Conduction Band Of TiO2 Nanoparticles Research Articles

Surface Ru-H Bipyridine Complexes-Grafted TiO2 Nanohybrids for Efficient Photocatalytic CO2 Methanation.

A series of novel surface Ru-H bipyridine complexes-grafted TiO2 nanohybrids were for the first time prepared by a combined procedure of surface organometallic chemistry with post-synthetic ligand exchange for photocatalytic conversion of CO2 to CH4 with H2 as electron and proton donors under visible light irradiation. The selectivity toward CH4 increased to 93.4% by the ligand exchange of 4,4'-dimethyl-2,2'-bipyridine (4,4'-bpy) with the surface cyclopentadienyl (Cp)-RuH complex and the CO2 methanation activity was enhanced by 4.4-fold. An impressive rate of 241.2 μL·g-1·h-1 for CH4 production was achieved over the optimal photocatalyst. The femtosecond transient IR absorption results demonstrated that the hot electrons were fast injected in 0.9 ps from the photoexcited surface 4,4'-bpy-RuH complex into the conduction band of TiO2 nanoparticles to form a charge-separated state with an average lifetime of ca. 50.0 ns responsible for the CO2 methanation. The spectral characterizations indicated clearly that the formation of CO2•- radicals by single electron reduction of CO2 molecules adsorbed on surface oxygen vacancies of TiO2 nanoparticles was the most critical step for the methanation. Such radical intermediates were inserted into the explored Ru-H bond to generate Ru-OOCH species and finally CH4 and H2O in the presence of H2.

Oxidized titanium carbide MXene-enabled photoelectrochemical sensor for quantifying synergistic interaction of ascorbic acid based antioxidants system

Antioxidants can protect organization from damage by scavenging of free radicals. When two kinds of antioxidants are consumed together, the total antioxidant capacity might be enhanced via synergistic interactions. Herein, we develop a simple, direct, and effective strategy to quantify the synergistic interaction between ascorbic acid (AA) and other different antioxidants by photoelectrochemical (PEC) technology. MXene Ti3C2–TiO2 composites fabricated via hydrogen peroxide oxidation were applied as sensing material for the antioxidants interaction study. Under excitation of 470 nm wavelength, the photogenerated electrons transfer from the conduction band of TiO2 nanoparticles to the Ti3C2 layers, and the holes in TiO2 can oxidize antioxidants, leading to an enhanced photocurrent as the detection signal. This PEC sensor exhibits a good linear range to AA concentrations from 12.48 to 521.33 μM as well as obvious antioxidants capability synergism. In particular, the photocurrents of AA + gallic acid (GA) and AA + chlorogenic acid (CHA) mixtures at 476.19 μM increase 1.95 and 2.35 times respectively comparing with the sum of photocurrents of AA and GA or CHA. It is found that the synergistic effect is mainly depending on the fact that AA with the low redox potential (0.246 V vs NHE) can reduce other antioxidants radical to promote regeneration, improving the overall antioxidant performance. Moreover, it is proved that the greater redox potential of antioxidants, the more obvious the synergistic effect. In addition, the sensor was used to real sample assay, which provides available information towards food nutrition analysis, health products design and quality inspection.

Visible-Light Active Titanium Dioxide Nanomaterials with Bactericidal Properties.

This article provides an overview of current research into the development, synthesis, photocatalytic bacterial activity, biocompatibility and cytotoxic properties of various visible-light active titanium dioxide (TiO2) nanoparticles (NPs) and their nanocomposites. To achieve antibacterial inactivation under visible light, TiO2 NPs are doped with metal and non-metal elements, modified with carbonaceous nanomaterials, and coupled with other metal oxide semiconductors. Transition metals introduce a localized d-electron state just below the conduction band of TiO2 NPs, thereby narrowing the bandgap and causing a red shift of the optical absorption edge into the visible region. Silver nanoparticles of doped TiO2 NPs experience surface plasmon resonance under visible light excitation, leading to the injection of hot electrons into the conduction band of TiO2 NPs to generate reactive oxygen species (ROS) for bacterial killing. The modification of TiO2 NPs with carbon nanotubes and graphene sheets also achieve the efficient creation of ROS under visible light irradiation. Furthermore, titanium-based alloy implants in orthopedics with enhanced antibacterial activity and biocompatibility can be achieved by forming a surface layer of Ag-doped titania nanotubes. By incorporating TiO2 NPs and Cu-doped TiO2 NPs into chitosan or the textile matrix, the resulting polymer nanocomposites exhibit excellent antimicrobial properties that can have applications as fruit/food wrapping films, self-cleaning fabrics, medical scaffolds and wound dressings. Considering the possible use of visible-light active TiO2 nanomaterials for various applications, their toxicity impact on the environment and public health is also addressed.

Quantum dot sensitized solar cell based on the different photoelectrodes for the enhanced performance

In this work, the TiO2 nanoparticles have been used for the fabrication of CdS/TiO2, CdSe/TiO2, ZnS/CdSe/CdS/TiO2, ZnS/CdSe:Cu/CdS/TiO2 and ZnS/CdSe:Mn/CdS/TiO2 quantum dot-sensitized solar cells. The TiO2 films are sensitized with consecutive layers of CdS, CdSe quantum dots. Further, Cu2+ or Mn2+ ions were doped on CdSe quantum dots by successive ion layer adsorption and reaction. The performance of the QDSSCs is examined in detail using polysulfide electrolyte with Cu2S counter electrode. The cells containing CdSe quantum dots doped with the these ions show an improved short circuit current density (∼20.01 mA/cm2) with a maximum power conversion efficiency of 4.31% under 1 sun illumination. This enhancement is mainly attributed due to the superior light harvesting ability of the CdSe:Cu or CdSe:Mn quantum dots and make large accumulation of photo-injected electrons in the conduction band of TiO2 nanoparticles. In addition, the combination of doped CdSe and the presence of CdS layers caused lower recombination of photo-injected electrons with the electrolyte. These changes are demonstrated in this studying by using photovoltaic and electrochemical impedance spectroscopy.

Optical Absorption Spectra and Electronic Properties of Symmetric and Asymmetric Squaraine Dyes for Use in DSSC Solar Cells: DFT and TD-DFT Studies.

The electronic absorption spectra, ground-state geometries and electronic structures of symmetric and asymmetric squaraine dyes (SQD1–SQD4) were investigated using density functional theory (DFT) and time-dependent (TD-DFT) density functional theory at the B3LYP/6-311++G** level. The calculated ground-state geometries reveal pronounced conjugation in these dyes. Long-range corrected time dependent density functionals Perdew, Burke and Ernzerhof (PBE, PBE1PBE (PBE0)), and the exchange functional of Tao, Perdew, Staroverov, and Scuseria (TPSSh) with 6-311++G** basis set were employed to examine optical absorption properties. In an extensive comparison between the optical data and DFT benchmark calculations, the BEP functional with 6-311++G** basis set was found to be the most appropriate in describing the electronic absorption spectra. The calculated energy values of lowest unoccupied molecular orbitals (LUMO) were 3.41, 3.19, 3.38 and 3.23 eV for SQD1, SQD2, SQD3, and SQD4, respectively. These values lie above the LUMO energy (−4.26 eV) of the conduction band of TiO2 nanoparticles indicating possible electron injection from the excited dyes to the conduction band of the TiO2 in dye-sensitized solar cells (DSSCs). Also, aromaticity computation for these dyes are in good agreement with the data obtained optically and geometrically with SQD4 as the highest aromatic structure. Based on the optimized molecular geometries, relative positions of the frontier orbitals, and the absorption maxima, we propose that these dyes are suitable components of photovoltaic DSSC devices.

Extensive Reduction in Back Electron Transfer in Twisted Intramolecular Charge‐Transfer (TICT) Coumarin‐Dye‐Sensitized TiO2 Nanoparticles/Film: A Femtosecond Transient Absorption Study

We report the synthesis, characterization, and optical and electrochemical properties of two structurally similar coumarin dyes (C1 and C2). These dyes have been deployed as sensitizers in TiO2 nanoparticles and thin films, and the effect of molecular structure on interfacial electron-transfer dynamics has been studied. Steady-state optical absorption, emission, and time-resolved emission studies on both C1 and C2, varying the polarity of the solvent and the solution pH, suggest that both photoexcited dyes exist in a locally excited (LE) state in solvents of low polarity. In highly polar solvents, however, C1 exists in an intramolecular charge-transfer (ICT) state, whereas C2 exists in both ICT and twisted intramolecular charge-transfer (TICT) states, their populations depending on the degree of polarity of the solvent and the pH of the solution. We have employed femtosecond transient absorption spectroscopy to monitor the charge-transfer dynamics in C1- and C2-sensitized TiO2 nanoparticles and thin films. Electron injection has been confirmed by direct detection of electrons in the conduction band of TiO2 nanoparticles and of radical cations of the dyes in the visible and near-IR regions of the transient absorption spectra. Electron injection in both the C1/TiO2 and C2/TiO2 systems has been found to be pulse-width limited (<100 fs); however, back-electron-transfer (BET) dynamics has been found to be slower in the C2/TiO2 system than in the C1/TiO2 system. The involvement of TICT states in C2 is solely responsible for the higher electron injection yield as well as the slower BET process compared to those in the C1/TiO2 system. Further pH-dependent experiments on C1- and C2-sensitized TiO2 thin films have corroborated the participation of the TICT state in the slower BET process in the C2/TiO2 system.

Research of fluorescent properties of photo-induced electron transfer of 5(6)-carboxyfluorescein dye-sensitized TiO2 nanoparticles

Anatased TiO2 nanoparticles were prepared by controlling hydrolysis of the TiCl4. Time-resolved fluorescence experiments were carried out to study the photo-induced electron transfer dynamics in the system of the 5(6)CFL dye-sensitized TiO2 nanoparticles. For the aboved system, the formation of the charge transfer complex is attributed to the coupling interaction between the wave functions of the excited electronic state of the dye ((D*)) and the charge separated state ((D++e-)). On excitation of 5(6)CFL dye-sensitized TiO2 nanoparticle system. The injection of electrons into the conduction band of TiO2 nanoparticles takes place in two different ways: through the excited state of the 5(6)CFL dye and through direct injection from the charge transfer complex. The time-resolved fluorescence experimental results indicate that the free 5(6)CFL dye in water has double-exponential decay with lifetimes1=41 ps (74.4%) and2=3.22 ns (25.6%). However, 5(6)CFL dye-sensitized TiO2 nanoparticles have triple-exponential decay with lifetimes of1=44 ps (90.4%),2=478 ps (8.6%) and3=2.41 ns (1.0%). Our research will provide a valuable reference for the mechanism of dye-sensitized solar cell.

Photoinduced Electron Transfer of Oxazine 1/TiO2 Nanoparticles at Single Molecule Level by Using Confocal Fluorescence Microscopy

Kinetics of photoinduced electron transfer (ET) from oxazine 1 dye to TiO(2) nanoparticles (NPs) surface is studied at a single molecule level by using confocal fluorescence microscopy. Upon irradiation with a pulsed laser at 630 nm, the fluorescence lifetimes sampled among 100 different dye molecules are determined to yield an average lifetime of 2.9 +/- 0.3 ns, which is close to the value of 3.0 +/- 0.6 ns measured on the bare coverslip. The lifetime proximity suggests that most interfacial electron transfer (IFET) processes for the current system are inefficient, probably caused by physisorption between dye and the TiO(2) film. However, there might exist some molecules which are quenched before fluorescing and fail to be detected. With the aid of autocorrelation analysis under a three-level energy system, the IFET kinetics of single dye molecules in the conduction band of TiO(2) NPs is evaluated to be (1.0 +/- 0.1) x 10(4) s(-1) averaged over 100 single molecules and the back ET rate constant is 4.7 +/- 0.9 s(-1). When a thicker TiO(2) film is substituted, the resultant kinetic data do not make a significant difference. The trend of IFET efficacy agrees with the method of fluorescence lifetime measurements. The obtained forward ET rate constants are about ten times smaller than the photovoltage response measured in an assembled dye-sensitized solar cell. The discrepancy is discussed. The inhomogeneous and fluctuation characters for the IFET process are attributed to microenvironment variation for each single molecule. The obtained ET rates are much slower than the fluorescence relaxation. Such a small ET quantum yield is yet feasibly detectable at a single molecule level.

Charge-Transfer-Induced Surface-Enhanced Raman Scattering on Ag−TiO2 Nanocomposites

In this paper, a series of silver-deposited TiO2 (Ag−TiO2) nanoparticles (NPs) with a varying content of Ag were prepared by a photoreduction method and were attempted to serve as SERS-active substrates for the first time. SERS signals of 4-MBA molecules adsorbed on Ag−TiO2 NPs were further enhanced considerably relative to those enhancements on pure TiO2 NPs. The surface-deposited Ag on TiO2 can inject additional electrons into molecules adsorbed on the TiO2 surface through the conduction band of TiO2 NPs because of plasmon resonance absorption of Ag under incident visible laser, besides the intrinsic TiO2-to-molecule charge-transfer (CT) contribution. The two contributions mentioned are responsible for the whole SERS intensity of the molecules adsorbed on Ag−TiO2 NPs. This work is valuable in developing nanosized TiO2 used as a promising, nontoxic and biologically compatible SERS-active substrate as well as in studying the CT mechanism between Ag and TiO2 for potential photoelectrochemical applications.

Photochemical behaviors during the photosensitization of colloidal TiO2 particles by a newly synthesized multidentate squaraine

A new squaraine dye Bis(4-N,N-dicarboxymethyl-2-hydroxyphenyl)squaraine (SQ) which could be used as organic photovoltaic materials, was synthesized, and its molecular structure was fully characterized by elemental analysis, IR, 1H NMR and MS. SQ exhibits strong absorption band over 600–700 nm. Addition of TiO2 colloids to the ethanol solution of SQ resulted in the increase of optical density, quenching of fluorescence and shortened fluorescence lifetime. The apparent association constant between the sensitizer and semiconductor as measured from the fluorescence quenching data, was 2427 M−1. Fluorescence lifetime measurements gave the rate constant for the electron injection process from the excited singlet of SQ to the conduction band of TiO2 nanoparticles as 2.55 × 10 8 s−1. In addition, SQ doped SiO2 gel glass slices were prepared and characterized by absorption and emission spectra.

Interfacial Electron Transfer between the Photoexcited Porphyrin Molecule and TiO2 Nanoparticles: Effect of Catecholate Binding

Interfacial electron transfer (ET) dynamics of 5,10,15-trisphenyl-20-(3,4-dihydroxybenzene) porphyrin (TPP-cat) adsorbed on TiO2 nanoparticles has been studied by femtosecond transient absorption spectroscopy in the visible and near-IR region exciting at 400 and 800 nm. TPP-cat molecule forms a charge transfer (CT) complex with TiO2 nanoparticles through the catechol moiety with the formation of a five-membered ring. Optical absorption measurements have shown that the Q-band of TPP-cat interacts strongly with TiO2 due to chelation; however, the Soret band is affected very little. Optical absorption measurements indicate that the catechol moiety also interacts with TiO2 nanoparticles showing the characteristic band of pure catechol-TiO2 charge transfer (CT) in the visible region. Electron injection has been confirmed by monitoring the cation radical, instant bleach, and injected electron in the conduction band of TiO2 nanoparticles. Electron injection time has been measured to be < 100 fs and recombination kinetics has been best fitted with a multiexponential function, where the majority of the injected electrons come back to the parent cation radical with a time constant of approximately 800 fs for both excitation wavelengths. However, the reaction channel for the electron injection process has been found to be different for both wavelengths. Excitation at 800 nm, found to populate the CT state of the Q-band, and from the photoexcited CT state electron injection into the conduction band, takes place through diffusion. On the other hand, with excitation at 400 nm, a complicated reaction channel takes place. Excitation with 400 nm light excites both the CT band of Cat-TiO2 and also the Soret band of TPP-cat. We have discussed the reaction path in the TPP-cat/TiO2 system after exciting with both 400 and 800 nm laser light. We have also compared ET dynamics by exciting at both wavelengths.

Revealing the Nature of Trapping Sites in Nanocrystalline Titanium Dioxide by Selective Surface Modification

Excess electrons in nanocrystalline TiO2 were studied in bare and dopamine-capped TiO2 nanoparticles by electron-beam pulse radiolysis. Reaction of hydrated electrons with dopamine-capped TiO2 nanoparticles was found to be at the diffusion-controlled limit, k = 1 × 1011 M-1 s-1, while the reaction with 1-hydroxy-1-methylethyl radicals, (CH3)2ĊOH, was 2 orders of magnitude slower, k = 4 × 108 M-1 s-1. The reactions result in injection of electrons into the conduction band of TiO2 nanoparticles. Optical absorption spectra of injected excess electrons in dopamine-capped nanoparticles display monotonic featureless wavelength dependence up to 1800 nm. In contrast, bare particles have shown two preferential optical transitions with energies in the visible region (λmax = 670 nm and λmax = 900 nm). Flat band potential of dopamine-capped TiO2 nanoparticles was shifted by 100 mV to more negative values. The strong coupling of dopamine to surface Ti atoms was also found to improve the separation of photogenerated charges. This was demonstrated by the enhanced efficiency of photogenerated electrons in reducing silver cations to metallic silver in systems linked via a dopamine bridge, compared to the same systems linked through carboxyl groups.