Reaction of NO and CO on a Rh(100) surface studied with gas-phase oriented NO

Brandt, Maynard A.; Müller, Helmut; Zagatta, Gunther; Böwering, N.; Heinzmann, Ulrich

doi:10.1016/0039-6028(95)01149-8

Cited by 21 publications

(29 citation statements)

References 27 publications

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“…10 Along this line, further measurements provided additional information on the role of steric effects on similar systems. [11][12][13][14] In all these experiments the molecular orientation in the incoming beam was forced by electrostatic fields, a method which can be applied only to polar symmetric-top molecules.…”

Section: Introductionmentioning

confidence: 99%

New insights on the stereodynamics of ethylene adsorption on an oxygen-precovered silver surface

Gerbi

Vattuone

Rocca

et al. 2005

The Journal of Chemical Physics

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The control of spatial orientation of molecules has a great influence on the stereodynamics of elementary processes occurring both in homogeneous and heterogeneous phases. Nonpolar molecules have so far escaped direct experimental investigations because of their poor sensitivity to several external constraints. Recently, it has been shown that the collisional alignment produced in supersonic expansions coupled with molecular-beam velocity selection can help solve such problems. Here we show that the sticking probability of ethylene, a nonpolar molecule prototypical of unsaturated hydrocarbons, on an O(2)-precovered Ag(001) surface is larger for molecules approaching in a helicopter-like motion than for those cartwheeling. A mechanism involving a weakly bound precursor state is suggested, with helicopter molecules having a lower chance of being scattered back into the gas phase than cartwheels when colliding with preadsorbed ethylene.

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Section: Introductionmentioning

confidence: 99%

New insights on the stereodynamics of ethylene adsorption on an oxygen-precovered silver surface

Gerbi

Vattuone

Rocca

et al. 2005

The Journal of Chemical Physics

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“…Some aspects of the dynamics of this reaction have been characterized with a supersonic molecular beam apparatus that affords the control of the molecular orientation of the incoming 56 NO molecules. Experiments on CO-precovered Rh(100) surfaces indicated a marked preference for CO 2 production with N-end collisions that cannot be explained solely by an orientationdependent sticking coefficient ( Figure 23) [290]. The authors interpreted their data in terms of a transition in the reaction mechanism from a direct Eley-Rideal step to an indirect surface reaction channel via a Langmuir Hinshelwood pathway.…”

Section: C Co + Nomentioning

confidence: 97%

“…Results from molecular beam experiments on the reaction of CO with NO on Rh(100) studied with oriented NO molecules[290]. Top: CO 2 partial pressure for bothextreme spatial orientations of the NO molecule, namely, with either the N (open squares) or the O (filled circles) end oriented towards the surface, as a function of time at a surface temperature of 393 K. Bottom: corresponding CO 2 reaction asymmetry parameter, A r , calculated from the raw data provided above, as a function of time.…”

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confidence: 99%

Use of molecular beams for kinetic measurements of chemical reactions on solid surfaces

Zaera

2017

Surface Science Reports

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In this review we survey the contributions that molecular beam experiments have provided to our understanding of the dynamics and kinetics of chemical interactions of gas molecules with solid surfaces. First, we describe the experimental details of the different instrumental setups and approaches available for the study of these systems under the ultrahigh vacuum conditions and with the model planar surfaces often used in modern surface-science experiments. Next, a discussion is provided of the most important fundamental aspects of the dynamics of chemical adsorption that have been elucidated with the help of molecular beam experiments, which include the development of potential energy surfaces, the determination of the different channels for energy exchange between the incoming molecules and the surface, the identification of adsorption precursor states, the understanding of dissociative chemisorption, the determination of the contributions of corrugation, steps, and other structural details of the surface to the adsorption process, the effect to molecular steering, the identification of avenues for assisting adsorption,

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“…Later, Xie et al explored the catalytic reduction mechanism of NO by CO on Rh 7 + clusters. 1,[11][12][13] The mechanism of CO 2 formation is experimentally in debate, with one mechanism being proposed to occur through the reaction between CO and NO, 14 and another through recombination of the CO and O atom, the latter originating from NO decomposition. 13 These theoretical studies support the process of the NO molecule dissociating into N and O atoms, and the mechanism of CO 2 formation accords to the recombination of CO and O atoms, the latter originating from NO decomposition.…”

Section: Introductionmentioning

confidence: 99%

Catalytic reduction of NO by CO on Rh₄⁺clusters: a density functional theory study

Yang

et al. 2015

Catal. Sci. Technol.

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An extensive study was conducted to explore the catalytic reduction of NO by CO on Rh 4 + clusters at the ground and first excited states at the B3LYP/6-311+GĲ2d), SDD level. The main reaction pathway includes the following elementary steps: (1) the coadsorption of NO and CO; (2) the recombination of NO and CO molecules to form CO 2 molecules and N atoms, or the decomposition of NO to N and O atoms; (3) the reaction of the N atom with the second adsorbed NO to form N 2 O; (4) the decomposition of N 2 O to N 2 molecules and O atoms; and (5) the recombination of O atoms and CO to form CO 2 . At low temperatures (300-760 K), the turnover frequency (TOF)-determining transition state (TDTS) is the simultaneous C-O bond formation and N-O bond cleavage, with a rate constant (s −1 ) of k Ps = 4.913 × 10 12 exp(−272 724/RT).The formation of CO 2 should originate in half from the reaction between the adsorbed CO and NO. The presence of CO in some degree decreases the catalytic reduction temperature of NO on the Rh 4 + clusters.At high temperatures (760-900 K), the TDTS is applied to the N-O bond cleavage, with a rate constant (s −1 ) of k Pa = 6.721 × 10 15 expĲ−318 376/RT). The formation of CO 2 should stem solely from the surface reaction between the adsorbed CO and the O atom, the latter originating from NO decomposition. The bridge N b Rh 4 + is thermodynamically preferred. Once the bridge N b Rh 4 + is formed, N 2 O-and NCO-contained species are predicted to exist, which is in good agreement with the experimental results.Catal. Sci. Technol. This journal is † Electronic supplementary information (ESI) available: Thermal correction to Gibbs free energy (G 0 , hartree), sum of electronic and thermal free energies (G c , hartree), and relative energies (G r , kJ mol −1 ) of various species with respect to the ground reactants calculated at the B3LYP/6-311+GĲ2d), SDD level in the gas phase under atmospheric pressure of 1 atm and room temperature of 300 K. The standard orientations of various species calculated at the B3LYP/6-311+GĲ2d), SDD level in the catalytic reduction of NO by CO on the Rh 4 + cluster.

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Reaction of NO and CO on a Rh(100) surface studied with gas-phase oriented NO

Cited by 21 publications

References 27 publications

New insights on the stereodynamics of ethylene adsorption on an oxygen-precovered silver surface

New insights on the stereodynamics of ethylene adsorption on an oxygen-precovered silver surface

Use of molecular beams for kinetic measurements of chemical reactions on solid surfaces

Catalytic reduction of NO by CO on Rh₄⁺clusters: a density functional theory study

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Reaction of NO and CO on a Rh(100) surface studied with gas-phase oriented NO

Cited by 21 publications

References 27 publications

New insights on the stereodynamics of ethylene adsorption on an oxygen-precovered silver surface

New insights on the stereodynamics of ethylene adsorption on an oxygen-precovered silver surface

Use of molecular beams for kinetic measurements of chemical reactions on solid surfaces

Catalytic reduction of NO by CO on Rh4+clusters: a density functional theory study

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Catalytic reduction of NO by CO on Rh₄⁺clusters: a density functional theory study