Direct Conversion of Syngas into Methyl Acetate, Ethanol, and Ethylene by Relay Catalysis via the Intermediate Dimethyl Ether

Zhou, Wei; Kang, Jincan; Cheng, Kang; He, Shun; Shi, Jiaqing; Zhou, Cheng; Zhang, Qinghong; Chen, Junchao; Peng, Luming; Chen, Mingshu; Wang, Ye

doi:10.1002/anie.201807113

Cited by 154 publications

(127 citation statements)

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“…To further examine the reaction mechanism, we investigated the possible radicals generated during the electrocatalysis process using 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) as a spin-trapping agent [5] (Table S6). With the addition of DMPO, the formation of ethanol is evidently suppressed, implying that ethanol is generated via free radical intermediates.…”

Section: Entrymentioning

confidence: 99%

“…[4] Among them, selective and direct methanol coupling to C 2 compound, ethanol, has become extremely attractive in catalytic chemistry for both academia and industry. [5] It's accepted that the oxygen-hydrogen (OÀ H) dissociation in methanol is the more favorable than the carbonhydrogen (CÀ H) and carbon-oxygen (CÀ O) bond scissions. As a result, ethanol has generally been synthesized from methanol via a carbonylation reaction followed by a reduction process.…”

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confidence: 99%

“…Moreover, Wang' s group found that ethanol with an selectivity of 65.0 % can achieve from methanol homologation using a [RuCl 2 (CO) 3 ] 2 /Co 4 (CO) 12 bimetallic catalyst in lower reaction temperature, 160°C. [5] However, direct concerted dissociation of CÀ H and CÀ O bond in methanol to ethanol still remains a great challenge. [7] Metallic cobalt is a conventional catalyst for CÀ C coupling reactions.…”

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confidence: 99%

“…A higher ethanol selectivity 95.1 % at 20°C is achieved with methanol conversion of 257.0 g · m À 2 · h À 1 and faradic efficiency of 12.5 % than conventional methanol homologation with an ethanol selectivity of 65.0 % in 160°C. [5] The overall reaction can be expressed as Equation (1).…”

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confidence: 99%

“…Under certain potentials, the activations of both CÀ H and CÀ O bond would become possible following methanol adsorption on the surface of the electrocatalyst. [5,13] We performed electrocatalytic conversion of methanol using a series of carbon-supported Ni, Ru, Rh, Co, and Co 3 ZnC catalysts, as listed in Table 1. Fascinatingly, Co 3 ZnC/NC shows better catalytic performance for direct conversion of methanol to ethanol than the others.…”

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Direct Conversion of Methanol to Ethanol on the Metal‐Carbon Interface

Jiang

Wang

et al. 2019

ChemCatChem

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Direct conversion of one-carbon (C 1 ) compounds to two-carbon (C 2 ) and multi-carbon compounds remains a critical challenge for converting non-petroleum resources to valuable chemicals or fuels. The key issue is the selective activation of C 1 compounds, methanol, as well as the controlled formation of carbon-carbon (CÀ C) bonds. Herein, we achieve the direct electrocatalytic methanol to ethanol, an important chemical and energy candidate, with methanol conversion, ethanol selectivity, and faradic efficiency of 257.0 g · m À 2 · h À 1 , 95.1 %, and 12.5 %, respectively. Furthermore, the appropriate participation of water, as a by-product from methanol electrocatalysis, in hydrogen evolution reaction (HER) facilitates electrocatalytic reaction of methanol. Mechanistic studies reveal hydroxymethyl and methyl radicals are formed on the electropositive low-valent metal sites and electronegative carbon vacancies, respectively, and then combined with each other to form ethanol at the metal/carbon interface. This work opens a unique route for high-efficient concerted redox conversion of methanol reactant to ethanol. . In situ ESR spectra of electrocatalytic reaction systems in TCR in the presence of DMPO with or without electricity. a) Electrochemical reaction conditions were a N 2 -saturated solution of 0.147 g NaCl in 25 mL methanol containing Co 3 ZnC/NC catalyst with DMPO (cathode chamber) and that of 25 mL 0.5 M aqueous Na 2 SO 4 (anode chamber). Characterization conditions were microwave frequency of 9.44 GHz, microwave power of 20 mW, modulation frequency of 100.00 kHz; b) Reaction and characterization conditions were consistent with a) except for no addition of electricity; c) Related conditions were consistent with b except for no addition of DMPO in cathode chamber. Figure 4. Schematic illustration of Co 3 ZnC/NC catalyst for direct electrocatalytic conversion of methanol to ethanol and the plausible reaction mechanism.

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