Homogeneous Hydrogenation of CO<sub>2</sub> to Methyl Formate Utilizing Switchable Ionic Liquids

Yadav, Mahendra; Linehan, John C.; Karkamkar, Abhijeet J.; Eide, Edwin F. van der; Heldebrant, David J.

doi:10.1021/ic501378w

Cited by 53 publications

(46 citation statements)

References 49 publications

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“…1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU) or 2-butyl-1,1,3,3-tetramethylguanidine (TMBG). [26][27][35][36] and also for CO 2 capturing [28][29] . The SILs have also been employed for a variety of purposes such for extraction [32][33][34] , dissolution of biopolymers (lignin, hemicelluloses, etc.)…”

Section: Introductionmentioning

confidence: 98%

Effect of DBU (1,8-Diazobicyclo[5.4.0]undec-7-ene) Based Protic Ionic Liquid on the Volumetric and Ultrasonic Properties of Ascorbic Acid in Aqueous Solution

Singh

Gardas

2015

Ind. Eng. Chem. Res.

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In order to understand the strength and type of interactions involved in ternary solutions, the effect of solute or cosolute concentration and temperature is needed, as an understanding of these interactions are helpful in biochemical and biophysical chemistry. In this regard, we have studied the volumetric and ultrasonic properties of one of the most important vitamin i.e. ascorbic acid in water and in presence of newly synthesized protic ionic liquid (1,8diazabicyclo[5.4.0]undec-7-en-8-ium trifluroacetate) at temperatures, (293.15 K to 328.15 K)and at atmospheric pressure. The experimentally measured density and speed of sound data were used to calculate apparent molar volume and isentropic compressibility, infinite dilution partial molar volume and partial molar isentropic compressibility. Volume of transfer (∆ t V 2 º and ∆ t K º s,2 ), expansion coefficients, pair and triplet volumetric interaction coefficients were also evaluated and discussed in terms of various interactions occurring between ascorbic acid and PIL on the basis of structural interaction model. . Tian, M.; Cheng, R.; Ye, J.; Liu, X.; Jia, Q. Preparation And Evaluation Of Ionic Liquid-Calixarene Solid-Phase Microextraction Fibres For the Determination of Triazines in Fruit and Vegetable Samples.

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Section: Introductionmentioning

confidence: 98%

Effect of DBU (1,8-Diazobicyclo[5.4.0]undec-7-ene) Based Protic Ionic Liquid on the Volumetric and Ultrasonic Properties of Ascorbic Acid in Aqueous Solution

Singh

Gardas

2015

Ind. Eng. Chem. Res.

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“…This is the main stumbling block that prevents the use of the low-temperature process,a nd given the potentiala dvantages of al ow-temperature-low-pressure process in energy applications, there is much interesti na lternatives that are activef or CO 2 reduction. [5] LTMS catalysts are composed of at ransition metal in combination witha ne xcess of strong base, typically,a na lkali metal alkoxide. The most active catalysts are based on Ni and Cu, of which the former is the subject of this study.…”

Section: Introductionmentioning

confidence: 99%

DFT Study of Nickel‐Catalyzed Low‐Temperature Methanol Synthesis

et al. 2017

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Low‐temperature methanol synthesis (CO+2 H2→CH3OH) catalyzed by a homogeneous nickel/alkali metal alkoxide system has been studied theoretically. Two broad mechanistic possibilities, the direct hydrogenation of CO by nickel formyl species and indirect hydrogenation via methyl formate formation, have been examined. The most favorable mechanism involves the methanolysis of CO to methyl formate catalyzed by an ether complex of sodium methoxide followed by the stepwise hydrogenation of methyl formate to formaldehyde and then to a nickel methoxide, in which both steps are mediated by a nickel hydride. In the final step the nickel methoxide is hydrogenated to release methanol. The conversion of methyl formate to the nickel methoxide is predicted to be rate limiting, and the nickel hydride is the most likely catalyst resting state. The theoretical results are discussed in the context of existing experimental observations, and a good agreement with past studies was obtained.

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“…18,19 Chen et al 20,21 employed the photocatalytic reduction of CO 2 to MF on B 2 S 3 and Ni-doped ZnS catalyst with the rate of MF production 175 of methanol to DMF, the concentration of CaO-ZrO 2 and Cu-Mn smaples on catalytic performance were thoroughly investigated. 18,19 Chen et al 20,21 employed the photocatalytic reduction of CO 2 to MF on B 2 S 3 and Ni-doped ZnS catalyst with the rate of MF production 175 of methanol to DMF, the concentration of CaO-ZrO 2 and Cu-Mn smaples on catalytic performance were thoroughly investigated.…”

Section: Introductionmentioning

confidence: 99%

A novel Cu–Mn/Ca–Zr catalyst for the synthesis of methyl formate from syngas

et al. 2015

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Cu-Mn mixed oxides and mesoporous CaO-ZrO 2 solid base were prepared by complexing method and alcohothermal route, respectively, and they were mixed together as combined Cu-Mn/Ca-Zr catalyst which was evaluated for the direct synthesis of methyl formate (MF) from syngas in a slurry reactor. Cu-Mn and CaO-ZrO 2 samples were characterized by N 2 isotherm adsorption-desorption, XRD, SEM, TEM, XPS and CO 2 -TPD techniques. Under the optimum reaction conditions of 160 o C, 3 MPa, 3:7 for the ratio of methanol to N, N dimethylformamide, 40 g L -1for Cu-Mn sample, and 30 g L -1 for CaO-ZrO 2 sample, a lower CO conversion of 22.4 % was obtained over Cu-Mn/Ca-Zr, whereas the MF selectivity of 82.3% was higher than that of traditional catalyst (e.g. Cu-catalyst and NaOCH 3 ), which was due to the synergism between Cu-Mn and CaO-ZrO 2 samples. µmol g -1 h -1 and 121 µmol g -1 h -1 , respectively, while the low yield and poor stability limit the application of this process. This has stimulated a desire for the development of an alternative process.Direct synthesis of MF from syngas in liquid-phase system is significantly concerned by researchers due to its atomic economy and short reaction process. [22][23][24][25][26] The direct process follows the stoichiometry: 2CO+2H 2 → HCOOCH 3 , △H 0 R = -157.2 kJ mol -1 (1). 27 In the direct synthesis process, MF formed as an intermediate of methanol synthesis from syngas on mixed catalyst comprised of alkali or alkali earth compounds and Cu-based catalysts, 22 which contains homogeneous carbonylation of methanol on alkali or alkali earth compounds and heterogeneous hydrogenation of MF on Cu-based catalysts. Palekar et al. 23 controlled the selectivity of methanol and MF by changing reaction temperature and the ratio of CO to H 2 . They found that high reaction temperature and low CO/H 2 were beneficial to methanol; on the contrary, low reaction temperature and high CO/H 2 condition favored MF formation, and the similar results were also reported by Chen et al. 28 However, a critical problem in this process is that homogeneous alkali or alkali earth compounds is susceptible to CO 2 or H 2 O in reaction system, which accelerate the fall of the catalytic activity. 29-31 Moreover, alkali or alkali earth compounds distributed on the surface of Cu-based catalyst caused the blockage of active sites. 32In this work, CaO-ZrO 2 solid base and Cu-Mn mixed oxides were prepared and characterized by N 2 isotherm adsorption-desorption, XRD, TEM, SEM, XPS and CO 2 -TPD measurements. More importantly, the combined Cu-Mn/Ca-Zr catalyst prepared by mechanical mixing above two as-prepared samples was applied to the direct synthesis of MF from syngas in a batch slurry reactor for the first time. In addition, the influences of reaction parameters such as temperature, pressure, the ratio ratio of Ca to Zr is 0.5. Preparation of Cu-Mn/Ca-Zr catalystCu-Mn/CaO-ZrO 2 combined catalyst, noted as Cu-Mn/Ca-Zr, was prepared by mechanical mixing Cu-Mn mixed oxides and CaO-ZrO 2 solid base. The mass ratio of Cu-Mn ...

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Homogeneous Hydrogenation of CO₂ to Methyl Formate Utilizing Switchable Ionic Liquids

Cited by 53 publications

References 49 publications

Effect of DBU (1,8-Diazobicyclo[5.4.0]undec-7-ene) Based Protic Ionic Liquid on the Volumetric and Ultrasonic Properties of Ascorbic Acid in Aqueous Solution

Effect of DBU (1,8-Diazobicyclo[5.4.0]undec-7-ene) Based Protic Ionic Liquid on the Volumetric and Ultrasonic Properties of Ascorbic Acid in Aqueous Solution

DFT Study of Nickel‐Catalyzed Low‐Temperature Methanol Synthesis

A novel Cu–Mn/Ca–Zr catalyst for the synthesis of methyl formate from syngas

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Homogeneous Hydrogenation of CO2 to Methyl Formate Utilizing Switchable Ionic Liquids

Cited by 53 publications

References 49 publications

Effect of DBU (1,8-Diazobicyclo[5.4.0]undec-7-ene) Based Protic Ionic Liquid on the Volumetric and Ultrasonic Properties of Ascorbic Acid in Aqueous Solution

Effect of DBU (1,8-Diazobicyclo[5.4.0]undec-7-ene) Based Protic Ionic Liquid on the Volumetric and Ultrasonic Properties of Ascorbic Acid in Aqueous Solution

DFT Study of Nickel‐Catalyzed Low‐Temperature Methanol Synthesis

A novel Cu–Mn/Ca–Zr catalyst for the synthesis of methyl formate from syngas

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Product

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Homogeneous Hydrogenation of CO₂ to Methyl Formate Utilizing Switchable Ionic Liquids