The effect of anatase TiO2 surface structure on the behavior of ethanol adsorption and its initial dissociation step: A DFT study

Zhang, Riguang; Liu, Zhixue; Ling, Lixia; Wang, Baojun

doi:10.1016/j.apsusc.2015.06.059

Cited by 43 publications

(28 citation statements)

References 60 publications

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“…3b) and dissociative ( Fig. 3d) adsorption of water at A 101 /vacuum interface, 50 as well as with temperature-programmed desorption spectra, which show a broad water desorption peak centered at ∼ 250 K. 24 Concerning ethanol adsorption, our results agree with previous DFT calculations 27,56 with close molecular (EtOH Ti ) and dissociative adsorption energies at A 101 surface in vac- with respect to a dissociative (−0.93 eV) process, with a difference in binding energy of 0.18 eV. 27 The close energetics between molecular and dissociative adsorption is in agreement with scanning tunneling microscopy measurements of A 101 surface exposed to ethanol in ultrahigh-vacuum 27 and subsurface V sub O sites.…”

Section: Water and Ethanol Adsorption At The A 101 Surfacesupporting

confidence: 90%

Wet Environment Effects for Ethanol and Water Adsorption on Anatase TiO₂ (101) Surfaces

et al. 2019

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Titanium dioxide exhibits superior photocatalytic properties, mainly occurring in liquid environments through molecular adsorptions and dissociations at the solid/liquid interface. The presence of these wet environments is often neglected when performing ab initio calculations for the interaction between the adsorbed molecules and the TiO 2 1 surface. In this study we consider two solvents, i.e. water and ethanol, and show that the proper inclusion of the wet environment in the methodological scheme is fundamental for obtaining reliable results. Our calculations are based on structure predictions at a density functional theory level for molecules interacting with the perfect and defective anatase (1 0 1) surface under both vacuum and wet conditions. A soft-sphere implicit solvation model is used to describe the polar character of the two solvents. As a result, we find that surface oxygen vacancies become energetically favorable with respect to subsurface vacancies at the solid/liquid interface. This aspect is confirmed by ab initio molecular dynamics simulations with explicit water molecules. Ethanol molecules are able to strongly passivate these vacancies, whereas water molecules only weakly interact with the (1 0 1) surface, allowing the coexistence of surface vacancy defects and adsorbed species. Infrared and photoluminescence spectra of anatase nanoparticles exposing predominantly (1 0 1) surfaces dispersed in water and ethanol support the predicted molecular-surface interactions, validating the whole computational paradigm. The combined analysis allows for a better interpretation of TiO 2 processes in wet environments based on improved computational models with implicit solvation features.

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Section: Water and Ethanol Adsorption At The A 101 Surfacesupporting

confidence: 90%

Wet Environment Effects for Ethanol and Water Adsorption on Anatase TiO₂ (101) Surfaces

et al. 2019

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“…In particular, the interaction of EtOH with the TiO 2 surface has been widely investigated for catalysis. Different mechanisms have been proposed, and at room or low temperatures (< 200 °C) the main pathway implicates the adsorption of EtOH through a hydroxyl group [31,32] . The adsorption initially takes place thanks to the O-H bond cleavage and is surfacestructure independent [31] .…”

Section: Resultsmentioning

confidence: 99%

Nanostructured Dielectric Fractals on Resonant Plasmonic Metasurfaces for Selective and Sensitive Optical Sensing of Volatile Compounds

Fusco

Rahmani

et al. 2018

Advanced Materials

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Advances in the understanding and fabrication of plasmonic nanostructures have led to a plethora of unprecedented optoelectronic and optochemical applications. Plasmon resonance has found widespread use in efficient optical transducers of refractive index changes in liquids. However, it has proven challenging to translate these achievements to the selective detection of gases, which typically adsorb non-specifically and induce refractive index changes below the detection limit. Here, it's shown that integration of tailored fractals of dielectric TiO nanoparticles on a plasmonic metasurface strongly enhances the interaction between the plasmonic field and volatile organic molecules and provides a means for their selective detection. Notably, this superior optical response is due to the enhancement of the interaction between the dielectric fractals and the plasmonic metasurface for thickness of up to 1.8 μm, much higher than the evanescent plasmonic near-field (≈30 nm) . Optimal dielectric-plasmonic structures allow measurements of changes in the refractive index of the gas mixture down to <8 × 10 at room temperature and selective identification of three exemplary volatile organic compounds. These findings provide a basis for the development of a novel family of dielectric-plasmonic materials with application extending from light harvesting and photocatalysts to contactless sensors for noninvasive medical diagnostics.

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“…The most stable adsorption and dissociation con gurations of water molecules on the surface were optimized, and these two con gurations were set as the initial state (reactant) and nal state (product), respectively. Complete linear synchronous transit (LST) and quadratic synchronous transit (QST) approaches were chosen to search for transition states, and then the nudged elastic band (NEB) method was used to determine the transition state on the minimum reaction energy path [36][37][38]. According to the calculated adsorption energy of these states, the reaction activity and energy of water splitting reaction on the surface of anatase TiO 2 (101) with different oxygen vacancy concentration were analyzed.…”

Section: Computational Methods and Modelsmentioning

confidence: 99%

Effect of oxygen vacancy concentration on the photocatalytic hydrogen evolution performance of anatase TiO2: DFT and experimental studies

Jia

Gao

Shen

et al. 2021

J Mater Sci: Mater Electron

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Oxygen vacancies (OVs) are important for changing the geometric and electronic structure as well as the chemical properties of anatase TiO 2 . In this work, we performed a DFT calculation on the electronic structure and catalytic performance of anatase TiO 2 (101) with different numbers of OVs. A comparison of the measured XRD results with the simulated ones of TiO 2 demonstrates that OVs can cause changes in the crystal structure. The changes in the electronic structure (Mulliken charges, band structure, and partial density of states) and water splitting on TiO 2 (101) surfaces were investigated as a function of oxygen vacancy concentration. The results show that the introduction of oxygen vacancy forms impurity levels below the conduction band of Ti 3d orbitals, and electrons can gradually transit from VB to CB through the impurity levels. However, when oxygen vacancy concentration is too high, the maximum electron transition energy increases and the promotion effect of oxygen vacancy on water splitting is weakened. This work would provide more enlightenment and information for the design of defective TiO 2 with higher photocatalytic activity.

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The effect of anatase TiO2 surface structure on the behavior of ethanol adsorption and its initial dissociation step: A DFT study

Cited by 43 publications

References 60 publications

Wet Environment Effects for Ethanol and Water Adsorption on Anatase TiO₂ (101) Surfaces

Wet Environment Effects for Ethanol and Water Adsorption on Anatase TiO₂ (101) Surfaces

Nanostructured Dielectric Fractals on Resonant Plasmonic Metasurfaces for Selective and Sensitive Optical Sensing of Volatile Compounds

Effect of oxygen vacancy concentration on the photocatalytic hydrogen evolution performance of anatase TiO2: DFT and experimental studies

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The effect of anatase TiO2 surface structure on the behavior of ethanol adsorption and its initial dissociation step: A DFT study

Cited by 43 publications

References 60 publications

Wet Environment Effects for Ethanol and Water Adsorption on Anatase TiO2 (101) Surfaces

Wet Environment Effects for Ethanol and Water Adsorption on Anatase TiO2 (101) Surfaces

Nanostructured Dielectric Fractals on Resonant Plasmonic Metasurfaces for Selective and Sensitive Optical Sensing of Volatile Compounds

Effect of oxygen vacancy concentration on the photocatalytic hydrogen evolution performance of anatase TiO2: DFT and experimental studies

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Wet Environment Effects for Ethanol and Water Adsorption on Anatase TiO₂ (101) Surfaces

Wet Environment Effects for Ethanol and Water Adsorption on Anatase TiO₂ (101) Surfaces