Antibacterial performance of nanoscaled visible-light responsive platinum-containing titania photocatalyst in vitro and in vivo

Background

Traditional antibacterial photocatalysts are primarily induced by ultraviolet light to elicit antibacterial reactive oxygen species. New generation visible-light responsive photocatalysts were discovered, offering greater opportunity to use photocatalysts as disinfectants in our living environment. Recently, we found that visible-light responsive platinum-containing titania (TiO₂–Pt) exerted high performance antibacterial property against soil-borne pathogens even in soil highly contaminated water. However, its physical and photocatalytic properties, and the application in vivo have not been well-characterized.

Methods

Transmission electron microscopy, energy dispersive spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction, ultraviolet–visible absorption spectrum and the removal rate of nitrogen oxides were therefore analyzed. The antibacterial performance under in vitro and in vivo conditions was evaluated.

Results

The apparent quantum efficiency for visible light illuminated TiO₂–Pt is relatively higher than several other titania photocatalysts. The killing effect achieved approximately 2 log reductions of pathogenic bacteria in vitro. Illumination of injected TiO₂–Pt successfully ameliorated the subcutaneous infection in mice.

Conclusions

This is the first demonstration of in vivo antibacterial use of TiO₂–Pt nanoparticles. When compared to nanoparticles of some other visible-light responsive photocatalysts, TiO₂–Pt nanoparticles induced less adverse effects such as exacerbated platelet clearance and hepatic cytotoxicity in vivo.

General significance

These findings suggest that the TiO₂–Pt may have potential application on the development of an antibacterial material in both in vitro and in vivo settings.     

Titanium dioxide nanomaterial doped with trivalent lanthanide ions of Tb, Eu and Sm: Preparation, characterization and potential applications

Mesoporous Ln(III)-TiO₂ (Ln = Tb, Eu, Sm) nanomaterials composites have been successfully synthesized by using sol-gel technique.XRD pattern, FT-IR, Raman spectra, and SEM were used to characterize the Ln(III)-TiO₂ nanomaterials. The prepared lanthanide doped TiO₂ nanomaterials have anatase phase and exhibit Ti-O-Ln bond. The absorption spectra of all prepared samples reflect the increasing photoresponse of doped samples to visible light over pure TiO₂. Surface area is remarkably increased due to lanthanide ion-doping.Two newly prepared Ln(III)-TiO₂ (Ln = Eu, Sm) luminescent nanomaterials exhibit enhanced pure red or orange light emission due to energy transfer from host TiO₂ to guest Eu(III) or Sm(III), respectively.In addition, the commercially available textile dye Remazol Red RB-133 degradation was used as a probe reaction to determine the efficiency of the Ln(III)-TiO₂ photocatalysts. The Ln(III) doping brought about remarkable improvement in the photoactivity over pure TiO₂.     

UPTAKE AND TRANSLOCATION OF TI FROM NANOPARTICLES IN CROPS AND WETLAND PLANTS

Bioavailability of engineered metal nanoparticles affects uptake in plants, impacts on ecosystems, and phytoremediation. We studied uptake and translocation of Ti in plants when the main source of this metal was TiO₂ nanoparticles. Two crops (Phaseolus vulgaris (bean) and Triticum aestivum (wheat)), a wetland species (Rumex crispus, curly dock), and the floating aquatic plant (Elodea canadensis, Canadian waterweed), were grown in nutrient solutions with TiO₂ nanoparticles (0, 6, 18 mmol Ti L^?1 for P. vulgaris, T. aestivum, and R. crispus; and 0 and 12 mmol Ti L^?1 for E. canadensis). Also examined in E. canadensis was the influence of TiO₂ nanoparticles upon the uptake of Fe, Mn, and Mg, and the influence of P on Ti uptake. For the rooted plants, exposure to TiO₂ nanoparticles did not affect biomass production, but significantly increased root Ti sorption and uptake. R. crispus showed translocation of Ti into the shoots. E. canadensis also showed significant uptake of Ti, P in the nutrient solution significantly decreased Ti uptake, and the uptake patterns of Mn and Mg were altered. Ti from nano-Ti was bioavailable to plants, thus showing the potential for cycling in ecosystems and for phytoremediation, particularly where water is the main carrier.     

The Improvement of Spinach Growth by Nano-anatase TiO<Subscript>2</Subscript> Treatment Is Related to Nitrogen Photoreduction

The improvement of spinach growth is proved to relate to N₂ fixation by nano-anatase TiO₂ in this study. The results show that all spinach leaves kept green by nano-anatase TiO₂ treatment and all old leaves of control turned yellow white under culture with N-deficient solution. And the fresh weight, dry weight, and contents of total nitrogen, , chlorophyll, and protein of spinach by nano-anatase TiO₂ treatment presented obvious enhancement compared with control. Whereas the improvements of yield of spinach were not as good as nano-anatase TiO₂ treatment under N-deficient condition, confirming that nano-anatase TiO₂ on exposure to sunlight could chemisorb N₂ directly or reduce N₂ to NH₃ in the spinach leaves, transforming into organic nitrogen and improving the growth of spinach. Bulk TiO₂ effect, however, was not as significant as nano-anatase TiO₂. A possible metabolism of the function of nano-anatase TiO₂ reducing N₂ to NH₃ was discussed.     

The effects of the bacterial interaction with visible-light responsive titania photocatalyst on the bactericidal performance

Bactericidal activity of traditional titanium dioxide (TiO₂) photocatalyst is effective only upon irradiation by ultraviolet light, which restricts the potential applications of TiO₂ for use in our living environments. Recently carbon-containing TiO₂ was found to be photoactive at visible-light illumination that affords the potential to overcome this problem; although, the bactericidal activity of these photocatalysts is relatively lower than conventional disinfectants. Evidenced from scanning electron microscopy and confocal Raman spectral mapping analysis, we found the interaction with bacteria was significantly enhanced in these anatase/rutile mixed-phase carbon-containing TiO₂. Bacteria-killing experiments indicate that a significantly higher proportion of all tested pathogens including Staphylococcus aureus, Shigella flexneri and Acinetobacter baumannii, were eliminated by the new nanoparticle with higher bacterial interaction property. These findings suggest the created materials with high bacterial interaction ability might be a useful strategy to improve the antimicrobial activity of visible-light-activated TiO₂.     

Enhanced Photocatalytic Activity for H2 Evolution under Irradiation of UV–Vis Light by Au-Modified Nitrogen-Doped TiO2

Background Purpose

Photocatalytic water splitting for hydrogen evolution is a potential way to solve many energy and environmental issues. Developing visible-light-active photocatalysts to efficiently utilize sunlight and finding proper ways to improve photocatalytic activity for H₂ evolution have always been hot topics for research. This study attempts to expand the use of sunlight and to enhance the photocatalytic activity of TiO₂ by N doping and Au loading.

Methods

Au/N-doped TiO₂ photocatalysts were synthesized and successfully used for photocatalytic water splitting for H₂ evolution under irradiation of UV and UV–vis light, respectively. The samples were characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), UV–vis diffuse reflectance spectroscopy (DRS), photoluminescence spectroscopy (PL), and photoelectrochemical characterizations.

Results

DRS displayed an extension of light absorption into the visible region by doping of N and depositing with Au, respectively. PL analysis indicated electron-hole recombination due to N doping and an efficient inhibition of electron-hole recombination due to the loaded Au particles. Under the irradiation of UV light, the photocatalytic hydrogen production rate of the as-synthesized samples followed the order Au/TiO₂ > Au/N-doped TiO₂ > TiO₂ > N-doped TiO₂. While under irradiation of UV–vis light, the N-TiO₂ and Au/N-TiO₂ samples show higher H₂ evolution than their corresponding nitrogen-free samples (TiO₂ and Au/TiO₂). This inconsistent result could be attributed to the doping of N and the surface plasmonic resonance (SPR) effect of Au particles extending the visible light absorption. The photoelectrochemical characterizations further indicated the enhancement of the visible light response of Au/N-doped TiO₂.

Conclusion

Comparative studies have shown that a combination of nitrogen doping and Au loading enhanced the visible light response of TiO₂ and increased the utilization of solar energy, greatly boosting the photocatalytic activity for hydrogen production under UV–vis light.     

Glucose biosensor based on the room-temperature phosphorescence of TiO2/SiO2 nanocomposite

The direct immobilization of glucose oxidase (GOD) on TiO₂/SiO₂ nanocomposite and its application as glucose biosensor were investigated. The room-temperature phosphorescence of TiO₂/SiO₂ nanocomposite can be quenched by hydrogen peroxide (H₂O₂). The detection of glucose may be accomplished by monitoring the formation of hydrogen peroxide which generated in the oxidation process of glucose with the catalysis of GOD. To our surprise, by using a 96-hole polyporous plate accessory of fluorescence spectrophotometer, the biosensor exhibits excellent linear response to glucose concentrations ranging from 1.0 × 10⁻⁹ to 1.0 × 10⁻² M with a detection limit of 1.2 × 10⁻¹⁰ M. The TiO₂/SiO₂ nanocomposite can be used as both supporting material and signal transducer. The phosphorescence intensity and color of the biosensor change obviously and even could be observed with naked eyes by continuous addition of glucose. Based on the room-temperature phosphorescence of TiO₂/SiO₂ nanocomposite, a new method of solid substrate-room-temperature phosphorimetry (SS-RTP) for glucose determination is proposed. A glucose biosensor was fabricated with wide determination concentration range, low detection limit, high sensitivity, and fast response time. And the biosensor has been successfully applied to the determination of glucose in human blood serum. The coacervation of GOD enzyme and its interaction with TiO₂/SiO₂ nanocomposite enlarge the surface area and enhance the chemical stability of GOD. The nice biocompatibility, large surface area, good chemical stability and nontoxicity of the TiO₂/SiO₂ nanocomposite have made this material suitable for functioning as biosensor.     

Physiochemical properties of n-n heterostructured TiO2/Mo-TiO2 composites and their photocatalytic degradation of gaseous toluene

The composite TiO₂/Mo-TiO₂ were prepared by a modified sol-gel method. The prepared catalysts were characterized by X-ray diffraction, BET analysis, SEM, X-ray photoelectron spectroscopy, and UV–vis diffused reflectance spectroscopy techniques. The structural characterization results demonstrated that Mo was successfully doped into the TiO₂ lattice and caused slight changes in the physiochemical properties. The UV–vis DRS showed a red shift of the adsorption edge to the visible region. The photocatalytic decomposition efficiencies of the catalysts were examined with toluene as a typical VOC in a continuous flow reactor. The photocatalytic activity of the n-n heterogeneous TiO₂/Mo-TiO₂ was greater than that of pure TiO₂ and Mo-TiO₂, and the catalyst containing a Mo/Ti mole ratio of 2.5% exhibited optimum photocatalytic properties. In general, a relative humidity of 35%, a higher oxygen content, a lower initial toluene concentration, and a higher UV intensity were beneficial for toluene decomposition.     

Effect of TiO2 NPs on the growth,anatomic features and biochemistry parameters of Baby sun rose (Aptenia cordifolia)

Rapid commercialization, industrialization and the use of nanotechnology has led to an increase in the distribution of nanoparticles (NPs) in the environment. The most common metal oxide NPs which is present within products is Titanium dioxide (TiO₂). TiO₂ NPs have photocatalytic nature and can affect plant growth. The current study investigated the morphological, anatomical and biochemical features of Baby sun rose (Aptenia cordifolia) after exposure to different concentrations of TiO₂ nanoparticles (0, 1, 5, 10 and 20 mg L⁻¹). Treatment with TiO₂ NPs showed changes in the morphological features and increased photosynthetic pigmentation within the plant. An increase in the level of phenolics (12%) and flavonoid compounds (13%) was observed when plants were treated with moderate levels of TiO₂ NPs. A reduction in the diameter of the vascular bundles and increased thickening of the transverse wall were observed in several samples. The number of scattered vascular bundles in the stems increased. The morphological, biochemical, and anatomical responses of Baby sun rose indicates that plants can adapt to environments contaminated with up to 20 mg L⁻¹ TiO₂ NPs_. The cultivation of Baby sun rose plants in environments polluted with TiO₂ NPs is recommended. This study enhances the knowledge of the effect of TiO₂ NPs on the growth of Baby sun rose which is an ornamental plant, widely cultivated in different regions of Iran. The results of this study suggest that contaminated environments up to 20 mg L⁻¹ TiO₂ NPs can be managed by phytoremediation. Further studies are needed to investigate this plant''s tolerance strategies against stress caused by TiO₂ NPs and bulk TiO₂ as well as the effect of other nanoparticles on plant.     

Was improvement of spinach growth by nano-TiO2 treatment related to the changes of Rubisco activase?

Characterized by a photo—catalysis property, nano-anatase TiO₂ is closely related to photosynthesis of spinach. It could not only improve light absorbance, transformation from light energy to electron energy and active chemical energy, but also promote the activity of Rubiso activase of spinach. However, the relation between the activity of Rubiso activase and the growth of spinach promoted by nano-anatase TiO₂ treatment remains largely unclear. In this study, we find that the amount and the activity of Rubiso activase are obviously increased by nano-anatase TiO₂ treatment, which led to the great promotion of Rubsico carboxylation and the high rate of photosynthesis, thus improving of spinach growth. The significant enhancement of Rubiso activase activity of nano-anatase TiO₂ treated spinach is also accompanied by conformational changes as determined by spectroscopic analysis. But bulk TiO₂ effect is not as significant as nano-anatase TiO₂, as the grain size of nano-anatase TiO₂ (5 nm) is much smaller than that of bulk TiO₂, which entered spinach cell more easily.     

The Effects of Nano-anatase TiO2 on the Activation of Lactate Dehydrogenase from Rat Heart

Lactate dehydrogenase (LDH, EC1.1.1.27), widely expressed in the heart, liver, and other tissues, plays an important role in glycolysis and glyconeogenesis. The activity of LDH is often altered upon inflammatory responses in animals. Nano-TiO₂ was shown to provoke various inflammatory responses both in rats and mice; however, the molecular mechanism by which TiO₂ exerts its toxicity has not been completely understood. In this report, we investigated the mechanisms of nano-anatase TiO₂ (5 nm) on LDH activity in vitro. Our results showed that LDH activity was greatly increased by low concentration of nano-anatase TiO₂, while it was decreased by high concentration of nano-anatase TiO₂. The spectroscopic assays revealed that the nano-anatase TiO₂ particles were directly bound to LDH with mole ratio of [nano-anatase TiO₂] to [LDH] was 0.12, indicating that each Ti atom was coordinated with five oxygen/nitrogen atoms and a sulfur atoms of amino acid residues with the Ti–O(N) and Ti–S bond lengths of 1.79 and 2.41 Å. We postulated that the bound nano-anatase TiO₂ altered the secondary structure of LDH, created a new metal ion-active site for LDH, and thereby enhanced LDH activity.     

Bactericidal Performance of Visible-Light Responsive Titania Photocatalyst with Silver Nanostructures

Background

Titania dioxide (TiO₂) photocatalyst is primarily induced by ultraviolet light irradiation. Visible-light responsive anion-doped TiO₂ photocatalysts contain higher quantum efficiency under sunlight and can be used safely in indoor settings without exposing to biohazardous ultraviolet light. The antibacterial efficiency, however, remains to be further improved.

Methodology/Principal Findings

Using thermal reduction method, here we synthesized silver-nanostructures coated TiO₂ thin films that contain a high visible-light responsive antibacterial property. Among our tested titania substrates including TiO₂, carbon-doped TiO₂ [TiO₂ (C)] and nitrogen-doped TiO₂ [TiO₂ (N)], TiO₂ (N) showed the best performance after silver coating. The synergistic antibacterial effect results approximately 5 log reductions of surviving bacteria of Escherichia coli, Streptococcus pyogenes, Staphylococcus aureus and Acinetobacter baumannii. Scanning electron microscope analysis indicated that crystalline silver formed unique wire-like nanostructures on TiO₂ (N) substrates, while formed relatively straight and thicker rod-shaped precipitates on the other two titania materials.

Conclusion/Significance

Our results suggested that proper forms of silver on various titania materials could further influence the bactericidal property.     

二氧化钛纳米颗粒对沼泽土壤反硝化和N2O排放的影响

近年来,二氧化钛纳米颗粒（TiO₂NPs）环境释放量不断增加,并通过多种途径进入湿地生态系统,不可避免地影响到湿地生态系统环境和功能。然而,关于TiO₂NPs对沼泽土壤反硝化作用和氧化亚氮（N₂O）排放的影响机及制尚不明确。选择典型沼泽土壤,通过室内培养实验研究土壤理化性质、反硝化酶活性、反硝化速率（DNR）和N₂O排放对不同剂量TiO₂NPs 0 mg/kg （CK）、10 mg/kg （A10）、100 mg/kg （A100）、1000 mg/kg （A1000）输入的响应,探讨TiO₂NPs输入对沼泽土壤反硝化作用和N₂O排放影响的内在机制。结果表明：不同剂量TiO₂NPs处理显著降低了土壤pH （P<0.05）,A10处理显著降低土壤总有机碳（TOC）含量（P<0.01）,A1000处理显著降低硝态氮（NO₃^--N）和亚硝态氮（NO₂^--N）含量（P<0.05）。TiO₂NPs处理抑制硝酸盐还原酶（NAR）活性,促进一氧化氮还原酶（NOR）和氧化亚氮还原酶（NOS）活性（P<0.01）,A1000处理先促进后抑制了亚硝酸盐还原酶（NIR）活性（P<0.05）。不同剂量TiO₂NPs处理抑制了土壤DNR,促进了N₂O排放,TiO₂NPs处理通过抑制NIR活性,降低土壤DNR,同时通过促进NOR活性,提高N₂O排放。综上,TiO₂NPs输入通过影响反硝化还原酶活性改变沼泽土壤反硝化过程,导致沼泽土壤N₂O排放增加,改变湿地氮的源、汇功能,影响全球气候变化。为TiO₂NPs输入的湿地环境风险评估研究提供理论基础。     

Photostabilized titanium dioxide and a fluorescent brightener as adjuvants for a nucleopolyhedrovirus

Titanium dioxide (TiO₂)reflects ultraviolet light, and so could beexpected to protect the occlusion bodies (OBs)of nucleopolyhedroviruses (NPVs) fromdegradation by sunlight. However, in thepresence of sunlight and water, TiO₂catalyzes the formation of hydrogen peroxide,which can degrade OBs. We tested microfineTiO₂ that had been photostabilized(particles were coated to prevent catalyticactivity), as a UV protectant for the OBs ofthe NPV of Helicoverpa zea (Boddie). Inthe absence of UV, activity of the OBs wasreduced by nonphotostabilized TiO₂ but wasunaffected by photostabilized TiO₂ or byzinc oxide (ZnO). None of these materialsinfluenced larval feeding rates. Undersimulated sunlight, photostabilizedTiO₂ protected the OBs to a greater degreethan did ZnO. Photostabilized TiO₂ wascompatible with a viral enhancer, thefluorescent brightener Blankophor HRS. Undersimulated sunlight, both materials increasedactivity of the OBs, relative to OBs withneither material, in a largely additive manner. In bioassays of foliage collected from fieldplots of lima bean plants sprayed with OBs withor without one or both of these materials,TiO₂ increased persistence of the OBs, butBlankophor HRS had no significant effect.     

Seasonal N uptake and N2fixation by common and adzuki bean at various spacings

The adzuki bean (Vigna angularis (Wild.) Ohwi and Ohashi) and common bean (Phaseolus vulgaris L.) have a high physiological demand for N. A 2-year field study was conducted to investigate the seasonal change of available soil N and symbiotic N₂ fixation usage. The beans were seeded at two densities, 22.2 plants m^–2 with a row spacing of 0.3 m and 11.1 plants m^–2 with a row spacing of 0.6 m. The amount of fixed N₂ in the shoot was calculated using the ¹⁵N natural abundance method. The common bean demonstrated low N₂ fixation and the ability to accumulate high levels of soil N. Soil nitrate under the common bean was continually absorbed. The adzuki bean, on the other hand, had a remarkable peak of N accumulation in the early reproductive stage. This was mainly due to N₂ fixation, though the soil nitrate level was high. Narrowing the plant row spacing increased the dry matter yield of both species, but the origin of the increased N differed between the species. For the first 77 DAP in 1999 (73 DAP in 2000) the N increase for both beans was due to both soil and atmospheric N₂. At harvest, though, the increase of N in common bean was mainly due to soil N, while that in adzuki bean was mainly due to atmospheric N₂. It can be concluded that the low symbiotic N₂ fixation ability of common bean was due to its high soil N uptake ability and constant N accumulation, which enabled an efficient soil N absorption. Adzuki bean absorbed N mainly for a short period and depended more on symbiotically fixed N₂ and, in contrast to common bean, left a high level of NO₃-N remaining in the soil after cropping.     

Influence of nano-anatase TiO2 on the nitrogen metabolism of growing spinach

Previous research showed that nano-TiO₂ could significantly promote photosynthesis and greatly improve growth of spinach, but, we also speculated that an increase of spinach growth by nano-TiO₂ treatment might be closely related to the change of nitrogen metabolism. The effects of nano-anatase TiO₂ on the nitrogen metabolism of growing spinach were studied by treating them with nano-anatase TiO₂. The results showed that, nano-anatase TiO₂ treatment could obviously increase the activities of nitrate reductase, glutamate dehydrogenase, glutamine synthase, and glutamic-pyruvic transaminase during the growing stage. Nano-anatase TiO₂ treatment could also promote spinach to absorb nitrate, accelerate, inorganic nitrogen (such as NO ₃ ^t- −N and NH ₄ ⁺ −N) to be translated into organic nitrogen (such as protein and chlorophyll), and enhance the fresh weight and dry weights.     

Inorganic and organic UV filters: Their role and efficacy in sunscreens and suncare products

Minerals such as titanium dioxide, TiO₂, and zinc oxide, ZnO, are well known active semiconductor photocatalysts used extensively in heterogeneous photocatalysis to destroy environmental pollutants that are organic in nature. They are also extensively used in sunscreen lotions as active broadband sunscreens that screen both UVB (290-320 nm) and UVA (320-400 nm) sunlight radiation and as high SPF makers. When so photoactivated by UV light, however, these two particular metal oxides are known to generate highly oxidizing radicals (OH and ) and other reactive oxygen species (ROS) such as H₂O₂ and singlet oxygen, ¹O₂, which are known to be cytotoxic and/or genotoxic. Hydroxyl (OH) radicals photogenerated from photoactive TiO₂ specimens extracted from commercial sunscreen lotions [R. Dunford, A. Salinaro, L. Cai, N. Serpone, S. Horikoshi, H. Hidaka, J. Knowland, FEBS Lett. 418 (1997) 87] induce damage to DNA plasmids in vitro and to whole human skin cells in cultures. Accordingly, the titanium dioxide particle surface was modified to produce TiO₂ specimens of considerably reduced photoactivity. Deactivation of TiO₂ diminishes considerably, in some cases completely suppresses damage caused to DNA plasmids, to human cells, and to yeast cells compared to non-modified specimens exposed to UVB/UVA simulated solar radiation. The photostabilities of sunscreen organic active agents in neat polar and apolar solvents and in actual commercial formulations have been examined [N. Serpone, A. Salinaro, A.V. Emeline, S. Horikoshi, H. Hidaka, J. Zhao, Photochem. Photobiol. Sci. 1 (2002) 970]. With rare exceptions, the active ingredients undergo photochemical changes (in some cases form free radicals) and the sunscreen lotions lose considerable Sun protection efficacy only after a relatively short time when exposed to simulated sunlight UVB/UVA radiation, confirming the recent findings by Sayre et al. [R.M. Sayre, J.C. Dowdy, A.J. Gerwig, W.J. Shields, R.V. Lloyd, Photochem. Photobiol. 81 (2005) 452].     

Promotion of Energy Transfer and Oxygen Evolution in Spinach Photosystem II by Nano-anatase TiO<Subscript>2</Subscript>

Being a proven photocatalyst, nano-anatase is capable of undergoing electron transfer reactions under light. In previous studies we had proven that nano-anatase improved photosynthesis and greatly promoted spinach growth. The mechanisms by which nano-anatase promotes energy transfer and the conversion efficiency of the process are still not clearly understood. In the present paper, we report the results obtained with the photosystem II (PSII) isolated from spinach and treated by nano-anatase TiO₂ and studied the effect of nano-anatase TiO₂ on energy transfer in PSII by spectroscopy and on oxygen evolution. The results showed that nano-anatase TiO₂ treatment at a suitable concentration could significantly change PSII microenvironment and increase absorbance for visible light, improve energy transfer among amino acids within PSII protein complex, and accelerate energy transport from tyrosine residue to chlorophyll a. The photochemical activity of PSII (fluorescence quantum yield) and its oxygen-evolving rate were enhanced by nano-anatase TiO₂. This is viewed as evidence that nano-anatase TiO₂ can promote energy transfer and oxygen evolution in PSII of spinach.     

Why Gratzel’s cell works so well

In Gratzel’s cell, the electrons injected by the photo-excitation of dye molecules, anchored to a mesoporous TiO₂ film, efficiently diffuse to the back contact achieving solar energy conversion at efficiencies exceeding 10%. The mesoporous TiO₂ surface constituted of randomly arranged nanocrystallites with a roughness factor of the order 1000 is heavily populated with traps, defects and adsorbed species which act as recombination centers. Nevertheless, the cell functions, mitigating recombination expected to occur via the interaction electrons at the surface. Evidence based mainly on 1/f noise measurements is presented to show that dye bonded to the TiO₂ surface passivates recombination centers. Furthermore the suppression of trapping-detrapping events at the surface increases the diffusion coefficient of the electrons through the nanocrystalline matrix facilitating electron transport to the back contact. The Gratzel cell is also unique, none of the high bandgap oxide materials other than TiO₂ yield energy conversion and quantum efficiencies as high as that of the cells based on TiO₂. 1/f noise measurements also reveal a distinct difference between TiO₂ and ZnO mesoporous films suggesting that the films made from the latter material are more intensely populated with surface states that mediate recombination.