Size effect of the carbon-supported bimetallic Fe-Co nanoparticles on the catalytic activity in the Fischer-Tropsch synthesis

Васильев, А. А.; Иванцов, М. И.; Dzidziguri, É. L.; Ефимов, М. Н.; Муратов, Д. Г.; Куликова, М. В.; Zhilyaeva, N. A.; Карпачева, Г. П.

doi:10.1016/j.fuel.2021.122455

Cited by 17 publications

(6 citation statements)

References 46 publications

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“…Small Fe nanoparticles, however, exhibit a lower chain growth probability and a higher CH 4 selectivity (Figure a). Vasilev et al has demonstrated that smaller FeCo nanoparticles could achieve the maximum selectivity toward C 5+ hydrocarbons at lower reaction temperatures, with the catalyst having an average particle size of 10 nm being the most active. However, a comprehensive understanding of the size-dependent catalytic activity and product selectivity remains challenging due to the interference of other factors, such as metal–support interaction, promoters and carbide-to-carbide transition during ther FTS reaction.…”

Section: Steering the Structural Evolution: The Role Of Catalyst Designmentioning

confidence: 99%

An Overview on Dynamic Phase Transformation and Surface Reconstruction of Iron Catalysts for Catalytic Hydrogenation of CO_x for Hydrocarbons

Ding,

Zhu,

Sun

et al. 2024

ACS Catal.

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Catalytic hydrogenation of CO x (CO and CO 2 ) with renewable H 2 represents a feasible practice for carbon capture and utilization and synthesis of chemical commodities, such as olefins, aromatics, and higher alcohols as well as liquid fuels. Direct synthesis via Fischer−Tropsch Synthesis (FTS) is considered as one of the most promising processes. Ironbased catalysts have been recognized as efficient candidates for catalytic hydrogenation of both CO and CO 2 to value-added hydrocarbons due to their superior activities for C−O bond dissociative activation, reverse/water gas shift reaction, and C−C chain growth. The structural complexity and dynamic evolution of iron-based catalysts under CO x -FTS conditions impose challenges on the understanding of the reaction mechanisms, the dynamic structure of active sites and further improvements of the catalytic performance. In this Review, we discussed the recent developments in characterization techniques for identifying the structural evolution of iron-based catalysts under reaction conditions. We also summarized feasible strategies to manipulate the process of the structural change via promoter interfacing, catalyst pretreating protocols, and application of external physical fields. Finally, we concluded the review by identifying current challenges and opportunities for the next generation of CO x catalytic hydrogenation process with an emphasis on the combinatorial contributions from in situ/operando characterizations, chemometrics and machine learning.

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Section: Steering the Structural Evolution: The Role Of Catalyst Designmentioning

confidence: 99%

An Overview on Dynamic Phase Transformation and Surface Reconstruction of Iron Catalysts for Catalytic Hydrogenation of CO_x for Hydrocarbons

Ding,

Zhu,

Sun

et al. 2024

ACS Catal.

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“…The structure–reactivity relationship of metal nanoparticles (NPs) remains a topic at the forefront of research in hydrogenation catalysis − since both activity and selectivity are often sensitive to the particle size, shape, and surface structure. − A prominent example is CO/CO 2 hydrogenation over Co catalysts, where the turnover frequency has been found to increase with Co particle size but becomes steady above ca. 10 nm. − The diminished hydrogenation efficiency of small Co NPs was attributed to CO-induced surface reconstruction, a larger fraction of corner and edge sites being irreversibly blocked by CO, and a higher propensity for Co oxidation by water under Fischer–Tropsch synthesis (FTS) conditions, for example. − These effects could reduce the number of step-edge sites that can efficiently catalyze CO dissociation on small Co nanoparticles, which is thought to be the key step in FTS in general …”

Section: Introductionmentioning

confidence: 99%

Size-Dependent Hydrogenation Activity of Cobalt Nanoparticles

Yang,

Goldbach,

Wei

et al. 2024

ACS Catal.

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Cobalt nanoparticles are widely used as hydrogenation catalysts but the chemical nature of the particle size effect in hydrogenation reactions remains a matter of debate. Here, the hydrogenation activity of 3.5−40 nm large Co particles supported on C 3 N 4 was probed employing acetone hydrogenation because two distinctive acetone conversion pathways exist: its direct hydrogenation to isopropanol and alternatively, its initial dehydration to mesityl oxide and subsequent hydrogenation to methyl isobutyl ketone. The acetone hydrogenation turnover frequency per Co surface atom increased with Co particle size up to 40 nm. In contrast, the acetone conversion rates were an order of magnitude smaller and declined with increasing particle size in the absence of H 2 . Moreover, only particles larger than ∼10 nm converted a 1:1 H 2 /acetone feed efficiently to isopropanol (>90%) between 150 and 250 °C. Acetone dehydration to mesityl oxide was increasingly favored on the smaller Co particles. Interestingly, the subsequent hydrogenation of mesityl oxide to methyl isobutyl ketone exhibited a Co particle size dependence analogous to isopropanol formation, while the secondary dehydration of isopropanol to propene was rather insensitive to the particle size. H−D exchange experiments demonstrated that H 2 activation via dissociative adsorption was increasingly retarded with decreasing Co particle size. Conversely, acetone activation became more difficult with increasing particle size according to its in parallel diminishing dehydration rate in the absence of H 2 . Hence, the activation of H 2 on the metal particles has to play a key role in the Co particle size dependence of acetone hydrogenation.

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“…Co/Fe-based supported catalysts are used in a wide range of reactions to produce sustainable fuels, such as hydrogenation of CO2 to olefins, [1] reforming of biomass to syngas, [2,3] hydrodeoxygenation (HDO) of bio-oils, [4] and Fischer-Tropsch synthesis. [5] The activity for these reactions is a function of textural, morphological and electronic characteristics of the catalyst. [6] Preparation techniques and pretreatment play an important role in improving these properties.…”

Section: Introductionmentioning

confidence: 99%

“…Co/Fe‐based supported catalysts are used in a wide range of reactions to produce sustainable fuels, such as hydrogenation of CO2 to olefins, [1] reforming of biomass to syngas, [2,3] hydrodeoxygenation (HDO) of bio‐oils, [4] and Fischer‐Tropsch synthesis [5] …”

Section: Introductionmentioning

confidence: 99%

Towards a Correlation Between Iron/Cobalt Content, Support Pore Size and Metal Particle Size in Supported Catalysts

Battiston,

Oliveira,

Lião

et al. 2023

ChemNanoMat

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Fe−Co‐based catalysts supported on γ‐Al2O3, Aerosil 200 silica and zeolite 4A were prepared by co‐precipitation of the respective nitrates in the presence of ammonium hydroxide. The objective was to demonstrate the influence of Fe/Co mass ratio and support pore size on metal particle size. Catalysts were characterized by thermogravimetric analysis (TGA), X‐ray diffraction (XRD), N2 physisorption, Fourier‐transformed infrared spectroscopy (FTIR), and scanning (SEM) and transmission (TEM) microscopies. It was demonstrated that the minimal presence of Fe was enough to reduce the average particle diameters by half. Increasing Fe content did not cause proportional decreases in the average particle diameter. The support pore diameter probably played a role in the crystallization step of bimetallic and Fe monometallic catalysts, whose particle diameters were similar to those observed for the pores. This phenomenon was not observed for Co monometallic catalysts.

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Size effect of the carbon-supported bimetallic Fe-Co nanoparticles on the catalytic activity in the Fischer-Tropsch synthesis

Cited by 17 publications

References 46 publications

An Overview on Dynamic Phase Transformation and Surface Reconstruction of Iron Catalysts for Catalytic Hydrogenation of CO_x for Hydrocarbons

An Overview on Dynamic Phase Transformation and Surface Reconstruction of Iron Catalysts for Catalytic Hydrogenation of CO_x for Hydrocarbons

Size-Dependent Hydrogenation Activity of Cobalt Nanoparticles

Towards a Correlation Between Iron/Cobalt Content, Support Pore Size and Metal Particle Size in Supported Catalysts

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Size effect of the carbon-supported bimetallic Fe-Co nanoparticles on the catalytic activity in the Fischer-Tropsch synthesis

Cited by 17 publications

References 46 publications

An Overview on Dynamic Phase Transformation and Surface Reconstruction of Iron Catalysts for Catalytic Hydrogenation of COx for Hydrocarbons

An Overview on Dynamic Phase Transformation and Surface Reconstruction of Iron Catalysts for Catalytic Hydrogenation of COx for Hydrocarbons

Size-Dependent Hydrogenation Activity of Cobalt Nanoparticles

Towards a Correlation Between Iron/Cobalt Content, Support Pore Size and Metal Particle Size in Supported Catalysts

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An Overview on Dynamic Phase Transformation and Surface Reconstruction of Iron Catalysts for Catalytic Hydrogenation of CO_x for Hydrocarbons

An Overview on Dynamic Phase Transformation and Surface Reconstruction of Iron Catalysts for Catalytic Hydrogenation of CO_x for Hydrocarbons