CO oxidation catalyzed by a single gold atom: benchmark calculations and the performance of DFT methods

Fang, Haocheng; Li, Zhen Hua; Fan, Kangnian

doi:10.1039/c1cp21160a

Cited by 37 publications

(59 citation statements)

References 84 publications

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“…1,74,75 The above ten functionals were then used to compute the relative barrier heights and the E CO 2:S N 2@C:S N 2@N relative distribution for these three reactions. The BW and CI parameters were used to check the robustness of the remaining functionals.…”

Section: Discussionmentioning

confidence: 99%

Assessment of density-functionals for describing the X⁻+ CH₃ONO₂gas-phase reactions with X = F, OH, CH₂CN

Proenza

Souza

Ventura

et al. 2014

Phys. Chem. Chem. Phys.

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The energetics of the E CO 2, S N 2@C and S N 2@N channels of X À + CH 3 ONO 2 (X = F, OH, CH 2 CN) gas-phase reactions were computed using the CCSD(T)/CBS method. This benchmark extends a previous study with X = OH [M. A. F. de Souza et al., J. Am. Chem. Soc., 2012, 134, 19004] and was used to ascertain the accuracy and robustness of nineteen density-functionals for describing these potential energy profiles (PEP) as well as the kinetic product distributions obtained from RRKM calculations. Assessments were based on the mean unsigned error (MUE), the mean signed error (MSE), the #best : #worst (BW) criterion and the statistical confidence interval (CI) for the MSE. In general, double-hybrid (DH) functionals perform better than the range-separated ones, and both are better than the global-hybrid functionals. Based on the MUE and CI criteria the B2GPPLYP, B2PLYP, M08-SO, BMK, oB97X-D, CAM-B3LYP, M06, M08-HX, oB97X and B97-K functionals show the best performance in the description of these PEPs. Within this set, the B2GPPLYP functional is the most accurate and robust. The RRKM results indicate that the DHs are the best for describing the selectivities of these reactions. Compared to CCSD(T), the B2PLYP method has a relative error of only ca. 1% for the selectivity and the accuracy to provide the correct conclusion concerning the nonstatistical behavior of these reactions.Scheme 1 Reaction channels for the X À + CH 3 ONO 2 (X = F, 18 OH, CH 2 CN) systems with their experimental relative product distributions 28,30 and experimental DH 0 values 31 (in kcal mol À1 ).

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Section: Discussionmentioning

confidence: 99%

Assessment of density-functionals for describing the X⁻+ CH₃ONO₂gas-phase reactions with X = F, OH, CH₂CN

Proenza

Souza

Ventura

et al. 2014

Phys. Chem. Chem. Phys.

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“…Whether supported singly dispersed Au atoms are active for CO oxidation remains unknown. Although theoretical calculations suggested that single Au atoms could be catalytically active for CO oxidation [53], there is, however, no experimental evidence to fully demonstrate that supported single Au atoms can provide appreciable activity for CO oxidation. It has been reported that cationic Au species dispersed on oxide supports showed activity for CO oxidation at room temperature; however, their activity was much lower than that of the small Au nanoparticles [18,54,55].…”

Section: Experimental Datamentioning

confidence: 98%

Ultrastable single-atom gold catalysts with strong covalent metal-support interaction (CMSI)

et al. 2015

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Supported noble metal nanoparticles (including nanoclusters) are widely used in many industrial catalytic processes. While the finely dispersed nanostructures are highly active, they are usually thermodynamically unstable and tend to aggregate or sinter at elevated temperatures. This scenario is particularly true for supported nanogold catalysts because the gold nanostructures are easily sintered at high temperatures, under reaction conditions, or even during storage at ambient temperature. Here, we demonstrate that isolated Au single atoms dispersed on iron oxide nanocrystallites (Au 1 /FeO x ) are much more sinteringresistant than Au nanostructures, and exhibit extremely high reaction stability for CO oxidation in a wide temperature range. Theoretical studies revealed that the positively charged and surface-anchored Au 1 atoms with high valent states formed significant covalent metal-support interactions (CMSIs), thus providing the ultra-stability and remarkable catalytic performance. This work may provide insights and a new avenue for fabricating supported Au catalysts with ultra-high stability.

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“…43 The charge state of the Ni adatom is tentatively assigned to positive as the Ni 2p core-level spectrum shifts to higher binding energy in Figure 4a; however, caution is required due to final state effects in core-level PES. 44 Further insight into the Ni charge state can be obtained from the Bader charge analysis on the basis of the DFT calculations.…”

Section: Discussionmentioning

confidence: 99%

Stabilizing Single Ni Adatoms on a Two-Dimensional Porous Titania Overlayer at the SrTiO₃(110) Surface

et al. 2014

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Nickel vapor-deposited on the SrTiO3(110) surface was studied using scanning tunneling microscopy, photoemission spectroscopy (PES), and density functional theory calculations. This surface forms a (4 × 1) reconstruction, composed of a 2-D titania structure with periodic six- and ten-membered nanopores. Anchored at these nanopores, Ni single adatoms are stabilized at room temperature. PES measurements show that the Ni adatoms create an in-gap state located at 1.9 eV below the conduction band minimum and induce an upward band bending. Both experimental and theoretical results suggest that Ni adatoms are positively charged. Our study produces well-dispersed single-adatom arrays on a well-characterized oxide support, providing a model system to investigate single-adatom catalytic and magnetic properties.

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CO oxidation catalyzed by a single gold atom: benchmark calculations and the performance of DFT methods

Cited by 37 publications

References 84 publications

Assessment of density-functionals for describing the X⁻+ CH₃ONO₂gas-phase reactions with X = F, OH, CH₂CN

Assessment of density-functionals for describing the X⁻+ CH₃ONO₂gas-phase reactions with X = F, OH, CH₂CN

Ultrastable single-atom gold catalysts with strong covalent metal-support interaction (CMSI)

Stabilizing Single Ni Adatoms on a Two-Dimensional Porous Titania Overlayer at the SrTiO₃(110) Surface

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CO oxidation catalyzed by a single gold atom: benchmark calculations and the performance of DFT methods

Cited by 37 publications

References 84 publications

Assessment of density-functionals for describing the X−+ CH3ONO2gas-phase reactions with X = F, OH, CH2CN

Assessment of density-functionals for describing the X−+ CH3ONO2gas-phase reactions with X = F, OH, CH2CN

Ultrastable single-atom gold catalysts with strong covalent metal-support interaction (CMSI)

Stabilizing Single Ni Adatoms on a Two-Dimensional Porous Titania Overlayer at the SrTiO3(110) Surface

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Product

Resources

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Assessment of density-functionals for describing the X⁻+ CH₃ONO₂gas-phase reactions with X = F, OH, CH₂CN

Assessment of density-functionals for describing the X⁻+ CH₃ONO₂gas-phase reactions with X = F, OH, CH₂CN

Stabilizing Single Ni Adatoms on a Two-Dimensional Porous Titania Overlayer at the SrTiO₃(110) Surface