Chemical Activity of Thin Oxide Layers: Strong Interactions with the Support Yield a New Thin‐Film Phase of ZnO

Schott, Vadim; Oberhofer, Harald; Birkner, Alexander; Xu, Mingchun; Wang, Yuemin; Mühler, Martin; Reuter, Karsten; Wöll, Christof

doi:10.1002/anie.201302315

Cited by 180 publications

(200 citation statements)

References 36 publications

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“…However, our studies of FeO(111) [10] and ZnO(0001) [13] films on Pt(111) showed that such a monolayer structure is unstable under realistic pressure conditions. Moreover, other DFT studies of ZnO(0001) films on noble metals (Pd(111) [35], Cu(111) [36], and Au(111) [37]) and experimental data available for ZnO/Ag(111) [21] revealed substantial interlayer relaxations such that ultrathin ZnO films resemble the co-planar sheets in the boron nitride (or graphite) structure, and they are only weakly bound to a metal support, in contrast to the models used by Sun et al [34].…”

Section: Reactivity Of Metal-supported Zno(0001) Films: Comparisonmentioning

confidence: 99%

Reactivity of Ultra-Thin ZnO Films Supported by Ag(111) and Cu(111): A Comparison to ZnO/Pt(111)

et al. 2014

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Abstract.We studied structure and reactivity of ZnO(0001) ultrathin films grown on Ag (111) and Cu(111) single crystal surfaces. Structural characterization was carried out by scanning tunneling microscopy, Auger electron spectroscopy, low-energy electron diffraction, and temperature programmed desorption. The CO oxidation behavior of the films was studied at low temperature (450 K) at near atmospheric pressures using gas chromatography. For ZnO/Cu(111), it is shown that under reaction conditions ZnO readily migrates into the Cu crystal bulk, and the reactivity is governed by a CuO x oxide film formed in the reaction ambient. In contrast, the planar structure of ZnO films on Ag(111) is maintained, similarly to the previously studied ZnO films on Pt(111). At sub-monolayer coverages, the "inverse" model catalysts are represented by two-monolayer-thick ZnO(0001) islands on Pt(111) and Ag(111) supports. While the CO oxidation rate is considerably increased on ZnO/Pt(111), which is attributed to active sites at the metal/oxide boundary, sub-monolayer ZnO films on Ag(111) did not show such an effect, and the reactivity was inhibited with increasing film coverage. The results are explained by much stronger adsorption of CO on Pt(111) as compared with Ag(111) in proximity to O species at the oxide/metal boundary. In addition, the water-gas shift and reverse water-gas shift reactions were examined on ZnO/Ag(111), which revealed no promotional effect of ZnO on the reactivity of Ag under the conditions studied. The latter finding suggests that wetting phenomena of ZnO on metals does not play a crucial role in the catalytic performance of ZnObased real catalysts in those reactions.

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Section: Reactivity Of Metal-supported Zno(0001) Films: Comparisonmentioning

confidence: 99%

Reactivity of Ultra-Thin ZnO Films Supported by Ag(111) and Cu(111): A Comparison to ZnO/Pt(111)

et al. 2014

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“…15 The formation of the graphitic-like ZnO overlayer with hexagonal BN structure (h-BN) on Cu has been reported by Lunkenbein et al 16 as the consequence of strong metal support interaction (SMSI) on real Cu/ZnO/Al2O3 catalysts. To this end, high-resolution electron microscopy images have been reported.…”

Section: Introductionmentioning

confidence: 90%

“…a From ref. 15 We consider now CO adsorption on ZnO/Ag(111). We notice only very minor changes going from the unsupported to the supported oxide film, see Table 3 and 4.…”

Section: Co Zno Wurtzite and Unsupported Graphitic Zno Bilayermentioning

confidence: 99%

“…This is relevant because the special catalytic activity of Cu/ZnO hybrid structures has been attributed to a modified oxidation state of the Zn ions and to the occurrence of a given charge transfer at the interface. 15 These conclusions have been largely based on the calculation of the vibrational properties of an adsorbed CO probe molecule. 15 supercell to a (5x5) metal substrate.…”

Section: Introductionmentioning

confidence: 99%

“…15 These conclusions have been largely based on the calculation of the vibrational properties of an adsorbed CO probe molecule. 15 supercell to a (5x5) metal substrate. 29 With the presently adopted PBE+U+D2' approach, the (4x4) ZnO on (5x5) Cu superlattice would lead to a compressive strain as large as 4.2%.…”

Section: Introductionmentioning

confidence: 99%

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CO adsorption on graphite-like ZnO bilayers supported on Cu(111), Ag(111) and Au(111) surfaces

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Moving Frontiers in Transition Metal Catalysis: Synthesis, Characterization and Modeling

et al. 2019

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Nanosized transition metal particles are important materials in catalysis witha key role not only in academic research but also in many processes with industrial and societal relevance. Although small improvements in catalytic properties can lead to significant economic and environmental impacts, it is only now that knowledge-based design of such materials is emerging, partly because the understanding of catalytic mechanisms on nanoparticle surfaces is increasingly improving. A knowledge-based design requires bottom-up synthesis of well-defined model catalysts, an understanding of the catalytic nanomaterials "at work" (operando), and both a detailed understanding and a prediction by theoretical methods. This article reports on progress in colloidal synthesis of transition metal nanoparticles for preparation of model catalysts to close the materials gap between the discoveries of fundamental surface science and industrial application. The transition metal particles, however, often undergo extensive transformations when applied to the catalytic process and much progress has recently been achieved operando characterization techniques under relevant reaction conditions. They allow better understanding of size/structure-activity correlations in these systems. Moreover, the growth of computing power and the improvement of theoretical methods uncover mechanisms on nanoparticles and have recently predicted highly active particles for CO/CO 2 hydrogenation or direct H 2 O 2 synthesis.

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Chemical Activity of Thin Oxide Layers: Strong Interactions with the Support Yield a New Thin‐Film Phase of ZnO

Cited by 180 publications

References 36 publications

Reactivity of Ultra-Thin ZnO Films Supported by Ag(111) and Cu(111): A Comparison to ZnO/Pt(111)

Reactivity of Ultra-Thin ZnO Films Supported by Ag(111) and Cu(111): A Comparison to ZnO/Pt(111)

CO adsorption on graphite-like ZnO bilayers supported on Cu(111), Ag(111) and Au(111) surfaces

Moving Frontiers in Transition Metal Catalysis: Synthesis, Characterization and Modeling

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