Design and synthesis of spherical-platelike ternary copper-cobalt-manganese catalysts for direct conversion of syngas to ethanol and higher alcohols

Sun, Kai; Tan, Min‐Yu; Bai, Yunxing; Gao, Xiaofeng; Wang, Peng; Gong, Nana; Zhang, Tao; Yang, Guohui

doi:10.1016/j.jcat.2019.08.013

Cited by 59 publications

(46 citation statements)

References 66 publications

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“…[24] In addition, the peaks located at 780.4 eV over all the catalysts can be attributed to the presence of CoO. [18,37] Moreover, the BE of Al 2p at about 74 eV was observed (Figure S4c), verifying the existence of Al 2 O 3 . [22] Hence, the XPS results were in accordance with the XRD and TEM characterization results.…”

Section: Catalyst Characterizationmentioning

confidence: 89%

“…[32] The diffraction peaks at 2θ of 30.3°, 35.2°, 50.4°, 50.6°and 60.1°were ascribed to tetragonal ZrO 2 crystal phase (JCPDS # 80-2155, t-ZrO 2 ). [32] For the CuCoAl samples (Figure 1a), the diffraction peaks at 2θ of 18 The XRD patterns of the reduced catalysts are presented in Figure 1b. For the reduced CuCoAl j t-ZrO 2 and CuCoAl j m-ZrO 2 catalysts, the tetragonal and monoclinic ZrO 2 crystal phases were maintained the same, suggesting that the ZrO 2 crystal phase structure did not change after reduction.…”

Section: Catalyst Characterizationmentioning

confidence: 99%

“…[48] The dual active sites were generally demanded for CuCobased catalysts, where cobalt active site acts for CO dissociation to form surface alkyl species (CH x ) and carbon chain growth, while copper active site functions for CO non-dissociation adsorption and subsequent insertion into alkyl species to form acyl intermediates (CH x CO). [18,19] Afterwards, the acyl intermediates can be further hydrogenated to generate higher alcohols. [18,19] Thus, the lower surface [H*]/[C*] ratio for the CuCoAl j t-ZrO 2 could inhibit the hydrogenation reaction of surface alkyl (CH x ) species to form CH 4 and light hydrocarbons, thereby facilitating CO inserting into the CH x species to increase the ROH selectivity.…”

Section: Chemisorption Behaviors Of Co and Hmentioning

confidence: 99%

“…[18,19] Afterwards, the acyl intermediates can be further hydrogenated to generate higher alcohols. [18,19] Thus, the lower surface [H*]/[C*] ratio for the CuCoAl j t-ZrO 2 could inhibit the hydrogenation reaction of surface alkyl (CH x ) species to form CH 4 and light hydrocarbons, thereby facilitating CO inserting into the CH x species to increase the ROH selectivity. Besides, Li et al [49] showed that lower H 2 /CO ratio could effectively promote the carbon chain growth to form heavier products.…”

Section: Chemisorption Behaviors Of Co and Hmentioning

confidence: 99%

“…Subsequently, the acyl intermediates can be further hydrogenated to form higher alcohols. [18,19] Therefore, obtaining uniform distribution of Cu and Co species to strengthen the synergetic catalysis is considered to be indispensable in HAS. For CuCo-based catalysts, Al 2 O 3 has been widely used as support to stabilize and disperse the active components and improve the alcohols selectivity.…”

Section: Introductionmentioning

confidence: 99%

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Direct Conversion of Syngas to Higher Alcohols over a CuCoAl|t‐ZrO₂ Multifunctional Catalyst

et al. 2021

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Selective synthesis of higher alcohols from syngas is promising but remains challenging owing to the low stability and selectivity towards higher alcohols. Here we introduce a CuCoAl j t-ZrO 2 (t denotes tetragonal crystal phase) multifunctional catalyst that can achieve an alcohol selectivity of 64.8 % with 79.6 % C 2 + OH, and a total selectivity of alcohols and olefins to 81.7 %. The proper proximity was tuned to increase selectivity towards alcohols and decrease the selectivity towards hydrocarbons. The lower surface [H*]/[C*] ratio due to the stronger basic sites of the CuCoAl j t-ZrO 2 limited alkyl (CH x ) species hydrogenation, and promoted CO insertion and carbon chain growth, resulting in improving the alcohols selectivity. Meanwhile, the weaker adsorption of bridge-type adsorbed CO and the lower decomposition rate of multi-bonded adsorbed CO over CuCoAl j t-ZrO 2 inhibited hydrocarbon generation. The selective promotion of the reaction route via the synergetic effect between CuCoAl and t-ZrO 2 was proposed to boost higher alcohols selectivity. This work may aid the rational design of effective multifunctional catalyst with synergistic effects for tuning selectivity.

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Section: Catalyst Characterizationmentioning

confidence: 89%

Section: Catalyst Characterizationmentioning

confidence: 99%

Section: Chemisorption Behaviors Of Co and Hmentioning

confidence: 99%

Section: Chemisorption Behaviors Of Co and Hmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Direct Conversion of Syngas to Higher Alcohols over a CuCoAl|t‐ZrO₂ Multifunctional Catalyst

et al. 2021

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High‐pressure CO, H₂, CO₂ and Ethylene Pulses Applied in the Hydrogenation of CO to Higher Alcohols over a Bulk Co‐Cu Catalyst

et al. 2022

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The reaction pathways of higher alcohol synthesis over a bulk CoÀ Cu catalyst (Co : Cu = 2 : 1) were investigated by applying high-pressure pulse experiments as a surface-sensitive operando method at 280 °C and 60 bar. Using high-pressure CO and H 2 pulses in a syngas flow with a H 2 :CO ratio of 1, it was shown that the surface of the working 2CoCu catalyst is saturated with adsorbed CO, but not with adsorbed atomic hydrogen, because only the H 2 pulses increased the yields of all alcohols and alkanes. The reverse water gas shift reaction (WGSR) was investigated by pulsing CO 2 . The CO 2 pulses poisoned the formation of methanol, ethanol, and 1-propanol, and the absence of significant CO and H 2 O responses indicates that the WGSR is not efficiently catalyzed by the applied 2CoCu catalyst excluding the presence of exposed Cu 0 sites. A series of ethylene pulses showed that when a threshold mole fraction of ethylene of about 1 vol % is surpassed, 2CoCu is an active catalyst for the hydroformylation of ethylene to 1-propanol pointing to the presence of highly coordinatively unsaturated Co sites.

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Sustainable Aviation Fuel from Syngas through Higher Alcohols

et al. 2022

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The current review critically summarizes recent developments in transformations of syngas to higher alcohols. Although higher alcohols have found applications as fuel additives, detergents and plastics for a long while, transformation of alcohols to jet fuel has attained recent interest due to an urgent need to develop jet fuels from sustainable sources. Fermentation of lignocellulosic‐based sugars to ethanol as a technology does not compete with the food chain supply being thus a potentially acceptable route if economically viable. An alternative method is to gasify biomass to produce syngas, which can further be transformed to higher alcohols through several pathways. Jet fuel range alkanes are obtained from alcohols via oligomerisation, dehydration and hydrogenation. The highest space time yields of higher alcohols of 0.61 g/(gcath) is obtained over a bimetallic copper‐iron catalyst supported on a hierarchical zeolite at 300 °C and 5 MPa. Furthermore, copper‐cobalt and cobalt‐manganese compositions are promising for the direct synthesis of higher alcohols from syngas, where one of the challenges is to suppress formation of alkanes and CO2 and increase selectivity to higher alcohols. From the mechanistic point of view, it has been proposed to use dual‐site catalysts, where one site promotes hydrogenation, while the other site is required for the chain growth. In addition to selection of the optimum reaction conditions and catalyst properties, kinetic modelling, thermodynamics and scale up issues are discussed.

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Design and synthesis of spherical-platelike ternary copper-cobalt-manganese catalysts for direct conversion of syngas to ethanol and higher alcohols

Cited by 59 publications

References 66 publications

Direct Conversion of Syngas to Higher Alcohols over a CuCoAl|t‐ZrO₂ Multifunctional Catalyst

Direct Conversion of Syngas to Higher Alcohols over a CuCoAl|t‐ZrO₂ Multifunctional Catalyst

High‐pressure CO, H₂, CO₂ and Ethylene Pulses Applied in the Hydrogenation of CO to Higher Alcohols over a Bulk Co‐Cu Catalyst

Sustainable Aviation Fuel from Syngas through Higher Alcohols

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Design and synthesis of spherical-platelike ternary copper-cobalt-manganese catalysts for direct conversion of syngas to ethanol and higher alcohols

Cited by 59 publications

References 66 publications

Direct Conversion of Syngas to Higher Alcohols over a CuCoAl|t‐ZrO2 Multifunctional Catalyst

Direct Conversion of Syngas to Higher Alcohols over a CuCoAl|t‐ZrO2 Multifunctional Catalyst

High‐pressure CO, H2, CO2 and Ethylene Pulses Applied in the Hydrogenation of CO to Higher Alcohols over a Bulk Co‐Cu Catalyst

Sustainable Aviation Fuel from Syngas through Higher Alcohols

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Direct Conversion of Syngas to Higher Alcohols over a CuCoAl|t‐ZrO₂ Multifunctional Catalyst

Direct Conversion of Syngas to Higher Alcohols over a CuCoAl|t‐ZrO₂ Multifunctional Catalyst

High‐pressure CO, H₂, CO₂ and Ethylene Pulses Applied in the Hydrogenation of CO to Higher Alcohols over a Bulk Co‐Cu Catalyst