Continuous‐Flow Hydrogenation of Carbon Dioxide to Pure Formic Acid using an Integrated scCO<sub>2</sub> Process with Immobilized Catalyst and Base

Wesselbaum, Sebastian; Hintermair, Ulrich; Leitner, Walter

doi:10.1002/anie.201203185

Cited by 176 publications

(89 citation statements)

References 26 publications

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“…Our findings are different from the literature reports on electrochemical reduction of CO 2 , which have showed that HCO 3 − was much easier to be reduced than aqueous dissolved CO 2 or CO 3 2− because protonation of CO 2 in ambient liquid water could significantly diminish the redox potential by 1 order of magnitude. 22,23 We think that the unique properties of subcritical water may overcome the barrier of the protonation of CO 3 2− to HCO 3 − . With a less extensive hydrogen-bond network, subcritical water is less capable of accepting the ejected proton than ambient liquid water.…”

Section: ■ Results and Discussioncontrasting

confidence: 85%

Simultaneously Converting Carbonate/Bicarbonate and Biomass to Value-added Carboxylic Acid Salts by Aqueous-phase Hydrogen Transfer

Yang

et al. 2014

ACS Sustainable Chem. Eng.

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A novel approach to coproduce value-added carboxylic acids has been developed via a "one-pot" aqueous-phase hydrogen transfer (APHT) process, in which hydrogen in biomass molecules is transferred to carbonate/ bicarbonate ions over supported noble metal nanocatalysts. In mild hydrothermal media, a variety of biomass derived alcohols or polyols have been efficiently converted to carboxylic acids, while simultaneously, formates have been obtained from the reduction of carbonates/bicarbonate salts without using external H 2 . In an APHT process at the optimized reaction conditions, a high yield of lactate, ∼55%, was achieved using glycerol as the hydrogen donor, and simultaneously, ∼30% of formate was produced by the reduction of sodium bicarbonates over the Pd on a carbon catalyst. The catalyst was stable after three-time consecutive reuse without regeneration, and the possible APHT reaction mechanism was proposed.

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Section: ■ Results and Discussioncontrasting

confidence: 85%

Simultaneously Converting Carbonate/Bicarbonate and Biomass to Value-added Carboxylic Acid Salts by Aqueous-phase Hydrogen Transfer

Yang

et al. 2014

ACS Sustainable Chem. Eng.

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“…The synthesis of FA via hydrogenation of carbon dioxide in the presence of trihexylamine has previously been reported . Using this synthetic route, the presence of a base is required for the reaction to be thermodynamically favorable, and, as a result, a variety of tertiary amines have been explored . BASF has also patented a number of synthetic routes to FA utilizing tertiary amines .…”

Section: Resultsmentioning

confidence: 99%

Identification of two novel trace impurities in mobile phases prepared with commercial formic acid

Bakota

Levine

2020

Rapid Comm Mass Spectrometry

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Rationale While liquid chromatography/high‐resolution mass spectrometry (LC/HRMS) is a versatile analytical technique, it is also sensitive to trace impurities. These impurities may come from a variety of sources, including reagents, solvents, and the sample matrix itself. Impurities in reagents may become concentrated and elute as peaks when a gradient method is used, and these peaks may cause suppression of peaks of interest both in the electrospray source, as well as in the C‐trap in systems that contain one. Methods We observed a notable increase in the size of several impurity peaks in a reversed‐phase gradient method upon switching suppliers of formic acid. We used LC/HRMS to separate and fragment these impurity compounds and assign probable formulae. Results The mass spectra were compared with those of compounds found in the literature with the same formulae, and the observed peaks were matched to two amine compounds not previously reported as impurities in LC/MS systems: trihexylamine and N‐methyldihexylamine. The identities were confirmed by high‐resolution accurate mass and retention time matching against commercially available standards of these compounds. Conclusions To the best of our knowledge, this is the first time that trihexylamine and N‐methyldihexylamine have been reported in such systems. We hypothesize that these are derived from the formic acid manufacturing process and recommend that users monitor purchased formic acid for the presence of impurities.

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“…An enhancement in the economic viability of a chemical process is directly related to the development of highly selective and easily recyclable new catalytic systems. In this sense, the Leitner group recently reported an elegant process that allows the continuous‐flow hydrogenation of supercritical CO 2 with integrated formic acid separation from a heterogeneous catalytic system based on Ru II active species 36…”

Section: Catalytic Processesmentioning

confidence: 99%

CO₂ Activation and Catalysis Driven by Iridium Complexes

et al. 2013

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Recent reports on homogeneous catalytic transformation of carbon dioxide by iridium complexes have prompted us to review the area. Progress on new iridium catalysts for carbon dioxide transformations should take into account the interaction of carbon dioxide with the iridium center, which seems to be governed by the oxidation state of iridium and the nature of the carbon dioxide molecule. Most examples of iridium catalyzed carbon dioxide reductions are based on IrIII centers. These reactions take place through outer‐sphere mechanisms, by means of nucleophilic attack on the carbon atom. In all the reported systems, the nucleophile is always a hydrido ligand coordinated to a IrIII center. Future challenges on iridium catalyzed functionalization of carbon dioxide include the development of efficient electrophiles, compatible with the inclusion of appropriate nucleophiles, which would allow the preparation of value‐added organic molecules using CO2 as C1 feedstock.

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Continuous‐Flow Hydrogenation of Carbon Dioxide to Pure Formic Acid using an Integrated scCO₂ Process with Immobilized Catalyst and Base

Cited by 176 publications

References 26 publications

Simultaneously Converting Carbonate/Bicarbonate and Biomass to Value-added Carboxylic Acid Salts by Aqueous-phase Hydrogen Transfer

Simultaneously Converting Carbonate/Bicarbonate and Biomass to Value-added Carboxylic Acid Salts by Aqueous-phase Hydrogen Transfer

Identification of two novel trace impurities in mobile phases prepared with commercial formic acid

CO₂ Activation and Catalysis Driven by Iridium Complexes

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Continuous‐Flow Hydrogenation of Carbon Dioxide to Pure Formic Acid using an Integrated scCO2 Process with Immobilized Catalyst and Base

Cited by 176 publications

References 26 publications

Simultaneously Converting Carbonate/Bicarbonate and Biomass to Value-added Carboxylic Acid Salts by Aqueous-phase Hydrogen Transfer

Simultaneously Converting Carbonate/Bicarbonate and Biomass to Value-added Carboxylic Acid Salts by Aqueous-phase Hydrogen Transfer

Identification of two novel trace impurities in mobile phases prepared with commercial formic acid

CO2 Activation and Catalysis Driven by Iridium Complexes

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Continuous‐Flow Hydrogenation of Carbon Dioxide to Pure Formic Acid using an Integrated scCO₂ Process with Immobilized Catalyst and Base

CO₂ Activation and Catalysis Driven by Iridium Complexes