Spectroscopic insights into cobalt-catalyzed Fischer-Tropsch synthesis: A review of the carbon monoxide interaction with single crystalline surfaces of cobalt

Weststrate, C.J.; Loosdrecht, J. van de; Niemantsverdriet, J.W.

doi:10.1016/j.jcat.2016.07.010

Cited by 86 publications

(125 citation statements)

References 72 publications

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“…The reference spectra depicted in Figure 6a relate to an initially clean Co surface. Without co-adsorbates, the CO band appears at ñ = 1996 cm À1 at the lowest CO coverage, which shifts to ñ = 2018 cm À1 with increasing coverage (final CO pressure: 10 mbar).O nt he basis of the IR results of CO adsorption on a Co(0 001)s ingle crystal by Weststrate et al, [23] we estimate the CO coverage to be 0.35 ML. In good agreement with this, we determined the total CO coverage and the reversibly adsorbed CO coverage of 0.38 and 0.31 ML at aC Op artial pressure of 15 mbar by Ne!…”

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confidence: 82%

Mechanism of Carbon Monoxide Dissociation on a Cobalt Fischer–Tropsch Catalyst

et al. 2017

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The way in which the triple bond in CO dissociates, a key reaction step in the Fischer–Tropsch (FT) reaction, is a subject of intense debate. Direct CO dissociation on a Co catalyst was probed by 12C16O/13C18O scrambling in the absence and presence of H2. The initial scrambling rate without H2 was significantly higher than the rate of CO consumption under CO hydrogenation conditions, which indicated that the surface contained sites sufficiently reactive to dissociate CO without the assistance of H atoms. Only a small fraction of the surface was involved in CO scrambling. The minor influence of CO scrambling and CO residence time on the partial pressure of H2 showed that CO dissociation was not affected by the presence of H2. The positive H2 reaction order was correlated to the fact that the hydrogenation of adsorbed C and O atoms was slower than CO dissociation. Temperature‐programmed in situ IR spectroscopy underpinned the conclusion that CO dissociation does not require H atoms.

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confidence: 82%

Mechanism of Carbon Monoxide Dissociation on a Cobalt Fischer–Tropsch Catalyst

et al. 2017

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“…Ad ecomposition of the DRIFTS bands was carried out to determine the contribution of bridged species (Supporting Information, Figure S4). Themolar fractions of linear and hollow-CO could be determined from the proportion of hollow-CO DRIFTS bands (Supporting Information, Figure S4), taking into account that the molar absorption coefficient of linear CO is twice as high as that of hollow-CO. [30] Thes pecific concentrations of reversibly adsorbed CO over each of the samples were determined through isotopic exchange under reaction conditions at 220 8 8C. According to Weststrate et al, [30] this band can be assigned to CO adsorbed on hollow sites (thereafter noted "hollow-CO").…”

Section: Angewandte Chemiementioning

confidence: 99%

“…A single band located at about 1860 cm À1 was sufficient to satisfactory represent the DRIFTS signal in this region. According to Weststrate et al, [30] this band can be assigned to CO adsorbed on hollow sites (thereafter noted "hollow-CO"). Themolar fractions of linear and hollow-CO could be determined from the proportion of hollow-CO DRIFTS bands (Supporting Information, Figure S4), taking into account that the molar absorption coefficient of linear CO is twice as high as that of hollow-CO. [30] Thes pecific concentrations of reversibly adsorbed CO over each of the samples were determined through isotopic exchange under reaction conditions at 220 8 8C.…”

Section: Angewandte Chemiementioning

confidence: 99%

“…According to Weststrate et al, [30] this band can be assigned to CO adsorbed on hollow sites (thereafter noted "hollow-CO"). Themolar fractions of linear and hollow-CO could be determined from the proportion of hollow-CO DRIFTS bands (Supporting Information, Figure S4), taking into account that the molar absorption coefficient of linear CO is twice as high as that of hollow-CO. [30] Thes pecific concentrations of reversibly adsorbed CO over each of the samples were determined through isotopic exchange under reaction conditions at 220 8 8C. Ty pical normalized exchange plots obtained during the exchange 12 CO- 13 CO are shown in the Supporting Information, Figure S5 and the results are gathered in Table 1.…”

Section: Angewandte Chemiementioning

confidence: 99%

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CO Hydrogenation on Cobalt‐Based Catalysts: Tin Poisoning Unravels CO in Hollow Sites as a Main Surface Intermediate

et al. 2017

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Site poisoning is a powerful method to unravel the nature of active sites or reaction intermediates. The nature of the intermediates involved in the hydrogenation of CO was unraveled by poisoning alumina-supported cobalt catalysts with various concentrations of tin. The rate of formation of the main reaction products (methane and propylene) was found to be proportional to the concentration of multi-bonded CO, likely located in hollow sites. The specific rate of decomposition of these species was sufficient to account for the formation of the main products. These hollow-CO are proposed to be main reaction intermediates in the hydrogenation of CO under the reaction conditions used here, while linear CO are mostly spectators.

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“…Methanol synthesis by carbon monoxide (CO) and carbon dioxide (CO 2 ) hydrogenation has been widely studied both experimentally and theoretically [1][2][3][4][5][6] because methanol is an important raw material of crucial importance in the chemical and energy industries.…”

Section: Introductionmentioning

confidence: 99%

Conversion of Carbon Monoxide into Methanol on Alumina-Supported Cobalt Catalyst: Role of the Support and Reaction Mechanism—A Theoretical Study

Hà¹,

Ha²,

Long³

et al. 2018

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Density functional theory (DFT) was used to calculate the step-by-step hydrogenation of carbon monoxide (CO) to form methanol over a Co4 cluster/Al2O3 surface. A three-dimensional Co4 tetrahedral structure was selected to explore its interaction with the supporting Al2O3 (104) surface. Co4 chemically reacted with Al2O3 to form a new chemical system. The calculated results show that Al2O3 support has strengthened the Co4 catalyst during the reaction since the formation of the Co–O bond. Loading Co4 on the Al2O3 surface increases CO adsorption ability but decreases the dissociation ability of C–O to produce hydrocarbons. As such, CH3OH formation becomes more favorable both kinetically and thermodynamically on Co4/Al2O3. In CO hydrogenation, methanol was synthesized through a CO reaction with hydrogen via either an Eley–Rideal or Langmuir–Hinshelwood pathway to form the intermediates C*-O-H, H-C*-OH, H2-C*-OH, and finally the hydrogenation of H2-C*-OH to methanol with both hydrogenation steps forming C*-OH and final product as rate-limiting. These results showed that the interaction between Co, Al2O3 and H2 pressure can change the pathway of CO hydrogenation on Co/Al2O3 and it may, therefore, influence distribution of the final products.

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Spectroscopic insights into cobalt-catalyzed Fischer-Tropsch synthesis: A review of the carbon monoxide interaction with single crystalline surfaces of cobalt

Cited by 86 publications

References 72 publications

Mechanism of Carbon Monoxide Dissociation on a Cobalt Fischer–Tropsch Catalyst

Mechanism of Carbon Monoxide Dissociation on a Cobalt Fischer–Tropsch Catalyst

CO Hydrogenation on Cobalt‐Based Catalysts: Tin Poisoning Unravels CO in Hollow Sites as a Main Surface Intermediate

Conversion of Carbon Monoxide into Methanol on Alumina-Supported Cobalt Catalyst: Role of the Support and Reaction Mechanism—A Theoretical Study

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