Density functional theory with nonlocal correlation: A key to the solution of the CO adsorption puzzle

Lazić, Predrag; Alaei, Mojtaba; Atodiresei, Nicolae; Caciuc, Vasile; Brako, R.; Blügel, Stefan

doi:10.1103/physrevb.81.045401

Cited by 98 publications

(97 citation statements)

References 29 publications

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“…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). In addition to this, recent calculations based on many-body perturbation theory, including the exact exchange and correlation energy using the random phase approximation (RPA), correctly predict the atop site to be the lowest energy adsorption configuration for Pt(111) and Rh(111) (39).…”

Section: Resultsmentioning

confidence: 99%

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%

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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“…Indeed, CO adsorption on Pt surfaces is indeed a non-trivial system to be calculated with DFT in general as the approach usually tends to overestimate the 3-fold hollow sites over atop sites, which in low temperature experiments were found to be preferred. As our aim is to investigate the co-adsorption of CO and OH, here we point the reader to the extensive discussions about the so-called "CO/Pt(111) puzzle" [41][42][43][44][45][46][47][48][49][50][51][52][53].…”

Section: Resultsmentioning

confidence: 99%

CO oxidation on stepped-Pt(111) under electrochemical conditions: insights from theory and experiment

Busó-Rogero

Herrero

Bandlow

et al. 2013

Phys. Chem. Chem. Phys.

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The co-adsorption of CO and OH on two Pt stepped surfaces vicinal to the (111) orientation has been evaluated by means of density functional theory (DFT) calculations. Focusing on Pt(533) and Pt(221), which contain (100) and (111)-steps, respectively, we find that (111)-steps are more reactive towards CO oxidation than surfaces containing (100)-steps. The DFT results are compared with electrochemical experiments on the CO adsorption and oxidation on these vicinal surfaces.

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“…This is in agreement with previous ab initio results. 76,[78][79][80] Multireference singles and doubles configuration interaction (MRSDCI) calculations resulted in that the bridge structure is about 0.98 eV stronger than the atop structure. 76 Collision-induced dissociation experiments also showed that the bridge structure is the most stable structure for the CO−Pt 2 anion.…”

Section: Co Interaction With Pt Atom and Dimermentioning

confidence: 99%

Influence of Carbon Support on Electronic Structure and Catalytic Activity of Pt Catalysts: Binding to the CO Molecule

2016

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Single-atom catalysts, especially with single Pt atoms, exhibit potentially improved catalytic activity as compared to metal clusters and metal surfaces. Here, the atop and bridged bondings of the CO molecule on the Pt/C system are studied. Vibrational frequencies, Mulliken populations, charge transfer, charge density differences and density of states are examined to determine the influence of the carbon support on electronic properties and catalytic activity of the Pt adatom and dimer. Comparing orbital populations and the amount of electron transfer to/from the CO molecule show that the net amount of electron transfer to the anti-bonding 2π * orbitals of the CO molecule is higher for the supported Pt dimer than for the substrate-free Pt dimer which leads to a lower vibrational frequency and a larger C−O bond distance. The hybridization between the π orbitals of the polycyclic aromatic hydrocarbons surface and the d orbitals of the Pt adatoms is responsible for enhancing the back donation of electrons to the 2π * orbitals of the CO molecule which results in a larger peak below the Fermi level for the 2π * states of the CO molecule in the corresponding density of state analysis. Therefore, it can be concluded that the carbon support significantly enhances the catalytic activity of the Pt atoms in contact with the surface for activating the CO molecule. The calculated C−O vibrational stretching frequencies provide valuable guidance for experiments considering the use of atom-type catalyst as building blocks for designing new catalysts.

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Density functional theory with nonlocal correlation: A key to the solution of the CO adsorption puzzle

Cited by 98 publications

References 29 publications

Influence of support morphology on the bonding of molecules to nanoparticles

Influence of support morphology on the bonding of molecules to nanoparticles

CO oxidation on stepped-Pt(111) under electrochemical conditions: insights from theory and experiment

Influence of Carbon Support on Electronic Structure and Catalytic Activity of Pt Catalysts: Binding to the CO Molecule

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