110th Anniversary: Ionic Liquid Promoted CO2 Hydrogenation to Free Formic Acid over Pd/C

We developed a series of new hydrotalcite functionalized Ru catalytic system to synthesize formic acid via CO2 hydrogenation reaction. Advance analytical procedures like FTIR, N2 physisorption, ICP-OES, XPS, and TEM analysis were applied to understand the physiochemical nature of functionalized hydrotalcite materials. This well-analyzed system was used as catalysts for CO2 hydrogenation reaction (with and without ionic liquid medium). Ru metal containing functionalized hydrotalcite materials were found highly active catalysts for formic acid synthesis via hydrogenation reaction. The concern of catalyst stability was studied via catalysts leaching and recycling experiments. We recycled the ionic liquid mediated functionalized hydrotalcite catalytic system up to 8 runs without any significant loss of catalytic activity. Surprisingly, no sign of catalyst leaching was recorded during the catalyst recycling experiment.

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Active γ –Alumina -Supported Ru Nanoparticles for CO2 Hydrogenation Reaction

Letters in Organic Chemistry ◽

10.2174/1570178617666191107112429 ◽

2020 ◽

Vol 17 (8) ◽

pp. 603-612

Author(s):

Prashant Gautam ◽

Vivek Srivastava

Keyword(s):

Ionic Liquid ◽

Formic Acid ◽

Reaction Medium ◽

Acid Synthesis ◽

Solvent System ◽

Co2 Hydrogenation ◽

Sustainable Chemistry ◽

Clear Correlation ◽

Ru Nanoparticles ◽

Molar Quantity

A series of alumina supported Ru nanoparticles (Ru γ -Al2O3-x (x=2-10 Ru wt%) was synthesized using the ethylene glycol reduction method. XRD, TEM, EDX, H2-chemisorption, XPS and H2-TPD analytical techniques were used to understand the physiochemical nature of alumina supported Ru nanoparticles. All the well-characterized Ru#Al2O3-x (x=2-10 Ru wt%) catalysts were used for high-pressure CO2 hydrogenation to formic acid synthesis. A clear correlation was recorded between the physiochemical properties of developed catalysts and the molar quantity of formic acid. Among all the developed catalysts, Ru#Al2O3-2 catalyst with or without ionic liquid reaction medium gave a good molar quantity of formic acid. Application of ionic liquid was also expanded, and ionic liquid medium appeared as a good solvent system as compared to the amine solvent system, which not only provides better solubility of reactants and catalysts but also found useful in the easy recovery of formic acid after the completion of the reaction. The catalyst recycled seven times with easy product isolation stem to make this system very useful and fulfill the requirement of sustainable chemistry.

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Versatile Rh- and Ir-Based Catalysts for CO2 Hydrogenation, Formic Acid Dehydrogenation, and Transfer Hydrogenation of Quinolines

Inorganic Chemistry ◽

10.1021/acs.inorgchem.8b02164 ◽

2018 ◽

Vol 57 (22) ◽

pp. 14186-14198 ◽

Cited By ~ 13

Author(s):

Jairo Fidalgo ◽

Margarita Ruiz-Castañeda ◽

Gabriel García-Herbosa ◽

Arancha Carbayo ◽

Félix A. Jalón ◽

...

Keyword(s):

Formic Acid ◽

Co2 Hydrogenation ◽

Transfer Hydrogenation ◽

Formic Acid Dehydrogenation

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2. CO2-based hydrogen storage: CO2 hydrogenation to formic acid, formaldehyde and methanol

Hydrogen Storage ◽

10.1515/9783110536423-002 ◽

2018 ◽

pp. 35-56

Author(s):

Thomas Schaub

Keyword(s):

Hydrogen Storage ◽

Formic Acid ◽

Co2 Hydrogenation

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Simple and recyclable ionic liquid based system for the selective decomposition of formic acid to hydrogen and carbon dioxide

Green Chemistry ◽

10.1039/c0gc00829j ◽

2011 ◽

Vol 13 (6) ◽

pp. 1411 ◽

Cited By ~ 29

Author(s):

M. E. M. Berger ◽

D. Assenbaum ◽

N. Taccardi ◽

E. Spiecker ◽

P. Wasserscheid

Keyword(s):

Carbon Dioxide ◽

Ionic Liquid ◽

Formic Acid

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Catalytic CO2 hydrogenation to formic acid over carbon nanotube-graphene supported PdNi alloy catalysts

RSC Advances ◽

10.1039/c5ra21017h ◽

2015 ◽

Vol 5 (128) ◽

pp. 105560-105566 ◽

Cited By ~ 53

Author(s):

Lan Thi Mai Nguyen ◽

Hunmin Park ◽

Marimuthu Banu ◽

Jae Yul Kim ◽

Duck Hyun Youn ◽

...

Keyword(s):

Carbon Nanotube ◽

Formic Acid ◽

Co2 Hydrogenation ◽

Water Solvent ◽

Alloy Catalysts ◽

Alloy Catalyst

Pure formic acid was produced via CO2 hydrogenation over a heterogeneous PdNi alloy catalyst on carbon nanotube-graphene support in water solvent without a base additive.

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Ionic Liquids as Bifunctional Cosolvents Enhanced CO2 Conversion Catalysed by NADH-Dependent Formate Dehydrogenase

Catalysts ◽

10.3390/catal8080304 ◽

2018 ◽

Vol 8 (8) ◽

pp. 304 ◽

Cited By ~ 2

Author(s):

Zhibo Zhang ◽

Bao-hua Xu ◽

Jianquan Luo ◽

Nicolas Solms ◽

Hongyan He ◽

...

Keyword(s):

Ionic Liquid ◽

Ionic Liquids ◽

Dft Calculations ◽

Formic Acid ◽

Formate Dehydrogenase ◽

Enzymatic Reaction ◽

Reaction System ◽

Co2 Concentration ◽

Co2 Conversion ◽

Low Co2

Efficient CO2 conversion by formate dehydrogenase is limited by the low CO2 concentrations that can be reached in traditional buffers. The use of ionic liquids was proposed as a manner to increase CO2 concentration in the reaction system. It has been found, however, that the required cofactor (NADH) heavily degraded during the enzymatic reaction and that acidity was the main reason. Acidity, indeed, resulted in reduction of the conversion of CO2 into formic acid and contributed to overestimate the amount of formic acid produced when the progression of the reaction was followed by a decrease in NADH absorbance (method N). Stability of NADH and the mechanism of NADH degradation was investigated by UV, NMR and by DFT calculations. It was found that by selecting neutral–basic ionic liquids and by adjusting the concentration of the ionic liquid in the buffer, the concentration of NADH can be maintained in the reaction system with little loss. Conversion of CO2 to methanol in BmimBF4 (67.1%) was more than twice as compared with the conversion attained by the enzymatic reaction in phosphate buffer (24.3%).

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A Recyclable Catalyst for Asymmetric Transfer Hydrogenation with a Formic Acid—Triethylamine Mixture in Ionic Liquid.

ChemInform ◽

10.1002/chin.200537030 ◽

2005 ◽

Vol 36 (37) ◽

Author(s):

Ikuo Kawasaki ◽

Kazuya Tsunoda ◽

Tomoko Tsuji ◽

Tomoko Yamaguchi ◽

Hiroki Shibuta ◽

...

Keyword(s):

Ionic Liquid ◽

Formic Acid ◽

Recyclable Catalyst ◽

Transfer Hydrogenation ◽

Asymmetric Transfer Hydrogenation

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Theoretical study of CO2 hydrogenation into formic acid on Lewis acid zeolites

Physical Chemistry Chemical Physics ◽

10.1039/c8cp03146k ◽

2018 ◽

Vol 20 (39) ◽

pp. 25179-25185 ◽

Cited By ~ 6

Author(s):

Worawaran Thongnuam ◽

Thana Maihom ◽

Saowapak Choomwattana ◽

Yuwanda Injongkol ◽

Bundet Boekfa ◽

...

Keyword(s):

Carbon Dioxide ◽

Density Functional Theory ◽

Formic Acid ◽

Density Functional ◽

Theoretical Study ◽

Co2 Hydrogenation ◽

Functional Theory ◽

Acid Zeolites ◽

Acidic Zeolites ◽

Hydrogenation Of Carbon Dioxide

The hydrogenation of carbon dioxide (CO2) to formic acid over Lewis acidic zeolites as catalyst has been investigated by means of density functional theory (DFT) with the M06-L functional.

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