Hydrogen Storage: Based on Hydrogenation and Dehydrogenation Reactions of Small Molecules

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Hydrogen Storage: Based on Hydrogenation and Dehydrogenation Reactions of Small Molecules
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Preface
Contents
List of contributing authors
1. Introduction: hydrogen storage as solution for a changing energy landscape
	1.1 Introduction
	1.2 Current energy landscape – US statistics
	1.3 Energy storage systems
		1.3.1 Large scale centralized energy storage
			1.3.1.1 Pumped hydroelectric energy storage (PHES)
			1.3.1.2 Compressed air energy storage (CAES)
		1.3.2 Smaller scale grids and distributed energy storage systems
			1.3.2.1 Flywheel energy storage(FES)
			1.3.2.2 Superconducting magnetic energy storage (SMES)
			1.3.2.3 Electrochemical storage: batteries
			1.3.2.4 Electrochemical capacitators (ECs)
			1.3.2.5 Gravimetric battery
			1.3.2.6 Thermal energy storage systems
			1.3.2.7 Phase change materials (PCMs)
			1.3.2.8 Thermal chemical energy storage (TCES)
	1.4 Energy transportation
	1.5 H2 storage – production of hydrogen
	1.6 Efficiencies of hydrogen economy
	1.7 Hydrogen storage – why hydrogen?
	1.8 Demands on hydrogen storage systems
	1.9 Classification of hydrogen storage systems
	1.10 Physical methods for hydrogen storage
		1.10.1 Compressing gaseous hydrogen (CGH2)
		1.10.2 Liquid hydrogen (LH2)
	1.11 Material based methods for hydrogen storage
		1.11.1 Hydrogen storage by absorption on solids with large surface area
	1.12 Chemical methods for hydrogen storage
		1.12.1 Hydride materials
		1.12.2 Hydrogenation and dehydrogenation reactions of small molecules
	References
2. CO2-based hydrogen storage: CO2 hydrogenation to formic acid, formaldehyde and methanol
	2.1 Introduction
	2.2 Methanol
		2.2.1 Heterogeneous catalyzed hydrogenation to methanol and reforming
		2.2.2 Homogeneous catalyzed hydrogenation to methanol and reforming
	2.3 Formic acid
		2.3.1 CO2 hydrogenation to formic acid
		2.3.2 Hydrogen generation from formic acid
		2.3.3 H2 storage in integrated systems via formic acid/formates
	2.4 Formaldehyde
		2.4.1 CO2 Hydrogenation to formaldehyde
		2.4.2 Hydrogen generation from formaldehyde
	2.5 Conclusion
	References
3. CO2-based hydrogen storage – formic acid dehydrogenation
	3.1 Introduction
	3.2 The concept of formic acid (FA) as hydrogen storage compound
	3.3 Selected catalytic processes for the hydrogen generation from FA
	3.4 Main group compounds as catalysts for FA dehydrogenation
	3.5 Noble metal catalysts for FA dehydrogenation
	3.6 Base-metal catalysts for FA dehydrogenation
	3.7 Heterogeneous catalysts for FA dehydrogenation
	3.8 Catalytic systems for the reversible storage of H2 in FA
	3.9 Conclusions and outlook
	References
4. CO2-based hydrogen storage – Hydrogen generation from formaldehyde/water
	4.1 Introduction
	4.2 Production of formaldehyde and related technologies
		4.2.1 Formaldehyde production and metabolism by biological systems
		4.2.2 Industrial production of formaldehyde
		4.2.3 Related technologies for formaldehyde synthesis
	4.3 Aqueous formaldehyde as hydrogen and energy carrier
	4.3.1 Base promoted dehydrogenation
	4.3.2 Metal catalyzed dehydrogenation
		4.3.2.1 Heterogeneous catalytic processes
			4.3.2.1.1 Cu catalysts
			4.3.2.1.2 Ag catalysts
			4.3.2.1.3 Au Catalyst
			4.3.2.1.4 Pd catalysts
			4.3.2.1.5 Zinc catalysts
		4.3.2.2 Homogeneous catalysts and mechanistic insights
	4.4 Future perspectives
	References
5. CO2-based hydrogen storage – hydrogen liberation from methanol/water mixtures and from anhydrous methanol
	5.1 Introduction
	5.2 Production of methanol
		5.2.1 Industrial bulk production
		5.2.2 Experimental approaches toward the formation of methanol
			5.2.2.1 The holy grail - direct methane oxidation
			5.2.2.2 Environmental benign methanol formation – CO2 reduction with dihydrogen under homogeneous conditions
	5.3 Aqueous methanol as hydrogen and energy carrier
		5.3.1 Biological systems
		5.3.2 Hydrogen production from aqueous methanol in artificial systems
			5.3.2.1 Heterogeneous metal -based catalysis
				5.3.2.1.1 Photo-catalytic processes
				5.3.2.1.2 Thermal dehydrogenation of methanol (methanol reforming processes)
			5.3.2.2 Molecular catalysts for dehydrogenation of methanol/water mixtures
				5.3.2.2.1 Electro-oxidation of methanol
				5.3.2.2.2 Photo-chemical dehydrogenation of methanol
				5.3.2.2.3 Thermal dehydrogenation of aqueous methanol
	5.4 Outlook
		5.4.1 Hydrogen as sustainable energy carrier and methanol as hydrogen storage material
		5.4.2 Dehydrogenation of methanol
	References
6. Hydrogenation of carbonyl compounds of relevance to hydrogen storage in alcohols
	6.1 Introduction
	6.2 Hydrogenation of ketones
		6.2.1 General considerations
		6.2.2 Ruthenium and osmium catalysts
		6.2.3 Iridium catalysts
		6.2.4 Non-noble metal catalysts
	6.3 Hydrogenation of esters
		6.3.1 General considerations
		6.3.2 Ruthenium and osmium catalysts
		6.3.3 Iridium catalysts
		6.3.4 Non-noble metal catalysts
	6.4 Hydrogenation of amides
		6.4.1 General considerations
		6.4.2 Ruthenium catalysts
		6.4.3 Non-noble metal catalysts
	6.5 Hydrogenation of carboxylic acids
		6.5.1 General considerations
		6.5.2 Noble metal catalysts
		6.5.3 Non-noble metal catalysts
	6.6 Conclusions and outlook
	References
7. Dehydrogenation of alcohols and polyols from a hydrogen production perspective
	7.1 Introduction
	7.2 General perspective on acceptorless alcohol dehydrogenation reaction
	7.3 Ethanol dehydrogenation
	7.4 Glycerol dehydrogenation
	7.5 Sugars and sugar alcohol dehydrogenation
	7.6 Conclusion
	References
8. Hydrogenation of nitriles and imines for hydrogen storage
	8.1 Introduction
	8.2 Catalytic hydrogenation of nitriles
		8.2.1 Nitrile hydrogenation – selectivity issues and homogeneous Ru-based catalysts
		8.2.2 Homogeneous earth-abundant metals-based catalysts
		8.2.3 Heterogeneous metals-based catalysts
	8.3 Imine hydrogenation
	8.4 Conclusions
	References
9. Transition metal-catalyzed dehydrogenation of amines
	9.1 Introduction
	9.2 Catalytic dehydrogenation of amines
		9.2.1 Primary amines to imines and secondary amines
		9.2.2 Selective catalytic dehydrogenation of primary amines to nitriles
		9.2.3 Catalytic dehydrogenation of N-heterocycles
	9.3 Conclusions
	References
10. Homogeneously catalyzed hydrogenation and dehydrogenation reactions – From a mechanistic point of view
	10.1 Introduction
	10.2 Non-cooperation mechanisms
		10.2.1 Oxidative addition/reductive elimination mechanism
		10.2.2 σ-Bond metathesis mechanism
	10.3 LB-TM cooperation mechanisms
		10.3.1 n-Type LB-TM cooperation mechanism
			10.3.1.1 LB-TM cooperation mechanism on the M-L bond
			10.3.1.2 LB-TM cooperation mechanism with a dissociative/pendant LB
			10.3.1.3 LB-TM cooperation mechanism with an external LB
		10.3.2 π-Type LB-TM cooperation mechanism: (de)aromatization/tautomerization
		10.3.3 σ-Type LB-TM cooperation mechanism
		10.3.4 Ligand-innocent non-LB-TM cooperation mechanism
	10.4 LA-TM cooperation mechanism
		10.4.1 p-Type LA-TM cooperation mechanisms
			10.4.1.1 M-L bond LA-TM cooperation mechanism
			10.4.1.2 LA-TM mechanism with a dissociative/pendant LA
			10.4.1.3 LA-TM cooperation mechanism with external LAs
		10.4.2 σ-Type LA-TM cooperation mechanism
		10.4.3 π*-Type LA-TM cooperation mechanism
		10.4.4 Ligand-innocent non-MLC mechanism in LA-TM systems
		10.4.5 Hydrogenation/dehydrogenation mechanism in LA-TM systems
	10.5 LA-LB cooperation (FLP) mechanism
		10.5.1 H2 activation mechanisms in LA-LB cooperation systems
		10.5.2 Hydrogenation/dehydrogenation reaction mechanisms in LA-LB cooperation systems
	10.6 Ambiphilic mechanism
		10.6.1 H2 activation mechanism in ambiphilic systems
		10.6.2 Hydrogenation mechanism via ambiphilic cooperation
	10.7 TM-TM cooperation mechanism
		10.7.1 Homolytic mechanism via TM-TM cooperation
		10.7.2 Heterolytic mechanism via TM-TM cooperation
		10.7.3 Oxidative addition mechanism
		10.7.4 Hydrogenation/dehydrogenation mechanism in TM-TM systems
	10.8 Key factors governing the mechanistic preferences
		10.8.1 The role of the metal and the ligand in MLC
		10.8.2 Proton shuttle
	10.9 Concluding remarks
	References
Index