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Chem Soc Rev
Cite this: Chem. Soc. Rev., 2012, 41, 4207–4217
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Adsorption of organic molecules on rutile TiO2 and anatase TiO2 single crystal surfaces
Andrew G. Thomas*a and Karen L. Syresb
Received 29th February 2012 DOI: 10.1039/c2cs35057b The interaction of organic molecules with titanium dioxide surfaces has been the subject of many studies over the last few decades. Numerous surface science techniques have been utilised to understand the often complex nature of these systems. The reasons for studying these systems are hugely diverse given that titanium dioxide has many technological and medical applications. Although surface science experiments investigating the adsorption of organic molecules on titanium dioxide surfaces is not a new area of research, the field continues to change and evolve as new potential applications are discovered and new techniques to study the systems are developed. This tutorial review aims to update previous reviews on the subject. It describes experimental and theoretical work on the adsorption of carboxylic acids, dye molecules, amino acids, alcohols, catechols and nitrogen containing compounds on single crystal TiO2 surfaces.

1. Introduction
Titanium dioxide is utilised in a range of technological applications including as a pigment, a biosensor support,1 photocatalyst2 and in the Gra ¨ tzel photovoltaic cell3 to name but a few. In addition, it is also found at the surface of Ti and Ti alloy

School of Physics and Astronomy and the Photon Science Institute, The University of Manchester, Oxford Road, Manchester M13 9PL. E-mail: b School of Chemistry, The University of Nottingham, University Park, Nottingham, NG7 2RD. E-mail:

biomaterials where its presence is thought to give rise to the excellent osseointegration properties of these materials.4 The surface properties and interactions of TiO2, particularly with small molecules such as water, oxygen, formate and methanol for example,5,6 have been widely studied for over thirty years. In many of the applications described above TiO2 is either intentionally functionalised or expected to interact with organic molecules. In the case of dye-sensitised solar cells (DSSCs) the titania surface is coated with a dye molecule, the most efficient of which to date is the N3-dye. However, new dyes which utilise the process of singlet fission (SF), whereby two charge carriers are produced following absorption of a single photon,

Andrew Thomas received his BSc in Chemistry from the University of Manchester and his MSc in instrumentation and Analytical Science from UMIST, before obtaining his PhD from the University of Liverpool. Following this he held three research appointments at UMIST before becoming an Experimental Officer in the Department of Physics. He was made a Research Fellow in Physics at UMIST in 2001 and moved to the Andrew G. Thomas Photon Science Institute at The University of Manchester following the merger of UMIST and The Victoria University of Manchester in 2004.
This journal is

Karen Syres obtained her MPhys degree from the University of Manchester before obtaining her PhD under the supervision of Andrew Thomas and Wendy Flavell. Following this she held a one-year PhD plus scholarship before moving to The School of Chemistry at the University of Nottingham where she is currently a Post-doctoral Research Fellow. Karen L. Syres

The Royal Society of Chemistry 2012

Chem. Soc. Rev., 2012, 41, 4207–4217


However. similarly to the rutile (110) surface. the rutile TiO2 (110) surface is the most widely studied of the three structural phases of TiO2 (anatase. 4208 Chem.28 directions. which are designed to cluster at the site of tumours. In order to overcome the energy storage problem TiO2 is also being investigated as a substrate for artificial photosynthesis. and a model based on [101] microfacets. The (100) surface forms a corrugated (1 Â 1) structure with rows of oxygens at the outermost surface.17 Subtle differences in both the surface electronic structure and adsorption strengths have been observed.5 It has long been known that O-vacancies at the TiO2 (110) surface lead to the formation of a band gap state around 1 eV below the Fermi level.6 Rather.12 This is thought to be due to the fact that the anatase TiO2 (101) surface has the lowest surface energy.7 In order to determine suitable SF dyes the TiO2-organic bonding.11 Due to its ready availability. As the molecules become larger their interactions also become more complex as the number of potential bonding groups on the molecule increases. energy level alignment and charge injection rates must be fully characterised. unlike rutile this peak is thought to arise from subsurface O-vacancies.8 Targeted biomaterials based upon TiO2 nanoparticles. This journal is c Published on 19 April 2012. Downloaded by UNIVERSIDADE FEDERAL SAO CARLOS on 29/07/2013 15:22:01. which result in formation of planes in the [103]27 or [014]20. this surface seems resilient to the formation of surface oxygen vacancies.9 Furthermore. Low energy electron diffraction (LEED) data suggests the surface forms (011) facets at the surface to minimise the surface energy. 2012. namely the adsorption of organic molecules on TiO2 surfaces. 41. Rev. rutile and brookite). However over the past ten years or so the quality of anatase single crystals and growth of thin films has improved. The rutile TiO2 (110) 1 Â 1 surface consists of rows of bridging oxygen ions (Obr) with 5 fold Ti4+ ions (Ti5c) and in plane oxygen ions. although the adsorption geometries of the molecules that have been studied on both surfaces are similar. have been functionalised with polyethylene glycol to evade the body’s immune system. This structure has been widely confirmed experimentally using various diffraction and scanning probe microscopy (SPM) techniques. However.14–16 This has allowed comparisons. The TiO2 (011) surface undergoes a (2 Â 1) reconstruction which exhibits Ti5c and two-fold coordinated oxygen atoms at the surface. The age and history of TiO2 single crystals has a large effect on the surface.25. The anatase TiO2 (101) surface is the most stable and most frequently observed surface of anatase TiO2. Anatase surfaces have been less widely studied as high quality single crystals have been difficult to obtain.24 The anatase TiO2 (001) surface is known to undergo a (1 Â 4)(4 Â 1) reconstruction when prepared in vacuum. Clean surfaces The reviews by Diebold5 and Pang et al. 4207–4217 2. Here molecules such as dopamine or dihydroxy phenylalanine (DOPA) have been used as the anchor groups.22 The twofold coordinated oxygen atoms partially block the Ti5c sites potentially blocking adsorption at these sites from gas phase molecules. Again. There have also been a number of studies of the (100).5 The (001) surface is inherently unstable due to the large number of broken bonds at the surface. It will concentrate mainly on the adsorption on highly-idealised vacuum-prepared single crystal surfaces. the charge is distributed over several Ti atoms and only a small amount remains on the topmost surface atoms. It is well established that TiO2 single crystal surfaces can be routinely prepared in vacuum by Ar+ ion sputter/anneal cycles.17 Although this peak is not removed by water adsorption it is removed by treatment with molecular oxygen. The interactions of TiO2 at the surface of biomaterials are numerous and extremely complex. We will also try to avoid repeating work described in the comprehensive review by Diebold5 and the more recent critical review by Pang et al. Many technological applications consist of TiO2 in the anatase form since this is the phase adopted by nanoparticulate TiO2.18–20 This review seeks to give a summary of adsorption of organic molecules on TiO2 from both an experimental and theoretical perspective. surface preparation in vacuum by Ar+ ion etching and annealing to 700 1C leads to a well-ordered surface.26 added and missing row models. A number of different models have been suggested for this structure including the added molecule model (ADM). Whilst dye sensitised solar cells are already commercially available the electricity can not be stored.23 In addition. pyrocatechol. Here light energy is used to drive photocatalytic redox reactions to produce hydrogen. have been shown to shift the optical absorption spectrum of TiO2 from the ultraviolet (UV) to the visible part of the electromagnetic spectrum. In order to fully appreciate the adsorption and interaction of organic molecules with the various surfaces we shall begin with a very brief overview of the geometric and electronic structure of the most widely studied rutile and anatase TiO2 surfaces.29 We will turn now to the main focus of this tutorial review. (001) and (011) rutile TiO2 surfaces. It has a sawtooth structure with fully co-ordinated six-fold and under co-ordinated five-fold Ti atoms.6 With reference to the surface chemistry and electronic structure some of the most interesting information obtained concerns surface oxygen vacancies.10 DOPA and dopamine are members of the catechol group of chemicals and along with the simplest catechol.13 Rutile TiO2 (110) in its (1 Â 1) termination is considered a prototypical metal oxide surface and much is now understood about this surface. Here we wish only to give a basic understanding of the structure.21 Apart from the (110) surface the three most commonly investigated rutile TiO2 surfaces are the (100). studies have shown dopamine to be effective both as an anchor molecule to bind DNA to titania nanoparticles and to enhance charge separation. SPM has indicated that the peak is associated with O-vacancies in the bridging oxygen rows. (001) and (011) surfaces. we hope to bring those articles up to date as well as describing why this area is so heavily researched. Soc.View Article Online are now being sought. particularly between the crystallographically equivalent rutile TiO2 (110) and anatase TiO2 (101) surfaces to be made. or other fuels from sunlight. The Royal Society of Chemistry 2012 .. As with the rutile phase.5 Annealing at higher temperatures leads to a (1 Â 3) reconstruction thought to consist of (110) microfacets. photoemission spectra of the valence band region often show a feature in the band gap region at a binding energy of 1 eV.20.6 describe the structures of clean TiO2 surfaces in some detail.

38 UV illumination in the absence of oxygen gas reproduced the results found for the TiO2 (110) surface. 4207–4217 4209 Fig. 1 The three adsorption geometries deduced for formate on the rutile TiO2 (110) surface. However.35 With regard to thermal and photodissociation of small carboxylic acids on the rutile TiO2 (110) surface. Downloaded by UNIVERSIDADE FEDERAL SAO CARLOS on 29/07/2013 15:22:01.37.2 Other rutile surfaces. The review by Pang et al.6 discussed the adsorption of formic acid on rutile TiO2 (110) thoroughly thus we shall summarise only the main points here.6 Benzoic acid adsorption on the rutile TiO2 (110) surface has been studied by LEED.5 More recently there have been a few experimental and theoretical studies of carboxylic acid adsorption on the TiO2 (011) (2 Â 1) surface23. i. there have been many studies. 3. 41..38 This bonding mode is favoured despite the larger Ti–Ti distances found on the (011) surface relative to the (110) surface. and as model molecules for understanding the (photo)catalytic activity of TiO2 surfaces.32.37 Temperature programmed desorption (TPD) measurements suggest the molecule decomposes above 500 1C with ketene. CO and CH4 being the main decomposition products.38 Quah et al.6 This journal is c The Royal Society of Chemistry 2012 . electron stimulated desorption ion angular distribution (ESDIAD).5 Pang et al.1. dicarboxylic acids and anhydrides Published on 19 April 2012. such as DSSCs.33 This geometry is also thought to allow interaction of another hydrogen atom in the molecule with the bridging oxygen rows. These are formed by interaction between the nitrogen lone pair and hydrogen atoms of nearest neighbours. 1).31 The proton lost from from formic acid upon adsorption is thought to bind to bridging oxygen atoms to form a bridging hydroxyl. NEXAFS. This then allows the formation of bonds between the hydrogen atoms of one ring and the p-system of its neighbour along the direction. Lyubinetsky et al. unlike the simple aliphatic acids benzoic acid is found to form dimers by rotation of the phenyl ring. It was found that this interaction was strongest for isonicotinic acid where tilting of the molecule led to increased interaction between the molecules.6 B is a minority species inferred from NEXAFS and STM measurements and C from STM. propionate and trimethyl acetate (TMA) form (2 Â 1) overlayers at saturation coverage. Similar results were obtained for adsorption on the (001) surface. on the rutile TiO2 (100) (1 Â 3) and TiO2 (100) (1 Â 1) show the adsorption is similar to that seen for the rutile (110) surface.38 which suggest adsorption in a bridging bidentate mode. roughly perpendicular to the [001] azimuth (B in Fig. In addition. This geometry (A) is shown in Fig. At temperatures lower than 500 1C the acetate recombines with an adsorbed proton and desorbs intact. 1)6 and another involves bonding through only one formate oxygen atom (site C in Fig. This observation was ascribed to a majority of molecules being adsorbed to Ti5c along the [001] azimuth and a smaller proportion to Obr vacancy sites. concluded that the formate is bound to two surface Ti5c atoms in a bridging geometry. Interestingly this work showed that the rate of molecular deposition onto the surface was critical to the degree of ordering. C 1s XPS spectra Chem.32–35 Like the aliphatic acids it is found to adsorb dissociatively in a bridging bidentate geometry. suggested that for TMA overlayers the proton is only weakly bound to the bridging oxygens and may oscillate between two oxygen atoms. the acid adsorbs dissociatively. X-ray photoelectron spectroscopy (XPS) and scanning tunneling microscopy (STM). Adsorption of small carboxylic acids. The motivation for these studies lies in technological applications of TiO2.6 Chemical-state specific scanned-energy mode photoelectron diffraction (PhD) carried out by Sayago et al. A is the geometry thought to be adopted by the majority of adsorbed formate.36 A detailed study of the adsorption of picolinic acid. and the sample temperature during dosing may all play a part in determining the adsorption geometry.1. 3. Pyridine carboxylic acids are found to adsorb to the rutile TiO2 (110) surface in a similar manner to benzoic acid. deduced from PhD and NEXAFS.1 Monocarboxylic acids 3.View Article Online 3. Carboxylic acids. that formic acid adsorbs at room temperature on all TiO2 surfaces which have been studied. via hydrogen bonds. acetate and propionate supported the existence of minority adsorption sites involving bridging-oxygen vacancies. Rev.6 A near edge absorption fine structure spectroscopy (NEXAFS) study of formate. Suffice to say.e. formate. anhydrides and di-carboxylic acids.e. Simple carboxylic acid adsorption on TiO2 surfaces has been widely studied. 2012. The adsorption occurs dissociatively as formate and is considered to be a model for all monocarboxylic acids adsorbed on TiO2. studied the photoexcited decomposition of acetic acid on the rutile TiO2 (011) surface using XPS and TPD. i. These are discussed in depth in the reviews of Diebold. We shall discuss photosensitising dyes and their ligands and amino acids separately in sections 4 and 5. The molecules were also found to be roughly perpendicular to the TiO2 (110) surface. acetate. The molecules were found to exhibit different twist angles relative to the [001] azimuth.6 and Henderson2 and the reader is referred to these works for more details. However. Soc.1 Adsorption on the rutile TiO2 (110) surface.30 It has been suggested that experimental conditions such as the surface preparation or history of the rutile TiO2 (110) crystal. We will concentrate here on simple carboxylic acids. One of these involves filling of an Obr site by one of the carboxyl oxygen atoms with the other bound to Ti5c (B in Fig. nicotinic acid and isonicotinic acid showed that slow deposition of these molecules onto the (110) surface led to the formation of monolayer dimer structures. 1.6 Although other experiments and theoretical treatments support this geometry there are also results which suggest alternative geometries. 1).34.

the structure which gives the highest adsorption energy) involves deprotonation of both carboxyl groups.. The adsorption of oxalic acid40 on TiO2 has been the subject of some theoretical work. Acetate gave rise to CO.3 Anhydrides The adsorption of acetic anhydride on the rutile TiO2 (110) surface at room temperature has been studied by XPS. Rev. The main decomposition products were found to be ethane and methane. indicating loss of acetate from the surface. As the temperature was increased above 850 1C it was found that a new phase was formed which the authors describe as a disordered (4 Â 4) overlayer. showed no change. As in the case of monocarboxylic acids. CO and CO2 were observed in TPD experiments. Formate appeared particularly resistant to annealing and formed strongly bound patches.e. 4207–4217 used in DSSC systems which are discussed below. 2j. ketene (CH2CO) and smaller amounts of water and acetic acid. The surfaces were modelled with simple TiO2 polymers to represent rutile and anatase surfaces.41 3. The adsorption then takes place through two oxygen atoms in a bridging mode. 3.26. or limiting the size of crystals in the preparation of nanoparticles. Tanner et al.29 similar to the rutile surfaces described above. In addition. resulting in a small coverage of acetate and decomposition products.3 Single crystal anatase TiO2 surfaces.42 Unlike acetic acid. have studied adsorption of acetic and formic acids on the anatase TiO2 (001) (1 Â 4)(4 Â 1) reconstructed surface epitaxially grown on a (100) Nb-doped SrTiO3 substrate.29 Acetate.39 To the best of the authors’ knowledge the only experimental studies of dicarboxylic acid adsorption on single crystal surfaces are those of dyes and dye ligands 4210 Chem. It was suggested that this occurred because surface oxygen was used up in the reaction and replaced by gas phase oxygen.40 Malonic acid adsorbed on P25 degussa particulate TiO2 has been studied using attenuated total reflection infrared spectroscopy. The interest in dicarboxylic acids lies in the fact that bonding via two acid groups to the TiO2 surface may lead to more efficient charge transfer between an adsorbed molecule and the oxide surface. Flashing the surfaces to around 850 1C gave different results for formate and acetate.1. The production of ethane could be restored by the introduction of more oxygen. The distance between the two carbonyl groups This journal is c The Royal Society of Chemistry 2012 . This is achieved if the bonding to the surface is sufficiently strong to prevent further reaction of the crystal with the growth medium. This work suggested adsorption of malonic acid on the TiO2 surface occurred via one bridging bidentate and one monodentate carboxylate group as shown in Fig. was simply lost from the surface at 850 1C. TPD measurements from anatase TiO2 (001) which had been Ar+ ion etched prior to exposure to formic or acetic acid showed desorption of a number of species between 300 and 750 1C. Adsorption was found to be stronger on the anatase surface than the rutile surface. C 1s peaks due to adsorbed acetate were found to decrease in intensity. Formate decomposed to form CO.View Article Online Published on 19 April 2012. 3. Soc.26 Neither acetate nor formate species could be desorbed by heating up to 700 1C. a chelating mode is unlikely at a Ti5c site since this would lead to 7-fold coordinated Ti ions. Preparation of a reduced TiO2 (011) surface by electron bombardment showed no difference in photocatalytic activity towards adsorbed acetate. However. LEED and high resolution electron energy loss spectroscopy (HREELS). on the other hand. 2 Possible binding modes of a dicarboxylic acid to a TiO2 surface. 41. Both acids were found to be adsorbed dissociatively to form a (4 Â 2) structure at saturation coverage. Fig. This structure was thought to arise due to adsorption of the deprotonated carboxyl groups to undercoordinated Ti atoms at the surface. Above 700 1C. 2 shows the various ways in which a dicarboxylic acid may be expected to adsorb on a TiO2 surface. CO2 and water.29 STM showed that the acids adsorb on the fully oxidised surface. formaldehyde (H2CO). Downloaded by UNIVERSIDADE FEDERAL SAO CARLOS on 29/07/2013 15:22:01. similar molecules are of interest in preventing crystal growth of particular surface planes. in the presence of O2 gas. The cross section for acetate removal was shown to decrease with decreasing oxygen partial pressure. Ethane production was reduced if the background oxygen partial pressure was not replenished. 2012. the anhydride does not have a terminal proton but instead has two carbonyl groups in an almost co-planar structure.2 Dicarboxylic acids Fig. The calculations suggest the most stable adsorption geometry (i. Illumination of the surface with UV showed decomposition of the malonic acid first to oxalic acid and eventually to CO and H2O.

42 however a p(2 Â 1) LEED pattern was observed. On the anatase TiO2 (001) surface. This journal is c Fig. This vacancy site is usually associated with the presence of Ti3+ at the surface. Scheme 1 is 0. resulting in two acetate adsorption. Soc.265 nm which is slightly smaller than the separation between Ti5c atoms in the (110) surface (B0. have studied adsorption of maleic anhydride (MA) on the rutile TiO2 (001) surface. However. Instead the molecule has been deposited by electrospray deposition46 in UHV or by removing vacuum prepared crystals capped with small molecules and Chem.44 The motivation lies in its wide use in chemical synthesis and also more recently as a potential dye anchor system for DSSCs. 3 Proposed adsorption geometry for maleic anhydride on the anatase TiO2 (101) surface determined from photoemission and NEXAFS spectroscopy.32 The dissociative adsorption process involves a surface bridging oxygen species as shown in Scheme 1a. The most widely used dye for these TiO2 nanoparticle cells is the so-called N3 dye. 4207–4217 4211 The Royal Society of Chemistry 2012 . A direct XPS comparison of adsorption of acetic anhydride and acetic acid showed that 12% more carbon was present on the anhydride dosed surface relative to the acetic acid dosed surface. This is also the LEED pattern one obtains at saturation coverage of acetic acid. MA adsorption on the (101). Although the chemical shifts of these two peaks were different from that of a multilayer of MA. Wilson et al.43 However.45 4.296 nm). Acetylene was also found to be desorbed from the surface. Downloaded by UNIVERSIDADE FEDERAL SAO CARLOS on 29/07/2013 15:22:01. the results for anhydride adsorption suggest the presence of the proton has little effect on the stability. However. here no redox reaction occurs since the surface oxygen binds to the oxygen deficient acetate moiety (Scheme 1b) thus the Ti atom retains its +4 oxidation state. The arrow indicates the surface bridging oxygen to which the molecule binds. This is despite the fact that the methyl fragment should be able to neutralise Obr as shown in Scheme 1b. It was suggested from the desorption products observed in TPD that adsorption on this surface occurred via ring cleavage at the central oxygen atom. The authors concluded that it was the requirement for the bridging geometry which governed the adsorption mechanism. resulting in a doubly-bidentate bridging geometry. the authors suggest that the ring opening process does not occur on the (001) surface.42 In doing so it allows the negatively charged acetate moiety to approach the Ti5c atom. This large molecule is labile so that the normal method of adsorption onto clean surfaces in ultra-high vacuum (evaporation by heating in vacuum) is not possible. For an intact acetic anhydride molecule one would expect a p(3 Â 1) LEED pattern.View Article Online Published on 19 April 2012.. i. CO2 and ketene dominating the TPD spectra for both surface treatments. 45 with permission of the author. 2012. Adsorption on the TiO2 (101) surface involves three surface titanium atoms as shown in Fig. Photosensitising dye molecules The adsorption of dye-sensitising molecules and charge transfer between these molecules and titania surfaces is of great fundamental and technological interest from the point of view of DSSCs.e.45 Adsorption on the (101) and (100) surfaces also occurs via ring opening and attachment through the three oxygen atoms of the molecule and a surface oxygen atom. 41. The authors also suggest some of the acetate species which had formed on Obr could convert to occupy two Ti5c sites resulting in a bridging oxygen vacancy. Theoretical work has suggested that the strength of carboxylic acid adsorption was partly due to the formation of bridging hydroxyl groups (OHbr) stabilising the carboxylate moiety. LEED and HREELS spectra indicated that acetic anhydride adsorbs dissociatively on the surface to form acetate ions. in this case the adsorption mode was deduced to be a bridging geometry. This. O 1s XPS spectra showed two peaks arising from MA which is indicative of oxygen in two different chemical environments. attempts to confirm the requirement to neutralise the bridging oxygen atoms using methyl acetate indicated that methyl acetate did not adsorb on the surface. Rev. Adapted from ref. TPD showed decomposition products which varied as a function of the surface stoichiometry with CO. This results in a bidentate chelating adsorption mode involving a surface oxygen atom.45 However. (001) and (100) anatase TiO2 surfaces has been studied by Johansson et al. 3. to reduce the negative charge of the bridging oxygen rows.2 0 -bipyridyl4. they argue leads to an excess positive charge on the bridging oxygen row which stabilises the bridging adsorption geometry in a similar way to the presence of OHbr.4 0 -dicarboxylic acid diisocyanate. ruthenium di-2. The authors rationalise that the part of the anhydride which attaches to the surface bridging oxygen acts in a similar manner to the proton in the acetic acid.

Figure adapted from ref.59 The highest adsorption energy was obtained for a model where the carbonyl oxygen of glycine bonds to a Ti5c site. dropping the dye from ethanolic solution. The results showed adsorption through the carboxyl group.48 Electrospray experiments suggests the dye bonds via one of the bi-isonicotinic acid (BINA) ligands in a bidentate geometry with further bonding through the sulfur atom of one of the thiocyanate groups as shown in Fig. One of the earliest studies of glycine adsorption on rutile TiO2 (110) showed that the molecule dissociated on the surface under synchrotron radiation.49 A number of studies have looked at the BINA ligand adsorbed on the rutile TiO2 (110) surface19. One may therefore expect there to be some competition as to which group will bind to the surface.35 and the anatase TiO2 (101) and (001) surfaces. 48 with permission of the author. have an acidic carboxyl group and a basic amine group.52. is very small thus it is possible all three modes of adsorption may be present.58 Hydrogen bonding occurs between the nitrogen atom and the proton lost (marked with an arrow) from the carboxylic acid group. This journal is c The Royal Society of Chemistry 2012 .51 The success of Ti based biomaterials is attributed to the layer of passivating oxide at the surface and it is this surface which will be exposed to the biological environment and govern the success or failure of the implant.58 They also showed hydrogen bonding via the amine group which led to further stabilisation of the adsorption as shown in Fig. Charge transfer from the BINA ligand to the TiO2 (110) surface was found to occur in o 3 fs.20 On the anatase (001) surface the tilt angle was much larger at 531 but the authors pointed out that this may be due to the surface reconstruction. electrons were found to be injected from the third lowest unoccupied molecular orbital (LUMO+3) to the surface in less than 16 fs. with proton transfer to the surface. Experimentally.20 Regarding the adsorption geometry of the ligand the mode of adsorption is the same on both the rutile and anatase surfaces studies. Amino acids have also been investigated to control the size and shape of TiO2 nanoparticles.46 4212 Chem.54–57 Tonner has carried out DFT calculations of proline and glycine adsorbed on the rutile TiO2 (110) surface. Rev. i. performed DFT calculations of glycine adsorption on the anatase (101) surface. Downloaded by UNIVERSIDADE FEDERAL SAO CARLOS on 29/07/2013 15:22:01. 41. Functional biomaterials based upon TiO2 nanoparticles are also being investigated. or indeed solely via the amine group. the authors point out that the energy difference between this model and one involving adsorption via the deprotonated carboxyl group. 2012.e. both acid groups become deprotonated and the molecule adsorbs in a doubly bidentate geometry. On the rutile TiO2 (110) surface the tilt angle was found to be 251 from the surface normal with an azimuthal twist of 441 relative to the [001] crystallographic direction. Soc.34. of course.4 0 -dicarboxylate2. this behaviour is echoed in amino acid adsorption where binding on TiO2 single crystal surfaces in vacuum occurs in a similar manner to that seen for carboxylic acids.53 It has been known for some time that pyridine does not form a strong bond to the TiO2 surface (see below).. 5 Proposed adsorption geometry for glycine on the rutile TiO2 (110) surface determined from DFT calculations. Amino acids. There are some difficulties in using photoelectron spectroscopy to investigate amino acid adsorption due to the instability of the molecules under high intensity radiation. There were some slight differences found in the adsorption angle with respect to the surface normal.2 0 -bipyridine)(CO)2I2 on the anatase TiO2 (101) surface also suggests bidentate bonding via the BINA ligand is the most stable configuration. Amino acid adsorption is also fundamentally interesting since TiO2 is an amphoteric oxide.47.39. Fig. A density functional theory (DFT) study of a simpler dye molecule (cis(CO)-trans(I)-Ru-(4. 4. Szieberth et al. In this model the hydroxyl group forms a hydrogen bond to a twofold coordinated oxygen ion and the amine group is bonded to Ti5c via the nitrogen lone pair. 4207–4217 Fig. On anatase TiO2 (101) the tilt angle was around 201 from the surface normal with a twist of around 401 from the [010] azimuth.50 For the complete dye molecule deposited by the electrospray method. 5. Published on 19 April 2012. However. 4 Proposed adsorption geometry of the N3 dye on the rutile TiO2 (110) surface deposited by the electrospray method.View Article Online 5. Amino acids The adsorption of amino acids on titania surfaces is of interest from the point of view of biomaterials and biosensors.

They suggest that due to steric effects and repulsion between neighbouring molecules that ethanol saturates at 0. reported a high cross-section for electronstimulated decomposition of methanol-related adsorbed species on TiO2 (110). Proline is found to adsorb in a bidentate geometry via the carboxyl group. Adsorption of phenylalanine on the rutile TiO2 (110) surface suggests the molecule adsorbs in a bidentate geometry following deprotonation of the acid group. 6. Rev. However. It was also found that co-adsorbed water had little effect on methanol at the surface. Downloaded by UNIVERSIDADE FEDERAL SAO CARLOS on 29/07/2013 15:22:01. 2012. like Henderson et al. static secondary ion mass spectroscopy (SSIMS) and LEED. Below room temperature molecular methanol desorbs from ´ n et al. More recently. Since the adsorption of small alcohols (methanol. Gamble et al.11 6. 6. Alcohols The decomposition of adsorbed alcohol molecules has been the subject of many studies aiming to understand the nature of photochemical reactions on the TiO2 surface. studied the adsorption of methanol onto a rutile TiO2 (110) surface using two-photon photoemission (2PPE). An earlier study by Henderson et al. Fleming and co-workers have carried out studies of glycine and proline adsorbed on rutile TiO2 (110) single crystal surfaces.5 Therefore.1 Adsorption on the rutile TiO2 (110) surface single crystal5 found. It is understood these species are formed by chemical reactions triggered by the photo-excited electron. Upon heating the zwitterion was lost from the surface due to loss of the additional proton in the amine. Under UV irradiation and an O2 atmosphere they observed a decrease in the peaks associated with ethanol adsorption and the rise of a peak due to CH3COO and HCOO. They were desorbed from the surface as ethanol gas (B250–400 K). It was found that under UV light methoxy is more reactive than molecularly adsorbed methanol for hole-mediated photo-oxidation.61 Following adsorption of methanol onto the surface they observed a resonance which they assign to a charge transfer from the reduced Ti5c+4-d ions to the free H atoms on surface hydroxyl groups.56 Again it was found that the molecule adsorbed preferentially via deprotonation of the carboxyl group and formed a (2 Â 1) overlayer similar to acetic and formic acids. Finally.5 Roma on the (100) and (110) surfaces increased with the number of defects created on the surface by electron or Ar+ bombardment.5 molecules of ethanol to every one Ti atom.58 The authors also observed the possible formation of hydrogen bonds between the amine group of the first layer and the carboxyl group of a second layer. ethanol and propanol) adsorbed on rutile TiO2 surfaces is covered comprehensively elsewhere. there was evidence of coexistence of anionic and zwitterionic glycine. UV light was found to lead to decomposition of methanol to formaldehyde and a surface OH group. Glycine adsorption on the TiO2 (011) surface studied using XPS found similar results. methanol and ethanol production from photocatalytic reactions are of particular interest for use as fuel. It was found that exposing the TiO2 surface to O2 resulted in more methoxy groups on the surface due to cleavage of the CH3O–H bond. with evidence of some dissociative adsorption (creating methoxy). in this section we point out that for peptides it is likely to be the side groups of the amino acids which control the overall adsorption mechanism. The difference to adsorption on the rutile surface was attributed to the difficulty in forming surface oxygen vacancies on the anatase TiO2 (101) surface..5.6 we shall mention only the main points and more recent findings. 41. Chem. prove difficult in characterising the methanol–TiO2 interface. Soc. used XPS to investigate the photoreaction under UV light of ethanol adsorbed on a rutile TiO2 (110) single crystal. found that methanol coverage the surface.15 It was found that methanol adsorbed molecularly on this surface with no signs of methoxy formation. particularly at oxygen vacancy sites. HREELS. They found the alcohols adsorbed molecularly and dissociatively at 200 K but only dissociatively at room temperature.60 There was little evidence for formation of the zwitterionic state in agreement with DFT calculations for glycine and proline adsorbed on this surface. In addition.View Article Online Published on 19 April 2012.5 Kim and Barteau have also studied the adsorption and decomposition of ethanol. Onda et al. This is because the terminal carboxyl and amine groups will form a small proportion of the overall molecule. ethoxy groups bound to bridging oxygen vacancies at the surface cannot react with water or hydroxyl groups on the surface (below B450 K)..5 Deuterated ethanol was found to adsorb dissociatively on the surface to create ethoxy groups (ethoxy groups were also formed by adsorption of tetraethoxysilane). where lowenergy electrons are fired at the surface.. They believe that the charge-transfer state is stabilised by the presence of the methanol molecules at the Ti5c+4-d sites.5 carried out an extensive study of methanol on a TiO2 (110) surface using TPD. used TPD and XPS to study the decomposition of ethoxy groups on a TiO2 (110) surface in the presence water or hydroxyl groups. The majority of methanol molecules were found to adsorb molecularly to the surface. The latter was again found to be lost upon heating due to conversion to the anion. which also agreed with their estimation based on the attenuation of the Ti 2p signal. As for the case of proline. They observed the presence of NH and NH2+ in proline suggesting two adsorption structures – a deprotonated anionic form and a zwitterionic form. Jayaweera et al. 4207–4217 4213 Henderson et al.5 They found that ethanol adsorbs dissociatively through its oxygen atom to one titanium atom on the surface. that molecular methanol was the majority surface species. Glycine adsorption on the rutile TiO2 (110) has been studied by STM. n-propanol and isopropanol on a TiO2 (001) surface using TPD and XPS.2 Alcohols on other TiO2 single crystal surfaces Kim and Barteau reported that on the TiO2 (001) surface methanol adsorbs molecularly and dissociatively at 200 K. They found that ethoxy groups bound to surface Ti atoms can be readily removed from the surface by combination with surface hydroxyl groups.5 Methanol adsorption on anatase TiO2 (101) has been studied by Diebold’s group using TPD and XPS. a TPD study of photochemical hole scavenging reactions of methanol adsorbed on a rutile TiO2 (110) This journal is c The Royal Society of Chemistry 2012 . methods such as LEED.

Dopamine and L-dihydroxyphenylalanine (L-DOPA) are being used to attach molecules. 41.63 In addition to their charge transfer properties. They propose that pyrocatechol adsorbs on the rutile TiO2 (110) surface in a mixed monolayer coverage of both monodentate and bridging bidentate structures and that the two can easily convert from one structure to another via proton exchange between the pyrocatechol and the surface.2 eV (370 nm) band gap of TiO2. 2012. 7. It has been proposed by Persson et al. Monodentate. In conjunction with DFT calculations they were able to interpret their experimental results. 7 Calculated adsorption geometry of pyrocatechol on rutile TiO2 (110) suggested by STM measurements.2 eV (300 nm) which is much larger than the 3.67 Published on 19 April 2012. in pyrocatechol-sensitised TiO2 nanoparticles there is an absorption shift to 3 eV (420 nm). Using angle-resolved UPS they calculated that the pyrocatechol molecules adsorbed in a bridging bidentate geometry (which give rise to the band gap state) are tilted by Æ15–301 from the surface normal. Fig. followed shortly after by neighbouring molecules. Bidentate bridging. A. Liu et al.65 have shown in theoretical calculations that the pyrocatechol molecule should adsorb on the anatase (101) surface in a bidentate bridging structure. In the bridging bidentate structure. with monodentate favoured at low-coverage and bidenate favoured at higher coverages. In a combined theoretical and experimental study. each oxygen atom is bonded to a different titanium atom on the surface. This is done by grafting the molecule via the amine side group resulting in a strong bridge between the TiO2 and the molecule.2-benzene-diol) shown in Fig. They also showed that on a defect site (common in nanoparticles) that it would adsorb in a chelating bidentate structure.. investigated the correlation between bonding geometry and band gap states for pyrocatechol adsorbed on rutile TiO2 (110).64 Pyrocatechol does not absorb light below 4. Rev. but bidentate pyrocatechol is much less mobile. B. Soc. On terraces they found both monodentate and bidentate structures present. Adapted with permission of the author from ref. Adsorbing pyrocatechol onto TiO2 nanoparticles is thought to result in interesting charge transfer processes62 and dopamine is widely used as a bridging molecule which facilitates electron/hole transfer between TiO2 nanoparticles and a biological system. C.66 studied the organization of pyrocatechol on an anatase TiO2 (101) surface using STM and DFT calculations.1 Pyrocatechol The simplest catechol is pyrocatechol (1. 4207–4217 This journal is c The Royal Society of Chemistry 2012 . They propose that monodentate pyrocatechol is mobile at room temperature and can move to preferential adsorption sites. This is caused by individual molecules ‘hopping’ to the next site along. However. The pyrocatechol-TiO2 system is of interest since it has potential applications in solar cells. Catechols Catechols (benzenediols) such as pyrocatechol and dopamine adsorbed on TiO2 surfaces are being studied for many applications. 6. 74. both the oxygen atoms are bonded to the same titanium atom. Li et al. In a monodentate structure. only one of the oxygen atoms is bonded to a titanium atom. This arrangement shows adjacent catechol molecules tilted in opposite directions in a mixture of bridging bidentate and monodentate adsorption geometries.62 that instead of the electron being excited in the adsorbate and then being transferred into the TiO2 conduction band. 6.62 This direct charge transfer is believed to be an excitation from the p orbital in the pyrocatechol to the Ti 3d levels at the bottom of the conduction band of the TiO2. This means the electron is directly photoinjected from the pyrocatechol into the conduction band of the TiO2 without the participation of excited states in the pyrocatechol. Bidentate chelating. Downloaded by UNIVERSIDADE FEDERAL SAO CARLOS on 29/07/2013 15:22:01. 6 Possible bonding modes of pyrocatechol to a TiO2 surface. In the bidentate chelating structure. Fig. In addition. 7 shows the calculated adsorption geometry of pyrocatechol on rutile TiO2 (110) proposed by Li et al. Redfern et al.66 They used STM to elucidate the bonding geometry and UV photoemission to investigate the presence of band gap states in the TiO2. they observed the formation of onedimensional islands that change shape over time without breaking up. catechols are used in many systems because they form strong bonds with TiO2. there is a direct pyrocatechol-to-TiO2 charge transfer.View Article Online 7. The three possible ways a catechol can adsorb on a TiO2 surface are shown in Fig. Fig. They found that isolated pyrocatechol molecules prefer to adsorb at step defects on the surface. which would not normally adsorb strongly on TiO2. They also proposed that only pyrocatechol adsorbed in a bridging bidentate geometry introduces states into the band gap of the TiO2. 4214 Chem.

Experimental and computational results indicated the appearance of new unoccupied states upon adsorption of dopamine.69 In these applications.72 using photoemission and NEXAFS.71 carried out a theoretical study of the TiO2/dopamine-DNA system. In many of these applications. also calculated that dissociative chelating bidentate adsorption of dopamine on corner/defects sites was more favourable than dissociative monodentate adsorption or molecular adsorption.75 However. 41.73 Ethylamine and diethylamine were both found to adsorb on the stoichiometric surface through formation of an N–Ti bond. In both cases the amines remained intact but on the defected surface less amine was adsorbed.74.75 have studied the adsorption of pyridine and 2.63 The system creates a lightinduced charge separation capable of carrying information about the electronic properties of the biomolecules.2 Pyridine Suzuki et al. Nitrogen containing compounds Nitrogen containing compounds are of interest due to their many industrial uses in the manufacture of dyes. there are few studies of dopamine on model single crystal anatase surfaces. 7. dopamine is often used to anchor other molecules. compared azobenzene and aniline adsorption on TiO2 and all three techniques gave almost identical results. Dopamine-modified TiO2 was found to be more efficient at charge separation than carboxyl-group-modified TiO2. Soc.71 The adsorption of dopamine on an anatase TiO2 (101) single crystal was studied by Syres et al. such as polymer chains.70 In addition. 2012. They found that the dopamine molecules provide a strong covalent bond to the TiO2 surface and they facilitate charge separation.e. XPS and LEED to study the conversion of azobenzene to aniline at anatase (101) and rutile (110) TiO2 surfaces. 8. The authors suggested that this may be due to adsorption at the defect sites blocking adsorption at more than one neighbouring Ti5c site. Calculations of dopamine on undercoordinated sites (defect sites) on the anatase TiO2 (101) surface carried out by this group. Pyridine molecules at the step edges were much less mobile than those on the terraces. targeted biomaterials. anti-fouling materials and bioelectronics. Unlike the aliphatic amines described above.View Article Online In a further investigation.10. Dopamine-modified TiO2 was found to be more photoactive because of the higher reducing power of the delocalized electrons and/or an increased absorption of visible light due to a shift of the absorption edge in the dopamine modified particles. This is in agreement with results for the pyrocatechol molecule on a defect site. the same group deduced that these pyrocatechol islands are responsible for a band-gap state found in the valence band spectra of the pyrocatechol-dosed TiO2 surface. an STM study of a rutile TiO2 (110) surface with single-atom height steps found that pyridine would attach to four-fold coordinated Ti atoms at the step edges. the authors suggested. 4207–4217 4215 The Royal Society of Chemistry 2012 . to the surface of TiO2 nanoparticles. The adsorbed pyridine molecules were able to exchange between these step adsorption sites and the terraces. ‘standing up’ on the surface).63. In addition.74 8. They propose that the NQN bond in azobenzene is cleaved by the TiO2 surface resulting in a phenyl Chem. On an anatase TiO2 (101) surface with few defects calculations suggested dopamine adsorbs in a bridging bidentate geometry. As with pyrocatechol. We have discussed amino acids and pyridine carboxylic acids above and here will concentrate on other nitrogen containing compounds. This is interesting for applications of dye-sensitised solar cells where dye molecules are often attached to TiO2 via carboxyl groups. neither pyridine nor 2. 8. This. knowledge of how these materials interact with particular materials is also of interest in the development of sensors for detection of trace amounts of explosives.76 The interaction of these molecules with TiO2 surfaces is driven by work which showed that TiO2 supported Au nanoparticles act as a high yield catalyst for synthesis of azobenzene via oxidation of anilines and reduction of nitroaromatic compounds to aniline. used STM. The dopamine/TiO2 interface also provides an electronic transition in a suitable range for photoexcitation. which could be due to hybridisation between the dopamine and the TiO2 surface.77 Li et al. They also found that the desorption activation energy decreased in the order diethylamine > ethylamine 4 ammonia which is also the order of decreasing Lewis basicity. On defected surfaces bonding also occurred at oxygen-vacancy (VO) sites.1 Aliphatic amines Farfan-Arribas and Madix used amine adsorption to determine the Lewis acidity of surface Ti4+ ions in rutile TiO2 (110) surfaces.3 Other nitroaromatics Li et al. Downloaded by UNIVERSIDADE FEDERAL SAO CARLOS on 29/07/2013 15:22:01.6-DMP form a strong bond to Ti5c on terraces of the TiO2 (110) surface but are rather weakly bound with the plane of the ring parallel to the surface.65 Vega-Arroyo et al. Carbon K edge NEXAFS spectra indicated that the dopamine molecules orientate themselves with their phenyl rings normal This journal is c 8. Dopamine has been employed as an anchoring molecule between DNA and TiO2 nanoparticles with an aim towards DNA-sequence recognition. explosives and polymers.2 Dopamine Dopamine adsorbed on TiO2 has been widely studied for biological and environmental applications such as photodegradation of bacteria. It was found that dopamine adsorbs in a bridging or chelating bidentate geometry.6-dimethylpyridine (2.71 concluded that the dopamine molecule would adsorb in a chelating bidentate structure following deprotonation. was evidence of adsorption driven by a Lewis acid–base interaction with the Ti4+ ions behaving as Lewis acids.6-DMP) on the rutile TiO2 (110) surface. The dopamine molecules in this system allow charge separation across the interface.9. Rev.68 Published on 19 April 2012..10. using dopamine to anchor carboxyethylb-cyclodextrin resulted in very efficient charge separation. Vega-Arroyo et al. Valence band photoemission spectra indicated that the adsorption of dopamine removes the band gap state at the surface present on the clean TiO2 surface. dopamine facilitates electron/hole transfer across the interface between the TiO2 and the biological system. to the surface (i.

Smith and J.View Article Online Published on 19 April 2012. Petersson. 9. Siegbahn. Thomas. 298–310. Bruhwiler. 8 Schematic reaction model of azobenzene and aniline on TiO2 determined from STM and photoelectron spectroscopy. Phys. H. C.. K. C. Chen. Lausmaa. 1017–1023. 75.. photon irradiation converted azobenzene from a flat-lying molecule to two upright phenyl imide species. P. resulting in an adsorbed phenyl imide species. when aniline is evaporated onto the surface it loses one or more hydrogen atoms. Phys. S. they discovered that at low coverages of azobenzene adsorbed on anatase. They propose that the NQN bond cleavage is facilitated by a photon-induced trans–cis isomerization. Li. Thornton. 6588–6594. T. Kumarasinghe. Pang. Scherer. 2 M. In addition. 2007. Dimitrijevic. Surf. Warren. 115. S. S. As outlined in the introduction TiO2 is still being heavily researched for novel applications involving photochemical reactions. 1991. A. 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