CO on Pt(111) puzzle: A possible solution

Grinberg, Ilya; Yourdshahyan, Yashar; Rappe, Andrew M.

doi:10.1063/1.1488596

Cited by 112 publications

(91 citation statements)

References 45 publications

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“…Nevertheless, whereas the tensile surface strain can lower the energy gap between the TB and HH structures, our calculations still predict that the HH overlayer is the most stable. However, it is well known that DFT underestimates the cost of breaking one of the bonds from a triply bonded CO molecule (36). Given that CO in an atop site is close to being doubly bonded and CO in a hollow site is close to being singly bonded, it follows that DFT overestimates the strength of CO adsorption in threefold hollow sites (36).…”

Section: Resultsmentioning

confidence: 99%

“…Given that CO in an atop site is close to being doubly bonded and CO in a hollow site is close to being singly bonded, it follows that DFT overestimates the strength of CO adsorption in threefold hollow sites (36). This explains the discrepancies found between experiment and calculation, where DFT fails to predict the experimentally observed atop-site occupation at low coverage for CO adsorption on both native Pt(111) and Rh(111) (36,37). To reduce or solve completely such site preference discrepancies in DFT, one can use the newly developed van der Waals-density functional (vdW-DF) of nonlocal correction as shown by Lazi c et al (38).…”

Section: Resultsmentioning

confidence: 99%

“…However, it is well known that DFT underestimates the cost of breaking one of the bonds from a triply bonded CO molecule (36). Given that CO in an atop site is close to being doubly bonded and CO in a hollow site is close to being singly bonded, it follows that DFT overestimates the strength of CO adsorption in threefold hollow sites (36). This explains the discrepancies found between experiment and calculation, where DFT fails to predict the experimentally observed atop-site occupation at low coverage for CO adsorption on both native Pt(111) and Rh(111) (36,37).…”

Section: Resultsmentioning

confidence: 99%

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Influence of support morphology on the bonding of molecules to nanoparticles

Yim

Pang

Hermoso

et al. 2015

Proc. Natl. Acad. Sci. U.S.A.

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Supported metal nanoparticles form the basis of heterogeneous catalysts. Above a certain nanoparticle size, it is generally assumed that adsorbates bond in an identical fashion as on a semiinfinite crystal. This assumption has allowed the database on metal single crystals accumulated over the past 40 years to be used to model heterogeneous catalysts. Using a surface science approach to CO adsorption on supported Pd nanoparticles, we show that this assumption may be flawed. Near-edge X-ray absorption fine structure measurements, isolated to one nanoparticle, show that CO bonds upright on the nanoparticle top facets as expected from single-crystal data. However, the CO lateral registry differs from the single crystal. Our calculations indicate that this is caused by the strain on the nanoparticle, induced by carpet growth across the substrate step edges. This strain also weakens the COmetal bond, which will reduce the energy barrier for catalytic reactions, including CO oxidation.nanoparticle | carpet growth | surface strain | adsorption | scanning tunneling microscopy N anoparticles exhibit properties distinct from their bulk counterparts (1-3). For instance, semiconductor particles smaller than ∼10 nm act as quantum dots (1-4) and oxide-supported gold nanoparticles are active for a variety of reactions including CO oxidation (5), water-gas-shift reaction (6), and epoxidation (7), whereas gold itself is not. Nanoclusters composed of ∼10 atoms have been shown to be exceptionally catalytically active for some reactions on some metals (8, 9). When the particle size is reduced, the relative number of undercoordinated atoms at the edges and corners increases. The proportion of perimeter sites at the interface between the metal and the support also increases. All these sites have been shown to play a crucial role in some reactions (10, 11). Reducing the particle size can also lead to a decrease in the interatomic bond length in small metal clusters (12, 13), which in the case of Pd nanoparticles results in lower adsorption energies for both CO (14,15) and O 2 (16), although such weakening of CO binding on the nanoparticle can also arise from other factors such as encapsulation of the nanoparticles by the support (17).The role of the support in modifying nanoparticle properties has also been recognized. For instance, the strong metal support interaction has been known for some time (2) and charge transfer either to or from the nanoparticles can lead to enhanced reactivity (18). More recently, it has come to light that the particle size itself may be governed by the interaction with the support (19). However, one effect that has not been discussed and yet should be present in any nanoparticle-support system is the influence of the support morphology such as steps.Here, we investigate the role of the support morphology on the reactivity of metal nanoparticles using scanning tunneling microscopy (STM). As our test system we choose Pd nanoparticles (20, 21) supported on TiO 2 (110) (22) simply because much is known about bo...

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Influence of support morphology on the bonding of molecules to nanoparticles

Yim

Pang

Hermoso

et al. 2015

Proc. Natl. Acad. Sci. U.S.A.

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“…The article initiated further studies, and in some of them, the top site was found to be lowest in energy: it was argued that the inclusion of relativistic effects should lead to the correct adsorption site [7,8]. Others [9] confirmed the wrong site preference with the top site higher in energy, although a relativistic pseudopotential was used. They argued that the failure was because different bond orders were treated with varying accuracy due to the generalized gradient approximation.…”

Section: Introductionmentioning

confidence: 99%

CO adsorption on the Pt(111) surface: a comparison of a gradient corrected functional and a hybrid functional

Doll

2004

Surface Science

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The adsorption of CO on the Pt(111) surface in a ( √ 3× √ 3) pattern has been studied with the gradient corrected functional of Perdew and Wang and the B3LYP hybrid functional. A slab which is periodic in two dimensions is used to model the system. The Perdew-Wang functional incorrectly gives the fcc site as the most favorable adsorption site, in accord with a set of previous studies. The B3LYP functional gives the top site as the preferred site. This confirms results from cluster studies where it was suggested that the different splitting, dependent on the functional, between highest occupied and lowest unoccupied molecular orbital, could be the reason for this change of the adsorption site. This is supported by an analysis based on the projected density of states and the Mulliken population.

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“…This was first discussed by Feibelman et al [7] where a variety of DFT-GGA methodologies and codes predicted adsorption at the fcc or hcp hollow site to be preferred over the experimentally preferred top site adsorption on the Pt(111) surface at low coverage. Since then this "puzzle" has been addressed [8,9,10,11] and the DFT-GGA inaccuracy traced to the incorrect description of CO electronic structure and bond-breaking.…”

Section: Introductionmentioning

confidence: 99%

First-principles extrapolation method for accurate CO adsorption energies on metal surfaces

2004

Self Cite

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We show that a simple first-principles correction based on the difference between the singlettriplet CO excitation energy values obtained by DFT and high-level quantum chemistry methods yields accurate CO adsorption properties on a variety of metal surfaces. We demonstrate a linear relationship between the CO adsorption energy and the CO singlet-triplet splitting, similar to the linear dependence of CO adsorption energy on the energy of the CO 2π* orbital found recently [Kresse et al., Physical Review B 68, 073401 (2003)]. Converged DFT calculations underestimate the CO singlet-triplet excitation energy ∆ES−T, whereas coupled-cluster and CI calculations reproduce the experimental ∆ES−T. The dependence of E chem on ∆ES−T is used to extrapolate E chem for the top, bridge and hollow sites for the (100) and (111) surfaces of Pt, Rh, Pd and Cu to the values that correspond to the coupled-cluster and CI ∆ES−T value. The correction reproduces experimental adsorption site preference for all cases and obtains E chem in excellent agreement with experimental results.

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CO on Pt(111) puzzle: A possible solution

Cited by 112 publications

References 45 publications

Influence of support morphology on the bonding of molecules to nanoparticles

Influence of support morphology on the bonding of molecules to nanoparticles

CO adsorption on the Pt(111) surface: a comparison of a gradient corrected functional and a hybrid functional

First-principles extrapolation method for accurate CO adsorption energies on metal surfaces

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