Adsorption of acetic and trifluoroacetic acid on the TiO2(110) surface

Foster, Adam S.; Nieminen, Risto M.

doi:10.1063/1.1802652

Cited by 24 publications

(24 citation statements)

References 39 publications

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“…Table 1 lists the internal bond distances and angles of acetate/acetic acid emerging from this study and previous literature values. There is excellent agreement with both previous experimental 26,27 and theoretical 28 work regarding the intramolecular bond distances. Discrepancies in bond angles are due to previous experimental work being on molecular acetic acid rather than acetate.…”

Section: ■ Results and Discussionsupporting

confidence: 89%

Quantitative Structure of an Acetate Dye Molecule Analogue at the TiO₂–Acetic Acid Interface

et al. 2016

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The positions of atoms in and around acetate molecules at the rutile TiO2(110) interface with 0.1 M acetic acid have been determined with a precision of ±0.05 Å. Acetate is used as a surrogate for the carboxylate groups typically employed to anchor monocarboxylate dye molecules to TiO2 in dye-sensitized solar cells (DSSC). Structural analysis reveals small domains of ordered (2 × 1) acetate molecules, with substrate atoms closer to their bulk terminated positions compared to the clean UHV surface. Acetate is found in a bidentate bridge position, binding through both oxygen atoms to two 5-fold titanium atoms such that the molecular plane is along the [001] azimuth. Density functional theory calculations provide adsorption geometries in excellent agreement with experiment. The availability of these structural data will improve the accuracy of charge transport models for DSSC.

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Section: ■ Results and Discussionsupporting

confidence: 89%

Quantitative Structure of an Acetate Dye Molecule Analogue at the TiO₂–Acetic Acid Interface

et al. 2016

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“…Data from both azimuths were fitted simultaneously so as to define a unique set of parameters, the results of the fit being shown in Figure 7 orientations [3]. The slightly tilted configuration evidenced here is consistent with theoretical work [25], although it is slightly larger than the figure derived by Gutiérrez-Sosa et al of 0° ± 5° [3]. A similarity of results is expected since as noted above, it is very likely that the surface studied in the earlier work was actually h-TiO2(110).…”

Section: Resultssupporting

confidence: 79%

Orientation of acetic acid hydrogen bonded to acetate terminated TiO2(110)

et al. 2020

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Acetic acid is a common pollutant for which photocatalytic degradation over titania provides a mitigating strategy. Knowledge of the bonding of acetate/acetic acid to this substrate is needed to aid interpretation of the photocatalytic data. In this work we use ambient pressure near edge X-ray absorption fine structure to measure the coverage and geometry of acetate in the TiO2( 110) contact layer as well as acetic acid in an additional layer. A saturation coverage of 0.5 monolayers in both layers is found up to an acetic acid pressure of 10 -1 Torr at 266 K.The geometry of acetate appears to be unchanged by adsorption of an additional layer of acetic acid, which involves a majority species bidentate bonded to neighboring Ti5c sites and a minority species bonded in a perpendicular geometry. Acetic acid has a similar geometry dictated by hydrogen bonding to the contact layer as well as the substrate.

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“…Our data suggest M2 to be the most stable structure, as previously found for acetic acid adsorption on the (110) TiO 2 surface in ref. 87. On the same (ADF) optimized cluster geometries, the relative stabilities calculated by the PBE functional by ADF, CP and G03 programs in vacuo are totally consistent, despite the different basis sets (Slater, Gaussian and Plane Waves), showing a similar description of the dye-TiO 2 interaction by all such computational approaches.…”

Section: Resultsmentioning

confidence: 67%

Adsorption of organic dyes on TiO2 surfaces in dye-sensitized solar cells: interplay of theory and experiment

Anselmi

Mosconi

Pastore

et al. 2012

Phys. Chem. Chem. Phys.

156

138

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First-principles computer simulations can contribute to a deeper understanding of the dye/semiconductor interface lying at the heart of Dye-sensitized Solar Cells (DSCs). Here, we present the results of simulation of dye adsorption onto TiO(2) surfaces, and of their implications for the functioning of the corresponding solar cells. We propose an integrated strategy which combines FT-IR measurements with DFT calculations to individuate the energetically favorable TiO(2) adsorption mode of acetic acid, as a meaningful model for realistic organic dyes. Although we found a sizable variability in the relative stability of the considered adsorption modes with the model system and the method, a bridged bidentate structure was found to closely match the FT-IR frequency pattern, also being calculated as the most stable adsorption mode by calculations in solution. This adsorption mode was found to be the most stable binding also for realistic organic dyes bearing cyanoacrylic anchoring groups, while for a rhodanine-3-acetic acid anchoring group, an undissociated monodentate adsorption mode was found to be of comparable stability. The structural differences induced by the different anchoring groups were related to the different electron injection/recombination with oxidized dye properties which were experimentally assessed for the two classes of dyes. A stronger coupling and a possibly faster electron injection were also calculated for the bridged bidentate mode. We then investigated the adsorption mode and I(2) binding of prototype organic dyes. Car-Parrinello molecular dynamics and geometry optimizations were performed for two coumarin dyes differing by the length of the π-bridge separating the donor and acceptor moieties. We related the decreasing distance of the carbonylic oxygen from the titania to an increased I(2) concentration in proximity of the oxide surface, which might account for the different observed photovoltaic performances. The interplay between theory/simulation and experiments appears to be the key to further DSCs progress, both concerning the design of new dye sensitizers and their interaction with the semiconductor and with the solution environment and/or an electrolyte upon adsorption onto the semiconductor.

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Adsorption of acetic and trifluoroacetic acid on the TiO2(110) surface

Cited by 24 publications

References 39 publications

Quantitative Structure of an Acetate Dye Molecule Analogue at the TiO₂–Acetic Acid Interface

Quantitative Structure of an Acetate Dye Molecule Analogue at the TiO₂–Acetic Acid Interface

Orientation of acetic acid hydrogen bonded to acetate terminated TiO2(110)

Adsorption of organic dyes on TiO2 surfaces in dye-sensitized solar cells: interplay of theory and experiment

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Adsorption of acetic and trifluoroacetic acid on the TiO2(110) surface

Cited by 24 publications

References 39 publications

Quantitative Structure of an Acetate Dye Molecule Analogue at the TiO2–Acetic Acid Interface

Quantitative Structure of an Acetate Dye Molecule Analogue at the TiO2–Acetic Acid Interface

Orientation of acetic acid hydrogen bonded to acetate terminated TiO2(110)

Adsorption of organic dyes on TiO2 surfaces in dye-sensitized solar cells: interplay of theory and experiment

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Product

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Quantitative Structure of an Acetate Dye Molecule Analogue at the TiO₂–Acetic Acid Interface

Quantitative Structure of an Acetate Dye Molecule Analogue at the TiO₂–Acetic Acid Interface