Bipyridyl Ru Research Articles

Unleashing synergistic co-sensitization of BOA dyes and Ru(ii) complexes for dye-sensitized solar cells: achieving remarkable efficiency exceeding 10% through comprehensive characterization, advanced modeling, and performance analysis.

Dye-sensitized solar cells (DSSCs) have emerged as a promising alternative for renewable energy conversion. The synthesis and characterization of the 2-acetonitrile-benzoxazole (BOA) sensitizer MSW-1-4 are presented along with their chemical structures. Four new organic dyes, MSW-1 through MSW-4, were synthesized using BOA as the main building block, with different additional donor groups. The dyes were characterized and their photophysical and electrochemical properties were studied. Computational modeling using density functional theory (DFT) was performed to investigate their potential as sensitizers/co-sensitizers for photovoltaic applications. The modeling showed a distinct charge separation between the donor and acceptor parts of the molecules. For dye-sensitized solar cells, MSW-4 performed the best out of MSW-1-3 and was also better than the reference dye D-5. Moreover, MSW-3 was co-sensitized along with a typical highly efficient bipyridyl Ru(ii) sensitizer, N719, reference dye D-5, and metal-free dye MSW-4, to induce light harvesting over the expanded spectral region and hence improve the efficiency. Co-sensitizer (MSW-3 + N719) showed an improved efficiency of 10.20%. This outperformed a solar cell that used only N719 as the sensitizer, which had an efficiency of 7.50%. The appropriate combined dye loading of MSW-3 + N719 enabled good light harvesting and maximized the photoexcitation. The synergistic effect of using both MSW-3 and N719 as co-sensitizers led to enhanced solar cell performance compared with using N719 alone.

Precise analyses of photoelectrochemical reactions on particulate Zn0.25Cd0.75Se photoanodes in nonaqueous electrolytes using Ru bipyridyl complexes as a probe.

Recombination of photoexcited carriers at interface states is generally believed to strongly govern the photoelectrochemical (PEC) performance of semiconductors in electrolytes. Sacrificial reagents (e.g., methanol or Na2SO3) are often used to assess the ideal PEC performance of photoanodes in cases of minimised interfacial recombination kinetics as well as accelerated surface reaction kinetics. However, varying the sacrificial reagents in the electrolyte means simultaneously changing the equilibrium potential and the number of electrons required to perform the sacrificial reaction, and thus the thermodynamic and kinetic aspects of the PEC reactions cannot be distinguished. In the present study, we propose an alternative methodology to experimentally evaluate the energy levels of interfacial recombination centres that can reduce PEC performance. We prepare nonaqueous electrolytes containing three different Ru complexes with different bipyridyl ligands; redox reactions of Ru complexes represent one-electron processes with similar charge transfer rates and diffusion coefficients. Therefore, the Ru complexes can serve as a probe to isolate and evaluate only the thermodynamic aspects of PEC reactions. Recombination centres at the interface between a nonaqueous electrolyte and a Zn0.25Cd0.75Se particulate photoanode are elucidated using this method as a model case. The energy level at which photocorrosion proceeds is also determined.

Revealing the Photophysical Dynamics of Selected Rigid Donor-Acceptor Systems: From Ligands to Ruthenium(II) Complexes.

Newly designed push-pull ligands (L1 and L2) with bithiophene (bth) as a donor and phenazine (phz) or quinoxalino[2,3-b]quinoxaline (qxq) as acceptors were synthesized and also incorporated with a bipyridyl Ru(II) complex to give Ru1 and Ru2, respectively. The ultrafast photophysical dynamics of the ligand and their respective Ru(II) complexes were well-characterized using time-resolved spectroscopies and quantum chemical calculations. Photoinduced charger transfer (CT) and intersystem crossing (ISC) processes were directly observed for L1 and L2. In addition, the interplay of three different triplet excited states was directly observed in the related Ru(II) complexes. The lowest-lying triplet excited states of the ligands and their respective Ru(II) complexes were both attributed to the CT transitions from donor (bth) to acceptor (phz or qxq) and result in 3ICT (intramolecular charge transfer) and 3ILCT (intraligand charge transfer) excited states, respectively. The lifetimes of the lowest-lying triplet excited states of L1, L2, Ru1, and Ru2 were measured to be 21.3, 50.4, 2.75, and 4.16 μs, respectively.

A Hybrid Ru(II)/TiO2 Catalyst for Steadfast Photocatalytic CO2 to CO/Formate Conversion Following a Molecular Catalytic Route

Herein, we employed a molecular Ru(II) catalyst immobilized onto TiO2 particulates of (4,4'-Y2-bpy)RuII(CO)2Cl2 (RuP; Y = CH2PO(OH)2), as a hybrid catalyst system to secure the efficient and steady catalytic activity of a molecular bipyridyl Ru(II)-complex-based photocatalytic system for CO2 reduction. From a series of operando FTIR spectrochemical analyses, it was found that the TiO2-fixed molecular Ru(II) complex leads to efficient stabilization of the key monomeric intermediate, RuII-hydride (LRuII(H)(CO)2Cl), and suppresses the formation of polymeric Ru(II) complex (-(L(CO)2Ru-Ru(CO)2L)n-), which is a major deactivation product produced during photoreaction via the Ru-Ru dimeric route. Active promotion of the monomeric catalytic route in a hetero-binary system (IrPS + TiO2/RuP) that uses TiO2-bound Ru(II) complex as reduction catalyst led to highly increased activity as well as durability of photocatalytic behavior with respect to the homogeneous catalysis of free Ru(II) catalyst (IrPS + Ru(II) catalyst). This catalytic strategy produced maximal turnover numbers (TONs) of >4816 and >2228, respectively, for CO and HCOO- production in CO2-saturated N,N-dimethylformamide (DMF)/TEOA (16.7 vol % TEOA) solution containing a 0.1 M sacrificial electron donor.

DFT and TD-DFT Investigation of a Charge Transfer Surface Resonance Raman Model of N3 Dye Bound to a Small TiO2 Nanoparticle

Raman spectroscopy is an important method for studying the configuration of Ru bipyridyl dyes on TiO2. We studied the [Ru(II)(4,4′-COOH-2,2′-bpy)2(NCS)2)] dye (N3) adsorbed on a (TiO2)5 nanoparticle using Density Functional Theory, DFT, to optimize the geometry of the complex and to simulate normal Raman scattering, NRS, for the isolated N3 and the N3–(TiO2)5 complex. Two configurations of N3 are found on the surface both anchored with a carboxylate bridging bidentate linkage but one with the two NCS ligands directed away from the surface and one with one NSC tilted away and the other NCS interacting with the surface. Both configurations also had another –COOH group hydrogen bonded to a Ti-O dangling bond. These configurations can be distinguished from each other by Raman bands at 2104 and 2165 cm−1. The former configuration has more intense Normal Raman Scattering, NRS, on TiO2 surfaces and was studied with Time-Dependent Density Functional Theory, TD-DFT, frequency-dependent Raman simulations. Pre-resonance Raman spectra were simulated for a Metal to Ligand Charge Transfer, MLCT, excited state and for a long-distance CT transition from N3 directly to (TiO2)5. Enhancement factors for the MLCT and long-distance CT processes are around 1 × 103 and 2 × 102, respectively. A Herzberg–Teller intensity borrowing mechanism is implicated in the latter and provides a possible mechanism for the photo-injection of electrons to titania surfaces.

Controlling and Optimizing Photoinduced Charge Transfer across Ultrathin Silica Separation Membrane with Embedded Molecular Wires for Artificial Photosynthesis.

Ultrathin amorphous silica membranes with embedded organic molecular wires (oligo(p-phenylenevinylene), three aryl units) provide chemical separation of incompatible catalytic environments of CO2 reduction and H2O oxidation while maintaining electronic and protonic coupling between them. For an efficient nanoscale artificial photosystem, important performance criteria are high rate and directionality of charge flow. Here, the visible-light-induced charge flow from an anchored Ru bipyridyl light absorber across the silica nanomembrane to Co3O4 water oxidation catalyst is quantitatively evaluated by photocurrent measurements. Charge transfer rates increase linearly with wire density, with 5 nm-2 identified as an optimal target. Accurate measurement of wire and light absorber densities is accomplished by the polarized FT-IRRAS method. Guided by density functional theory (DFT) calculations, four wire derivatives featuring electron-donating (methoxy) and -withdrawing groups (sulfonate, perfluorophenyl) with highest occupied molecular orbital (HOMO) potentials ranging from 1.48 to 0.64 V vs NHE were synthesized and photocurrents evaluated. Charge transfer rates increase sharply with increasing driving force for hole transfer from the excited light absorber to the embedded wire, followed by a decrease as the HOMO potential of the wire moves beyond the Co3O4 valence band level toward more negative values, pointing to an optimal wire HOMO potential around 1.3 V vs NHE. Comparison with photocurrents of samples without nanomembrane indicates that silica layers with optimized wires are able to approach undiminished electron flux at typical solar intensities. Combined with the established high proton conductivity and small-molecule blocking property, the charge transfer measurements demonstrate that oxidation and reduction catalysis can be efficiently integrated on the nanoscale under separation by an ultrathin silica membrane.

DNA Electrochemical Biosensor Based on Iron Oxide/Nanocellulose Crystalline Composite Modified Screen-Printed Carbon Electrode for Detection of Mycobacterium tuberculosis.

Death from tuberculosis has resulted in an increased need for early detection to prevent a tuberculosis (TB) epidemic, especially in closed and crowded populations. Herein, a sensitive electrochemical DNA biosensor based on functionalized iron oxide with mercaptopropionic acid (MPA-Fe3O4) nanoparticle and nanocellulose crystalline functionalized cetyl trimethyl ammonium bromide (NCC/CTAB) has been fabricated for the detection of Mycobacterium tuberculosis (MTB). In this study, a simple drop cast method was applied to deposit solution of MPA-Fe3O4/NCC/CTAB onto the surface of the screen-printed carbon electrode (SPCE). Then, a specific sequence of MTB DNA probe was immobilized onto a modified SPCE surface by using the 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide/N-hydroxysuccinimide (EDC/NHS) coupling mechanism. For better signal amplification and electrochemical response, ruthenium bipyridyl Ru(bpy)32+ was assigned as labels of hybridization followed by the characteristic test using differential pulse voltammetry (DPV). The results of this biosensor enable the detection of target DNA until a concentration as low as 7.96 × 10−13 M with a wide detection range from 1.0 × 10−6 to 1.0 × 10−12 M. In addition, the developed biosensor has shown a differentiation between positive and negative MTB samples in real sampel analysis.

Efficiency enhancement of ruthenium-based DSSCs employing A-π-D-π-A organic Co-sensitizers.

A new bipyridyl Ru(ii) sensitizer incorporating triphenylamine and the 3,4-ethylenedioxythiophene (EDOT) ancillary ligand IMA5 was synthesized for dye-sensitized solar cells (DSSCs). The performance of these DSSCs has been enhanced via di-anchoring metal-free organic sensitizers, denoted IMA1–4, with structural motif A–π–D–π–A and incorporating phenyl-dibenzothiophene-phenyl (Ph-DBT-Ph) as the main building block but with different anchoring groups (A). These new organic sensitizers were well-characterized and used as efficient co-sensitizers. Their photophysical, electrochemical and photovoltaic properties were studied. Furthermore, molecular modeling studies using DFT calculations were used to investigate their suitability as effective sensitizers/co-sensitizers. The molecular orbital isodensity showed distinguishable delocalization of the intramolecular charge in the DBT moiety. The photovoltaic characterization showed that IMA3 had the best DSSC performance (η = 2.41%). In addition, IMA1–4 was co-sensitized in conjunction with the newly synthesized IMA5 complex to enhance light harvesting across expanded spectral regions and thus improve efficiency. The solar cells co-sensitized with IMA2, IMA3 and IMA4 exhibited improved efficiency (η) of 6.25, 6.19 and 5.83%, respectively, which outperformed the device employing IMA5 alone (η = 5.54%) owing to the improvement in the loading of IMA2, IMA3 and IMA4 in the presence of IMA5 on the surface of the TiO2 nanoparticles, and charge recombination was suppressed.

Novel metal-free organic dyes constructed with the D-D|A-π-A motif: Sensitization and co-sensitization study

A new structural motif, D-D|A-π-A, was suggested for the design of novel metal-free organic sensitizers, where “D|A” represents a fused donor-acceptor conjugated building block. Three organic dyes, coded FS07, FS08 and FS09, were synthesized accordingly with the incorporation of indolo [2,3-b] quinoxaline (IQ) as the main building block but different additional donors. The synthesized dyes were well-characterized and their photophysical and electrochemical properties were well-studied. Additionally, molecular modeling via DFT method was employed to probe their photovoltaic behaviors as sensitizers/co-sensitizers. The isodensity of the molecular orbitals displays the distinguished intramolecular charge delocalization in the IQ moiety, even though its donor and acceptor sections are coplanar-fused. In the photovoltaic characterization, FS08 exhibited the best DSSC performance. Moreover, FS07, FS08 and FS09 were co-sensitized along with a typical high efficient bipyridyl Ru(II) sensitizer, HD-2, in order to induce the light harvesting over expanded spectral region and hence improve the efficiency. The solar cell co-sensitized with FS08 displayed improved efficiency of 7.94% with JSC of 19.37 mA⋅cm−2, VOC of 0.654 V and FF of 62.7%, which outperformed the device employing HD-2 alone (efficiency of 7.46%). Owing to the appropriate dye loading of FS08 in the presence of HD-2 and CDCA mixed dye solution, the benign coordination for light harvesting was guaranteed and the photoexcitation was maximized, the co-sensitized JSC was improved; due to the well-modified TiO2 surface coverage with the tight attachment of FS08 and HD-2, the dye aggregation was diminished and the undesired charge recombination was suppressed, the co-sensitized VOC was improved.

Investigations into structure-property relationships of novel Ru(II) dyes with N,N′-Diethyl group in ancillary ligand for dye-sensitized solar cells

Structure-property relationships of four novel bipyridyl Ru(II) complexes, denoted as SD-22, SD-24, SD-26 and SD-28, are reported herein. The molecular structures of all four photosensitizers were confirmed using FT-IR, 1H NMR and mass spectrometry. Photovoltaic characteristics of the photosensitizers were evaluated under 1.5 a.m. standard illumination condition, in presence of deoxycholic acid as co-adsorbent, and subsequently compared to the performance of the benchmark, Z907. SD-22 showed an IPCE of 52% and 50% at 440 nm and 550 nm, respectively, a short-circuit photocurrent density (JSC) of 17.37 mA cm−2, open-circuit photovoltage (VOC) of 0.63 V and fill factor (FF) of 0.66, producing an overall conversion efficiency (η) of 7.31%, which outperformed Z907 (7.02%) under the same experimental device conditions. The η of the other photosensitizers is in the following order: SD-22 > SD-28 > SD-26 > SD-24. Photosensitizer SD-22 has N,N′-dialkyl group attached to a benzene ring while SD-24 has N,N′-dialkyl without a benzene ring. The extended conjugation in SD-22 translated into higher overall solar-to-electric conversion efficiency. Substitution of dialkylamino-based ancillary ligands of Ru(II) dyes SD-26 and SD-28 with –OCH3 and –OC6H13 also demonstrated that the photovoltaic performance of polypyridyl ruthenium photosensitizers is a function of the donating power of ancillary ligands as well as the steric effect of alkoxy auxochromes at –ortho position.

Interaction between disulfide/thiolate mediators and ruthenium complex in dye-sensitized solar cells

Abstract The intermolecular interactions of thiolate anions and disulfide molecules as disulfide/thiolate ( T 2 / T − , S 2 / S − ) redox couples with a Ru bipyridyl complex (Z907) are investigated using density functional theory. T and S are 1-methyl- 1H -tetrazole-5-thiolate and 2-methyl-5-trifluoromethyl- 2H -1,2,4-triazole-3-thiolate, respectively. Similar to the typical reductant I − , the S atoms of thiolate anions interact with the oxidized Z907 (Z907 + ) via the terminal S atoms of the isothiocyanate (NCS) ligands. However, nearly 40% of the atomic charge and spin still remain after complexation. If a second thiolate anion, as well as I − , is considered, the atomic charge and spin are transferred completely. The distances of the formed S S bonds for the Z907 + –two anions species correspond to isolated dithiolate radicals. These results suggest that Z907 + can be completely regenerated by two thiolate anions via a two-step mechanism rather than by only one thiolate anion through a one-step mechanism as previously suggested. Unlike the I 2 molecule, the unfound Z907–disulfide complex structure supports the slower recombination process with the disulfide/thiolate electrolyte compared with the I 3 − /I − system in dye-sensitized solar cells.

Amperometric Analysis of Ru π-Conjugated Polymers: Prospective Co-Supports for Enantioselective Ru Catalysts

Subtractively normalized interfacial Fourier transform infrared spectroscopy (SNIFTIRS) and electrochemical monitoring demonstrated how insertion of Os or Ru bipyridyl substituents into the backbone of regioregular polythiophenes provided low energy access to the polymer backbone. The good coordination between the polymeric backbone and the metal complex effectively enables delocalization of charge across the polymeric structure, while the metallic centers act as “electronic gates” (during MLCT) or “hole injectors” (during LMCT) thus enabling the polymers to be redox switched (and hence rendered conductive) at lower potentials, and at faster rate, than their unsubstituted counterparts.

Interfacial and Film‐Formation Behaviour of Photoactive RuII–Bipyridyl‐Based Metallosurfactants and a Rare Example of a Monolayer‐Based Logic‐Gate Approach

AbstractThree derivatives of tris(bipyridyl)–ruthenium(II) complexes with different alkyl‐chain lengths (nC18H37 (1), nC14H29 (2) and nC10H21 (3)) were synthesised. All these complexes behaved as an amphiphile and their surface properties were studied at the air–water interface by measuring surface pressure–area (Π–A) isotherms. The surface morphology of the resulting films at the air–water interface was also studied by using Brewster angle microscopy. Mean molecular areas of these complexes were measured from the Π–A isotherms, which were approximately 200 Å2, thereby indicating a parallel arrangement of the Ru–bipyridyl moiety of the complexes. Mono‐ and multilayer Langmuir–Blodgett (LB) films were formed on different solid surfaces with transfer ratios close to one. Similarities in the absorption and fluorescence spectra of these amphiphiles in solution as well as in LB films deposited on a quartz surface confirmed the successful transfer of these films onto the substrates. The latter provided information about the arrangements of metallosurfactant molecules within the LB films. The two‐dimensional concentrations of these films were calculated from the Lambert–Beer law as well as from the Π–A isotherm, which confirmed regular and reproducible transfer of the complex monolayers from the air–water interface onto the quartz surface. The surface morphology of these films on various substrates was characterised by atomic force microscopy. Furthermore, by oxidising the monolayer of complex 3, a one‐input sequential logic gate was constructed.

Tunable Energy Transfer Rates via Control of Primary, Secondary, and Tertiary Structure of a Coiled Coil Peptide Scaffold

Herein we report energy transfer studies in a series of Ru(II) and Os(II) linked coiled-coil peptides in which the supramolecular scaffold controls the functional properties of the assembly. A general and convergent method for the site-specific incorporation of bipyridyl Ru(II) and Os(II) complexes using solid-phase peptide synthesis and the copper-catalyzed azide-alkyne cycloaddition is reported. Supramolecular assembly positions the chromophores for energy transfer. Using time-resolved emission spectroscopy we measured position-dependent energy transfer that can be varied through changes in the sequence of the peptide scaffold. High level molecular dynamics simulations were used in conjunction with the spectroscopic techniques to gain molecular-level insight into the observed trends in energy transfer. The most efficient pair of Ru(II) and Os(II) linked peptides as predicted by molecular modeling also exhibited the fastest rate of energy transfer (with k(EnT) = 2.3 × 10(7) s(-1) (42 ns)). Additionally, the emission quenching for the Ru(II) and Os(II) peptides can be fit to binding models that agree with the dissociation constants determined for the peptides via chemical denaturation.

Effect of Side Groups for Ruthenium Bipyridyl Dye on the Interactions with Iodine in Dye-Sensitized Solar Cells

A density functional theory (DFT) study was performed to elucidate the effect of the side group (X) in Ru(H2dcbpy)(X2bpy)(NCS)2 dye on the interactions with iodide ions (I– and I3–) and iodine molecule (I2), where X is a carboxyl, nonyl, amino, or 1-pyrrolyl group, and dcbpy and X2bpy represent 4,4′-dicarboxy-2,2′-bipyridine and 4,4′-X2-2,2′-bipyridine, respectively. Oxidized dyes interact with I– via the S atom of the NCS ligand perpendicular to the H2dcbpy ligand. The relative interaction strength between the dye and I– is amino < nonyl <1-pyrrolyl < carboxyl group. Except for dye possessing amino groups, a second I– bonds to the first I–, and the iodides weakly interact with the C–H bond of X2dcbpy ligand. Additionally, I2 interacts via the S atom of the NCS ligand perpendicular to H2dcbpy of the neutral dye, and this interaction becomes stronger in the order of carboxyl < 1-pyrrolyl < nonyl < amino group dye. Only the neutral dye possessing amino groups interacts with I3– via N–H···I bonds. On the basis of theoretical results, the effect of side groups for Ru bipyridyl dye on both regeneration of oxidized dye with I– species and recombination related to the interactions with I2 and I3– species in the dye-sensitized solar cells is discussed.

Synthesis, spectral characterization and cytotoxicity of Ru–bipyridyl complexes containing hexakis(pyrazol-1-yl)benzene (hpzb) as a co-ligand

A novel ruthenium bisbipyridine complex, [Ru(bpy) 2(hpzb)](PF 6) 2 ( 1) (hpzb = hexakis(pyrazol-1-yl)benzene) was obtained in the reaction between [Ru(bpy) 2Cl 2], the tritopic ligand hpzb and NH 4PF 6. A high selectivity has been found in the reaction and when the hpzb ligand was made to react with more than one ruthenium fragment, it coordinated selectively only to the first metallic fragment, and it was not possible to introduce two or three ruthenium centres. A similar complex with a deuterated bipyridine has also been obtained. The reaction with the methylated ligand hexakis(3,5-dimethylpyrazol-1-yl)benzene does not take place. A complete assignment of all the proton and carbon NMR signals of 1 was carried out. The orientation of the free pyrazolyl groups is also discussed. The redox properties and the anticancer activity of complex 1 have been studied.

Photovoltaic Performance of Plastic Dye-Sensitized Electrodes Prepared by Low-Temperature Binder-Free Coating of Mesoscopic Titania

Mesoporous film was prepared at low temperatures, , on a conductive indium-tin oxide (ITO)-coated polyethylene naphthalate (PEN) plastic sheet by doctor-blade coating of a binder-free paste consisting of nanocrystalline and interparticle binding agent. -loaded ITO-PEN electrodes were dye-sensitized with Ru bipyridyl complexes to construct photoanodes of plastic dye-sensitized solar cells using iodide/triiodide-based organic redox electrolytes. A solar cell with optimized particle size and electrolyte composition yielded highest conversion efficiencies of 5.8% and 6.4% for an incident solar energy of 100 and , respectively.

Low-Temperature Fabrication of Dye-Sensitized Plastic Electrodes by Electrophoretic Preparation of Mesoporous TiO2 Layers

A mesoporous nanocrystalline layer was prepared on a conductive indium-tin oxide (ITO)-coated poly(ethylene terephthalate) (PET) film by low-temperature fabrication processes comprising high-field electrophoretic deposition of particles and post-treatments with a titanium oxide sol for interparticle binding. -coated ITO-PET film was dye-sensitized with Ru bipyridyl complex (N719) and used as the photoanode of an electrochemical solar cell using methoxyacetonitrile-based iodide/triiodide redox electrolyte. The solar cell yielded high conversion efficiencies of 4.1 and 4.3% for incident solar energies of 100 and © 2004 The Electrochemical Society. All rights reserved.

Dye-sensitized solar cells: a successful combination of materials

Dye-sensitized TiO2 solar cells, DSSC, are a promising alternative for the development of a new generation of photovoltaic devices. DSSC are a successful combination of materials, consisting of a transparent electrode coated with a dye-sensitized mesoporous film of nanocrystalline particles of TiO2, an electrolyte containing a suitable redox-couple and a Pt coated counter-electrode. In general, Ru bipyridyl complexes are used as the dye sensitizers. The light-to-energy conversion performance of the cell depends on the relative energy levels of the semiconductor and dye and on the kinetics of the electron-transfer processes at the sensitized semiconductor | electrolyte interface. The rate of these processes depends on the properties of its components. This contribution presents a discussion on the influence of each of the materials which constitute the DSSC of the overall process for energy conversion. An overview of the results obtained for solid-state dye-sensitized TiO2 solar cells assembled with polymer electrolytes is also presented.

The effect of chemisorbed dyes on I– V characteristics of mesoporous TiO 2 observed in scanning tunnelling spectroscopy

We report UHV STM/scanning tunnelling spectroscopy (STS) studies on mesoporous TiO 2 films in the presence and absence of adsorbed dye sensitisers (chlorophyll and a Ru bipyridyl dye). Interconnected and aggregated TiO 2 nanocrystallites with mean diameters typically of 30– 80 nm and different pore sizes are observed in STM images. The results show that, under controlled tunnelling conditions, the surface apparent band gap of as-prepared thin films is consistent with the bulk band gap of 3.2 eV , but that a quite different, lower surface apparent band gap is observed when a sensitising dye is adsorbed. Moreover, the characteristic measured in this case is dependent on the choice of dye, showing that the STM I/ V characteristic is sensitive to the adsorbed dye, rather than merely to the effect of surface adsorbed water. We discuss possible mechanisms for this effect, and the use of this effect in the optimisation of dye-sensitised photovoltaic cells.