Organic Reactions at Well-Defined Oxide Surfaces

Barteau, Mark A.

doi:10.1021/cr950222t

Cited by 330 publications

(318 citation statements)

References 137 publications

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“…This scenario and the observed reaction products are consistent with reactions of carboxylic acids occurring on single crystal TiO 2 surfaces, as reviewed by Barteau. 70 The observed peak temperatures for the dissociation products also are in reasonably good agreement with those of formate decomposition, which is around 560 K. 70 Further support of the dissociation pathway proposed above is that (aminopropyl)triethoxysilane, which has been shown to bind to the surface with its amine group, does not dissociate on single crystal TiO 2 . 71 In other words, the initial dissociation reactions for glycine on TiO 2 are expected to occur in the carboxyl group and not in the amine group.…”

Section: Glycine-tio 2 Interactionmentioning

confidence: 54%

Adsorption and coadsorption of water and glycine on TiO2

Lausmaa

Löfgren

Kasemo

1999

J. Biomed. Mater. Res.

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Adsorption of water, ions, and biomolecules constitutes the first events occurring at biomaterial-biosystem interfaces. In this work, the adsorption and coadsorption of water and glycine on TiO2 were studied by thermal desorption spectroscopy (TDS). The first water monolayer desorbs in three peaks around 180K, 300K, and 400K, which are assigned to water molecularly adsorbed at oxygen sites, at Ti4+ sites, and to recombination of dissociated water, respectively. A fourth desorption peak (160K), appearing at coverages > 0.8 monolayer, is attributed to water clusters and multilayers. The water-TiO2 interaction is changed if the surface is annealed in vacuum, which leads to increased hydroxylation. Desorption spectra from glycine overlayers evaporated on TiO2 in situ show that around 40% of the first monolayer desorbs as intact molecules ( approximately 300-450 K) and the remainder as dissociation fragments and surface reaction products around 600 K. At coverages > 0.6 monolayers, intact molecules desorbing from cluster multilayers at 310 K are detected. The glycine desorption spectra are unaffected by coadsorbed water. In contrast, coadsorption of glycine displaces water from more strongly bound states in the monolayer to more weakly bound states and clusters, making the surface more hydrophobic. The study shows that TDS is a powerful method for characterizing biomaterial surfaces with regard to their interaction with biologically relevant molecules.

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Section: Glycine-tio 2 Interactionmentioning

confidence: 54%

Adsorption and coadsorption of water and glycine on TiO2

Lausmaa

Löfgren

Kasemo

1999

J. Biomed. Mater. Res.

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“…For oxides, on the other hand, only since the mid-1980s, studies have blossomed on planar model surfaces of metal oxides. Today, the amount of information on molecule-substrate interactions available for these binary compounds [11,12] is much smaller than in case of metals. This lack of information does not reflect missing interest, but rather results from the larger complexity and, more importantly, from the low electrical conductivity of these dielectric materials.…”

Section: Introductionmentioning

confidence: 99%

IR spectroscopy applied to metal oxide surfaces: adsorbate vibrations and beyond

Yang

Wöll

2017

Advances in Physics: X

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Metal oxides are among the technologically most important materials. Almost all metals are covered by one oxide layer under ambient conditions. The characterization of oxide surface properties, therefore, is still attracting an increasing amount of attention in surface science. A challenge is provided by the fact that these materials cannot be studied with standard techniques in a straightforward fashion. In this review, we summarize recent results obtained by IRspectroscopy applied in a reflection-geometry to macroscopic oxide monocrystals. These results provide new insights in the adsorption and subsequent reactions and photoreactions of molecules on these highly interesting, very complex class of materials. In addition, the IR-spectroscopy can also be used to probe photophysical properties, e.g. the generation and decay of electron or hole polarons.

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“…[16,17] Most adsorption studies of organic molecules on crystalline TiO 2 surfaces focused on carboxylic acids, alcohols and aldehydes. [6,18] Formic acid, which shares the carboxyl functional group with amino acids, has been found in several studies to adsorb as anionic formate with the two oxygen atoms bridging two surface Ti-atoms and hydroxylation of a surface O-atom (for an overview see ref. [6] and references therein).…”

Section: Introductionmentioning

confidence: 99%

Adsorption of Proline and Glycine on the TiO₂(110) Surface: A Density Functional Theory Study

Tonner

2010

ChemPhysChem

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The optimal adsorption modes for the amino acids glycine and proline on the ideal TiO(2)(110) surface are investigated by using density functional theory (PBE) applying periodic boundary conditions. Binding modes with anionic acid moieties bridging two titanium atoms after transferring a proton to the surface are the most stable configurations for both molecules investigated-similar to previous results for carboxylic acids. In contrast to the latter compounds, amino acids can form hydrogen bonds via the amino group towards the surface-bound proton; this provides an additional stabilisation of 15-20 kJ mol(-1). Zwitterionic binding modes are less stable (by 10-20 kJ mol(-1)) and are less important for proline. Neutral modes are energetically even less favourable. Calculations of vibrational frequencies and core-level shifts complement the adsorption study and provide guidance for future experimental investigations. Control of the computational parameters is crucial for the derivation of accurate results. The layout and thickness of the slab model used are also shown to be decisive factors. Calculations with a different GGA-functional (PW91) provide very similar relative energies, although the absolute energies change by about 20 kJ mol(-1). Results derived with the hybrid functional PBE0 show an even greater stabilisation of the anionic binding modes with respect to the zwitterionic modes. A previously observed discrepancy between experimental and theoretical results for glycine could be solved, although the experimentally proposed free rotation of the C-C bond could not be reproduced.

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Organic Reactions at Well-Defined Oxide Surfaces

Cited by 330 publications

References 137 publications

Adsorption and coadsorption of water and glycine on TiO2

Adsorption and coadsorption of water and glycine on TiO2

IR spectroscopy applied to metal oxide surfaces: adsorbate vibrations and beyond

Adsorption of Proline and Glycine on the TiO₂(110) Surface: A Density Functional Theory Study

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Organic Reactions at Well-Defined Oxide Surfaces

Cited by 330 publications

References 137 publications

Adsorption and coadsorption of water and glycine on TiO2

Adsorption and coadsorption of water and glycine on TiO2

IR spectroscopy applied to metal oxide surfaces: adsorbate vibrations and beyond

Adsorption of Proline and Glycine on the TiO2(110) Surface: A Density Functional Theory Study

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Product

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Adsorption of Proline and Glycine on the TiO₂(110) Surface: A Density Functional Theory Study