Interfacial oxygen under TiO2 supported Au clusters revealed by a genetic algorithm search

Vilhelmsen, Lasse B.; Hammer, Bjørk

doi:10.1063/1.4829640

Cited by 15 publications

(27 citation statements)

References 51 publications

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“…In the low-level setup the Kohn–Sham wave-functions are expanded as a linear combination of atomic orbitals (LCAO) using a double zeta-polarized basis set. LCAO is known to reproduce structures obtained by using a real space grid representation for the wave-function accurately and has already been used successfully in previous GA-searches. ,− In this low-level setup, the Cu(111) slab is represented by just one atomic layer, and the Brillouin zone is sampled using the Γ-point only. Structures are optimized using a force convergence criterium with a threshold of 0.1 eV/Å.…”

Section: Methods and Computational Detailsmentioning

confidence: 99%

Effects of Gas-Phase Conditions and Particle Size on the Properties of Cu(111)-Supported Zn_yO_x Particles Revealed by Global Optimization and Ab Initio Thermodynamics

et al. 2019

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The characterization of the interaction between nano or sub-nanoparticles with a support nowadays increasingly relies on computational modeling by means of the density functional theory calculations. These provide valuable atomic-detail understanding of the structure and energetics of supported clusters, but it is still challenging to find (or design) structural models that are representative of real systems in terms of size, structure, and composition. In this study, we have applied an extensive and systematic approach combining global optimization based on an evolutionary algorithm with atomistic ab initio thermodynamics for finding stable structures of a relevant material for catalytic methanol synthesis: Cu(111)-supported Zn y O x clusters. We identify the ZnO3 motif as the elementary building block of such clusters, on which we recently have investigated the full catalytic process for methanol synthesis [Reichenbach, T.; Mondal, K.; Jäger, M.; Vent-Schmidt, T.; Himmel, D.; Dybbert, V.; Bruix, A.; Krossing, I.; Walter, M.; Moseler, M. J. Catal., 2018, 360, 168–174]. With the collection of global minima of Cu(111)-supported Zn y O x clusters resulting from this large-scale global optimization effort, we assess the effect of size, gas-phase conditions, and support interactions on the phase diagrams, reactivity, and structural properties of the Zn y O x particles. We find moderate size-effects that are mostly related to the differences in stable Zn/O ratios of the identified global minima and to the formation of different sites in larger clusters. In contrast, large differences in the oxidation state of the clusters as defined by the gas-phase conditions significantly affect the geometry, electronic structure, and reactivity of the Zn y O x particles. This highlights the importance of thoroughly sampling structures with different stoichiometry and appropriately assessing their stability using a detailed thermodynamics analysis.

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Section: Methods and Computational Detailsmentioning

confidence: 99%

Effects of Gas-Phase Conditions and Particle Size on the Properties of Cu(111)-Supported Zn_yO_x Particles Revealed by Global Optimization and Ab Initio Thermodynamics

et al. 2019

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“…Previous studies have reported that the active catalytic sites for Au could be under-coordinated Au atoms [4,18], ionic Au atoms, [13,19,20] or interfacial sites between metal and metal-oxide support [3,[21][22][23]. For example, Nakamura and Fujitani investigated the reaction mechanism and active sites for CO oxidation over Au/TiO 2 catalysts, concluding that O 2 reacts with H 2 O forming a hydroperoxide species at the interface between the Au nanoparticles and TiO 2 support [24].…”

Section: Introductionmentioning

confidence: 99%

Intrinsic kinetics of plasmon-enhanced reverse water gas shift on Au and Au–Mo interfacial sites supported on silica

Carrasquillo‐Flores

Dumesic

et al. 2016

Applied Catalysis A: General

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Well characterized AuMo x catalysts were synthesized by controlled surface reactions (CSR) and studied in reverse water gas shift (RWGS) reaction with and without visible light addition. The numbers of Au and Au-Mo interfacial sites on these catalysts were quantified using low temperature (173 K) CO adsorption with Fourier transform infrared spectroscopy (FT-IR) and electron microscopy. Due to the localized surface plasmon resonance (LSPR) effect, visible light irradiation of the catalyst caused a decrease in the apparent activation energy from 80.2 ± 3.9 kJ/mol to 55.5 ± 3.1 kJ/mol and 67.5 ± 1.3 kJ/mol to 38.7 ± 1.9 kJ/mol with visible light irradiation over Au/SiO 2 and Au 1 Mo 0.1 /SiO 2 , respectively. The catalytic activity went through a maximum upon addition of Mo, with Au 1 Mo 0.1 /SiO 2 being the most active catalyst. The Au 1 Mo 0.1 catalyst with LSPR was 30 times more active than the reference Au catalyst under dark conditions. Visible light irradiation increased the reaction rate 4.7-4.8 times at 573 K for all catalysts. The turnover rates (CO mole produced per mole of Au or AuMo x site per min) on the Au and AuMo x interfacial sites were measured to be 0.98 min-1 and 14 min-1 in the dark conditions and 4.4 min-1 and 63 min-1 under the light conditions at 573 K. The rate per AuMo x interfacial site is 14 times greater than the rate per Au site under both dark and light conditions. These results indicate that the LSPR has the same enhancement effect on both Au and AuMo x catalytic sites.

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“…Extended to a (100)-oriented Au nanorod upon TiO 2 (110), the authors predict an unusual interfacial layer of oxygen, which was unlikely to be predicted from a biased search. 115 The thermodynamics and kinetics of CO oxidation on this system were subsequently examined, as depicted in Fig. 4 .…”

Section: Global Optimizationmentioning

confidence: 99%

Towardsoperandocomputational modeling in heterogeneous catalysis

et al. 2018

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Interfacial oxygen under TiO2 supported Au clusters revealed by a genetic algorithm search

Cited by 15 publications

References 51 publications

Effects of Gas-Phase Conditions and Particle Size on the Properties of Cu(111)-Supported Zn_yO_x Particles Revealed by Global Optimization and Ab Initio Thermodynamics

Effects of Gas-Phase Conditions and Particle Size on the Properties of Cu(111)-Supported Zn_yO_x Particles Revealed by Global Optimization and Ab Initio Thermodynamics

Intrinsic kinetics of plasmon-enhanced reverse water gas shift on Au and Au–Mo interfacial sites supported on silica

Towardsoperandocomputational modeling in heterogeneous catalysis

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Interfacial oxygen under TiO2 supported Au clusters revealed by a genetic algorithm search

Cited by 15 publications

References 51 publications

Effects of Gas-Phase Conditions and Particle Size on the Properties of Cu(111)-Supported ZnyOx Particles Revealed by Global Optimization and Ab Initio Thermodynamics

Effects of Gas-Phase Conditions and Particle Size on the Properties of Cu(111)-Supported ZnyOx Particles Revealed by Global Optimization and Ab Initio Thermodynamics

Intrinsic kinetics of plasmon-enhanced reverse water gas shift on Au and Au–Mo interfacial sites supported on silica

Towardsoperandocomputational modeling in heterogeneous catalysis

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Product

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Effects of Gas-Phase Conditions and Particle Size on the Properties of Cu(111)-Supported Zn_yO_x Particles Revealed by Global Optimization and Ab Initio Thermodynamics

Effects of Gas-Phase Conditions and Particle Size on the Properties of Cu(111)-Supported Zn_yO_x Particles Revealed by Global Optimization and Ab Initio Thermodynamics