Carbid‐Dihydride: kohlenstoffhaltige Spezies identifiziert in der Ta<sub>4</sub><sup>+</sup>‐vermittelten Methandehydrierung

Lengyel, Jozef; Levin, Nikita; Wensink, Frank J.; Lushchikova, Olga V.; Barnett, R. N.; Landman, Uzi; Bakker, Joost M.; Tschurl, Martin

doi:10.1002/ange.202010794

Cited by 3 publications

(2 citation statements)

References 45 publications

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“…Since the higher number of atoms leads to an increase in structural complexity, several structural isomers of the involved species must be considered. In our previous study, [12c] structures and energetics of the possible initial structural isomers have already been discussed in detail. It was found that carbyne hydride (HTa 4 CH + ) and carbide dihydride (H 2 Ta 4 C + ) isomers are favored over the carbene one.…”

Section: Resultsmentioning

confidence: 99%

Direct Coupling of Methane and Carbon Dioxide on Tantalum Cluster Cations

Lengyel

Levin

Ončák

et al. 2022

Chemistry A European J

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Understanding molecular‐scale reaction mechanisms is crucial for the design of modern catalysts with industrial prospect. Through joint experimental and computational studies, we investigate the direct coupling reaction of CH4 and CO2, two abundant greenhouse gases, mediated by Ta1,4+ ions to form larger oxygenated hydrocarbons. Coherent with proposed elementary steps, we expose products of CH4 dehydrogenation [Ta1,4CH2]+ to CO2 in a ring electrode ion trap. Product analysis and reaction kinetics indicate a predisposition of the tetramers for C−O coupling with a conversion to products of CH2O, whereas atomic cations enable C−C coupling yielding CH2CO. Selected experimental findings are supported by thermodynamic computations, connecting structure, electronic properties, and catalyst function. Moreover, the study of bare Ta1,4+ compounds indicates that methane dehydrogenation is a significant initial step in the direct coupling reaction, enabling new, yet unknown reaction pathways.

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Section: Resultsmentioning

confidence: 99%

Direct Coupling of Methane and Carbon Dioxide on Tantalum Cluster Cations

Lengyel

Levin

Ončák

et al. 2022

Chemistry A European J

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“…Typical time-of-flight (TOF) mass spectra for the reactions of mass-selected Ta 4 + and Ta 4 O 1−5 + clusters with methane at room temperature are shown in Figure 1. It is noteworthy that the reaction systems of Ta 4 O 2−5 + are newly investigated while the reactivity of Ta 4 + and Ta 4 O + that had been previously reported by other research groups 42,43,45 was reexamined for comparison. Upon the interaction of bare Ta 4 + with 910 mPa CH 4 for about 1.5 ms in our ion funnel trap reactor, 49 the dehydrogenation reaction occurred to produce Ta 4 CH 2 + ions (1, Figure 1a1).…”

Section: Cluster Reactivitymentioning

confidence: 99%

Conversion of Methane at Room Temperature Mediated by the Ta–Ta σ-Bond

Li,

Liu,

Zhao

et al. 2024

JACS Au

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Metal−metal bonds constitute an important type of reactive centers for chemical transformation; however, the availability of active metal−metal bonds being capable of converting methane under mild conditions, the holy grail in catalysis, remains a serious challenge. Herein, benefiting from the systematic investigation of 36 metal clusters of tantalum by using mass spectrometric experiments complemented with quantum chemical calculations, the dehydrogenation of methane at room temperature was successfully achieved by 18 cluster species featuring σ-bonding electrons localized in single naked Ta−Ta centers. In sharp contrast, the other 18 remaining clusters, either without naked Ta−Ta σ-bond or with σbonding electrons delocalized over multiple Ta−Ta centers only exhibit molecular CH 4adsorption reactivity or inertness. Mechanistic studies revealed that changing cluster geometric configurations and tuning the number of simple inorganic ligands (e.g., oxygen) could flexibly manipulate the presence or absence of such a reactive Ta−Ta σ-bond. The discovery of Ta−Ta σ-type bond being able to exhibit outstanding activity toward methane conversion not only overturns the traditional recognition that only the metal−metal πor δ-bonds of early transition metals could participate in bond activation but also opens up a new access to design of promising metal catalysts with dual-atom as reactive sites for chemical transformations.

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Conversion of CH₄ Catalyzed by Gas Phase Ions Containing Metals

Yang

Zhao

2022

Chemistry A European J

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Methane is an abundant and cheap feedstock to produce valuable chemicals. The catalytic reaction of methane conversion generally requires the participation of multiple molecules (such as two or three CH4 molecules, O2, CO2, etc.). Such complex process includes the cleavage of original chemical bonds, formation of new chemical bonds, and desorption of products. The gas phase study provides a unique arena to gain molecular‐level insights into the detailed mechanisms of bond‐breaking and bond‐forming involved in complicated catalytic reactions. In this Review, we introduce the methane conversion catalyzed by gas phase ions containing metals and three topics will be discussed: (1) the direct coupling of methane molecules, (2) the conversion of CH4 with O2, O3 and N2O, and (3) the conversion of CH4 with CO2 and H2O. The obtained mechanistic aspects may provide new clues for rational design of better‐performing catalysts for conversion of methane to value‐added products.

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Carbid‐Dihydride: kohlenstoffhaltige Spezies identifiziert in der Ta₄⁺‐vermittelten Methandehydrierung

Cited by 3 publications

References 45 publications

Direct Coupling of Methane and Carbon Dioxide on Tantalum Cluster Cations

Direct Coupling of Methane and Carbon Dioxide on Tantalum Cluster Cations

Conversion of Methane at Room Temperature Mediated by the Ta–Ta σ-Bond

Conversion of CH₄ Catalyzed by Gas Phase Ions Containing Metals

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Carbid‐Dihydride: kohlenstoffhaltige Spezies identifiziert in der Ta4+‐vermittelten Methandehydrierung

Cited by 3 publications

References 45 publications

Direct Coupling of Methane and Carbon Dioxide on Tantalum Cluster Cations

Direct Coupling of Methane and Carbon Dioxide on Tantalum Cluster Cations

Conversion of Methane at Room Temperature Mediated by the Ta–Ta σ-Bond

Conversion of CH4 Catalyzed by Gas Phase Ions Containing Metals

Contact Info

Product

Resources

About

Carbid‐Dihydride: kohlenstoffhaltige Spezies identifiziert in der Ta₄⁺‐vermittelten Methandehydrierung

Conversion of CH₄ Catalyzed by Gas Phase Ions Containing Metals