Singlet Delta Oxygen Production from a Gas���Solid Reaction

Alfano, Angelo J.

doi:10.1002/1521-3773(20020902)41:17<3252::aid-anie3252>3.0.co;2-g

Cited by 11 publications

(7 citation statements)

References 15 publications

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“…Chemical oxidation of alkaline peroxides in non-aqueous media is known to generate singlet oxygen ( 1  g or 1 O 2 ), the first excited state of triplet ground state dioxygen ( 3  g -) [29][30][31][32] . Based on the reversible potential of Li 2 O 2 formation and the energy difference between triplet and singlet oxygen, the formation of 1 O 2 in the Li-O 2 cell has been hypothesized to be possible at charging potentials exceeding 3.5 to 3.9 V vs. Li/Li +11,23 .…”

mentioning

confidence: 99%

Singlet oxygen generation as a major cause for parasitic reactions during cycling of aprotic lithium–oxygen batteries

et al. 2017

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Non-aqueous metal-oxygen batteries depend critically on the reversible formation/decomposition of metal oxides on cycling. Irreversible parasitic reactions cause poor rechargeability, efficiency, and cycle life and have predominantly been ascribed to the reactivity of reduced oxygen species with cell components. These species, however, cannot fully explain the side reactions. Here we show that singlet oxygen forms at the cathode of a lithium-oxygen cell during discharge and from the onset of charge, and accounts for the majority of parasitic reaction products. The amount increases during discharge, early stages of charge, and charging at higher voltages, and is enhanced by the presence of trace water. Superoxide and peroxide appear to be involved in singlet oxygen generation. Singlet oxygen traps and quenchers can reduce parasitic reactions effectively. Awareness of the highly reactive singlet oxygen in non-aqueous metal-oxygen batteries gives a rationale for future research towards achieving highly reversible cell operation.

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confidence: 99%

Singlet oxygen generation as a major cause for parasitic reactions during cycling of aprotic lithium–oxygen batteries

et al. 2017

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“…Singlet oxygen has been generated by the reaction of akali-metal or alkaline-earth metal peroxides and dry hydrogen (deuterium) halide gases at room temperature, without the use of external energy sources such as light, heat or electricity. 99 The chemical source of 1 O 2 , calcium peroxide diperoxohydrate (CaO 2 ؒ2H 2 O), is a useful material that can be stored at Ϫ80 ЊC for several days. The yield of singlet oxygen generation is about 25% and the peroxide has been used to oxidise a series of olefins in situ at a reaction temperature of 50 ЊC.…”

Section: Oxygenmentioning

confidence: 99%

7 Oxygen, sulfur, selenium and tellurium

Skabara

2003

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

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This chapter reviews original highlights in the chemistry of the Group 16 elements reported during 2002. The bulk of the review focuses on the chemistry/interaction of the chalcogens with other p-block elements. Due to the vast abundance and diversity of research into chalcogen chemistry, the report has been limited to materials with discrete molecular structure, either as novel products or reagents, or obtained by new synthetic strategies. The most important advances in 2002 include the isolation of hitherto unknown functionalities or bonding modes 28,56,60,64 and unusual, unique or unexpected structures. 53,63,79,81 Sulfur, selenium and telluriumAs in previous years, we start by looking at the ability of the heavier chalcogens to form compounds with other p-block elements, and do so by working from left to right across the periodic table starting with Group 13. The preparation of crystalline thioboric acid, (HBS 2 ) 3 , involves the reaction of hydrogen sulfide gas bubbled through molten B 2 S 3 at 500 ЊC. 1 The experimental procedure has several advantages over previous methodologies (e.g. higher purity, lower reaction temperatures) and the material is an important precursor to thioborate glasses and polycrystals. Studies on chalcogen-containing boron clusters included: the S-alkylation and S-amination of methyl thioethers of closo-[B 12 H 12 ] Ϫ derivatives as potential materials for boron neutron capture therapy of cancer; 2 the structural analysis by microwave spectroscopy and quantum chemical calculations of 1-thia-closo-decaborane( 9), 1-SB 9 H 9 ; 3 the single crystal X-ray characterisation of three dinuclear half-sandwich complexes containing bridging dicarba-closo-dodecaboranes:A two-coordinate thallium compound {[Me 2 Si(µ-N t Bu) 2 P᎐ ᎐ S(NPh)-κN-κS]Tl} and two tetrahedral aluminium complexes {[Me 2 Si(µ-N t Bu) 2 P᎐ ᎐ S(NPh)-κN-κE ]AlMe 2 } and {[Me 2 Si(µ-N t Bu) 2 P᎐ ᎐ Se(NPh)-κN-κE ]AlMe 2 } have been synthesised from the reaction of P-anilino-P-chalcogeno(imino)diazasilaphosphetidines and thallium monochloride and trimethylaluminium. 5 The first X-ray crystal structures of homoleptic aluminium alkanethiolate complexes have been reported; [Al(µ-SR)-(SR) 2 ] 2 (R = t-Bu and i-Pr) were prepared from the reactions of NaCSMe 3 with AlBr 3

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“…Experimentally it has been established that the molecular reaction plays a leading role in generation of singlet oxygen,

{Cl}_{2} + H_{2} O_{2} \to 2 H^{+} + 2 {Cl}^{-} + O_{2} ((), {}^{1}{normalΔ}_{g})

where a strong acceptor of proton was added into the aqueous solution, which removes the proton produced by the reaction and is in favor of the O 2 ( 1 Δ g ) generation. In addition, a gas–solid reaction of Na 2 O 2 with dry HCl gases at room temperature was used to produce O 2 ( 1 Δ g ),

2 HCl + {Na}_{2} O_{2} \to 2 NaCl + H_{2} normalO + \frac{1}{2} O_{2} ((), {}^{1}{normalΔ}_{g})

which takes place spontaneously and efficiently.…”

Section: Introductionmentioning

confidence: 99%

“…Although numerous experimental studies have been devoted to generation of singlet oxygen for the chemical oxygen iodine laser and for its application in other laser technology, there is a general lack of information on how to generate O 2 ( 1 Δ g ) from the reaction of Cl 2 with H 2 O 2 in the basic aqueous solution. As far as we know, only three relevant articles were published till now in the field of electronic structure calculation.…”

Section: Introductionmentioning

confidence: 99%

“…At least,

{{}^{3}Σ}_{g}^{-}

and 1 Δ g electronic states are involved for the O 2 ( 1 Δ g ) generation from the reaction of the dissolved Cl 2 with the basic H 2 O 2 aqueous solution. Therefore, the 1 Δ g →

{{}^{3}Σ}_{g}^{-}

intersystem crossing (ISC) may have a considerable influence on the yield and efficiency of the O 2 ( 1 Δ g ) generation, which has not been explored in the experimental and theoretical studies . In addition, it has been established experimentally that O 2 ( 1 Δ g ) has the solvent‐dependent lifetime, which indicates that the interaction between solvent and O 2 ( 1 Δ g ) has a considerable influence on the nonadiabatic 1 Δ g →

{{}^{3}Σ}_{g}^{-}

process.…”

Section: Introductionmentioning

confidence: 99%

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Mechanism of the O₂(¹Δ_g) generation from the Cl₂/H₂O₂ basic aqueous solution explored by the combined ab initio calculation and nonadiabatic dynamics simulation

Wang

Fang

2018

J Comput Chem

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In the present work, mechanism of the O 2 ( 1 Δ g ) generation from the reaction of the dissolved Cl 2 with H 2 O 2 in basic aqueous solution has been explored by the combined ab initio calculation and nonadiabatic dynamics simulation, together with different solvent models. Three possible pathways have been determined for the O 2 ( 1 Δ g ) generation, but two of them are sequentially downhill processes until formation of the OOCl − complex with water, which are of high exothermic character. Once the complex is formed, singlet molecular oxygen is easily generated by its decomposition along the singlet-state pathway. However, triplet molecular oxygen of O 2 ( 3 Σ − g ) can be produced with considerable probability through nonadiabatic intersystem crossing in the 1 Δ g / 3 Σ − g intersection region. It has been found that the coupled solvent, heavy-atom, and nonadiabatic effects have an important influence on the quantum yield of the O 2 ( 1 Δ g ) generation.

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Singlet Delta Oxygen Production from a Gas��Solid Reaction

Cited by 11 publications

References 15 publications

Singlet oxygen generation as a major cause for parasitic reactions during cycling of aprotic lithium–oxygen batteries

Singlet oxygen generation as a major cause for parasitic reactions during cycling of aprotic lithium–oxygen batteries

7 Oxygen, sulfur, selenium and tellurium

Mechanism of the O₂(¹Δ_g) generation from the Cl₂/H₂O₂ basic aqueous solution explored by the combined ab initio calculation and nonadiabatic dynamics simulation

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Singlet Delta Oxygen Production from a Gas���Solid Reaction

Cited by 11 publications

References 15 publications

Singlet oxygen generation as a major cause for parasitic reactions during cycling of aprotic lithium–oxygen batteries

Singlet oxygen generation as a major cause for parasitic reactions during cycling of aprotic lithium–oxygen batteries

7 Oxygen, sulfur, selenium and tellurium

Mechanism of the O2(1Δg) generation from the Cl2/H2O2 basic aqueous solution explored by the combined ab initio calculation and nonadiabatic dynamics simulation

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About

Singlet Delta Oxygen Production from a Gas��Solid Reaction

Mechanism of the O₂(¹Δ_g) generation from the Cl₂/H₂O₂ basic aqueous solution explored by the combined ab initio calculation and nonadiabatic dynamics simulation