Ionic liquid based Cu₂S@C catalyst for effective coupling of diaryl diselenide with aryl halides under ligand-free conditions

Chaugule, Avinash A.,Pawar, Atul A.,Tamboli, Ashif H.,Bandal, Harshad A.,Chung, Wook-Jin,Kim, Hern Elsevier 2018 CHEMICAL ENGINEERING JOURNAL -LAUSANNE- Vol.351 No.-

<P><B>Abstract</B></P> <P>Diaryl selenide is the main drug candidate today. An efficient, easy and ligand free cross-coupling reaction of aryl halide and diaryl diselenide was carried out by as-prepared copper sulfide functionalized carbon (Cu<SUB>2</SUB>S@C) catalyst. Cu<SUB>2</SUB>S@C catalyst was developed using novel tri-cationic ionic liquid (IL) as a precursor and sulfur source. Catalyst found to having rich content of heteroatoms (S and N) by EDX and Elemental mapping characterization techniques. Effective utilization of catalyst was carried out by synthesis of variety of aryl selenide in excellent yield from readily halides and diaryl diselenides. Active centers in the catalyst provide efficient activation for crosscoupling reaction. Moreover, catalyst where easily reusable for three times without any obvious loss in catalytic activity.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Preparation of Poly-GLY(1-vinyl)<SUB>3</SUB>(OMs)<SUB>3</SUB>. </LI> <LI> Synthesis of Cu<SUB>2</SUB>S@C catalyst. </LI> <LI> Efficient synthesis of aryl selenide. </LI> <LI> Catalyst able to reuse for three times. </LI> </UL> </P>

Glycerol functionalized imidazolium tricationic room temperature ionic liquids synthesis and application for 2-azidoalcohol synthesis from epoxide

( Avinash Chaugule ),( Ashif Tamboli ),김헌 한국공업화학회 2015 한국공업화학회 연구논문 초록집 Vol.2015 No.1

The new tricationic room temperature ionic liquids (RTILs) based on 3-methylimidazolium were synthesized form glycerol. The RTILs presented interesting physicochemical properties at different temperature. The Lewis acidity of prepared ionic liquid was determined by IR spectroscopy. The [GLY(mim)₃][OMs] IL showed highest Lewis acidic behavior. The catalytic activity and reusability of these tricationic RTILs were investigated for 2-azidoalcohol synthesis from epoxide and sodium azide. The prepared tricationic RTILs in presence of water as proton source exhibited high catalytic activity compared to monotri-cationc ILs.

Highly efficient synthesis of dimethyl carbonate from methanol and carbon dioxide using metal oxy chloride/hydroxyl ionic Liquid as a trifunctional catalytic system

( Avinash Chaugule ),김헌 한국공업화학회 2015 한국공업화학회 연구논문 초록집 Vol.2015 No.0

Dimethyl carbonate (DMC) was synthesized in excellent yield by direct physically or chemically adsorption of carbon dioxide on [EmimOH][NTf2] IL in presence of SmOCl and super base. Meaningfully, novel ternary catalyst system was found to display noticeable conversion of methanol (13.01%) with excellent selectivity (99.13%) towards DMC. The interaction of CO2 with IL in presence of superbase was discussed by FT-IR and 13C characterization as well as catalytic reactivity was proved by predictable mechanism. Various conditions such as reaction temperature, pressure and time were investigated for DMC.

Ionic liquid as a catalyst for utilization of carbon dioxide to production of linear and cyclic carbonate

Chaugule, Avinash A.,Tamboli, Ashif H.,Kim, Hern Elsevier 2017 Fuel Vol.200 No.-

<P><B>Abstract</B></P> <P>In this review, primary focus on the ionic liquid (IL) catalysts and related catalytic systems for utilization of carbon dioxide to a production of linear as well as cyclic carbonate, and describes the innovative progress observed during last ten years. This review covers trend of various catalysts starting from first conventional ILs (tetrabutylammonium bromide and imidazolium IL) to the latest metal containing IL systems employed for the efficient production of dimethyl carbonate. Moreover, recent advances in DMC production also summarizes using the catalysts which contain novel super base facilitated tri-cationic IL systems. Similarly, cyclic carbonate synthesis reveals the benefits of using IL based catalyst on the verity of different supporting materials such as alumina, silica, carbon nanotubes, magnetic nanoparticles, poly(ethylene glycol), polystyrene, cellulose, and chitosan. The summary of ammonium, phosphonium and both functionalized and unfunctionalized imidazolium salts indicates that the turnover frequency for epoxide and propylene oxide enhances under mild reaction condition. Overall, it is clear that metal ions or super base in the combination of ILs can improve the conversions and the presence of hydroxyl, carboxyl, and other functional groups will enhance the yield multiple folds through hydrogen bonding interaction.</P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

CuCl₂@Poly-IL catalyzed carboxylation of terminal alkynes through CO₂ utilization

Chaugule, Avinash A.,Tamboli, Ashif H.,Kim, Hern Elsevier 2017 CHEMICAL ENGINEERING JOURNAL -LAUSANNE- Vol.326 No.-

<P><B>Abstract</B></P> <P>The carboxylation of terminal alkynes from CO<SUB>2</SUB> is a most attractive route in green chemistry point of view. Herein, we synthesized a novel CuCl<SUB>2</SUB>@Poly-GLY(1-Vim)<SUB>3</SUB>(OMs)<SUB>3</SUB> catalyst and employed to the efficient carboxylation of terminal alkynes (phenyl carboxylate esters) by utilizing CO<SUB>2</SUB> under 4MPa, at 40°C. In presence of catalyst, various terminal alkynes found to be easily reacting with CO<SUB>2</SUB> and organic halide to affording a high yield of carboxylic ester. Moreover, CuCl<SUB>2</SUB>@Poly-GLY(1-vim)<SUB>3</SUB>(OMs)<SUB>3</SUB> catalyst is capable to obtain a high yield of corresponding carboxylic ester using various types organic halide. Furthermore, CuCl<SUB>2</SUB>@Poly-GLY(1-vim)<SUB>3</SUB>(OMs)<SUB>3</SUB> catalyst able to easily recover and reuse for four times without any obvious loss in catalytic activity. The catalytic reactivity of CuCl<SUB>2</SUB>@Poly-GLY(1-vim)<SUB>3</SUB>(OMs)<SUB>3</SUB> catalyst is explained on the basis of predicted mechanism.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Preparation of Poly-GLY(mim)<SUB>3</SUB>(OMs)<SUB>3</SUB>. </LI> <LI> Synthesis of Cu@Poly-GLY(mim)<SUB>3</SUB>(OMs)<SUB>3</SUB> catalyst. </LI> <LI> Efficient carboxylation of terminal alkyne. </LI> <LI> Catalyst able to reuse for four times. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

Synthesis of Ce-Ni based nanofiber as novel catalyst for hydrogen production from sodium borohydride hydrolysis

( Ashif Tamboli ),( Avinash Chaugule ),김헌 한국공업화학회 2015 한국공업화학회 연구논문 초록집 Vol.2015 No.1

The cerium-nickel loaded on titanium nanofibers were fabricated by simple electrospinning technique for hydrogen production. The catalytic activity of derived composite oxides after calcinations was studied at different parametric conditions. The prepared nanofibers were characterized by the SEM, EDX, FTIR, XRD, BET and TEM technique. The catalytic activities results showed that the activity of catalyst is due to the synergic affect of cerium and nickel composite oxide. The activation energy and recycling ability of prepared nanofiber was evident a beneficial effect of cerium in the catalytic activity for hydrogen production.

Catalytic developments in the direct dimethyl carbonate synthesis from carbon dioxide and methanol

Tamboli, Ashif H.,Chaugule, Avinash A.,Kim, Hern Elsevier 2017 Chemical Engineering Journal Vol.323 No.-

<P><B>Abstract</B></P> <P>The present review compiles the recently published literature for the single step dimethyl carbonate (DMC) synthesis from carbon dioxide (CO<SUB>2</SUB>) and methanol. The various routes of DMC synthesis are also discussed in short with their advantages and disadvantages in order to distinguish the merits of direct DMC synthesis route. Next, the major applications of DMC such as in electrochemistry, as fuels additive, as solvent and building block in organic synthesis are described. The major problems in the direct DMC synthesis route such as low yield, reaction rate, thermodynamic limitations and hydrolysis of produced DMC are also pointed out. Furthermore, the significance of fabricating an effective dehydrating agent for the removal of water from the reaction is narrated for the enhancement of DMC yield. The type of catalyst materials based on their nature i.e. metal carbonates, tin-based catalysts, metal oxides, organic catalysts and polymer based materials, etc. used for title reaction are separately discussed in details. The varieties of dehydrating agents and their role in DMC production is explained with the help of most recent reported literature.</P> <P><B>Highlights</B></P> <P> <UL> <LI> DMC are commonly used as fuel additive, in electrochemistry and organic synthesis. </LI> <LI> This study presents an overview of advances in direct DMC synthesis from CO<SUB>2</SUB> and methanol. </LI> <LI> It also summarizes the challenges such as necessity of dehydrating agents. </LI> <LI> And the uses of various catalysts to address challenges like low yield and thermodynamic limitations. </LI> </UL> </P>

Diethylenetriamine assisted synthesis of mesoporous Co and Ni-Co spinel oxides as an electrocatalysts for methanol and water oxidation

Jadhav, Amol R.,Bandal, Harshad A.,Chaugule, Avinash A.,Kim, Hern Elsevier 2017 ELECTROCHIMICA ACTA Vol.240 No.-

<P><B>Abstract</B></P> <P>The electrocatalytic oxidation of small molecules such as methanol and water is the crucial part of energy storage/generation technologies such as fuel cell and metal-air batteries. However, the high overpotential, sluggish reaction dynamics and low stability of electrode materials are the main barriers in developing an excellent catalyst for the anodic electro-oxidation process. To overcome such problems, we developed an easy synthesis root for the preparation of novel mesoporous (MP) Co<SUB>3</SUB>O<SUB>4</SUB> and NiCo<SUB>2</SUB>O<SUB>4</SUB> using a template-free hydrothermal and subsequent annealing method. In which, we used diethylenetriamine as a complexing agent, which was able to control crystal growth of corresponding metal hydroxide, leading to the formation of a mesoporous structure. Results show that the MP-NiCo<SUB>2</SUB>O<SUB>4</SUB> exhibits a current density of 10.0mAcm<SUP>−2</SUP> even at a lower potential (286mV vs. Ag/AgCl) for methanol oxidation reaction compared to that of MP-Co<SUB>3</SUB>O<SUB>4</SUB>. On the other hand, both MP-Co<SUB>3</SUB>O<SUB>4</SUB> and MP-NiCo<SUB>2</SUB>O<SUB>4</SUB> display excellent electrocatalytic activity towards water oxidation with lower onset potential and overpotential (MP-Co<SUB>3</SUB>O<SUB>4</SUB> ɳ<SUB>10</SUB> =302mV and MP-NiCo<SUB>2</SUB>O<SUB>4</SUB> ɳ<SUB>10</SUB> =322mV). The excellent electrochemical performance suggests that this mesoporous MP-NiCo<SUB>2</SUB>O<SUB>4</SUB> and MP-Co<SUB>3</SUB>O<SUB>4</SUB> could be potential candidates for energy and environmentally related applications.</P>

Iron-based heterogeneous catalysts for oxygen evolution reaction; change in perspective from activity promoter to active catalyst

Bandal, Harshad,Reddy, K. Koteshwara,Chaugule, Avinash,Kim, Hern Elsevier 2018 Journal of Power Sources Vol.395 No.-

<P><B>Abstract</B></P> <P>Oxygen evolution reaction is an integral part of energy storage technologies such as metal air batteries, water splitting, and regenerative fuel cells. However, oxygen evolution is 4 electron transfer process that suffers from sluggish reaction kinetics and indolent thermodynamics which mandates the use of a suitable noble metal catalyst. Considering the availability and cost of these precious metal catalysts, development of catalyst based on more abundant metal such as Fe is of vital interest for practical implication of these technologies. In this regards, over past few years several Fe based heterogeneous electrocatalysts are investigated for their electrocatalytic activity. Significant advances in improving the catalytic activity as well as exploring the catalytic mechanism are achieved in this area. Herein, we present an in-depth review on the recent progress in this field. Specific attention is given to design, synthesis, catalytic performance and strategies for improving their performance. A brief overview of existing challenges and future directions in the field of OER catalyst is also summarized.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Recent progress in development of Fe-based heterogeneous catalyst are reviewed. </LI> <LI> Role of Fe in mixed metal catalyst is also highlighted. </LI> <LI> A brief overview of existing challenges and future directions is summarized. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>