 9 Polymeric surfactant
Figure 10 Vesicles
Figure 11 Whole cells
Figure 12 CMC of biosurfactants
Figure 13 Biosurfactants functions and their applications
Figure 14 Advantages and disadvantages associated with cheaper substrates in biosurfactant production
Figure 15 Various cheaper/renewable substrates available from different industrial sectors
Solvent Systems for Sustainable Chemistry
Figure 1 Two amphiphilic solvents (glycerol 1-monobutylether and isosorbide monobutylether) derived from bio-derived polyols
Figure 2 Solvent molecules that can be prepared from carbohydrate feedstocks: ethanol, ethyl lactate, 2-MeTHF, and γ-valerolactone
Figure 3 Selected examples of transition metal-catalyzed reactions performed in glycerol
Figure 4 Structures of the oxygen-free renewable solvents:
D
-limonene and
p
-cymene
Figure 5 TPPTS, a trisulfonated triphenylphosphine, used in industrial biphasic rhodium-catalyzed hydroformylation of propene
Figure 6 Diels–Alder and Michael addition reactions perform in water
Figure 7 Metal-catalyzed oxidation of alcohols and cross-dehydrogenative coupling reactions performed under air or oxygen in water
Figure 8 Hydrogenation of CO
2
in scCO
2
Figure 9 A fluorinated analog of triphenylphosphine used for homogeneous catalysis in scCO
2
Figure 10 Example of a CO
2
-switchable polarity solvent. (Adapted from Ref. 23 with permission of The Royal Society of Chemistry)
Figure 11 CO
2
-switchable polarity solvents based on single components (amines or diamines)
Figure 12 Example of a switchable hydrophilicity solvent
Figure 13 Piperylone sulfone, a thermally switchable solvent of variable volatility
Figure 14 Some cations and anions prepared from biomass or artificial sweeteners and used in RTILS
Figure 15 Examples of catalytic reactions performed in RTILs
Figure 16 Solventless synthesis of a range of inorganic compounds
Fluorous Hydrocarbon Oxidation
Figure 1 Application of the FBS concept to the aerobic oxidation of hydrocarbons
Figure 2 Examples of fluorinated solvents for hydrocarbon oxidation
Figure 3 Examples of heavy fluorous polydentate N ligands
Figure 4 Fluorous solid-phase extraction
Figure 5 Aerobic oxidation of liquid hydrocarbons under fluorous-organic, solid–liquid biphasic conditions
Figure 6 Fluorous porphyrins used as photocatalysts
Figure 7 Photooxidation of a liquid diene in scCO
2
/HFE-7500 promoted by fluorous porphyrin
9
. (Adapted from Ref. 19 with permission from The Royal Society of Chemistry)
Figure 8 Fluorous ligands for PFC-free oxidations
Ionic Liquids: Industrial Applications
Figure 1 Cations and anions frequently used in the formation of ILs
Figure 2 Cations containing heterocyclic ring
Scheme 1 General reaction of metathesis
Scheme 2 N-alkylation of imidazoles
Scheme 3 Acid base neutralization reaction
Scheme 4 Involvement of carbene intermediate
Scheme 5 Functionalization of ILs
Ionic Liquids: Enzymatic Hydrolysis of Lignocellulose
Figure 1 The main material flow and unit operations in second generation production of biofuels and chemicals from lignocellulosic polysaccharides via the sugar pathway
Figure 2 The structure of cellulose, showing the intra- and interchain hydrogen bonds that make the cellulose such a rigid and hard material
Figure 3 Enzymatic polysaccharides hydrolysis is a reaction in which an enzyme, a cellulase, or hemicellulase, catalyzes the cleavage of glycosidic bonds in carbohydrate chains by addition of water. The end product is a monosaccharide. Glucose is obtained as end product from the hydrolysis of cellulose
Figure 4 Schematic view of enzymatic cellulose hydrolysis and synergy between endoglucanases, lytic polysaccharide mono-oxygenases, cellobiohydrolases, and β-glucosidases. (Reproduced with permission from VTT - Technical Research Centre of Finland Ltd
5
)
Figure 5 Chemical structures of the most studied cellulose-dissolving ionic liquids based on the imidazolium cation: 1-ethyl-3-methylimidazolium acetate ([EMIM]AcO), 1-butyl-3-methylimidazolium chloride ([BMIM]Cl), 1-allyl-3-methylimidazolium chloride ([AMIM]Cl) and 1,3-dimethylimidazolium dimethylphosphate ([DMIM]DMP)
Figure 6 Comparison between one-pot hydrolysis and the regeneration with washing hydrolysis procedure
Figure 7 Structures of specially designed enzyme-compatible cellulose-dissolving ILs
Ionic Liquids: Applications by Computational Design
Figure 1 A general scheme of two feasible cation structures. (Reproduced with permission from Karunanithi, A. T., Mehrkesh, A. Computer-aided design of tailor-made ionic liquids. AIChE Journal, 59(12), 4627–4640. © John Wiley & Sons, 2013)
Figure 2 Examples of feasible and non-feasible ionic liquids. (Reproduced with permission from Karunanithi, A. T., Mehrkesh, A. Computer-aided design of tailor-made ionic liquids. AIChE Journal, 59(12), 4627–4640. © John Wiley & Sons, 2013)
Figure 3
σ
profile of four common industrial solvents
Figure 4
σ
profile of an ionic liquid calculated by group contribution (red) and DFT (blue)
Figure 5 Optimal ionic liquid structure for ibuprofen dissolution:
Cation core – Imidazolium
+
; Anion: bis(trifluoromethylsulfonyl) imide, [Tf
2
N]
−
Figure 6 Optimal ionic liquid structure for heat transfer fluid:
Cation core – Pyridinium; Anion: tetra fluoroborate, [BF
4
]
−
Ionic Liquids: Recycling
Figure 1 Applications of ionic liquids
Figure 2 Major ionic liquid recycling methods
Figure 3 A simple method of parameterization of protic ionic liquids to predict their excess boiling points. (Adapted from Ref. 21)
Figure 4 Enthalpy of proton transfer between gas-phase species as being exothermic for all [emim]-anion combinations. (Adapted from Ref. 24)
Figure 5 All positive dissociation energies for conversion of single [emim]-anion pairs to [emim]: carbene and the anions conjugate acids, in the gas phase. (Adapted from Ref. 25)
Figure 6 Distillation mechanism for [TMF][OTf]. (Adapted from Ref. 26)
Figure 7 Distillation mechanism for [TMSmim]Br. (Adapted from Ref. 27)
Figure 8 Distillation mechanisms for the different classes of ionic liquids, depending on lability of certain functionalities. [C]
+
and [CR]
+
are cations in solution, [A]
−
is the anion in solution. C and RA are the unconjugated neutral species. [C][A] and [CR][A] are the condensed ionic liquids
Figure 9 Decomposition of [bmim]Cl over via E2 elimination, S
N
2 retroalkylation, and S
N
2 transalkylation. (Adapted from Ref. 33)
Figure 10 Distillation apparatus used for increased rate of distillation of ionic liquids. 1. engine, 2. product entry, 3. heating medium inlet/outlet, 4. wiper system, 5. heating jacket, 6. splash guard, 7. internal condenser, 8. heating medium inlet/outlet, 9. residue outlet, 10. vacuum outlet, 11. coolant inlet/outlet, 12. coolant inlet/outlet, 13. condensate outlet. (Illustrations by BASF. Refs 31 and 32)
Figure 11 Kugelrohr distillation and X-ray structure of [TMGH][CO
2
Et]. (King, A.W.T., Asikkala, J., Mutikainen, I., Järvi, P., Kilpeläinen, I., Distillable Acid-Base Conjugate Ionic Liquids for Cellulose Dissolution and Processing, Angew. Chem. Int. Ed., 2011, 50: 6301-6305. Copyright Wiley-VCH Verlag GmbH & Co. KGaA. Reproduced with permission)
Figure 12 X-ray structure for [DBNH][OAc], as a distillable ionic liquid finding application in the IONCELL-F (lyocell) process. (Parviainen, A., King, A.W.T., Mutikainen, I., Hummel, M., Selg, C., Hauru, L.K.J., Sixta, H., Kilpeläinen, I., Predicting cellulose solvating capabilities of acid-base conjugate ionic liquids. ChemSusChem, 2013, 6: 2161–2169. Copyright Wiley-VCH Verlag GmbH & Co. KGaA. Reproduced with permission)
Figure 13 The Hofmeister series as an order of the ion effect on protein stability
Figure 14 Process for the recovery of ionic liquids from contaminated aqueous streams using aluminum-based salts (Neves
et al.
60
)
Ionic Liquids: Bacterial Degradation in Wastewater Treatment Plants
Figure 1 Relationship between toxicity and polarity of ILs
Figure 2 Comparison between cytotoxicity and biodegradability of ILs. (Data taken from Ref. 55)
Figure 3 Time-evolution of the specific oxygen uptake rate (SOUR) and BmimAcetate concentration during the short biodegradability test
Figure 4 Time-evolution of the specific oxygen uptake rate (SOUR) of imidazolium ILs with anion Cl
−
(a), BF
4
−
(b) and NTf
2
−
(c) in presence of glucose
Figure 5 Ecotoxicity classification of some ILs according to Passino and Smith
83
In brackets: EC
50
values in mg L
−1
.
a
Markiewicz
et al.
,
34 b
This study. (Data taken from Refs 34 and 83)
Water Treatment by Electrocoagulation
Figure 1 Phenomenon interactions in an EC system—a conceptual framework of a “synthesis technology”.
2
(Reprinted from P. K. Holt, G. W. Barton, and C. A. Mitchell, Chemosphere, 2005, 59, 355–367 with permission from Elsevier)
Figure 2 Structure of the electrical double layer.
11
(Reprinted from L. Besra and M. Liu, Prog. Mater. Sci., 2007, 52, 1–61 with permission from Elsevier)
Figure 3 Repulsive and attractive energies as a function of distance between particles.
12
(Reprinted from D. N. Thomas, S. J. Judd, and N. Fawcett, Water Res., 1999, 33, 1579–1592 with permission from Elsevier)
Figure 4 Base reactions and interactions occurring in an EC system.
14
(Reprinted from P. K. Holt, G. W. Barton, M. Wark, and C. A. Mitchell, Colloids Surf., 2002, 59, 233–248 with permission from Elsevier)
Figure 5 Mole fractions of dissolved hydrolysis products in equilibrium with amorphous hydroxides for Fe(III) and Al(III) in dilute solutions.
10
(Reprinted from J. Duan and J. Gregory, Adv. Colloid Interfac. Sci., 2003, 100–102, 475–502 with permission from Elsevier)
Figure 6 Monopolar (a) and bipolar (b) electrode connections in an EC system.
1
(Reprinted from G. Chen, Sep. Purif. Technol., 2004, 38, 11–41 with permission from Elsevier)
Figure 7 Current wave of alternating pulse current.
25
(Reprinted from M. Eyvaz, M. Kirlaroglu, T. S. Aktas, and E. Yuksel, Chem. Eng. J., 2009, 153, 16–22 with permission from Elsevier)
Sustainable Water Remediation
Figure 1 Structure of chitin and chitosan
Figure 2 Basic structure of zeolites
Figure 3 Various cations and anions of ionic liquids
Figure 4 Surfactants used for water remediation
Dimethylcarbonate for the Catalytic Upgrading of Amines and Bio-Based Derivatives
Scheme 1 The methods of synthesis of dimethyl carbonate
Scheme 2 The general reactivity of DMC
Scheme 3 Mono-
N
-methylation of anilines with DMC
Scheme 4 The synthesis of unsymmetrical alkyl methyl carbonates (MACs)
Scheme 5 The selective mono-
N
-methylation of functionalized anilines with DMC
Scheme 6 The selective mono-
N
-methylation of aniline with DMC in a faujasite supercavity
Scheme 7 Most common glycerol acetals
Scheme 8 The mechanism of etherification of glycerol acetals with DMC in the presence of a catalytic base (B = K
2
CO
3
)
Scheme 9 The transesterification of DMC with glycerol formal (top) and solketal (bottom)
Figure 1 Effects of temperature and pressure on the non-catalytic (thermal) continuous-flow transesterification of DMC with glycerol formal. (Reproduced from Ref. 29 with permission from the Royal Society of Chemistry)
Scheme 10 The tunable selectivity of reaction of cinnamyl alcohol (top) and 4-(3-hydroxypropyl)phenol (bottom) with DMC
Scheme 11 Reactions between lactones and dimethyl carbonate with K
2
CO
3
as a catalyst
Scheme 12 Base-catalyzed alkylation of 5-membered ring Lactones with DMC
Scheme 13 The ring-opening reaction of DVL by DMC in the presence of catalytic base (B: K
2
CO
3
)
Sustainable Syntheses with Microwave Irradiation
Figure 1 Applications of microwaves
Figure 2 Nanoparticles synthesized in water medium
Figure 3 Nanoparticles synthesized in polyols
Figure 4 Nanoparticles synthesized in ionic liquids
Figure 5 Nanoparticles synthesized in multicomponent solvents
Radical Reactions, β-Cyclodextrin and Chitosan and Aqueous Media: From Fundamental Reactions to Potential Applications
Figure 1 β-CD molecular reactor prototype
Scheme 1 Reduction of 1-BrAd to Ad under various free radical conditions in water
Scheme 2 Radical addition of RX to C=N bond of (
E
)-
N
-benzylidene-1-phenylethanamine under various free radical conditions in water
Figure 2 β-CD-based molecular reactor prototype and reactions of interest CC bond formation through reductive radical cyclization/termination and oxidative radical cyclization/termination
Scheme 3 Proposed approach and methodology
Scheme 4 General outline of the investigation
Scheme 5 Schematic representation of the prototype molecular devices under investigation
Scheme 6 Radical cyclization reaction under flow-through conditions
Scheme 7 Schematic diagram of the “teabag methodology” protocol
Figure 3 SEM photographs of interior morphology of the selected gels under investigation for (a) Gel-2, (b) Gel-3, and (c) Gel-4
Figure 4 Shear bond strength of hydrogels after 24 h of bonding to dentin
Figure 5 Cumulative release (%) of naproxen from 5% w/w chitosan IPN gels in phosphate buffer pH 6.8
Figure 6 Slow release profile of Gel 4 as a function of time with ibuprofen as potential therapeutic agent
Figure 7 Release profile of Gel as a function of time with asprin as active ingredient
Figure 8 Effect of the time duration on the modulus of elasticity following the hydrogel treatment
Figure 9 SEM images of the dentin surface exposed to Gels 1–4 for 2 weeks
Figure 10 Plot of changes in water solubility of the model protein bovine serum albumin (BSA) over a time (12 h) exposed to free radicals generated by a Fe
2+
/EDTA/H
2
O
2
/ascorbate system as a source of free radicals
Catalytic Epoxidation of Organics from Vegetable Sources
Figure 1 Most common methods for the epoxidation of alkenes in synthetic organic chemistry
Figure 2 Most common fatty acids found in oleochemicals
Figure 3 Two-step reaction pathway in the enzymatic epoxidation of alkenes
Figure 4 Unsaturated terpenes from vegetable sources
Figure 5 Peroxyisourea intermediate formed during the epoxidation of pinenes with the carbodiimide–hydrogen peroxide system
Figure 6 Epoxidation of α-pinene (6) and citronellol (7) in the presence of lipase
Figure 7 Minisci epoxidation
Figure 8 Methyltrioxorhenium-based epoxidation of alkenes
Catalytic Cyclic Carbonate Synthesis with Sustainable Metals
Scheme 1 Synthesis of cyclic carbonates from epoxides and CO
2
Scheme 2 General mechanism for catalyzed addition of CO
2
to epoxides
Scheme 3 The cooperative effect of two hydroxyl groups on ring opening of epoxides with KI
Scheme 4 Suggested cocatalysis mechanism for cyclodextrin (
3
)
Scheme 5 Mechanism for activation of CO
2
by amines in conjunction with hydroxyl groups as a cocatalyst
Scheme 6 Preparation of Kleij's amino tris-phenolate aluminum complexes
Scheme 7 Conversion of bimetallic complex
26
to monometallic complex
27
Scheme 8 Stereochemistry of cyclic carbonate formation
Solid Catalysts for Epoxidation with Dilute Hydrogen Peroxide
Figure 1 Mechanisms of H
2
O
2
activation
Figure 2 Side reactions in the epoxidation of alkenes (cyclohexene as an example) with diluted H
2
O
2
Figure 3 Peroxy-hydroperoxy mechanism of epoxidation
Figure 4 Formation of the titanium-hydroperoxy intermediate from a Ti-zeolite
Figure 5 Mechanism of Ti leaching from TS-1 in the epoxidation of allyl alcohol with diluted H
2
O
2
Figure 6 Species in Ti-silica catalysts prepared by grafting
Figure 7 Examples of immobilized W catalysts
Figure 8 Ta-silica catalyst modified with group IV elements
Figure 9 Oxo mechanism of epoxidation
Figure 10 Examples of immobilized Mn catalysts
Figure 11 Hydroperoxide anion mechanism of epoxidation
TiO2-Based Heterogeneous Catalysis for Photocatalytic Hydrogen Generation and Photodegradation
Figure 1 Schematic representation of the CB and VB positions of TiO
2
and the redox potentials versus NHE at pH = 0
Figure 2 Various schemes illustrating the possible origin of light absorption in doped TiO
2
: narrowing of bandgap resulting from broadening of (a) CB or (b) VB; introduction of localized dopant levels (c) below CB or (d) above VB; (e) introduction of multiple localized dopant levels from co-doping; and (f) electronic transitions from localized levels near the VB to their corresponding excited states for Ti
3+
and F
+
centers
Figure 3 Energy levels of impurity ions in rutile TiO
2
Figure 4 Partial geometry and schematic sketch of the model for (a) interstitial and (b) substitutional N-doping in an anatase matrix. The N atom is represented by a black sphere, O atoms are represented by yellow spheres, and Ti atoms are represented by small brown spheres. (c) Crystal lattice model for carbonate-doped TiO
2
. The sky blue, red, and black balls represent Ti, O, and C atoms respectively. (d) Diffuse reflectance spectra of carbonate-doped TiO
2
microspheres prepared at various post-synthesis annealing temperatures: (i) as-prepared, (ii) annealed at 100 °C for 2 h, (iii) annealed at 200 °C for 2 h, (iv) calcined at 300 °C for 2 h, and (v) calcined at 400 °C for 2 h. The inset is a digital photograph of TiO
2
microspheres calcined at various temperatures for 2 h. ((a,b) Reprinted with permission from Valentin
et al
. © 2005 American Chemical Society and (c,d) Reproduced from Ref. 68. © 2015 with permission of The Royal Society of Chemistry)
Figure 5 (a) Optical photograph of the prepared red TiO
2
sample; (b) UV–visible absorption of the white TiO
2
and red TiO
2
; and (c) DOS of anatase TiO
2
, anatase TiO
2
doped with an interstitial boron in a [BO
4
] unit (denoted as B–TiO
2
), and anatase TiO
2
doped with a [BO
4−
x
N
x
] (
x
= 4) (denoted as B/N–TiO
2
). (d) Diffuse reflectance spectra of (i) TiOF
2
precursor, (ii) TiOFN sample prepared by nitriding TiOF
2
in NH
3
gas flow at 773 K, and (iii) TiOFN sample obtained by calcining sample (ii) in air at 673 K. The inset presents the photographs of the three samples. ((a–c) Reproduced from Ref. 116. © 2012 with permission of The Royal Society of Chemistry and (d) Reproduced from Ref. 117. © 2011 The Royal Society of Chemistry)
Figure 6 (a) The interface diffusion–redox diagram. The green arrows indicate ion diffusion. A photograph comparing unmodified white and disorder-engineered black TiO
2
nanocrystals. (b) An atomic model showing the location of the Ti
3+
and V
O
defects. (c) The UV–visible diffuse reflectance spectra for the blue TiO
2−
x
(blue line) and the commercial anatase (black line). The inset in (c) shows the corresponding photographs. ((a) Reproduced from Ref. 127. © 2013 with permission of The Royal Society of Chemistry and (b,c) Reproduced from Ref. 128. © 2014 with permission of The Royal Society of Chemistry)
Figure 7 Band structures and charge–carrier migration mechanisms of different systems: charge–carrier transfer for (a–c) co-catalysts with different band structure alignments, (d) metal NPs, (e) sensitization by photosensitizers, and (f) direct Z-scheme system (yellow quadrangle: TiO
2
; other quadrangles: foreign materials)
Figure 8 Electronic structures of TiO
2
and the metal oxides that are often used as co-catalysts
Figure 9 (a,b) CdS/Au/TiO
2
heterostructures at high magnification, in which the Au/CdS core–shell structure was formed on TiO
2
surfaces. The inset shows a schematic illustration. (c,d) SEM images of TiO
2
@CdS and CdS@TiO
2
double-shelled hollow spheres. (e) SEM and (f) TEM images, and (g) UV–vis absorption spectra of MoS
2
nanosheets on TiO
2
nanowires. ((a,b) Reprinted from Ref. 177 © 2014 with permission from Elsevier, (c,d) Reprinted from Ref. 178 © 2012 with permission from Elsevier, and (e–g) Reproduced from Ref. 179 © 2014 with permission of The Royal Society of Chemistry)
Figure 10 (a) SEM and (b) TEM images of the suspended Pt NPs over the top opening of TiO
2
nanotubes, and (c) HRTEM image of Pt NPs showing a lattice constant of 2.22 Å corresponding to the (111) crystallographic plane. (d) HRTEM image and (e) element mapping patterns of a single Ag/TiO
2
nanotube. (f) Cu NPs oxidized to Cu
2
O on the TiO
2
surface. (g) Co nanocluster-decorated TiO
2
. ((a–c) Reproduced from Ref. 193 © 2014 with permission of The Royal Society of Chemistry, (d,e) Reproduced with permission from Ref. 194 © Wiley, 2014, (f) Reproduced from Ref. 195 © 2012 with permission of The Royal Society of Chemistry, and (g) Reproduced from Ref. 196 © 2012 with permission of The Royal Society of Chemistry)
Figure 11 (a) SEM and (b) TEM images, and (c) PL spectra of rGO/TiO
2
nanotubes. Digital photos of CDs solutions with different particle sizes under (d) daylight and (e) UV light. (f) TEM image of TiO
2
/CDs nanocomposites. (g) PL emission spectra of CDs solutions under different excitation wavelength. (h) Schematic illustrations of TiO
2
/CDs nanocomposites under solar and visible light. (a–c) Reproduced with permission from Ref. 210 © Wiley, 2014, (d–f) Reproduced with permission from Ref. 211 © Wiley, 2010, (g) Reproduced from Ref. 212 © 2012 with permission of The Royal Society of Chemistry, and (h) Reproduced from Ref. 213 © 2013 with permission of The Royal Society of Chemistry)
Figure 12 (a,c) Chemical structure of
CoP
and
RuP
, with the molecular structure of (Et
3
NH)[
CoP
] shown in (b). (d) Schematic representation of photocatalytic H
2
production of
CoP
/
RuP
-TiO
2
composites. (Reproduced from Ref. 226 © 2011 with permission of The Royal Society of Chemistry)
Figure 13 (a) SEM and (b) TEM images of CdS QDs-sensitized TiO
2
inverse opals (pore diameter: 288 nm). (c) Digital photos of (1) bare TiO
2
film; (2) the TiO
2
/CuInS
2
QDs film; (3) the TiO
2
/CdS, and (4) the TiO
2
/CuInS
2
/CdS film. (d) Plots of (
αE
)
2
against the photon energy (
E
) for the nanocrystalline TiO
2
film sensitized with 3.5 nm CuInS
2
QDs and varying cycles of CdS. (e) Schematic illustration showing the band energy levels and the synergistic effect of a nanocrystalline TiO
2
film co-sensitized with CuInS
2
QDs and CdS. ((a,b) Reproduced with permission from Ref. 228 © Wiley, 2012 and (c–e) Reproduced from Ref. 229 © 2011 with permission of The Royal Society of Chemistry)
Figure 14 SEM images of various TiO
2
-based hierarchical nanostructures built up from (a) nanoparticles, (b) nanosheets, (c) nanoflakes, (d) nanowires, (e) nanothorns, and (f) nanorods. ((a) Reprinted from Ref. 277 © 2014 with permission from Elsevier, (b) Reprinted from Ref. 278 © 2013 with permission of The Royal Society of Chemistry, (c) Reprinted from Ref. 281 © 2014 with permission of The Royal Society of Chemistry, (d) Reprinted from Ref. 280 © 2015 with permission of The Royal Society of Chemistry, (e) Reprinted from Ref. 279 © 2010 with permission of The Royal Society of Chemistry, (f) Reprinted with permission from Sun
et al
. © 2011 American Chemical Society)
Figure 15 (a) Optical photographs of (top) PS/TiO
2
composite films templated by PS microspheres at different sizes and (bottom) corresponding TiO
2
inverse opal films after calcination. (b) SEM image of the PS photonic crystal template, with its photograph under daylight shown in the inset. (c) SEM and (d) TEM images of the TiO
2
inverse opal films duplicated from the PS template. (e) Digital photographs of the butterfly
Papilio helenus Linnaeus
. Inset shows the SEM image of its upper-layer wing structure. (f) SEM image of the butterfly-templated TiO
2
architecture. (g) Light harvesting efficiency of TiO
2
with (red) and without (blue) the template. ((a) Reproduced with permission from Ref. 305 © Wiley, 2011, (b–d) Reprinted from Ref. 306 © 2013 with permission of The Royal Society of Chemistry, and (e–g) Reprinted from Ref. 307 © 2011 with permission of The Royal Society of Chemistry)
Photocatalytic Production of Hydrogen with Earth-Abundant Metal Catalysts
Figure 1 An overall photocatalytic cycle of H
2
evolution employing EDTA, [Ru(bpy)
3
]
2+
, methyl viologen (MV
2+
), and Pt nanoparticles as a sacrificial electron donor, a photosensitizer, an electron relay, and an H
2
-evolution catalyst, respectively (ISC: intersystem crossing). (Copyright (2014) From Fuel Production with Heterogeneous Catalysis by J. Sa, ed. Reproduced by permission of Taylor and Francis Group, LLC, a division of Informa PLC)
Figure 2 Chemical structure of 2-phenyl-4-(1-naphthyl)quinolinium ion (QuPh
+
–NA) and overall photocatalytic cycle for producing H
2
without an electron relay. NADH, QuPh
+
–NA, and metal nanoparticles (MNPs) act as a sacrificial electron donor, a photosensitizer, and an H
2
evolution catalyst, respectively. (Adapted with permission from Y. Yamada, T. Miyahigashi, H. Kotani,
et al.
, J. Am. Chem. Soc., 2011, 133, 16136–16145. Copyright 2011 American Chemical Society.)
Figure 3 (a) Transmission electron microscope (TEM) image of Na
+
–exchanged sAlMCM-41. (b) Diffuse reflectance UV–vis spectrum of QuPh
+
–NA@sAlMCM-41 composite (red solid line) compared with UV–vis absorption spectrum of QuPh
+
–NA ion in MeCN (black dotted line). Positions of peaks and shoulders are indicated with broken lines. (Reproduced from Ref. 23—Published by The Royal Society of Chemistry)
Figure 4 (a) EPR spectrum of QuPh
+
–NA@sAlMCM-41 composite in the presence of adsorbed water under photoirradiation using a high-pressure mercury lamp and UV cut-off filter (
λ
> 390 nm). (b) Time course of the EPR signal intensity for QuPh
•
–NA
•+
@sAlMCM-41 in the absence (red dotted) or presence (black solid) of water at 316 K. (c) Time course of the EPR signal intensity for QuPh
•
–NA
•+
@sAlMCM-41 in the presence of water upon intermittent photoirradiation for 2 s followed by 48 s in the dark at 316 K. (Reproduced from Ref. 23—Published by The Royal Society of Chemistry)
Figure 5 Photograph of the dispersions containing QuPh
+
–NA@sAlMCM-41 and oxalate anion (a) in the absence of photoirradiation and (b, c) after photoirradiation (
λ
> 340 nm) for 15 min (b) in the presence of K
2
PtCl
6
and (c) in the presence of PtNPs. (Reproduced from Ref. 24 with permission from the Royal Society of Chemistry)
Figure 6 (a) Time courses of H
2
evolution under photoirradiation (
λ
> 340 nm) of a deaerated dispersion (2.0 mL) of a phthalate buffer (pH 4.5) containing QuPh
+
–NA@sAlMCM-41 (QuPh
+
–NA: 0.22 mM) and oxalate (50 mM) with PtNPs (blue square) or K
2
PtCl
6
(red circle). (b) Time courses of H
2
evolution in repetitive experiments using NADH (1.0 mM) as a sacrificial electron donor (first cycle, red circle; second cycle, blue square). (Reproduced from Ref. 24 with permission from the Royal Society of Chemistry)
Figure 7 (a) Time courses of H
2
evolution under photoirradiation (
λ
> 340 nm) of a phthalate buffer dispersion (pH 4.5) containing QuPh
+
–NA@sAlMCM-41 (QuPh
+
–NA: 0.22 mM) and oxalate (50 mM) with 0.05 mM Cu(NO
3
)
2
(circle), FeSO
4
(triangle), Ni(NO
3
)
2
(square), and Co(NO
3
)
2
(diamond). (b) Time courses of the photocatalytic H
2
evolution in the presence of Cu(NO
3
)
2
in different concentrations [0.05 mM (circle) and 0.5 mM (triangle)]. (Reproduced from Ref. 24 with permission from the Royal Society of Chemistry)
Figure 8 Time courses of H
2
evolution under photoirradiation (
λ
> 340 nm) of a deaerated mixed solution (2 mL) of a phthalate buffer (pH 4.5) and MeCN [1:1 (v/v)] containing QuPh
+
–NA (0.44 mM), NADH (1.0 mM) and various catalysts [12.5 mg L
−1
, NiNPs (6 nm, square) and PtNPs (2 nm, closed circle)] at 298 K. (Reproduced from Ref. 25 with permission from the Royal Society of Chemistry)
Figure 9 (a, b) Time courses of H
2
evolution under photoirradiation (
λ
> 340 nm) of mixed solutions of deaerated phthalate buffer (pH 4.5) and MeCN [1:1 (v/v)] containing NADH (1.0 mM), QuPh
+
–NA (0.44 mM), and (a) hcp-NiNPs or (b) fcc-NiNPs with different sizes (12.5 mg L
−1
) at 298 K. (c) Plots of H
2
-evolution rates normalized by weight concentration of NiNPs vs. the size of NiNPs. (Reproduced from Ref. 25 with permission from the Royal Society of Chemistry)
Figure 10 Time courses of H
2
evolution by photoirradiation (
λ
> 340 nm) of a mixed suspension (2.0 mL) of a phthalate buffer (pH 4.5) and MeCN [1:1 (v/v)] containing QuPh
+
–NA (0.88 mM), NADH (1.0 mM), and (a) 3 wt% Ni-M/TiO
2
or (b) 3 wt% Ni–M/SiO
2
(100 mg L
−1
, M = Cu (red circle), Co (green triangle), and Fe (blue square). (Reproduced from Ref. 26—Published by The Royal Society of Chemistry)
Figure 11 Time courses of H
2
evolution by photoirradiation (
λ
> 340 nm) of a mixed suspension (2.0 mL) of a phthalate buffer (pH 4.5) and MeCN [1:1 (v/v)] containing QuPh
+
–NA (0.88 mM), NADH (1.0 mM), and (a) 3 wt% Ni–Cu/TiO
2
(100 mg L
–1
) prepared by a sequential impregnation method (Cu loaded on Ni/TiO
2
, red circle, and Ni loaded on Cu/TiO
2
, blue square) and (b) 3 wt% Ni–Cu/SiO
2
catalysts (100 mg L
−1
) prepared by a sequential impregnation (Cu loaded on Ni/SiO
2
, red circle, and Ni loaded on Cu/SiO
2
, blue square). (Reproduced from Ref. 26—Published by The Royal Society of Chemistry)
Figure 12 Diffuse reflectance UV–vis spectra of Ni–Cu/SiO
2
catalysts prepared by co-impregnation (red) and sequential impregnation methods (Cu impregnated to Ni/SiO
2
, blue, and Ni impregnated to Cu/SiO
2
, green). (Reproduced from Ref. 26—Published by The Royal Society of Chemistry)
Figure 13 HAADF-STEM and energy-dispersive X-ray spectroscopy (EDS) elemental mapping of Ni–Cu/SiO
2
prepared by (a) the co-impregnation method for Si, Cu, and Ni and (b) the sequential method. (Reproduced from Ref. 26—Published by The Royal Society of Chemistry)
Figure 14 TEM images and powder X-ray diffraction peaks of (a,d) Cu nanoparticles, (b,e) Ni–Cu alloy nanoparticles, and (c,f) Ni nanoparticles from (111) plane. (Reproduced from Ref. 28 with permission from the Royal Society of Chemistry)
Figure 15 Time courses of H
2
evolution under photoirradiation (
λ
> 340 nm) of an N
2
-saturated mixed solution (2.0 mL) of a phthalate buffer (pH 4.5) and MeCN [1:1 (v/v)] containing QuPh
+
–NA (0.88 mM), NADH (1.0 mM), and 3.5 wt% Ni–CuNPs/TiO
2
(red circle), 1.3 wt% NiNPs/TiO
2
(green square) or (c) 3.2 wt% CuNPs/TiO
2
(blue triangle) (100 mg L
–1
). (Reproduced from Ref. 28 with permission from the Royal Society of Chemistry)
Figure 16 A schematic drawing of non-formation of Ni–CuNPs on cation exchangeable surfaces of Al
2
O
3
–SiO
2
. (Reproduced from Ref. 28 with permission from the Royal Society of Chemistry)
Figure 17 Time courses of H
2
evolution under photoirradiation (
λ
> 340 nm) of a deaerated mixed solution of a phthalate buffer and MeCN [1:1 (v/v)] containing QuPh
+
–NA (0.88 mM), NADH (1.0 mM) and 3 wt% Ni–Cu/Al
2
O
3
–SiO
2
(100 mg L
–1
, black square) or 6.5 wt% Ni–Cu/Al
2
O
3
–SiO
2
(100 mg L
–1
, red circle). (Reproduced from Ref. 28 with permission from the Royal Society of Chemistry)
Multifunctional MOF-Based Photocatalysis
Figure 1 General mechanism for semiconductor photocatalysis
Figure 2 (a) Photophysical processes that occur after the irradiation of the MOF-5 (Reproduced with permission from Ref. 5. Copyright 2007, Wiley-VCH) and (b) different strategies for the inclusion of catalytic moieties into a MOF scaffold
Figure 3 The reaction scheme of photochemical hydrogen production from water using Ru-MOFs in the presence of Ru(bpy)
3
2+
, MV
2+
, and EDTA-2Na. (Reprinted with permission from Ref. 7. Copyright 2009, Royal Society of Chemistry)
Figure 4 (a) UV/vis spectra of UiO-66 and NH
2
-UiO-66 and (b) volume of hydrogen evolved (V
H2
) during the photocatalytic reactions using UiO-66 (▪), Pt/UiO-66 (▪), NH
2
-UiO-66 (•), and Pt/NH
2
-UiO-66 (○). (Reproduced with permission from Ref. 8. Copyright 2010, Wiley-VCH)
Figure 5 Schematic illustration of photocatalytic hydrogen production reaction over Pt/NH
2
-MIL-125(Ti) on the basis of the LMCT mechanism. (Reprinted with permission from Ref. 9. Copyright 2012, American Chemical Society)
Figure 6 Scheme of the synergistic photocatalytic hydrogen evolution process via photoinjection of electrons from the light-harvesting MOF frameworks into the Pt NPs. (Reprinted with permission from Ref. 10. Copyright 2012, American Chemical Society)
Figure 7 Proposed photocatalytic reactions using Al-PMOF in the presence of MV (i) or in the absence of MV (ii). (Reproduced with permission from Ref. 11. Copyright 2012, Wiley-VCH)
Figure 8 (a) UV/vis spectra of MIL-125(Ti) and NH
2
-MIL-125(Ti); (b) CO
2
adsorption isotherms (1 atm, 273 K) of (□) MIL-125(Ti) and (▪) NH
2
-MIL-125(Ti); (c) the amount of HCOO
−
produced as a function of the time of irradiation over (▪) NH
2
-MIL-125(Ti), (□) MIL-125(Ti), (○) a mixture of TiO
2
and H
2
ATA (19 mg + 32 mg) and (▴) visible-light irradiation without a sample; and (d) proposed mechanism for the photocatalytic CO
2
reduction over NH
2
-MIL-125(Ti) under visible-light irradiation. (Reproduced with permission from Ref. 12. Copyright 2012, Wiley-VCH)
Figure 9 (a) UV-DRS spectra of MIL-101(Fe) and NH
2
-MIL-101(Fe); (b) in situ FT-IR analyses of CO
2
adsorption over pretreated MIL-101(Fe); and (c) dual excitation pathways over amino-functionalized Fe-based MOFs. (Reprinted with permission from Ref. 14. Copyright 2014, American Chemical Society)
Figure 10 (a) UV/vis spectra of NH
2
-Uio-66(Zr) and mixed NH
2
-UiO-66(Zr) and (b) amount of HCOO
−
produced as a function of irradiation time over NH
2
-Uio-66(Zr) and mixed NH
2
-Uio-66(Zr). (Reproduced with permission from Ref. 13. Copyright 2013, Wiley-VCH)
Figure 11 (a) Change in the amount of the Ti moiety in solids with the incubation period at 120 °C (•) and 100 °C (▪) and change in the amount of the Zr moiety in the solutions with the incubation period at 120 °C (○) and 100 °C (□); (b) amount of HCOO
−
produced as a function of irradiation time over different samples; and (c) proposed enhanced mechanism for the photocatalytic reactions over NH
2
-Uio-66(Zr/Ti). (Reprinted with permission from Ref. 15. Copyright 2015, Royal Society of Chemistry)
Figure 12 The amount of the product formed as a function of irradiation time over the as-prepared samples: (a) hydrogen; (b) HCOO
−
; and (c) proposed mechanism for the photocatalytic reactions over M/NH
2
-MIL-125(Ti). (Reproduced with permission from Ref. 16. Copyright 2014, Wiley-VCH)
Figure 13 (a) Chemical structure of Co-ZIF-9. Ball-and-stick representation of the second building units showing the coordination environment around cobalt (up). Packing diagram of Co-ZIF-9 (down). Hydrogen atoms are omitted for clarity. Co, light blue; C, gray; and N, blue. (b) The effect of the amount of Co-ZIF-9 on the evolution of CO and H
2
from the CO
2
photoreduction system. (Reproduced with permission from Ref. 17. Copyright 2014, Wiley-VCH)
Figure 14 (a) Structure model of Zr
6
(μ
3
-O)
4
(μ
3
-OH)
4
(bpdc)
5.83
(L
Re
)
0.17
and (b) plots of CO evolution turnover number (CO-TON) versus time in the photocatalytic CO
2
reduction over the prepared samples. (Reprinted with permission from Ref. 18. Copyright 2011, American Chemical Society)
Figure 15 (a) The amount of products produced as a function of irradiation time over MOF-253–Ru(CO)
2
Cl
2
and (b) the amount of products produced over Ru(5,5′-dcbpy)(CO)
2
Cl
2
and MOF-253–Ru(CO)
2
Cl
2
after 8 h irradiations. (Reprinted with permission from Ref. 19. Copyright 2015, Royal Society of Chemistry)
Figure 16 (a) DMPO spin-trapping ESR spectra of NH
2
-MIL-125(Ti) in methanol dispersion in dark, under UV and visible-light irradiations and (b) proposed mechanism of the photocatalytic amines oxidation over NH
2
-MIL-125(Ti). (Reprinted with permission from Ref. 20. Copyright 2015, Elsevier)
Figure 17 (a) Proposed mechanism for one-pot tandem photocatalytic oxidation/Knoevenagel condensation over bifunctional NH
2
-MIL-101(Fe) and (b) CO
2
-TPD profiles of CO
2
adsorbed different MOFs. (Reprinted with permission from Ref. 21. Copyright 2015, the Royal Society of Chemistry)
Figure 18 Schematic representation of mirror image structures of Zn-BCIP1 and Zn-BCIP2 and their deprotected forms Zn-PYI1 or Zn-PYI2. (Reprinted with permission from Ref. 23. Copyright 2012, American Chemical Society)
Figure 19 Synthetic procedure for the 3D CR–BPY1 MOF that is composed of wavy-like Cu–BPY sheets and [SiW11O40Ru]
7−
anions showing the combination of the dual catalytic units and channels for chemical transformations. (Reprinted with permission from Ref. 24. Copyright 2015, Royal Society of Chemistry)
Figure 20 The proposed mechanism for photodegradation of phenol with MOF-5. (Reproduced with permission from Ref. 5. Copyright 2007, Wiley-VCH)
Figure 21 (a) UV–vis absorption spectra of methyl orange solution degraded by [InRu(dcbpy)
3
][(CH
3
)
2
NH
2
]·6H
2
O after the UV–vis light irradiation for different time intervals; (b) control experiments on the photodegradation of MO: in the dark, without catalyst, and [InRu(dcbpy)
3
][(CH
3
)
2
NH
2
]·6H
2
O with visible light; and (c) photograph showing the photocatalytic degradation under visible-light irradiations for different times. (Reprinted with permission from Ref. 29. Copyright 2013, American Chemical Society)
Sustainable Synthesis of Metal Oxide Nanostructures
Figure 1 Nanomaterials and their dimensions
Figure 2 (a) Structure of Nano Fe
2
O
3
, CoO, Mn
2
O
3
, and Cr
2
O
3
. (Reprinted with permission from V. Polshettiwar, B. Baruwati and R. S. Varma, ACS Nano., 2009, 3, 728–736 © 2009 American Chemical Society); (b) TiO
2
nanostructures. (Reproduced from Ref. 2 with permission from The Royal Society of Chemistry); (c) Nanoroses of Nickel oxide. (Repoduced with permission from Ref. 3 © Wiley, 2012)
Figure 3 Synthetic strategies in nanomaterials synthesis
Figure 4 Vapor condensation process
Figure 5 Inert gas condensation instrument
Figure 6 Sol–gel technology and nanometal oxide synthesis
Figure 7 Schematic illustration of nanoparticles preparation using microemulsion techniques
Figure 8 Schematic representation of ball milling
Figure 9 Microwave-assisted synthesis of Fe
2
O
3
micropine structure. (Reproduced from Ref. 10 with permission from The Royal Society of Chemistry)
Figure 10 (a) SEM image of Ta
2
O
5
; (b) TEM image of Ta
2
O
5
. (Reprinted with permission from B. Baruwati and R. S. Varma, Cryst. Growth Des., 2010, 10, 3424–3428 © 2010 American Chemical Society)
Figure 11 SEM images of iron oxide with different shapes; (a) Nanorods; (b) Nanohusk; (c) Distorted cubes; (d) Nanocubes; (e) Porous spheres; (f) Self-oriented flowers. (Reproduced from Ref. 12)
Figure 12 Toxicity profile of metal oxide nanoparticles obtained through SAR study
Figure 13 (a) Plot of experimentally observed versus predicted value of zeta potential; (b) Simulation of zeta potential based on ψ and
ϵ
HOMO
/
n
Me
descriptor. (Reprinted with permission from A. Mikolajczyk, A. Gajewicz, B. Rasulev, N. Schaeublin, E. Maurer-Gardner, S. Hussain, J. Leszczynski, and T. Puzyn, Chem. Mater. 2015, 27, 2400–2407 © 2015 American Chemical Society)
Micellar Nanoreactors
Figure Chart 1 Classes and structures of surfactants. (G. La Sorella, G. Strukul, A. Scarso, Green Chem. 2015, 17, 644–683. Reproduced by permission of The Royal Society of Chemistry)
Scheme 1 Dodecylbenzenesulfonic acid catalyzed esterification of apolar acids and apolar alcohols in water
Scheme 2 Environmentally benign Friedel–Crafts acylation of 1-halo-2-methoxynaphthalenes and its related compounds under micellar conditions
Figure 1 Approaches to metal catalysis in micellar media: (a) solubilization of metal catalysts on the surface or within micelles; (b) covalent metal–surfactant units forming metallomicelles
Scheme 3 Dramatic micellar rate enhancement of the Cu(II) catalyzed vinylogous Friedel–Crafts alkylation in water. (Adapted from Ref. 30 with permission from Royal Society of Chemistry)
Scheme 4 Room temperature CH arylation of aryl urea derivatives mediated by Pd(II) in water with Brij 35. (Adapted from Ref. 31 with permission from Wiley)
Scheme 5 Micellar catalysis in the Ru(II) mediated nitrile hydration in water. (Adapted from Ref. 32 with permission from Royal Society of Chemistry)
Scheme 6 Anionic micellar catalysis in the Pt(II) mediated hydroformylation of terminal alkenes in water. (Adapted from Ref. 33 with permission from Wiley)
Scheme 7 Examples of asymmetric transfer hydrogenation reactions of ketones in micellar media: (a) neutral transition metal catalysts with cationic surfactant cetyl trimethylammonium bromide (CTAB) (Adapted from Wang
et al
.
34
with permission from American Chemical Society); (b) In situ formed anionic transition metal catalysts with different surfactants. (Adapted from Ref. 35 with permission from Royal Society of Chemistry)
Scheme 8 Anionic micellar media promoted Co(salen) mediated enantioselective Baeyer–Villiger oxidation of cyclic ketones with hydrogen peroxide. (Adapted from Ref. 36 with permission from Royal Society of Chemistry)
