Kinetic study of ethylene hydrogenation

Cortright, Randy D.; Goddard, Scott A.; Rekoske, James E.; Dumesic, James A.

doi:10.1016/0021-9517(91)90230-2

Cited by 137 publications

(129 citation statements)

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“…Understanding differentc hemical transformationsa tt he atomic level is important in particularf or polyfunctional molecules but also for simpleo rganic species such as ethylene, which has been extensively studied both experimentally and computationally. [1][2][3][4][5][6] The reactions of ethylene over transition metals show av ery complexr eaction network, including four types of reactions:1,2-hydrogen shift, hydrogenation, dehydrogenation, and CÀCb ond cleavage.T he complexityo ft he reaction network makes it difficult to obtain the complete reaction mechanism even under well-defined experimental conditions. Theoretical approaches based on first-principles calculations are usefult oc larify the detailed mechanism of ethylene transformationso nt he various transition metal surfaces, for example on Pd(111), [1,[7][8][9][10][11][12] and Pt(111).…”

Section: Introductionmentioning

confidence: 99%

“…[23,30] Following adsorption,e thylene also undergoes self-hydrogenation by startingw ithaC ÀH bond breaking step whichp rovidesh ydrogena toms to other ethylene molecules. [27] For ethylene hydrogenation, many experimental evidences strongly support the Horiuti-Polanyi mechanism, [2,31] which includes as eries of surfacec atalyzed hydrogen addition steps.T he ethylidyne species, which is also observed under as ufficient hydrogen concentration,h owever, is not directly involved in the hydrogenation mechanism and are only spectator species. [5,32,33] Considering the vast number of experimental and theoretical investigations on ethylene transformationso vert ransition metals, [22][23][24][25][26][27][28][29][30][31][32][33][34][35] ac omplete theoreticals tudy on ethylene transformations reaction on Ir(111)i ss till missing.…”

Section: Introductionmentioning

confidence: 99%

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Mechanistic Insights into Ethylene Transformations on Ir(111) by Density Functional Calculations and Microkinetic Modeling

et al. 2017

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Ethylidyne, ethane, and carbon monomer formations from ethylene over Ir(111) at different coverages are investigated using density functional theory methods. Two possible reaction mechanisms for ethylidyne formation are investigated. The calculations show that vinyl prefers the dehydrogenation to yield vinylidene (M2) over the hydrogenation to produce ethylidene (M1) kinetically and thermodynamically at 1/9 (1/3) ML. Ethylidyne formation could be a competitive side reaction of ethylene hydrogenation, however, the ethylidyne species does not directly participate in the ethylene hydrogenation mechanism. The mechanism for C monomer formation is also studied. Microkinetic modeling shows that the ethylene hydrogenation reactivity decreases in the sequence Ir(111)>Rh(111)>Pd(111)>Pt(111) under typical hydrogenation conditions. The catalytic activity of ethylene hydrogenation decreases with increased stability of ethylene adsorption and reaction barrier of the rate-limiting step.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Mechanistic Insights into Ethylene Transformations on Ir(111) by Density Functional Calculations and Microkinetic Modeling

et al. 2017

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“…Ethylene hydrogenation on platinum is ac lassical model heterogeneous catalytic reaction for hydrocarbons,which has been extensively investigated on av ariety of metal oxide supported particles,a sw ell as single crystals. [24][25][26][27][28][29] This reaction has been customarily classified as structure-insensitive,that is the activity does not change with particle size,or single crystal facet. However,arecent reassessment has concluded against the applicability of such classification for platinum catalyst particles of sub-nanometer dimensions.This was shown in ajoint theoretical and experimental approach to coincide with the suppression of ethylene dehydrogenation on Pt 13 ,which induces structure insensitivity,atlow temperature (< 400 K).…”

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confidence: 99%

Controlling Ethylene Hydrogenation Reactivity on Pt₁₃ Clusters by Varying the Stoichiometry of the Amorphous Silica Support

et al. 2016

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Ethylene hydrogenation was investigated on size-selected Pt13 clusters supported on three amorphous silica (a-SiO2 ) thin films with different stoichiometries. Activity measurements of the reaction at 300 K revealed that on a silicon-rich and a stoichiometric film, Pt13 exhibits a similar activity to that of Pt(111), in line with the known structure insensitivity of the reaction. On an oxygen-rich film, a threefold increased rate was measured. Pulsing ethylene at 400 K, then measuring the activity at 300 K, resulted in complete loss of activity on the silicon-rich surface compared to only marginal losses on the other surfaces. The measured reactivity trends correlate with charging characteristics of a Pt13 cluster on the SiO2 films, predicted through first-principle calculations. The results reveal that the stoichiometry-dependent charging by the support can be used to tune the selectivity of reaction pathways during a catalytic hydrogenation reaction.

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“…Therefore, recording XAS data on at ime-scale of s-ms is important in elucidating rapid (intermediate) chemical reactions. [67] Notably,o ther photochemical, electrochemical and catalytic reactions with time-scales much shorter than ms are called "ultrafast". Notably,even transitions between states or structural deformation,w hich may be slower processes, take place too swiftly to be trackedu sing the currently available beamline at most synchrotron facilities.…”

Section: Discussionmentioning

confidence: 99%

In Situ/Operando X‐ray Spectroscopies for Advanced Investigation of Energy Materials

Dong

Vayssières

2018

Chemistry A European J

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Issues relatedt oe nergy and the environment have now become of central and crucial importance in our societies. Low-carbon green energy will have ac ritical role in an ecessary third industrial revolution.T or educe global greenhouse gas emissions in response to globalization and increasingly stringent carbone mission policies, large scale green energy production technologiesm ust be established worldwide. An ew age of human demandf or green energy is thus cominga nd scientists are focusedo nf inding new functional efficient and low-cost materialst ogenerate clean and sustainable energy.I mproving the energy conversion, generation, and storagee fficiency of energy materials has always been ad aunting challenge. For many important energy materials ystems, such as nanostructured catalysts, artificial photosynthetic systems, smart energy saving materials, and energy storaged evices, monitoring the atomica nd electronic structures close to the interfacial region in ar eal working environment is of paramount importance.D esigning ab etter-performing materialw ithoutc omprehendingi ts fundamentalp roperties such as chemical states, atomica nd electronic structures and how they are altered close to the interfacial regions during the physical and chemicalr eactions involved in their applications is very challenging. Understanding, controlling and tuning the interfaces in energy conversion and storagem aterials requires in situ/operando characterization tools, of which synchrotron X-ray spectroscopies, whichh ave severalu nique features, are very suitable ones. X-ray absorption spectroscopy can be used to elucidate the local unoccupied electronic structure in the con-ductionb and, and X-ray emission spectroscopy can be used to characterizet he occupied electronic structurei nt he valence band. The derived resonanti nelastic X-ray scattering reveals inter-and/ori ntra-electric transitions (i.e. d-d, f-f excitation and charge-transfer excitation) that reflect intrinsic chemicala nd physicalp roperties. Scanning transmission Xray microscopy is ac hemicalm apping technique with elemental sensitivity and spatial selectivity,w hich can therefore yield information about chemical composition in various spatialr egions. This unique characteristic makest he method effectivef or investigating interfacial phenomena (such as electront ransport, interface formation/deformation,d efects, doping etc.). In situ/operandoa pproaches have made the probinga nd understanding of changes in the atomica nd electronic structures of energy materials in an operational environment feasible. This article presentsaperspective of the pioneering developments as wella st he recent achievements in in situ/operando synchrotron X-ray spectroscopies for the advanced investigationo fe nergy materials. Four major energy materials ystems are identified:e nergy storage, energy generation,e nergy conversion,a nd energy saving materials ystems. Selected representative investigations of each systems are showcased and discussed demonstratingt hat in situ/operando sy...

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Kinetic study of ethylene hydrogenation

Cited by 137 publications

References 22 publications

Mechanistic Insights into Ethylene Transformations on Ir(111) by Density Functional Calculations and Microkinetic Modeling

Mechanistic Insights into Ethylene Transformations on Ir(111) by Density Functional Calculations and Microkinetic Modeling

Controlling Ethylene Hydrogenation Reactivity on Pt₁₃ Clusters by Varying the Stoichiometry of the Amorphous Silica Support

In Situ/Operando X‐ray Spectroscopies for Advanced Investigation of Energy Materials

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Kinetic study of ethylene hydrogenation

Cited by 137 publications

References 22 publications

Mechanistic Insights into Ethylene Transformations on Ir(111) by Density Functional Calculations and Microkinetic Modeling

Mechanistic Insights into Ethylene Transformations on Ir(111) by Density Functional Calculations and Microkinetic Modeling

Controlling Ethylene Hydrogenation Reactivity on Pt13 Clusters by Varying the Stoichiometry of the Amorphous Silica Support

In Situ/Operando X‐ray Spectroscopies for Advanced Investigation of Energy Materials

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Controlling Ethylene Hydrogenation Reactivity on Pt₁₃ Clusters by Varying the Stoichiometry of the Amorphous Silica Support