Nitrile Electrolyte Strategy for 4.9 V-Class Lithium-Metal Batteries Operating in Flame

Challenges facing high-voltage/high-capacity cathodes,in addition to the longstanding problems pertinent to lithium(Li)-metal anodes,should be addressed to develop high-energy-density Li-metal batteries.This issue mostly stems from interfacial instability between electrodes and electrolytes.Conventional carbonate-or ether-based liquid electrolytes suffer from not only volatility and flammability but also limited electrochemical stability window.Here,we report a nitrile electrolyte strategy based on concentrated nitrile electrolytes(CNEs)with co-additives.The CNE consists of high-concentration lithium bis(fluorosulfonyl)imide(LiFSI)in a solvent mixture of succinonitrile(SN)/acetonitrile(AN).The SN/AN solvent mixture is designed to ensure high oxidation stability along with thermal stability,which are prerequisites for high-voltage Li-metal cells.The CNE exhibits interfacial stability with Li metals due to the coordinated solvation structure.Lithium nitrate(LiNO_(3))and indium fluoride(InF_(3))are incorporated in the CNE as synergistic co-additives to further stabilize solid-electrolyte interphase(SEI)on Li metals.The resulting electrolyte(CNE+LiNO_(3)/InF_(3))enables stable cycling performance in Li||LiNi_(0.8)Co_(0.1)Mn_(0.1)and 4.9 V-class Li||LiNi_(0.5)Mn_(1.5)O_(4)cells.Notably,the Li||LiNi_(0.5)Mn_(1.5)O_(4)cell maintains its electrochemical activity at high temperature(100℃)and even in flame without fire or explosion.

Synthesis and characterization of new soluble poly(aryl ether nitrile)s containing phthalazinone moiety

A series of novel poly（aryl ether nitrile）s containing phthalazinone moiety were synthesized by the nucleophilic displacement reaction of bisphenol-like monomers （I） with 2,6-difluorobenzonitrile. The inherent viscosities ranged from 0.46 to 1.07 dL g^-1. The glass transition temperatures were in the range of 277-295℃, and the temperatures for 10% weight loss in nitrogen atmosphere were found between 495 and 527 ℃. The structures of these resultant polymers were confirmed by FT-IR and 1^H NMR. Moreover, the properties of poly（aryl ether nitrile）s including solubility and crystallinity were also studied.

Environment friendly protocol for the synthesis of nitriles from aldehydes

A rapid and eco-friendly one-pot protocol for the synthesis of nitriles has been developed by treating various araldehydes bearing electron withdrawing as well as electron donating groups with hydroxylamine hydrochloride in the presence of non-toxic,non-corrosive and reusable zinc oxide（ZnO） as the catalyst under solvent-free microwave irradiation.The present approach offers the advantages of a clean reaction,simple methodology,employing readily available catalyst,short reaction duration（〈1 min）,high selectivity;and high yield（90-98%）.

Preparation of cross-linked enzyme aggregates of nitrile hydratase ES-NHT-118 from E.coli by macromolecular cross-linking agent

Cross-linked enzyme aggregates(CLEAs) of nitrile hydratase(NHase) ES-NHT-118 from Escherichia coli were prepared by using ammonium sulfate as precipitating agent followed by cross-linking with dextran polyaldehyde for the first time. In this process, egg white was added as protein feeder for facilitating the formation of CLEAs. The optimal conditions of the immobilization process were determined. Michaelis constants(Km) of free NHase and NHase CLEAs were also determined. The NHase CLEAs exhibited increased stability at varied pH and temperature conditions compared to its free counterpart. When exposed to high concentrations of acrylamide, NHase CLEAs also exhibited effective catalytic activity.

COORDINATION CROSSLINKING OF NITRILE RUBBER FILLED WITH COPPER SULFATE PARTICLES

By incorporating copper sulfate （CuSO4） particles into acrylonitrile butadiene rubber （NBR） followed by heat pressing, a novel vulcanization method is developed in rubber through the formation of coordination crosslinking. This method totally differs from traditional covalent or non-covalent vulcanization approaches of rubber. No other vulcanizing agent or additional additive is involved in this process. By analyzing the results of DMA, XPS and FT-IR, it is found that the crosslinking of CuSO4 particles filled NBR was induced by in situ coordination between nitrogen atoms of nitrile groups （-CN） and copper ions （Cu^2＋） from CuSO4. SEM and EDX results revealed the generation of a core （CuSO4 solid particle）- shell （adherent NBR） structure, which leads to a result that the crosslinked rubber has excellent mechanical properties. Moreover, poly（vinyl chloride） （PVC） and liquid acrylonitrile-butadiene rubber （LNBR） were used as mobilizer to improve the coordination crosslinking of CuSO4/NBR. The addition of PVC or LNBR could lead to higher crosslink density and better mechanical properties of coordination vulcanization. In addition, crystal water in CuSO4 played a positive role to coordination crosslinking of rubber because it decreased the metal point of CuSO4 and promoted the metal ionization.

Separation of Biphenyl Nitrile Compounds by Microemulsion Electrokinetic Chromatography with Mixed Surfactants

A mixture of nine biphenyl nitrile compounds with high hydrophobicity and similar structures was successfully separated by microemulsion electrokinetic chromatography (MEEKC) within 30 min. The buffer system contained 100 mmol/L sodium dodecyl sulfate (SDS), 80 mmol/L sodium cholate (SC), 0.81% heptane, 7.5% n-butanol, 10% acetonitrile and 10 mmol/L borate. The addition of SC, organic modifiers, sample preparation and temperature all showed remarkable effect on the separation. Meanwhile, the MEEKC method was briefly compared with micellar electrokinetic chromatography (MEKC) method.

Direct Synthesis of Nitriles from Aldehydes in Ionic Liquids

1 Introduction Ionic liquids（ILs） are environmentally acceptable solvents because they have low vapor pressure, high thermal stability and chemical stability, excellent solvent for organic and inorganic compounds. Therefore, they can be used as green solvents for a number of chemical processes, such as separa- tions and reactions. ILs are also used as catalysts in chemical reactions to accelerate reaction rate and improve selectivity.

Facile Synthesis of Amidines via Intermolecular Reductive Coupling of Nitriles with Azobenzene Promoted by Samarium Diiodide

The intermolecular reductive coupling of nitrites with azobenzene induced by SmI2 was studied. Amidine derivatives were prepared in good yields under neutral and mild conditions.

Synthesis and characterization of poly(phthalazinone ether nitrile) (PPEN)-polydimethylsiloxane (PDMS) block copolymers

Block copolymers with different backbone compositions have been prepared by the condensation of dimethylamino terminated poly（dimethylsiloxane） （PDMS） and hydroquinone terminated poly（phthalazinone ether nitrile） （PPEN） in the presence of chlorobenzcne/N-methyl pyrrolidone （NMP） as solvents. The products were characterized by FTIR, ^1H NMR and gel permeation chromatography. Differential scanning calorimetry analysis indicated that the block copolymers showed separated microphase.

AROMATIC AND HETEROCYCLIC NITRILES AND THEIR POLYMERS ⅩⅥ. THE POLYMERIZATION KINETICS OF 4, 4′-BIPHENYLDICARBONITRILE CATALYZED BY LEWIS ACID-METAL SYSTEM

The polymerization kinetics of 4, 4′-biphenyldicarbonitrile using cuprous chloride-zinc system as catatyst was investigated. the concentration of unreacted cyano group was measured by infrared spectroscopic analysis using potassium ferricyanide as the internal reference. It was found that the polymerization rate is directly proportional to the concentrations ofcyano group, cuprous chloride and zinc, and the activation energy of the polymerization is as Tow as 18.4 KJ/mol. In addition, the other kinetics parameters were obtained and discussed.

A Convenient Synthesis of α-Phenylsclcno-α, β-unsaturated Nitriles via Arsonium Salt

α-Phenylseleno-α,β-unsaturated nitriles were synthesized under mild condition viaarsonium salt 1 in one pot reaction.

A new one-pot neat synthesis of 1,2,4-triazol-3-ones through 4-(N,N-dimethylamino) pyridine (DMAP) catalyzed cyclocondensation of ethyl carbazate with aryl nitriles

A new one-pot neat synthesis of some 5-aryl-2,4-dihydro-3H- 1,2,4-triazol-3-ones through cyclocondensation of ethyl carbazate with aryl nitriles catalyzed by DMAP as an efficient and basic nucleophilic catalyst is described.

Highly-Efficient Conversion of Primary Amides to Nitriles Using Indium(III) Triflate as the Catalyst

Indium(III) triflate, a trivalent indium reagent, was shown to be a highly-efficient catalyst for the conversion of primary amides to the corresponding nitriles. The successful reactions required 5 mol% of indium(III) triflate, and toluene was proved to be the most suitable solvent. Various amides were subjected to this method, and each produced the corresponding nitriles in excellent yields.

A New Mathod for Conversion of Nitriles to Primary Alcohols

A new method for direct conversion of nitriles to primary alcohols using ZnCoCl2 reagent in AcOH/EtOH system is reported.

Improved Electrochemical Synthesis of Nitro-substituted 1-Aryl-2-pyrrolidinecarbonitriles

In this paper, we described an improved electrochemical method for synthesis of some 1-aryl-2-pyrrolidinecarbonitrile derivatives bearing an electron-withdrawing group （NO2）. The electrochemical synthesis of titile compounds has been successfully performed in an undivided cell in reasonable yields.

AROMATIC AND HETEROCYCLIC NITRILES AND THEIR POLYMERS ⅩⅦ. THE POLYMERIZATION KINETICS OF CYANOPYRIDINES AND CHARACTERIZATION OF THE FORMED POLYMER

The polymerization rates of three cyanopyridines catalyzed by cuprous chloride-zinc system are measured, and the structure of the formed polymer is also determined. Compared with aromatic nitrile, cyanopyridines polymerize faster and form polyconjugated polymer with skeleton—（C=N）—;instead of triazine structure. This chain-polymer possesses semiconductive property, and can be converted into conductive material by thermal treatment. In addition, the polymerization kinetics of 3-cyanopyridine catalyzed by 3-cyanopyridinium perchlorate is investigated. It is found that the polymerization rate is directly proportional to the concentrations of monomer and catalyst, and the activation energy of the polymerization is 103.1 KJ/mol.

Study on nitrile-degrading microorganisms

Two strains of bacteria were isolated from nitrile polluted soils, and identified as Corynebacterium boffmanii and Arthrobacter flavescens. Acetonitrile, propionitrile, butyronitrile and acrylonitrile were degraded by these bacteria to yield corresponding amides, carboxylic acids and ammonia. The nitrile-degrading abilities of these strains were investigated. The removal rates for the nitrile were nearly 100%, after these bacteria were grown in medium containing 10000 ppm of aceto-, propio-, or butyronitrile at 28 ℃ for 24h. When the reaction mkture consisting of 5000 ppm of above mentioned nitriles or acrylonitrile and 20g (dry cell) /L resting cells of the two strains in 0.06mol/L phosphate buffer (pH7.5) was incubated separately at 25 ℃ with moderate shaking for 15 or 45 min, the nitrile could be degraded completely. The optimum growth conditions for C.hoffmanii and A.flavescens were studied as well.

Recent developments in electrosynthesis of nitriles and electrocatalytic cyanations

Nitrile compounds are a class of high-value chemicals and versatile intermediates which can easily be transformed into a variety of useful products bearing functional groups such as carboxyl, carbamoyl, aminomethyl, ketyl and heterocyclic derivatives. Various thermal catalytic cyanation procedures have been devised and scaled up industrially while developing alternative methods are actively pursued. The access to these classes of molecules electrochemically offers greener alternatives to their preparation. The development of electrochemical synthesis of cyano-containing compounds under mild conditions with low energy consumption will imminently become indispensable approaches for industrial production of nitriles. The electrochemical cyanation presents many challenges from the toxicity of cyanide to the development of catalysts and the design of electrochemical cells. Electrochemical cyanation reaction offers promise to conveniently accessing nitriles but still requires efficient electro-catalysts, safe protocols and scale up considerations. This review discusses recent progress in the field of electrochemical synthesis of nitrile compounds placing emphasis on electro-synthetic and electro-catalytic mechanism aspects while making reference to original works to highlight the progress in this area.

AROMATIC AND HETEROCYCLIC DINITRILES AND THEIR POLYMERS ⅪⅤ.STUDY ON THE CATALYSTS OF THE POLYMERIZATION OF AROMATIC NITRILES

Various catalysts for the polymerization ot aromatic nitriles were investigated. It was found that Lewis acid-metal is a preferable catalyst system for the polymerization of aromatic nitriles, and the polymerization rate is about 10 times faster than Lewis acid alone. The polymerization rate of benzonitrile catalyzed by Lewis acid and different metals was measured, and the activity of metals was in the following decreasing order ,magnesium, zinc, sodium, calcium. Furthermore, the polymerization of benzonitrile catalyzed by different Lewis acid and zinc was also investigated.

Samarium Diiodide-Induced Reductive Cleavage of Se-St Bond in Arylselenotrimethylsilane Leading to the Formation of Samarium Arylselenolate: Synthesis of β-Arylseleno Estsrs and β-Arylseleno Nitriles

The Se-St bond in arylselenotrimethylsilane was reduced by samarium diiodide to produce samarium arylselenolate, which reacted with a,β-unsaturated esters or α,β-unsaturated nitriles to give β-selenoesters and β-selenonitriles, respectively.