Comprehensive Inorganic Chemistry III. Volume 6: Heterogeneous Inorganic Catalysis

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Comprehensive Inorganic Chemistry III. Volume 6: Heterogeneous Inorganic Catalysis
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Contents of Volume 6
Editor Biographies
Volume Editors
Contributors to Volume 6
Preface
	Vol. 1: Synthesis, Structure, and Bonding in Inorganic Molecular Systems
	Vol. 2: Bioinorganic Chemistry and Homogeneous Biomimetic Inorganic Catalysis
	Vol. 3: Theory and Bonding of Inorganic Non-molecular Systems
	Vol. 4: Solid State Inorganic Chemistry
	Vol. 5: Inorganic Materials Chemistry
	Vol. 6: Heterogeneous Inorganic Catalysis
	Vol. 7: Inorganic Electrochemistry
	Vol. 8: Inorganic Photochemistry
	Vol. 9: NMR of Inorganic Nuclei
	Vol. 10: X-ray, Neutron and Electron Scattering Methods in Inorganic Chemistry
6.01. Introduction: A short history of single site catalysis
	Content
	Abstract
	6.01.1 Introduction
	6.01.2 Single site catalystsdThe modern age of heterogeneous catalysis
		6.01.2.1 Introduction
		6.01.2.2 The disproportionation or metathesis reaction, polymerization catalysis
		6.01.2.3 Selective oxidation
			6.01.2.3.1 Propylene epoxidation
			6.01.2.3.2 Other oxidation reactions catalyzed by zeolites
		6.01.2.4 Bifunctional catalysts; hydrocarbon activation
			6.01.2.4.1 Activation of short alkanes by Ga or Zn
			6.01.2.4.2 Methane to aromatics catalysis; the methane dehydro-aromatization reaction
		6.01.2.5 Single atom catalysis
			6.01.2.5.1 Single atoms; reducible supports
			6.01.2.5.2 Solid solution catalysts
		6.01.2.6 Summary; from solid state to molecular nano-clusters catalyst
	References
6.02. Synthesis and application of (nano) zeolites
	Content
	Abstract
	6.02.1 Introduction
	6.02.2 The structure of zeolites
	6.02.3 The properties of zeolites
		6.02.3.1 The properties of nanosized zeolites
	6.02.4 The synthesis of zeolites
		6.02.4.1 Components of the synthesis mixture
		6.02.4.2 Nucleation and crystal growth
		6.02.4.3 Interzeolite conversion
		6.02.4.4 Zeolite synthesis by the assembly of pre-formed layers
		6.02.4.5 The synthesis of nanosized zeolites
			6.02.4.5.1 The conventional synthesis of nanosized zeolites
			6.02.4.5.2 Synthesis of nanosized zeolites via interzeolite conversion
			6.02.4.5.3 Seed-assisted synthesis of nanosized zeolites
			6.02.4.5.4 Synthesis of nanosized zeolites by modifying the initial precursor
			6.02.4.5.5 Special cases of nanosized zeolites
				6.02.4.5.5.1 Bi-dimensional zeolitesdzeolite nanosheets
				6.02.4.5.5.2 Embryonic zeolites
			6.02.4.5.6 Alternative reaction conditions for the synthesis of nanosized zeolites
	6.02.5 The application of (nano) zeolites
		6.02.5.1 Catalysis
			6.02.5.1.1 FCC process
			6.02.5.1.2 MTO process
			6.02.5.1.3 Abatement of nitrogen oxides (deNOx)
			6.02.5.1.4 Biomass valorization
			6.02.5.1.5 Other reactions
		6.02.5.2 Adsorption and gas separation
		6.02.5.3 Ion-exchange
		6.02.5.4 Other application fields
	6.02.6 Summary and outlook
	References
6.03. Mesostructured materials
	Content
	Abstract
	6.03.1 Introduction
	6.03.2 Synthesis of mesoporous materials
		6.03.2.1 Ordered mesoporous silicas (OMSs)
		6.03.2.2 Mesoporous metals and metal oxides
		6.03.2.3 Hybrid mesoporous materials
			6.03.2.3.1 Ordered mesoporous organosilicas (OMOSs)
			6.03.2.3.2 Mesoporous metal-organic frameworks (MOFs)
		6.03.2.4 Ordered mesoporous carbons (OMCs)
		6.03.2.5 Mesoporous zeolites
			6.03.2.5.1 Bottom-up zeolite synthetic strategies
			6.03.2.5.2 Top-down synthetic strategy via demetallization
			6.03.2.5.3 Mixed synthetic strategy
	6.03.3 Catalytic applications of mesoporous materials
		6.03.3.1 Mesoporous metals and metal oxides for catalysis
		6.03.3.2 Catalytic applications of representative ordered mesoporous materials
			6.03.3.2.1 Ordered mesoporous silicas for catalysis
			6.03.3.2.2 Ordered mesoporous organosilicas for catalysis
			6.03.3.2.3 Ordered mesoporous carbons for catalysis
		6.03.3.3 Mesoporous metal-organic frameworks for catalysis
		6.03.3.4 Mesoporous zeolites for catalysis
	6.03.4 Summary and perspective
	References
6.04. Surface organometallic and coordination chemistry approach to formation of single site heterogeneous catalysts
	Content
	Abstract
	6.04.1 Complexity of heterogeneous catalysis
	6.04.2 Single-site catalyst concept
	6.04.3 The core principles of the surface organometallic chemistry approach
	6.04.4 Surface of the supporting material as a ligand
	6.04.5 Tailored molecular precursors for well-defined surface species
	6.04.6 Characterization techniques utilized in the SOMC approach
	6.04.7 Selected success stories in SOMC single site catalysis
	6.04.8 Conclusion
	References
6.05. Challenges with atomically dispersed supported metal catalysts: Controlling performance, improving stability, and enhancing metal loading
	Content
	Abstract
	6.05.1 Introduction
	6.05.2 Challenges with atomically dispersed supported metal catalysts
		6.05.2.1 Limited ability to tune catalytic performance
			6.05.2.1.1 Effects of non-support ligands
			6.05.2.1.2 Effects of supports as ligands
			6.05.2.1.3 Effects of metal nuclearity
			6.05.2.1.4 Effects of promoters
		6.05.2.2 Limited ability to control stability
		6.05.2.3 Limited metal loadings
	6.05.3 Summary
	References
6.06. Metal containing nanoclusters in zeolites
	Content
	Abstract
	6.06.1 Introduction
	6.06.2 Synthesis
		6.06.2.1 Encapsulation of nanoclusters in zeolite
		6.06.2.2 Isolated single metal atom sites in zeolites
	6.06.3 Advanced characterization techniques for zeolite encapsulated metal species
		6.06.3.1 Electron microscopy
		6.06.3.2 X-ray absorption spectroscopy
		6.06.3.3 Vibrational spectroscopy
		6.06.3.4 Solid-state nuclear magnetic resonance
	6.06.4 Catalytic applications
		6.06.4.1 C1 molecules conversion
		6.06.4.2 Active site cooperation and multifunctionality in confined space
		6.06.4.3 Confined space for selectivity control
	6.06.5 Computational modeling
		6.06.5.1 Structure prediction by operando thermodynamic analysis
		6.06.5.2 Reactivity scaling relationship and beyond
		6.06.5.3 Micro-kinetic modeling and dynamics
	6.06.6 Conclusion and perspective
	Acknowledgment
	References
6.07. Single site spectroscopy of transition metal ions and reactive oxygen complexes in zeolites
	Content
	Abstract
	6.07.1 Introduction
	6.07.2 Transition metal ions in zeolites
	6.07.3 Achieving site selective spectroscopy
		6.07.3.1 Bare mononuclear transition metal ions
			6.07.3.1.1 UV-Vis-NIR and EPR spectroscopy on Cu2+
			6.07.3.1.2 Site selective spectroscopy on Fe2+ and Fe3+
			6.07.3.1.3 UV-Vis-NIR spectroscopy on Co2þ
		6.07.3.2 Complexes of metal ions in zeolites with extraframework oxygen atoms
			6.07.3.2.1 [CuOCu]2+ and [CuOOCu]2+
			6.07.3.2.2 [Fe=O]2+
			6.07.3.2.3 Zn-, Ga-, Co- and Ni-zeolites
	6.07.4 Site selective spectroscopy and oxo/oxyl-catalysis
	6.07.5 Conclusions and outlook
	References
6.08. Dynamic evolution of catalytic active sites within zeolite catalysis
	Content
	Abstract
	6.08.1 Introduction
	6.08.2 Experimental and theoretical evidence for active site mobility in zeolites
		6.08.2.1 Proton mobility in Brønsted-acidic zeolites
			6.08.2.1.1 BAS mobility in the pristine zeolite framework
			6.08.2.1.2 Protic molecules mediated hopping and solvation of the BAS
		6.08.2.2 Framework-associated and extra framework aluminum (EFAL)
		6.08.2.3 Mobility of active sites in TM-exchanged zeolites
			6.08.2.3.1 Mobility of copper sites in Cu-CHA during low-temperature NH3-SCR-NOx
			6.08.2.3.2 Solvation and mobility of Pd in SSZ-13
			6.08.2.3.3 Mobility of Rh in zeolite Y and consequences for ethene hydrogenation & oligomerization
			6.08.2.3.4 Mobility of Ag sites in MFI during C3H8-SCR reactivity
	6.08.3 Computational assessment of active site mobility in zeolites
		6.08.3.1 Overview of enhanced sampling methods over static methods
		6.08.3.2 Case studies
			6.08.3.2.1 Proton mobility in zeolites
			6.08.3.2.2 Ni-SSZ-24 for ethene oligomerization
			6.08.3.2.3 Mobility of active sites in H-SSZ13 during fast NH3-SCR-NOx
			6.08.3.2.4 Mobility of multinuclear Cu sites in chabazites for the selective catalytic reduction (SCR) of nitrogen oxides
	6.08.4 Conclusions and perspectives
	References
6.09. Nanocluster heterogeneous catalysts: Insights from theory
	Content
	Abstract
	6.09.1 Unique properties in nanocluster catalysis
		6.09.1.1 Reactant induced cluster reconstruction
		6.09.1.2 Cluster fluxionality
	6.09.2 Methods
		6.09.2.1 Descriptors for adsorption
		6.09.2.2 BEP relationship
		6.09.2.3 Global optimization methods to explore structures of nanoclus
		6.09.2.4 Machine learning methods in nanocluster catalysis
			6.09.2.4.1 Machine learning aided global optimizations
			6.09.2.4.2 Machine learning for surface chemistry of nanoclusters
			6.09.2.4.3 Machine learning methods for extracting structural information for x-ray adsorption spectroscopy
	6.09.3 Conclusion and perspective
	References
6.10. Imaging of single atom catalysts
	Content
	Abstract
	6.10.1 Development of electron microscopy for achieving atomic resolution
	6.10.2 Imaging single atoms in heterogenous catalysts
		6.10.2.1 Imaging modes
		6.10.2.2 Determining the concentration of surface atoms
		6.10.2.3 Determining the identity of surface atoms
		6.10.2.4 Applying artificial intelligence for quantification of single atom images
	6.10.3 Deriving chemical information from single atom catalysts
		6.10.3.1 Electron-energy loss spectroscopy (EELS)
		6.10.3.2 Energy dispersive x-ray spectroscopy (EDS)
	6.10.4 Deriving 3-D information on single atoms in heterogeneous catalysts
	6.10.5 Adding rigor to the imaging of single atom catalysts
	6.10.6 Perspective
	Acknowledgments
	References
6.11. Metal-support interfaces in ceria-based catalysts
	Content
	Abstract
	6.11.1 Introduction
	6.11.2 Structure and redox properties
	6.11.3 Synthesis of ceria
	6.11.4 Characterization of ceria materials
	6.11.5 Metal-support interfaces in ceria catalysts
	6.11.6 Catalysis by single-atom ceria-based catalysts
	6.11.7 Summary
	References
6.12. Solid acid catalysis; Part I, the zeolite protonic site
	Content
	Abstract
	6.12.1 Introduction
	6.12.2 The proton strength of the zeolite Brønsted acid
		6.12.2.1 The physical chemistry of the protonic bond
			6.12.2.1.1 Vibrational spectroscopy of zeolite hydroxyls
			6.12.2.1.2 The proton bond as a function of zeolite lattice Al/Si concentration ratio
		6.12.2.2 The OH chemical bond
			6.12.2.2.1 The deprotonation energy
			6.12.2.2.2 Flexibility of zeolite lattice
			6.12.2.2.3 Site dependence
		6.12.2.3 Proton activity of other than Al/Si framework materials
			6.12.2.3.1 Al substitution by Fe3þ and Ga3þ
			6.12.2.3.2 Non framework substituted systems
		6.12.2.4 In summary
	References
6.13. Solid acid catalysis; Part II, catalytic chemistry of proton activation
	Content
	Abstract
	6.13.1 Introduction
	6.13.2 Elementary proton activated reactions
	6.13.3 Contribution of the adsorption free energy
	6.13.4 Confinement
		6.13.4.1 Transition state stabilization
		6.13.4.2 Stereoselectivity
		6.13.4.3 Micro pore equilibration
	6.13.5 Conclusion
	References
6.14. Heterogeneous catalysts for the non-oxidative conversion of methane to aromatics and olefins
	Content
	Abstract
	Introduction
	6.14.1 Introduction
	6.14.2 Non-oxidative dehydroaromatization of methane
		6.14.2.1 Mo/ZSM-5
			6.14.2.1.1 Preparation of Mo/ZSM-5
			6.14.2.1.2 Induction period and catalyst deactivation
			6.14.2.1.3 Reaction mechanism
		6.14.2.2 Alternative catalysts
			6.14.2.2.1 Zeolite-based catalysts
			6.14.2.2.2 Non-zeolite based catalysts
		6.14.2.3 Zeolite modification
			6.14.2.3.1 Tuning zeolite acidity
			6.14.2.3.2 Constructing hierarchical and core-shell zeolite structures
	6.14.3 Non-oxidative dehydrodimerization of methane
		6.14.3.1 Fe©SiO2
		6.14.3.2 Other metal oxide-based catalysts
		6.14.3.3 Metal phosphides and metal nitrides
		6.14.3.4 Zeolite-based catalysts
		6.14.3.5 Alternative catalysts
	6.14.4 Summary and outlook
	References
6.15. Inorganic catalysis for methane conversion to chemicals
	Content
	Abstract
	6.15.1 Background
	6.15.2 Physicochemical properties of methane
	6.15.3 Development of methane activation and conversion technologies
		6.15.3.1 Thermo-catalytic conversion of methane
			6.15.3.1.1 Indirect methane conversion
			6.15.3.1.2 Direct methane conversion
		6.15.3.2 Electrocatalytic conversion of methane
			6.15.3.2.1 Introduction
			6.15.3.2.2 Fundamentals of electrocatalytic conversion of methane
			6.15.3.2.3 Electrocatalytic conversion of methane to fuels and chemicals
			6.15.3.2.4 Photoelectrocatalytic conversion of methane
		6.15.3.3 Summary
	References
6.16. Promoted Fischer-Tropsch catalysts
	Content
	Abstract
	6.16.1 Fischer-Tropsch synthesis: Past, present and future
		6.16.1.1 The past, an historical perspective
		6.16.1.2 Present commercial operations
			6.16.1.2.1 Fischer-Tropsch catalysts and processes
			6.16.1.2.2 Fe catalysts
			6.16.1.2.3 Co catalysts
		6.16.1.3 The future role of FT in achieving net zero carbon
			6.16.1.3.1 Power-to-liquids, a future beyond biomass?
	6.16.2 Mechanism of the Fischer-Tropsch reaction
		6.16.2.1 Reactant adsorption
		6.16.2.2 Monomer formation and chain initiation
		6.16.2.3 Chain growth
		6.16.2.4 Chain termination and product desorption
		6.16.2.5 Readsorption and further reaction
		6.16.2.6 Mechanistic models
			6.16.2.6.1 Carbide mechanism
			6.16.2.6.2 CO-insertion mechanism
	6.16.3 Structure sensitivity
	6.16.4 Kinetics of the Fischer-Tropsch reaction
		6.16.4.1 Kinetic modeling
		6.16.4.2 Mechanistic insights
	6.16.5 Fischer-Tropsch to chemicals (Chem FT)
		6.16.5.1 Lower olefin synthesis
		6.16.5.2 Higher alcohol synthesis
	6.16.6 Outlook
	References
6.17. Selective oxidation by mixed metal nanoparticles
	Content
	Abstract
	6.17.1 Introduction
	6.17.2 Importance of selective catalytic oxidation
	6.17.3 Multimetallic nanoparticle catalysts
	6.17.4 Classes of well-defined bimetallic nanoparticle catalysts
		6.17.4.1 Single atom alloys (SAAs)
		6.17.4.2 Near surface alloys
	6.17.5 Cluster beam deposition catalyst synthesis
	6.17.6 Bimetallic nanoalloys
	6.17.7 Selective oxidation reactions
		6.17.7.1 Catalytic oxidation of alkanes
		6.17.7.2 Biomass oxidation
		6.17.7.3 Glucose oxidation
	6.17.8 Glycerol
	6.17.9 Oxidation of bio-derived furanics
	6.17.10 Conclusions
	References
6.18. Doped semiconductor photocatalysts
	Content
	Abstract
	6.18.1 Introduction
	6.18.2 Effects of doping on the physicochemical and semiconducting properties of photocatalysts
		6.18.2.1 Modification of electronic states via aliovalent ion doping
		6.18.2.2 Visible light absorption via excitation of mid-gap states
		6.18.2.2.1 TiO2
		6.18.2.2.2 SrTiO3
	6.18.3 Concluding remarks and prospects
	References
6.19. Structure-reactivity relations in electrocatalysis
	Contact
	Abstract
	6.19.1 Introduction
		6.19.1.1 Fundamentals of electrocatalysis
		6.19.1.2 Electrocatalytic reactions in electrolyzers and fuel cells
	6.19.2 Structure-reactivity relations
		6.19.2.1 The generalized coordination number
		6.19.2.2 Direct instrumental investigation of active sites
	6.19.3 Structural change of catalysts during the reaction
	6.19.4 Summary
	References