Mechanism of the Poisoning Action Of Sulfur on Catalytically Active Pd(100)

Rutkowski, M.; Wetzig, D.; Zacharias, H.

doi:10.1103/physrevlett.87.246101

Cited by 21 publications

(16 citation statements)

References 21 publications

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“…16 -18 While the stability of Pd͑331͒ has been questioned, 19 it provides a useful point of comparison in order to understand the electronic structures and geometries of the different stepped surfaces. Additionally, since poisoning is one of the negative attributes in catalysis, and S is well known to act as a poison on, e.g., Pd, Pt, and Ni surfaces, [20][21][22][23][24][25] we have undertaken a comprehensive study of S on Pd surfaces. The understanding of the poisoning processes may help in the design of better catalysts, where one can possibly avoid the poisoning by tuning the surface either by doping or introducing different steps, kinks, etc., than originally present.…”

Section: Introductionmentioning

confidence: 99%

Ab initiostudies of stepped Pd surfaces with and without S

et al. 2003

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We have performed a comprehensive first-principles study of the electronic and geometric structure of a set of clean and S covered vicinal Pd surfaces of ͑111͒ and ͑110͒, namely Pd͑211͒, Pd͑331͒, Pd͑320͒, and Pd͑551͒, each having three-atom wide terraces. The trends in the multilayer relaxation patterns can generally be explained on the basis of charge smoothening which makes the vicinals of Pd͑110͒ prone to larger and deeper relaxations in comparison to the Pd͑111͒ counterparts. A range of adsorption energies for preferred adsorption sites for S is found on all four surfaces, with Pd͑320͒ being the most receptive. We show that the adsorbate can have considerable effect on multilayer relaxations and registry of the substrate atoms. We discuss the nature of the S-Pd bonding and how this bonding is affected by the surface geometry and coordination. We relate the poisoning effect of S to the changes in the electronic structure of the substrate atoms.

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Section: Introductionmentioning

confidence: 99%

Ab initiostudies of stepped Pd surfaces with and without S

et al. 2003

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“…For the two rovibrational states for which measured energy resolved rotational quadrupole alignment parameters are available, and for the energies for which statistically accurate rotational quadrupole alignment parameters could be computed, statistically significant results of our AIMD calculations are that, on average, (i) including the effect of the experimental surface temperature (925 K) in the AIMD simulations leads to decreased rotational quadrupole alignment parameters, and (ii) including this effect leads to increased agreement with experiment. DOI: 10.1103/PhysRevLett.108.236104 PACS numbers: 68.43.Bc, 34.35.+a, 82.65.+r Experiments on the alignment dependence of moleculesurface reactions yield detailed information on the interaction of molecules with surfaces [1][2][3]. Because the rotational alignment parameter of reacting molecules is connected with the local anisotropy of the potential energy surface (PES), measurements of this parameter in conjunction with theory can lead to the identification of the reaction site [4,5].…”

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confidence: 99%

“…Experiments on the alignment dependence of moleculesurface reactions yield detailed information on the interaction of molecules with surfaces [1][2][3]. Because the rotational alignment parameter of reacting molecules is connected with the local anisotropy of the potential energy surface (PES), measurements of this parameter in conjunction with theory can lead to the identification of the reaction site [4,5].…”

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confidence: 99%

Effect of Surface Motion on the Rotational Quadrupole Alignment Parameter ofD2Reacting on Cu(111)

Nattino

Dı́az²,

Jackson³

et al. 2012

Phys. Rev. Lett.

101

160

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Ab initio molecular dynamics (AIMD) calculations using the specific reaction parameter approach to density functional theory are presented for the reaction of D 2 on Cu(111) at high surface temperature (T s ¼ 925 K). The focus is on the dependence of reaction on the alignment of the molecule's angular momentum relative to the surface. For the two rovibrational states for which measured energy resolved rotational quadrupole alignment parameters are available, and for the energies for which statistically accurate rotational quadrupole alignment parameters could be computed, statistically significant results of our AIMD calculations are that, on average, (i) including the effect of the experimental surface temperature (925 K) in the AIMD simulations leads to decreased rotational quadrupole alignment parameters, and (ii) including this effect leads to increased agreement with experiment. DOI: 10.1103/PhysRevLett.108.236104 PACS numbers: 68.43.Bc, 34.35.+a, 82.65.+r Experiments on the alignment dependence of moleculesurface reactions yield detailed information on the interaction of molecules with surfaces [1][2][3]. Because the rotational alignment parameter of reacting molecules is connected with the local anisotropy of the potential energy surface (PES), measurements of this parameter in conjunction with theory can lead to the identification of the reaction site [4,5]. Measurement of this parameter as a function of translational energy may also reveal important mechanistic information on, for instance, the importance of orientational steering for reaction [3].The sensitivity of the alignment of reacting molecules to the details of the molecule-surface interaction makes experiments addressing this topic ideal for testing electronic structure theories that attempt to model this interaction. Such tests are highly relevant, and pose huge challenges. About 90% of the chemical manufacturing processes used worldwide employ heterogeneous catalysts [6]. However, the best ab initio theory that can now be used to map out PESs for elementary molecule-surface reactions, density functional theory (DFT) at the generalized gradient approximation (GGA) or meta-GGA level, can provide reaction barriers with an accuracy of no better than 2:2 kcal=mol for gas phase reactions [7]. Even this accuracy has only recently become available [7], and it is therefore not surprising that quantum dynamics calculations using DFT PESs on the rotational quadrupole alignment parameter of H 2 desorbing from metal surfaces such as Pd(100) [8] and Cu(111) [9,10] have not yet been able to quantitatively reproduce the experiments.Dihydrogen-metal surface systems are ideal for testing electronic structure methods as accurate reaction probabilities can be computed within the Born-Oppenheimer (BO) approximation [11]. Making the static surface approximation (neglecting energy transfer involving phonons) should likewise lead to accurate results for low surface temperature (T s ) [12]. Taking advantage of this, it was recently shown that specific reaction pa...

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“…In particular, adsorbed species such as C, S, and N have been the subject of much discussion in the literature on chemisorption and chemical reactivity. Several experimental studies have focussed on the poisoning effect of these adsorbates, [15][16][17][18][19][20] although open questions remain about the impact of C on chemical reactivity. 21 From a theoretical stand point, the prior question is how to measure the poisoning or the promotion of chemical reactivity.…”

Section: Introductionmentioning

confidence: 99%

Site selectivity in chemisorption of C on Pd(211)

et al. 2004

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Site selectivity in chemisorption of C on Pd(211) Results of ab initio electronic structure calculations of C on Pd(211), a vicinal of Pd (111), show a hierarchy of adsorption sites with adsorption energy ranging from −8.21 to − 5.46 eV (0.33 ML coverage) and scaling almost linearly with the effective coordination at the site. In the most preferred site, C atoms sit almost under the Pd step atoms and influence drastically multilayer relaxations and surface registry of Pd(211). The adsorption energy at this site is −9.10 eV for 0.17 ML coverage. The local densities of electronic states indicate strong hybridization between C p states and neighboring Pd d states leading to the formation of strong covalent C u Pd bonds. The depletion of the electronic density of states of the Pd surface atoms at the Fermi level suggests a poisoning effect of C which is found to be coverage dependent. We compare the changes in the electronic structure of Pd(211) on C adsorption with those on S adsorption.

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Mechanism of the Poisoning Action Of Sulfur on Catalytically Active Pd(100)

Cited by 21 publications

References 21 publications

Ab initiostudies of stepped Pd surfaces with and without S

Ab initiostudies of stepped Pd surfaces with and without S

Effect of Surface Motion on the Rotational Quadrupole Alignment Parameter ofD2Reacting on Cu(111)

Site selectivity in chemisorption of C on Pd(211)

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