Preferential Carbon Monoxide Oxidation over Copper‐Based Catalysts under In Situ Ball Milling

Eckert, Rene; Felderhoff, Michael; Schüth, Ferdi

doi:10.1002/ange.201610501

Cited by 27 publications

(9 citation statements)

References 20 publications

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“…Further experiments were performed in a Retsch MM400 shaker mill equipped with a tungsten carbide (WC) milling jar modified for continuous gas flow reactions (inset, Figure 2A), as described in previous publications (further details are given in the SI). 21,22 Effluent gases were collected and analyzed by means of a GC-FID.…”

Section: Resultsmentioning

confidence: 99%

Methane to Chloromethane by Mechanochemical Activation: A Selective Radical Pathway

et al. 2019

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State-of-the-art processes to directly convert methane into CH3Cl are run under corrosive conditions and typically yield a mixture of chloromethanes requiring subsequent separation. We report a mechanochemical strategy to selectively convert methane to chloromethane under overall benign conditions, employing trichloroisocyanuric acid (TCCA) as a cheap and noncorrosive solid chlorinating agent. TCCA is shown to release active chlorine species upon milling with Lewis acids such as alumina and ceria to functionalize methane at moderate temperatures (<150 °C). A thorough parameter optimization led to a maximum methane chlorination rate of 0.8 μmol(CH4,conv) (g(catalyst) s)−1. Findings were compared to the thermal reaction of methane with TCCA and evidenced that mechanochemical activation permitted significantly lower reaction temperatures (90 vs 200 °C) at a drastically improved CH3Cl selectivity (95% vs 66% at 30% conversion). Considering the characterization of the interaction between TCCA and Lewis acids as well as the in-depth analysis of byproducts, we suggest a plausible reaction mechanism and a possible regeneration of the chlorinating agent.

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Section: Resultsmentioning

confidence: 99%

Methane to Chloromethane by Mechanochemical Activation: A Selective Radical Pathway

et al. 2019

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“…Other strategies to follow mechanochemical reactions include manometric real‐time monitoring to study reaction mechanisms in the mechanosynthesis of zeolitic imidazolate frameworks, [24] palladium‐catalyzed carbonylative reactions, [210] and cyclodehydrogenation reactions [211] . Complementarily, formation of volatile products in ball milling reactions has been monitored by gas chromatography (Scheme 10), [168] while online spectroscopic identification of gaseous products generated by ball milling has been achieved by nondispersive infrared spectroscopy [212,213] . On the other hand, the formation of bulk atomic and electronic structure during a mechanochemical reactions have been recently monitored by coupling X‐ray absorption spectroscopy and X‐ray diffraction, [214] and in 2020 in situ monitoring of mechanochemical reactions with solid state NMR was also described [215] …”

Section: Mechanochemistry and The Twelve Principles Of Green Chemistrymentioning

confidence: 99%

Sustainability Assessment of Mechanochemistry by Using the Twelve Principles of Green Chemistry

2021

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In recent years, mechanochemistry has been growing into a widely accepted alternative for chemical synthesis. In addition to their efficiency and practicality, mechanochemical reactions are also recognized for their sustainability. The association between mechanochemistry and Green Chemistry often originates from the solvent-free nature of most mechanochemical protocols, which can reduce waste production. However, mechanochemistry satisfies more than one of the Principles of Green Chemistry. In this Review we will present a series of examples that will clearly illustrate how mechanochemistry can significantly contribute to the fulfillment of Green Chemistry in a more holistic manner.

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“…New possibilities for heating [32][33][34] , cooling 35,36 and conducting gaseous 37,38 mechanochemical reactions are established. Furthermore, analytical techniques for in situ monitoring of the reactions are described [39][40][41][42][43][44][45] . Along with these developments, the application of mechanochemistry for the synthesis of various polyarenes has also been increasing [46][47][48][49][50][51] .…”

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Mechanochemical transformation of planar polyarenes to curved fused-ring systems

et al. 2021

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The transformation of planar aromatic molecules into π-extended non-planar structures is a challenging task and has not been realized by mechanochemistry before. Here we report that mechanochemical forces can successfully transform a planar polyarene into a curved geometry by creating new C-C bonds along the rim of the molecular structure. In doing so, mechanochemistry does not require inert conditions or organic solvents and provide better yields within shorter reaction times. This is illustrated in a 20-minute synthesis of corannulene, a fragment of fullerene C60, in 66% yield through ball milling of planar tetrabromomethylfluoranthene precursor under ambient conditions. Traditional solution and gas-phase synthetic pathways do not compete with the practicality and efficiency offered by the mechanochemical synthesis, which now opens up a new reaction space for inducing curvature at a molecular level.

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Preferential Carbon Monoxide Oxidation over Copper‐Based Catalysts under In Situ Ball Milling

Cited by 27 publications

References 20 publications

Methane to Chloromethane by Mechanochemical Activation: A Selective Radical Pathway

Methane to Chloromethane by Mechanochemical Activation: A Selective Radical Pathway

Sustainability Assessment of Mechanochemistry by Using the Twelve Principles of Green Chemistry

Mechanochemical transformation of planar polyarenes to curved fused-ring systems

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