Atomic Structure of the Anatase TiO<sub>2</sub>(001) Surface

Xia, Yaobiao; Zhu, Kun Yan; Kaspar, Tiffany C.; Du, Yingge; Birmingham, Blake; Park, Kenneth T.; Zhang, Zhenrong

doi:10.1021/jz401284u

Cited by 52 publications

(50 citation statements)

References 36 publications

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“…We noticed that very similar ad-row reconstruction has been observed in experiment for anatase (001) surface [45][46][47] , suggesting the potential to form four-coordinated TiO 4 row on anatase surface. In the TiO 4 , the bond length of Ti-O bond increases to 2.19 Å, being 0.24 Å longer than typical Ti-O distance in the anatase bulk.…”

Section: Reconstruction Of Anatase Surfacessupporting

confidence: 85%

Nature of Rutile Nuclei in Anatase-to-Rutile Phase Transition

2015

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The solid phase transition of TiO2, in particular anatase to rutile, has been extensively studied in the past 30 years. To seek the nucleation site at the beginning of phase transition is highly challenging, which asks for new theoretical techniques with high spatial and temporal resolution. This work reports the first evidence on the atomic structure of the nucleation sites in the TiO2 anatase-to-rutile phase transition. Novel automated theoretical methods, namely stochastic surface walking based pathway sampling methods, are utilized to resolve the lowest energy pathways at the initial stage of phase transition. We show that among common anatase surfaces, only the (112) ridged surface provides the nucleation site for phase transition, which can lead to the formation of both TiO2-II and brookite thin slabs. The TiO2-II phase is kinetically preferred product; the propagation into the subsurface is still hindered by high barriers that is the origin for the slow kinetics of nuclei formation. The rutile nuclei are thus not rutile phase but nascent metastable TiO2-II phase in an anatase matrix. The phase transition kinetics is found to be sensitive to the compressive strain and the crystallographic directions. The results rationalize the size and morphology dependence of the anisotropic phase transition kinetics of anatase particles and could facilitate the rational design of material via controlled solid phase transition.

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Section: Reconstruction Of Anatase Surfacessupporting

confidence: 85%

Nature of Rutile Nuclei in Anatase-to-Rutile Phase Transition

2015

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“…While we recognise that (101) is the dominant surface, there has been significant interest in the less stable (001) surface of anatase [95][96][97][98][99][100][101] as it is considered more active for photocatalysis than the dominant (101) surface and therefore there has been significant effort devoted to devising routes to prepare materials with dominant (001) facets.…”

Section: + To Induce Visible Light Absorptionmentioning

confidence: 99%

Design of Novel Visible Light Active Photocatalyst Materials: Surface Modified TiO₂

et al. 2016

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Type of publicationArticle (peer-reviewed) AbstractThis progress review describes our work on the design of new TiO2 based photocatalysts. The key concept is the formation of composite structures through the modification of anatase and rutile TiO2 with molecular-sized nanoclusters of metals oxides. Our density functional theory (DFT) level simulations have been compared with experimental work synthesizing and characterizing surface modified TiO2. We use DFT to show that nanoclusters of metal oxides such as TiO2, SnO/SnO2, PbO/PbO2, ZnO and CuO are stable when adsorbed at rutile and anatase surfaces and can lead to a significant red shift in the absorption edge which will induce visible light absorption; this is the first requirement for a useful photocatalyst. We determine the origin of the red shift and the fate of excited electrons and holes. For p-block metal oxides the oxidation state of Sn and Pb can be used to modify the magnitude of the red shift and its mechanism. We describe comparisons of recent experimental studies of surface modified TiO2 that validate our DFT simulations. These nanocluster-modified TiO2 structures 2 form the basis of a new class of photocatalysts which will be useful in oxidation reactions and with a correct choice of nanocluster modified can be applied to other reactions.

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“…The lowest energy pathways at the initial stage of phase transition, as shown in Figure , occurs on (1 1 2) ridged surface, which can lead to the formation of both TiO 2 (II) and brookite thin slabs. The other anatase surfaces, although may reconstruct, do not lead to the formation of new phases (the best known example is anatase (0 0 1) surface, where recent experiment studies provide new model for the (1 × 4) reconstruction on the top surface layer, originally rationalized by the added molecule (ADM) model). The TiO 2 (II) phase is kinetically preferred product, the propagation of which into subsurface is still hindered by high barriers that is the origin for the slow kinetics of nuclei formation.…”

Section: Applicationsmentioning

confidence: 99%

Structure and water oxidation activity of 3d metal oxides

Liu

2015

WIREs Comput Mol Sci

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Water splitting driven by solar energy is regarded as the candidate for the next generation of power source. The reaction is however kinetically hindered by the oxygen evolution reaction (OER) involving four proton–electron transfer steps. The ideal OER catalyst should avoid using precious elements, such as Ir, Ru, and Pt, and have a long‐term stability under positive bias potential. Recent experiments have shown that most 3d oxides are OER active catalysts, while some can even achieve comparable activities to commercial Ir/Ru catalysts in lab condition. In this article, we review the recent theoretical progress for characterizing the structure of 3d oxides and understanding the photo‐electrocatalytic water splitting mechanism over these catalysts. The methodology for global structure exploration, including evolutionary algorithm and stochastic surface walking method, is first introduced together with their applications in exploring the potential energy surface of TiO2 and NiOx systems. The current theoretical approaches to investigate the thermodynamics and kinetics of photo‐/electrochemical reactions are discussed and the latest understanding for OER reactions are summarized. WIREs Comput Mol Sci 2016, 6:47–64. doi: 10.1002/wcms.1236 This article is categorized under: Structure and Mechanism > Computational Materials Science Computer and Information Science > Computer Algorithms and Programming Theoretical and Physical Chemistry > Reaction Dynamics and Kinetics

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Atomic Structure of the Anatase TiO₂(001) Surface

Cited by 52 publications

References 36 publications

Nature of Rutile Nuclei in Anatase-to-Rutile Phase Transition

Nature of Rutile Nuclei in Anatase-to-Rutile Phase Transition

Design of Novel Visible Light Active Photocatalyst Materials: Surface Modified TiO₂

Structure and water oxidation activity of 3d metal oxides

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Atomic Structure of the Anatase TiO2(001) Surface

Cited by 52 publications

References 36 publications

Nature of Rutile Nuclei in Anatase-to-Rutile Phase Transition

Nature of Rutile Nuclei in Anatase-to-Rutile Phase Transition

Design of Novel Visible Light Active Photocatalyst Materials: Surface Modified TiO2

Structure and water oxidation activity of 3d metal oxides

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Product

Resources

About

Atomic Structure of the Anatase TiO₂(001) Surface

Design of Novel Visible Light Active Photocatalyst Materials: Surface Modified TiO₂