High-Resolution STM Studies of Terephthalic Acid Molecules on Rutile TiO<sub>2</sub>(110)-(1 <i>×</i> 1) Surfaces

Prauzner‐Bechcicki, Jakub S.; Godlewski, Szymon; Tekiel, Antoni; Cyganik, Piotr; Budzioch, Janusz; Szymoński, Marek

doi:10.1021/jp901184t

Cited by 42 publications

(59 citation statements)

References 33 publications

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“…Recently, combined STM and DFT calculations [14][15][16] suggested that at saturation coverage, TPA molecules undergo dimerization on TiO 2 (110) via attractive intermolecular interactions within the monolayer. The TPA dimers prefer to adopt a plane-to-plane configuration with a C 2 local symmetry, where the BTA dimer is stabilized by the formation of double hydrogen bonds between the hydroxyl and carbonyl oxygen of both apical carboxylic groups.…”

Section: Discussionmentioning

confidence: 99%

“…the occurrence of mono-and bidentate species) and into the question whether dimers of BA and TPA adsorbate species are present on TiO 2 (110). This question is particularly interesting in case of TPA, since for an upright species (as proposed in previous works [13][14][15][16]), one would assume the occurrence of both protonated and deprotonated carboxylic acid groups.…”

Section: Introductionmentioning

confidence: 93%

“…1). In addition, the combined experimental and theoretical studies revealed dimerization of TPA molecules at saturation coverage [14][15][16].…”

Section: Introductionmentioning

confidence: 98%

“…The adsorption of TPA molecules on TiO 2 (110) has also been studied by means of near-edge x-ray absorption fine structure (NEXAFS) spectroscopy, STM, and noncontact atomic force microscopy (NC-AFM) [13][14][15][16]. On the basis of the experimental results, the occurrence of two different adsorbate species was reported: at low coverages (up to 0.30 ML), the TPA molecules were found to adopt a disordered and flat-lying adsorption geometry, while at full monolayer, a conversion from a flat-lying to an upright orientation was detected (Fig.…”

Section: Introductionmentioning

confidence: 99%

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Interaction of carboxylic acids with rutile TiO2(110): IR-investigations of terephthalic and benzoic acid adsorbed on a single crystal substrate

Buchholz

Noei

et al. 2016

Surface Science

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a b s t r a c t a r t i c l e i n f oThe adsorption of two carboxylic acids, benzoic acid (BA) and terephthalic acid (TPA), on a single crystal rutile TiO 2 (110) substrate was studied using infrared reflection-absorption spectroscopy (IRRAS) in conjunction with DFT calculations. On the basis of the high-quality IR data (in particular for the OH bands), various adsorbate species with different geometries could be identified. The adsorption of both, BA and TPA, on TiO 2 (110) leads to deprotonation of carboxylic acids and protonation of substrate O-atoms. At low coverage, the deprotonated BA molecule adsorbs on TiO 2 (110) in an upright, bidentate configuration, while the TPA molecule adopts a flatlying geometry with both carboxylates bound to the surface in a monodentate geometry. At higher coverages, a transition from flat-lying to upright-oriented TPA molecules occurs. At saturation coverage, both BA and TPA molecules undergo dimerization indicating the presence of pronounced attractive intermolecular interactions. We propose that the BA dimers are stabilized by the interaction between adjacent phenyl rings, while the TPA dimerization is attributed to the formation of double hydrogen bonds between adjacent apical carboxylic groups.

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Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 93%

“…1). In addition, the combined experimental and theoretical studies revealed dimerization of TPA molecules at saturation coverage [14][15][16].…”

Section: Introductionmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Interaction of carboxylic acids with rutile TiO2(110): IR-investigations of terephthalic and benzoic acid adsorbed on a single crystal substrate

Buchholz

Noei

et al. 2016

Surface Science

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“…Here we stress that discussed changes in the appearance of molecules do not involve tip apex modifications. [37,38] …”

Section: Tip-induced Lateral Manipulation Of Vl Molecules On the Tio mentioning

confidence: 99%

Adsorption of Large Organic Molecules on Clean and Hydroxylated Rutile TiO₂(110) Surfaces

et al. 2009

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Behavior of large organic molecules equipped with spacer groups (Violet Landers, VL) on the TiO(2)(110)-(1x1) surfaces is investigated by means of high-resolution scanning tunneling microscopy (STM). Two distinct adsorption geometries are observed. We demonstrate that the molecule adsorption morphology can be alternated by well-controlled STM tip-induced manipulation. It is used to probe the mobility of molecules and reveals locking in one of the analyzed adsorption sites, thus allow to enhance or reduce the mobility along the [001] direction. Field induced hydrogen desorption is used to perform lateral STM manipulation on a hydroxyl-free surface, which provides insight into the influence of surface hydroxyl groups on the molecule behavior. The ability to image with submolecular resolution both the central board and the spacer groups of the VL molecule is demonstrated.

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Structure‐Dependent Anchoring of Organic Molecules to Atomically Defined Oxide Surfaces: Phthalic Acid on Co₃O₄(111), CoO(100), and CoO(111)

Schwarz

Werner

et al. 2016

Chemistry A European J

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We have performed a model study to explore the influence of surface structure on the anchoring of organic molecules on oxide materials. Specifically, we have investigated the adsorption of phthalic acid (PA) on three different, well-ordered, and atomically defined cobalt oxide surfaces, namely 1) Co3O4(111), 2) CoO(111), and 3) CoO(100) on Ir(100). PA was deposited by physical vapor deposition (PVD). The formation of the PA films and interfacial reactions were monitored in situ during growth by isothermal time-resolved IR reflection absorption spectroscopy (TR-IRAS) under ultrahigh vacuum (UHV) conditions. We observed a pronounced structure dependence on the three surfaces with three distinctively different binding geometries and characteristic differences depending on the temperature and coverage. 1) PA initially binds to Co3O4(111) through the formation of a chelating bis-carboxylate with the molecular plane oriented perpendicularly to the surface. Similar species were observed both at low temperature (130 K) and at room temperature (300 K). With increasing exposure, chelating mono-carboxylates became more abundant and partially replaced the bis-carboxylate. 2) PA binds to CoO(100) in the form of a bridging bis-carboxylate for low coverage. Upon prolonged deposition of PA at low temperature, the bis-carboxylates were converted into mono-carboxylate species. In contrast, the bis-carboxylate layer was very stable at 300 K. 3) For CoO(111) we observed a temperature-dependent change in the adsorption mechanism. Although PA binds as a mono-carboxylate in a bridging bidentate fashion at low temperature (130 K), a strongly distorted bis-carboxylate was formed at 300 K, possibly as a result of temperature-dependent restructuring of the surface. The results show that the adsorption geometry of PA depends on the atomic structure of the oxide surface. The structure dependence can be rationalized by the different arrangements of cobalt ions at the three surfaces.

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High-Resolution STM Studies of Terephthalic Acid Molecules on Rutile TiO₂(110)-(1 × 1) Surfaces

Cited by 42 publications

References 33 publications

Interaction of carboxylic acids with rutile TiO2(110): IR-investigations of terephthalic and benzoic acid adsorbed on a single crystal substrate

Interaction of carboxylic acids with rutile TiO2(110): IR-investigations of terephthalic and benzoic acid adsorbed on a single crystal substrate

Adsorption of Large Organic Molecules on Clean and Hydroxylated Rutile TiO₂(110) Surfaces

Structure‐Dependent Anchoring of Organic Molecules to Atomically Defined Oxide Surfaces: Phthalic Acid on Co₃O₄(111), CoO(100), and CoO(111)

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High-Resolution STM Studies of Terephthalic Acid Molecules on Rutile TiO2(110)-(1 × 1) Surfaces

Cited by 42 publications

References 33 publications

Interaction of carboxylic acids with rutile TiO2(110): IR-investigations of terephthalic and benzoic acid adsorbed on a single crystal substrate

Interaction of carboxylic acids with rutile TiO2(110): IR-investigations of terephthalic and benzoic acid adsorbed on a single crystal substrate

Adsorption of Large Organic Molecules on Clean and Hydroxylated Rutile TiO2(110) Surfaces

Structure‐Dependent Anchoring of Organic Molecules to Atomically Defined Oxide Surfaces: Phthalic Acid on Co3O4(111), CoO(100), and CoO(111)

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High-Resolution STM Studies of Terephthalic Acid Molecules on Rutile TiO₂(110)-(1 × 1) Surfaces

Adsorption of Large Organic Molecules on Clean and Hydroxylated Rutile TiO₂(110) Surfaces

Structure‐Dependent Anchoring of Organic Molecules to Atomically Defined Oxide Surfaces: Phthalic Acid on Co₃O₄(111), CoO(100), and CoO(111)