CH4 dissociation in the early stage of graphene growth on Fe–Cu(100) surface: Theoretical insights

Tian, Baoyang; Liu, Tianhui; Li, Kai; Wu, Zhijian; Wang, Ying

doi:10.1016/j.apsusc.2017.09.088

Cited by 12 publications

(13 citation statements)

References 66 publications

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“…Moreover, methane dissociation on copper is a much investigated method for creating high quality graphene. [3][4][5][6][7][8][9] However, due to the complexity of the interaction between metals and molecules and of describing both metals and molecules accurately, this reaction remains difficult for theoretical studies. [10][11][12][13][14] Recently, it has been shown that chemically accurate results can be obtained for moleculesurface reactions by using a so-called Specific Reaction Parameter (SRP) approach.…”

Section: Introductionmentioning

confidence: 99%

Dissociation of CHD3 on Cu(111), Cu(211), and single atom alloys of Cu(111)

Gerrits

Migliorini

Kroes

2018

The Journal of Chemical Physics

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In order to model accurately reactions of polyatomic molecules with metal surfaces important for heterogeneous catalysis in industry, the Specific Reaction Parameter (SRP) approach to density functional theory has been developed. This approach has been shown to describe the dissociation of CHD 3 on Ni(111), Pt(111), and Pt(211) with chemical accuracy. In this work, predictions have been made for the reaction of CHD 3 on Cu(111) and Cu(211) using barriers, elbow plots, and ab initio molecular dynamics. Future experiments could hopefully prove the transferability of the SRP functional to systems in which methane reacts with flat and stepped surfaces of adjacent groups of the periodic table, by comparison with our predictions. Moreover, the effect of a so-called single atom alloy on the reactivity of methane is investigated by making predictions for CHD 3 on Pt-Cu(111) and Pd-Cu(111). It is found that the reactivity is only increased for Pt-Cu(111) near the alloyed atom, which is not only caused by the lowering of the barrier height but also by changes in the dynamical pathway and reduction of energy transfer from methane to the surface.

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Section: Introductionmentioning

confidence: 99%

Dissociation of CHD3 on Cu(111), Cu(211), and single atom alloys of Cu(111)

Gerrits

Migliorini

Kroes

2018

The Journal of Chemical Physics

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“…In this work, we focus on the dissociative chemisorption of CHD 3 on Cu(111) because the system exhibits a low reactivity, making reactive AIMD studies untractable for most incidence energies achievable in molecular beams. Moreover, high-quality graphene can be synthesized using methane dissociation on copper, − and this warrants additional study of the rate-controlling step, namely, the breaking of the first CH bond. The Eley–Rideal reaction of D with CD 3 preadsorbed on Cu(111) has also been studied .…”

mentioning

confidence: 99%

Accurate Probabilities for Highly Activated Reaction of Polyatomic Molecules on Surfaces Using a High-Dimensional Neural Network Potential: CHD₃ + Cu(111)

Gerrits

Shakouri

Behler

et al. 2019

J. Phys. Chem. Lett.

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An accurate description of reactive scattering of molecules on metal surfaces often requires the modeling of energy transfer between the molecule and the surface phonons. Although ab initio molecular dynamics (AIMD) can describe this energy transfer, AIMD is at present untractable for reactions with reaction probabilities smaller than 1%. Here, we show that it is possible to use a neural network potential to describe a polyatomic molecule reacting on a mobile metal surface with considerably reduced computational effort compared to AIMD. The highly activated reaction of CHD3 on Cu(111) is used as a test case for this method. It is observed that the reaction probability is influenced considerably by dynamical effects such as the bobsled effect and surface recoil. A special dynamical effect for CHD3 + Cu(111) is that a higher vibrational efficacy is obtained for two quanta in the CH stretch mode than for a single quantum.

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“…High value of c ensures minimal interaction between neighboring periodic images. The resulting layer of vacuum is wider than typically found in literature for similar systems 16,17,26 . The system is comprised of 32 in-plane carbon atoms and a single adsorbate molecule (left side of reaction equations).…”

Section: A Computational Approachmentioning

confidence: 54%

“…CH 4 decomposition reactions on other metals were also studied with DFT in a few earlier papers, namely on copper 14 , iridium 15 , and copper alloys, Cu-Fe 16 and Ni-Cu 17 .…”

Section: Introductionmentioning

confidence: 99%

Free energy landscape of dissociative adsorption of methane on ideal and defected graphene from ab initio simulations

Wlazło

Majewski

2018

The Journal of Chemical Physics

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We study the dissociative adsorption of methane at the surface of graphene. Free energy profiles, which include activation energies for different steps of the reaction, are computed from constrained ab initio molecular dynamics. At 300 K, the reaction barriers are much lower than experimental bond dissociation energies of gaseous methane, strongly indicating that graphene surface acts as a catalyst of methane decomposition. On the other hand, the barriers are still much higher than on nickel surface. Methane dissociation therefore occurs at a higher rate on nickel than on graphene. This reaction is a prerequisite for graphene growth from precursor gas. Thus, the growth of the first monolayer should be a fast and efficient process while subsequent layers grow at diminished rate and in a more controllable manner. Defects may also influence reaction energetics. This is evident from our results, in which simple defects (Stone-Wales defect and nitrogen substitution) lead to different free energy landscapes at both dissociation and adsorption steps of the process.

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CH4 dissociation in the early stage of graphene growth on Fe–Cu(100) surface: Theoretical insights

Cited by 12 publications

References 66 publications

Dissociation of CHD3 on Cu(111), Cu(211), and single atom alloys of Cu(111)

Dissociation of CHD3 on Cu(111), Cu(211), and single atom alloys of Cu(111)

Accurate Probabilities for Highly Activated Reaction of Polyatomic Molecules on Surfaces Using a High-Dimensional Neural Network Potential: CHD₃ + Cu(111)

Free energy landscape of dissociative adsorption of methane on ideal and defected graphene from ab initio simulations

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CH4 dissociation in the early stage of graphene growth on Fe–Cu(100) surface: Theoretical insights

Cited by 12 publications

References 66 publications

Dissociation of CHD3 on Cu(111), Cu(211), and single atom alloys of Cu(111)

Dissociation of CHD3 on Cu(111), Cu(211), and single atom alloys of Cu(111)

Accurate Probabilities for Highly Activated Reaction of Polyatomic Molecules on Surfaces Using a High-Dimensional Neural Network Potential: CHD3 + Cu(111)

Free energy landscape of dissociative adsorption of methane on ideal and defected graphene from ab initio simulations

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Accurate Probabilities for Highly Activated Reaction of Polyatomic Molecules on Surfaces Using a High-Dimensional Neural Network Potential: CHD₃ + Cu(111)