Preferential activation of CO near hydrocarbon chains during Fischer–Tropsch synthesis on Ru

Hibbitts, David; Dybeck, Eric; Lawlor, Thomas; Neurock, Matthew; Iglesia, Enrique

doi:10.1016/j.jcat.2016.01.010

Cited by 60 publications

(133 citation statements)

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“…The experimentally measured CO consumption rate reported by Iglesia et al show that the rates increase linearly with increasing hydrogen pressure and decrease linearly with CO [6,8,9]. The results suggest that CO covers the surface where KPCO >>1 and the rate can be well-modeled by equation ( 6) [6,8,9,10]. The elementary steps used to derive equation 6 are shown in Figure (1-a).…”

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confidence: 91%

“…That these models may be a better representation of the metal nanoparticles which catalyze FTS is suggested by kinetic studies which indicate that the CO consumption rate is of negative order in CO, indicating that CO is the most abundant surface intermediate (MASI) under reaction conditions. [6,8,9,10,14,17]. Additionally, recent studies have…”

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confidence: 99%

“…Recent kinetic and theoretical studies have shown that CO* is likely activated through hydrogen assisted pathways during FTS on Ru and Co catalysts [6,8,9,10] where hydrogen is first added to CO*. The addition of hydrogen to CO transfers electrons into the antibonding 2* states on CO*.…”

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confidence: 99%

“…More recent studies have used curved Ru201 cubooctahedral particles to study C-O activation at CO* coverages of 1 ML [8,9,10]. That these models may be a better representation of the metal nanoparticles which catalyze FTS is suggested by kinetic studies which indicate that the CO consumption rate is of negative order in CO, indicating that CO is the most abundant surface intermediate (MASI) under reaction conditions.…”

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confidence: 99%

“…DFT studies at high CO* coverage on such particles have shown that of the different coordinated Ru atoms present on the cubooctahedral particle (CN 6-9) that the Ru atoms with higher coordination number which represent the Ru atoms on the lowindex face of the (111) terrace are able to activate CO most easily. The reason the Ru atoms on the (111) terrace sites are most active for C-O activation during FTS is because the CO* is bound least strongly at those sites and is more likely to desorb from those sites forming "a vacancy" next to a vicinal CO* which can subsequently be activated by H2 [6,8,9,10].…”

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Theoretical Insights on Chain Growth Mechanisms in Fischer-Tropsch Synthesis at High CO Coverage on Ru Particles

Lawlor¹

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The global demand for energy is projected to increase by over 70% by 2050 [43] . Such demands coupled with decreasing oil reserves will ultimately require sustainable strategies for the production of clean fuels. Fischer Tropsch Synthesis (FTS) is a well-established industrial process that can be used to convert syngas derived from emerging energy sources such as natural gas and biomass feedstocks into fuels and chemicals [1,2,3,4]. FTS involves the activation of CO in the presence of hydrogen to form hydrocarbon monomers that subsequently polymerize to form nalkanes, 1-alkenes, aldehydes and alcohols. The reaction is typically carried out on group VIII metals including Fe, Co, Ru, Rh and Ni favorable than CO insertion, the kinetics associated with the probability of CHx intermediates finding one another in the dense CO adlayer may limit such paths.

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confidence: 91%

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confidence: 99%

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Theoretical Insights on Chain Growth Mechanisms in Fischer-Tropsch Synthesis at High CO Coverage on Ru Particles

Lawlor¹

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Oxide Supported Cobalt Catalysts for CO₂ Hydrogenation to Hydrocarbons: Recent Progress

Scarfiello

Minh

Soulantica

et al. 2023

Adv Materials Inter

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Carbon capture and utilization represents a promising strategy to meet the global energy and climate goals. Under specific conditions, CO2 catalytic hydrogenation with renewable H2 can transform waste CO2 into a chemical feedstock for added‐value energy carriers and chemicals. CO2‐Fischer–Tropsch synthesis‐based‐hydrocarbons should contribute to the creation of a circular carbon economy with a significant impact on anthropogenic emission into the atmosphere. This review summarizes the progress achieved toward the single‐step hydrogenation of CO2 to long‐chain hydrocarbons over oxide‐supported Co‐based catalysts. Mechanistic aspects are discussed in relation to thermodynamic and kinetic limitations. The main parameters that must be taken into consideration to increase the activity and the selectivity toward compounds of two or more carbon atoms (C2+) are discussed in detail: cobalt active phase, support and metal‐support interfaces, and promoters. Finally, particular focus is dedicated to the role of reducible oxide supports and their surface defects on the activation of CO2, as well as on the regulation and evolution of metal‐support interactions.

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Supra‐monolayer coverages on small metal clusters and their effects on H₂ chemisorption particle size estimates

Almithn

Hibbitts

2018

AIChE Journal

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H 2 chemisorption measurements are used to estimate the size of supported metal particles, often using a hydrogen-tosurface-metal stoichiometry of unity. This technique is most useful for small particles whose sizes are difficult to estimate through electron microscopy or X-ray diffraction. Undercoordinated metal atoms at the edges and corners of particles, however, make up large fractions of small metal clusters, and can accommodate multiple hydrogen atoms leading to coverages which exceed 1 ML (supra-monolayer). Density functional theory was used to calculate hydrogen adsorption energies on Pt and Ir particles (38-586 atoms, 0.8-2.4 nm) at high coverages (3.63 ML). Calculated differential binding energies confirm that Pt and Ir (111) single-crystal surfaces saturate at 1 ML; however, Pt and Ir clusters saturate at supra-monolayer coverages as large as 2.9 ML. Correlations between particle size and saturation coverage are provided that improve particle size estimates from H 2 chemisorption for Pt-group metals.

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Preferential activation of CO near hydrocarbon chains during Fischer–Tropsch synthesis on Ru

Abstract: 2016-11-03T14:11:40

Cited by 60 publications

References 50 publications

Theoretical Insights on Chain Growth Mechanisms in Fischer-Tropsch Synthesis at High CO Coverage on Ru Particles

Theoretical Insights on Chain Growth Mechanisms in Fischer-Tropsch Synthesis at High CO Coverage on Ru Particles

Oxide Supported Cobalt Catalysts for CO₂ Hydrogenation to Hydrocarbons: Recent Progress

Supra‐monolayer coverages on small metal clusters and their effects on H₂ chemisorption particle size estimates

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Preferential activation of CO near hydrocarbon chains during Fischer–Tropsch synthesis on Ru

Abstract: 2016-11-03T14:11:40

Cited by 60 publications

References 50 publications

Theoretical Insights on Chain Growth Mechanisms in Fischer-Tropsch Synthesis at High CO Coverage on Ru Particles

Theoretical Insights on Chain Growth Mechanisms in Fischer-Tropsch Synthesis at High CO Coverage on Ru Particles

Oxide Supported Cobalt Catalysts for CO2 Hydrogenation to Hydrocarbons: Recent Progress

Supra‐monolayer coverages on small metal clusters and their effects on H2 chemisorption particle size estimates

Contact Info

Product

Resources

About

Oxide Supported Cobalt Catalysts for CO₂ Hydrogenation to Hydrocarbons: Recent Progress

Supra‐monolayer coverages on small metal clusters and their effects on H₂ chemisorption particle size estimates