Mechanistic Insight into the Synthesis of Higher Alcohols from Syngas: The Role of K Promotion on MoS<sub>2</sub> Catalysts

Santos, Vera P.; Linden, Bart van der; Chojecki, Adam; Budroni, Gerolamo; Corthals, Steven; Shibata, Hirokazu; Meima, Garry R.; Kapteijn, Freek; Makkee, Michiel; Gascón, Jorge

doi:10.1021/cs4003518

Cited by 119 publications

(79 citation statements)

References 35 publications

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“…When the oxide form of the MoS 2 based catalyst is sulfided, potassium ions build a complex with the sulfide phase . The nature of the complex was not established.…”

Section: Discussionmentioning

confidence: 99%

Effect of Promoter Nature on Synthesis Gas Conversion to Alcohols over (K)MeMoS₂/Al₂O₃ Catalysts

et al. 2020

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The influence of the promoter nature and of a modifier in (K)(Me)MoS2/Al2O3 (Me=Fe, Co, Ni) catalysts on the conversion and selectivity of products of synthesis gas conversion to alcohols and jnl oxygenates was investigated. Relationships between promoter nature, hydrocarbon chain length and selectivity in the formed alcohols were established. Electronic structure of a promoter atom in an active site (AS) was found to strongly affect selectivity of alcohol formation. Promotion of the S‐edge by Fe, Co or Ni suppressed hydrogen activation, which resulted in a lower synthesis gas conversion. Promotion of the M‐edge by Fe, Co, or Ni entailed the formation of double vacancies which are active sites of synthesis gas conversion. Potassium affected the oxophilicity of Mo atoms and reduced Co/Ni‐promoted MoS AS. It decreased the probability of C−O bond breaking in the adsorbed intermediate and shifted selectivity from the formation of alkyl towards alkoxide fragments over these catalysts.

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“…When the oxide form of the MoS 2 based catalyst is sulfided, potassium ions build a complex with the sulfide phase . The nature of the complex was not established.…”

Section: Discussionmentioning

confidence: 99%

Effect of Promoter Nature on Synthesis Gas Conversion to Alcohols over (K)MeMoS₂/Al₂O₃ Catalysts

et al. 2020

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“…K/ β ‐Mo 2 C and K/ γ ‐Mo 2 N both suffer from high hydrocarbon selectivities . MoS 2 catalysts need to be cofed with H 2 S, a poisonous and corrosive gas, to prevent deactivation during syngas conversion. Moreover, sulfur is incorporated in the products, which is in conflict with environmental legislation .…”

Section: Introductionmentioning

confidence: 99%

Development of Molybdenum Phosphide Catalysts for Higher Alcohol Synthesis from Syngas by Exploiting Support and Promoter Effects

et al. 2019

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Molybdenum phosphide (MoP) catalysts have recently attracted attention due to their robust methanol synthesis activity from CO/CO2. Synthesis strategies are used to steer MoP selectivity toward higher alcohols by investigating the promotion effects of alkali (K) and CO‐dissociating (Co, Ni) and non‐CO‐dissociating (Pd) metals. A systematic study with transmission electron microscopy, X‐ray diffraction, X‐ray photoelectron spectroscopy, and X‐ray absorption spectroscopy (XAS) showed that critical parameters governing the activity of MoP catalysts are P/Mo ratio and K loading, both facilitating MoP formation. The kinetic studies of mesoporous silica‐supported MoP catalysts show a twofold role of K, which also acts as an electronic promoter by increasing the total alcohol selectivity and chain length. Palladium (Pd) increases CO conversion, but decreases alcohol chain length. The use of mesoporous carbon (MC) support has the most significant effect on catalyst performance and yields a KMoP/MC catalyst that ranks among the state‐of‐the‐art in terms of selectivity to higher alcohols.

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“…Layered systems have special properties which make them very promising in various applications such as nanoelectronics and catalysis [1][2][3][4][5][6]. Several transition-metal dichalcogenides exhibit a transformation from indirect to direct band gap semiconductors as they are thinned down to a single monolayer.…”

Section: Introductionmentioning

confidence: 99%

Metallization and stiffness of the Li-intercalated MoS2 bilayer

Петрова

Yakovkin

Zeze

2015

Applied Surface Science

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Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. The band structures, DOS, and Fermi surfaces for the MoS 2 bilayer with adsorbed (a,c,e) and intercalated (b,d,f) Li (1×1) layer. Graphical Abstract (for review)To Reviewer #1:"1. The authors showed the frequencies of phonon modes at Gamma point. In Fig. 6 -We have to confess that the relationship of the phonon frequencies at Gamma with the topic of the paper is only marginal, and therefore have canceled Table 1, Fig. 6 and Fig. 7 (with the related text), as advised. To our view, as a result, the paper has become more focused. Of course, within LDA, one cannot achieve a "chemical accuracy" of the estimates of the interlayer interaction, but for the purposes of the present study of the role of Li intercalation, it is important to use the same approximation for both (pristine and Li-intercalated) systems, and here LDA is a good choice. It should be noted in this regard that, rigorously speaking, vdW description *Response to Reviewers is valid until wave functions of species do not overlap -otherwise, the exchange interaction must be considered instead. Li concentrations, the character of metallization for the adsorbed layer substantially differs from that of the MoS 2 -Li -MoS 2 layered system. In particular, for the adsorbed (1×1) Li monolayer, the increased density of the layer leads to the nonmetal-to-metal transition, which is evident from the appearance of the band crossing E F with an upward dispersion, pertinent to simple metals. It has been demonstrated that intercalated Li substantially increases the interlayer interaction in MoS 2 .Specifically, the estimated 0.12 eV energy of the interlayer interaction in the MoS 2 bilayer increases to 0.60 eV. This result is also consistent with results of earlier DFT calculations and available experimental results for alkali-intercalated graphene layers, which have demonstrated a substantial increase in the stiffness due to intercalation of alkalis.

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Mechanistic Insight into the Synthesis of Higher Alcohols from Syngas: The Role of K Promotion on MoS₂ Catalysts

Cited by 119 publications

References 35 publications

Effect of Promoter Nature on Synthesis Gas Conversion to Alcohols over (K)MeMoS₂/Al₂O₃ Catalysts

Effect of Promoter Nature on Synthesis Gas Conversion to Alcohols over (K)MeMoS₂/Al₂O₃ Catalysts

Development of Molybdenum Phosphide Catalysts for Higher Alcohol Synthesis from Syngas by Exploiting Support and Promoter Effects

Metallization and stiffness of the Li-intercalated MoS2 bilayer

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Mechanistic Insight into the Synthesis of Higher Alcohols from Syngas: The Role of K Promotion on MoS2 Catalysts

Cited by 119 publications

References 35 publications

Effect of Promoter Nature on Synthesis Gas Conversion to Alcohols over (K)MeMoS2/Al2O3 Catalysts

Effect of Promoter Nature on Synthesis Gas Conversion to Alcohols over (K)MeMoS2/Al2O3 Catalysts

Development of Molybdenum Phosphide Catalysts for Higher Alcohol Synthesis from Syngas by Exploiting Support and Promoter Effects

Metallization and stiffness of the Li-intercalated MoS2 bilayer

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Mechanistic Insight into the Synthesis of Higher Alcohols from Syngas: The Role of K Promotion on MoS₂ Catalysts

Effect of Promoter Nature on Synthesis Gas Conversion to Alcohols over (K)MeMoS₂/Al₂O₃ Catalysts

Effect of Promoter Nature on Synthesis Gas Conversion to Alcohols over (K)MeMoS₂/Al₂O₃ Catalysts