Water Dissociation and Hydroxyl Ordering on Anatase 
<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" display="inline"><mml:mrow><mml:msub><mml:mrow><mml:mi>TiO</mml:mi></mml:mrow><mml:mrow><mml:mn>2</mml:mn></mml:mrow></mml:msub><mml:mo stretchy="false">(</mml:mo><mml:mn>001</mml:mn><mml:mo stretchy="false">)</mml:mo><mml:mtext>−</mml:mtext><mml:mo stretchy="false">(</mml:mo><mml:mn>1</mml:mn><mml:mo>×</mml:mo><mml:mn>4</mml:mn><mml:mo stretchy="false">)</mml:mo></mml:mrow></mml:math>

Beinik, Igor; Bruix, Albert; Li, Zheshen; Adamsen, Kræn C.; Koust, Stig; Hammer, Bjørk; Wendt, Stefan; Lauritsen, Jeppe V.

doi:10.1103/physrevlett.121.206003

Cited by 39 publications

(58 citation statements)

References 41 publications

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“…At low coverage, one dissociative H2O adsorbs stably at the Ti4c site by transforming the H atom to the adjacent O2c atom and cleaving the Ti4c-O2c bond. With increasing coverage, the stability of dissociatively adsorbed H2O structure decreases because of the increased stress in the reconstructed substrate, which agrees recently reported results (25). Instead, the relative stability of the structure with two symmetric protrusions (each is an OH-H2O group (Figs.…”

supporting

confidence: 91%

Visualizing H ₂ O molecules reacting at TiO ₂ active sites with transmission electron microscopy

Yuan

Zhu

et al. 2020

Science

200

132

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Imaging a reaction taking place at the molecular level could provide direct information for understanding the catalytic reaction mechanism. We used in situ environmental transmission electron microscopy and a nanocrystalline anatase titanium dioxide (001) surface with (1 × 4) reconstruction as a catalyst, which provided highly ordered four-coordinated titanium “active rows” to realize real-time monitoring of water molecules dissociating and reacting on the catalyst surface. The twin-protrusion configuration of adsorbed water was observed. During the water–gas shift reaction, dynamic changes in these structures were visualized on these active rows at the molecular level.

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supporting

confidence: 91%

Visualizing H ₂ O molecules reacting at TiO ₂ active sites with transmission electron microscopy

Yuan

Zhu

et al. 2020

Science

200

132

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“…The high degree of unsaturation and the strained bonding situation lead to the well-known increased reactivity of this surface. It can undergo reconstruction under ultra-high vacuum conditions, 20 yet also the unreconstructed surface has been observed. 19 As adsorption of water prevents reconstruction in an aqueous environment, 21,22 the slab models employed in this work correspond to the unreconstructed surface.…”

Section: Introductionmentioning

confidence: 99%

Band positions of anatase (001) and (101) surfaces in contact with water from density functional theory

Geiger

Sprik

May

2020

The Journal of Chemical Physics

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Titanium dioxide in the anatase configuration plays an increasingly important role for photo(electro)catalytic applications due to its superior electronic properties when compared to rutile. In aqueous environments, the surface chemistry and energetic band positions upon contact with water determine charge-transfer processes over solid-solid or solid-electrolyte interfaces. Here, we study the interaction of anatase (001) and (101) surfaces with water and the resulting energetic alignment by means of hybrid density functional theory. While the alignment of band positions favours charge-transfer processes between the two facets for the pristine surfaces, we find the magnitude of this underlying driving force to crucially depend on water coverage and degree of dissociation. It can be largely alleviated for intermediate water coverages. Surface states and their passivation by dissociatively adsorbed water play an important role here. Our results suggest that anatase band positions can be controlled over a range of almost one eV via its surface chemistry. File list (2) download file view on ChemRxiv Band_positions_anatase.pdf (4.85 MiB) download file view on ChemRxiv Supplementary_material.pdf (3.53 MiB)

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“…The CO 2 adsorption on the reconstructed (001)-(1×4) surface have not been explored so far. In particular, only limited reports are there for water, formic acid and methanol adsorption on the (001)-(1×4) surface [49][50][51][52][53] . It is reported that the water and methanol molecules dissociatively adsorb on the ridge positions, while they are weakly adsorbed at terrace sites.…”

Section: Introductionmentioning

confidence: 99%

Facet Dependent Catalytic Activities of Anatase TiO$_2$ for CO$_2$ Adsorption and Conversion

Mishra,

Nanda

2020

Preprint

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Understanding the atomic-scale interaction mechanism of CO 2 and H 2 O on TiO 2 surface is crucial to establish a correlation between the catalytic efficiency with its exposed facet. Here, with the aid of a three-state model, nudged elastic band simulations, and DFT calculations, we examine the chemical restructuring of these molecules during the process of adsorption, coadsorption and conversion on (001) including (1×4)reconstructed, (010), and (101) facets of anatase TiO 2 and thereby, evaluate the step selective reactivity order. In addition, the results reveal the unexplored non-trivialities in the reaction mechanisms. For the most stable (101) facet, we show that the unfavorable carbonate complex formation becomes favorable by switching the reaction from endothermic to exothermic in the presence of water. Further, we find that the small binding energy does not necessarily imply physisorption. It can also give rise to chemisorption, where loss in energy due to repulsive Hartree and Madelung interactions is comparable to the energy gained through the chemical bonding. Such a scenario is demonstrated for the CO 2 adsorption on (010) and ( 101) facets. Though (001) remains

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Water Dissociation and Hydroxyl Ordering on Anatase TiO2(001)−(1×4)

Cited by 39 publications

References 41 publications

Visualizing H ₂ O molecules reacting at TiO ₂ active sites with transmission electron microscopy

Visualizing H ₂ O molecules reacting at TiO ₂ active sites with transmission electron microscopy

Band positions of anatase (001) and (101) surfaces in contact with water from density functional theory

Facet Dependent Catalytic Activities of Anatase TiO$_2$ for CO$_2$ Adsorption and Conversion

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Water Dissociation and Hydroxyl Ordering on Anatase TiO2(001)−(1×4)

Cited by 39 publications

References 41 publications

Visualizing H 2 O molecules reacting at TiO 2 active sites with transmission electron microscopy

Visualizing H 2 O molecules reacting at TiO 2 active sites with transmission electron microscopy

Band positions of anatase (001) and (101) surfaces in contact with water from density functional theory

Facet Dependent Catalytic Activities of Anatase TiO$_2$ for CO$_2$ Adsorption and Conversion

Contact Info

Product

Resources

About

Visualizing H ₂ O molecules reacting at TiO ₂ active sites with transmission electron microscopy

Visualizing H ₂ O molecules reacting at TiO ₂ active sites with transmission electron microscopy