Oxidative carbonylation of methane in the presence of Rh complexes in aqueous acetic acid

Чепайкин, Е. Г.; Boyko, Grigoriy N.; Bezruchenko, A. P.; Лещева, А. А.; Grigoryan, E. H.

doi:10.1016/s1381-1169(97)00134-9

Cited by 35 publications

(11 citation statements)

References 11 publications

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“…Further study demonstrated that both acetic acid and trifluoroacetic acid accelerated the reaction in the RhCl 3 system. 55,56 More homogeneous systems for methane conversion have been introduced in the other reviews. 38,57 It has been proved that in the homogeneous systems, production protection through the formation of methyl esters in the concentrated acid reaction medium (sulfuric or trifluoroacetic acid) is the key to realizing greatly improved methane conversion and product selectivity.…”

Section: Direct Methane Oxidation In Homogeneous Systemsmentioning

confidence: 99%

Direct Methane Conversion under Mild Condition by Thermo-, Electro-, or Photocatalysis

Meng

Cui

Rajan

et al. 2019

Chem

407

333

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Direct conversion of earth-abundant methane into value-added chemicals under mild conditions is an attractive technology in response to the increasing industrial demand of feedstocks and worldwide appeal of energy conservation. Exploring advanced low-temperature C-H activation catalysts and reaction systems is the key to converting methane in a direct and mild manner. The recently developed reaction processes operated at low-temperature thermocatalysis systems or driven in electro-and photocatalysis systems shine light on the way to achieve efficient methane conversion with much economical energy input. In this review, we summarize the typical catalytic processes employed in these reaction systems and in particular highlight the potential heterogeneous catalysts with noteworthy C-H activation performance. We also present the progress along with our perspectives on catalyst design, theoretical simulations, the choice of reaction condition, and the method of reaction product analysis to encourage more viable technology for low-temperature methane conversion in the future.

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Section: Direct Methane Oxidation In Homogeneous Systemsmentioning

confidence: 99%

Direct Methane Conversion under Mild Condition by Thermo-, Electro-, or Photocatalysis

Meng

Cui

Rajan

et al. 2019

Chem

407

333

View full text Add to dashboard Cite

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“…Chepaikin and co-workers − found that both acetic acid (HOAc) and trifluoroacetic acid (HOTFA) accelerate the reaction (compared to no added acid) in the RhCl 3 /NaCl/KI system. When the less coordinating HOTFA was used in place of perfluorobutyric acid utilized by Sen, the authors report faster catalytic rates with less selective product distribution.…”

Section: Catalytic Systems That Utilize O2/o2-regenerable Oxidants An...mentioning

confidence: 99%

Homogeneous Functionalization of Methane

et al. 2017

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One of the remaining "grand challenges" in chemistry is the development of a next generation, less expensive, cleaner process that can allow the vast reserves of methane from natural gas to augment or replace oil as the source of fuels and chemicals. Homogeneous (gas/liquid) systems that convert methane to functionalized products with emphasis on reports after 1995 are reviewed. Gas/solid, bioinorganic, biological, and reaction systems that do not specifically involve methane functionalization are excluded. The various reports are grouped under the main element involved in the direct reactions with methane. Central to the review is classification of the various reports into 12 categories based on both practical considerations and the mechanisms of the elementary reactions with methane. Practical considerations are based on whether or not the system reported can directly or indirectly utilize O as the only net coreactant based only on thermodynamic potentials. Mechanistic classifications are based on whether the elementary reactions with methane proceed by chain or nonchain reactions and with stoichiometric reagents or catalytic species. The nonchain reactions are further classified as CH activation (CHA) or CH oxidation (CHO). The bases for these various classifications are defined. In particular, CHA reactions are defined as elementary reactions with methane that result in a discrete methyl intermediate where the formal oxidation state (FOS) on the carbon remains unchanged at -IV relative to that in methane. In contrast, CHO reactions are defined as elementary reactions with methane where the carbon atom of the product is oxidized and has a FOS less negative than -IV. This review reveals that the bulk of the work in the field is relatively evenly distributed across most of the various areas classified. However, a few areas are only marginally examined, or not examined at all. This review also shows that, while significant scientific progress has been made, greater advances, particularly in developing systems that can utilize O, will be required to develop a practical process that can replace the current energy and capital intensive natural gas conversion process. We believe that this classification scheme will provide the reader with a rapid way to identify systems of interest while providing a deeper appreciation and understanding, both practical and fundamental, of the extensive literature on methane functionalization. The hope is that this could accelerate progress toward meeting this "grand challenge."

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Section: Artificial Monooxygenasesmentioning

confidence: 99%

“…In the second (slower) system, RhCl 3 , in the presence of several equivalents of Cl - and I - ions, was found to catalyze the direct functionalization of methane in the presence of carbon monoxide and dioxygen at 80−85 °C 34a. However, a much higher rate was observed in a 6:1 (v/v) mixture of perfluorobutyric acid and water, with the products being methanol and acetic acid 34b.…”

Section: Artificial Monooxygenasesmentioning

confidence: 99%

Catalytic Functionalization of Carbon−Hydrogen and Carbon−Carbon Bonds in Protic Media

1998

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Oxidative carbonylation of methane in the presence of Rh complexes in aqueous acetic acid

Cited by 35 publications

References 11 publications

Direct Methane Conversion under Mild Condition by Thermo-, Electro-, or Photocatalysis

Direct Methane Conversion under Mild Condition by Thermo-, Electro-, or Photocatalysis

Homogeneous Functionalization of Methane

Catalytic Functionalization of Carbon−Hydrogen and Carbon−Carbon Bonds in Protic Media

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