Dye-sensitized solar cells based on double-layered TiO2 composite films and enhanced photovoltaic performance

Dye-sensitized solar cells (DSSCs) are fabricated based on double-layered composite films of TiO₂ nanoparticles and hollow spheres. The photoelectric conversion performances of DSSCs based on nanoparticles/nanoparticles (PP), hollow spheres/hollow spheres (HH), hollow spheres/nanoparticles (HP), and nanoparticles/hollow spheres (PH) double-layered films are investigated, and their photo-electric conversion efficiencies are 4.33, 4.72, 4.93 and 5.28%, respectively. The enhanced performance of TiO₂ nanoparticles/hollow spheres double-layered composite film solar cells can be attributed to the combined effect of following factors. The light scattering of overlayer hollow spheres enhances harvesting light of the DSSCs and the underlayer TiO₂ nanoparticle layer ensures good electronic contact between film electrode and the F-doped tin oxide (FTO) glass substrate. Furthermore, the high surface areas and pore volume of TiO₂ hollow spheres are respectively beneficial to adsorption of dye molecules and transfer of electrolyte solution.     

Effective incorporation of TiO2 nanoparticles into polyamide thin‐film composite membranes

The effectiveness of TiO₂ nanoparticles in improving the performance of polyamide (PA) thin‐film composite (TFC) membranes has been investigated. PA TFC membranes were prepared by interfacial polymerization with m‐phenylenediamine (MPD) and 1,3,5‐benzene tricarbonyl trichloride (TMC) where TiO₂ particles were added during and after interfacial polymerization. To distribute the TiO₂ nanoparticles uniformly in the PA films, colloidally stable TiO₂ sols were synthesized and added to the aqueous MPD solution rather than to an organic TMC solution. Through the use of different incorporation methods, TiO₂ particles were located on the top surface, in PA film layer, and in both positions. In the case of dense PA layers, the hydrophilicity of the membranes was significantly improved due to the presence of TiO₂ particles, resulting in an increased water flux. On the other hand, the enhancement of water flux was less significant when TiO₂ particles were incorporated into a loose PA film that was prepared with additives. In addition, a BSA fouling test confirmed that TiO₂ nanoparticles effectively improve the antifouling properties of the membranes for both dense and loose PA films. This effect is possibly due to increased hydrophilicity, covering of the fouling space, and a reduction in surface roughness. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43383.     

Tunable electrochemical properties of liquid phase deposited TiO2 films

Titanium dioxide (TiO₂) films on glassy carbon (GC) electrode surface were prepared by the liquid phase deposition (LPD) process for different deposition times. The morphological structure, interfacial property and electrocatalytic activity of as-prepared LPD TiO₂ films on GC surface were studied by field-emission scanning electron microscopy (FE-SEM), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The FE-SEM observation showed that the deposition time controlled the morphology of film on GC surface. With increasing deposition time, TiO₂ formed nanoparticles at the initial 5-h stage and compact thick films after 20 h. Due to the semiconducting properties of TiO₂, the LPD films inhibited the electron transfer process of [Fe(CN)₆]³⁻/[Fe(CN)₆]⁴⁻ on GC by increasing the redox reaction peak potential separation of CV curve and electron transfer resistance of EIS. The inhibition was increased with TiO₂ film thickness. Nevertheless, the onset reduction potential of maleic acid decreased with increasing LPD TiO₂ film thickness while the cathodic and anodic currents increased, demonstrating the useful electrocatalytic activity of LPD TiO₂ films.     

Preparation of photodegradable polypropylene/clay composites based on nanoscaled TiO2 immobilized organoclay

Photodegradable polypropylene (PP) composites were prepared via melting blending using PP and titanium dioxide (TiO₂) immobilized organically modified montmorillonite (organoclay). TiO₂ immobilized organoclay (TiO₂‐OMT) was synthesized by immobilizing anatase TiO₂ nanoparticles on organically modified clay via sol–gel method. The structure and morphology of TiO₂‐OMT were characterized by XRD and scanning electron microscope (SEM), which showed that anatase TiO₂ nanoparticles with the size range of 8–12 nm were uniformly immobilized on the surface of organoclay layers. Diffuse reflection UV–vis spectra revealed TiO₂‐OMT had similar absorbance characters to that of commercial photocatalyst, Degussa P25. The solid‐phase photocatalytic degradation of PP/TiO₂‐OMT composites was investigated by FTIR, DSC, GPC and SEM. The results indicated that TiO₂‐OMT enhanced the photodegradation rate of PP under UV irradiation. This was due to that immobilization of TiO₂ nanoparticles on organoclay effectively avoided the formation of aggregation, and thereby increased the interface between PP and TiO₂ nanoparticles. After 300 h irradiation, the average molecular weight was reduced by two orders of magnitude. This work presented a promising method for preparation of environment‐friendly polymer nanocomposites. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers.     

Characterization of acrylic acid‐grafted PP membranes prepared by plasma‐induced graft polymerization

Acrylic acid (AA)‐g‐polypropylene (PP) membranes were prepared by grafting AA on to a microporous PP membrane via plasma‐induced graft polymerization. The grafting of AA to the PP membrane was investigated using Fourier transform infrared spectroscopy (FTIR). Pore‐filling of the membranes was confirmed by field emission‐scanning electron microscopy (FESEM) and energy dispersing X‐ray (EDX). Ion exchange capacity (IEC), membrane electric resistance, transport number and water content were measured and analyzed as a function of grafting reaction time. The prepared AA‐g‐PP membranes showed moderate electrochemical properties as a cation‐exchange membrane. In particular, membranes with a degree of grafting of 155% showed good electrical properties, with an IEC of 2.77 mmol/g dry membrane, an electric resistance of 0.4 Ω cm² and a transport number of 0.96. Chronopotentiometric measurements indicated that AA‐g‐PP membranes, with a high IEC had a sufficient conducting region in the membrane. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Surface functionalization of polypropylene by entrapment of polypropylene‐grafted‐poly(ethylene glycol)

A surface functionalization polypropylene was prepared by entrapment a copolymer of polypropylene‐grafted‐poly(ethylene glycol) into polypropylene. The effects of structure of copolymer, contact dies, and content of modifiers were studied. The results of attenuated total reflection infrared spectroscopy(ATR‐FTIR) and contact angle measurements indicated that PP‐g‐PEG could preferably diffuse onto the surface and effectively increase the hydrophilicity of PP. PPw‐g‐PEG with lower PEG contents, lower molecular weight of PPw and PEG had better selective enrichment on the surface of PP blend film. By grafting of PEG‐OH onto the MPP, PP macromolecular surface modifier with better solvent‐resistance than that of PEG can be achieved. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Facile construction of silica-based surface coating onto polypropylene microporous film through dopamine-assisted hydrolysis of tetraethoxysilane

Surface modification with silica-based coating is widely used to attain high performance and construct special functions for thin films. In this paper, dopamine (DA) and tetraethoxysilane (TEOS) were used as initial building blocks to construct a biomimetic hydrophilic and mechanical robust silica-based coating onto polypropylene (PP) microporous film. It was found that the final DA/TEOS coating can be steadily immobilized onto PP film and greatly improve the hydrophilic property of PP film as evidenced by the decreased contact angle. Furthermore, the coating structures were comparatively investigated through one-step synthesis and two-step synthesis of DA and TEOS with a fixed ratio. Interestingly, the one-step synthesized coating possesses a loosely-packed layer with dispersed SiO₂ nanoparticles within polydopamine matrix while the two-step synthesized coating shows a high loading of SiO₂ nanoparticles. As a result, the two-step approach leads to a continuous SiO₂ layer with abundant hydroxyl groups, indicating a better lyophilic property and depressed thermal shrinkage. In addition, the concentric SiO₂ layer results in a significant increase of the tensile strength of PP films.     

Supercritical carbon dioxide-assisted preparation of polypropylene grafted acrylic acid with high grafted content and small gel percent

This work was aimed at preparing polypropylene grafted acrylic acid (PP-g-AA) with high grafted content and small gel percent by using a supercritical carbon dioxide (scCO₂)-assisted solid-state free radical grafting process. The effects of various factors on both the grafted acrylic acid content and gel percent in PP-g-AA were investigated. Those factors included the reaction time, reaction temperature, CO₂ pressure, monomer and initiator concentrations. Results showed that self-polymerization of acrylic acid resulted in crosslinking of PP chains and production of gel in PP-g-AA. There exists an optimal reaction time to produce PP-g-AA with high grafted content and small gel percent at a certain temperature. Both the initial AA/PP mass ratio and CO₂ pressure constituted very sensitive process parameters that could control the gel percent and grafted content in PP-g-AA to a significant extent and with ease. The crystallization temperature, melting temperature and crystallinity increased with the increasing of the grafted content of PP-g-AA. Moreover, the PP-g-AA removal of gel has a higher thermal stability than the blank PP.     

Microstructure and properties of porous nanocomposite films: effects of composition and process parameters

Porous nanocomposite films based on polypropylene (PP) and titanium dioxide (TiO₂) nanoparticles were prepared by melt extrusion followed by uniaxial stretching. The effects of drawing temperature, extension rate, stretching ratio and composition of the base films on the final properties and microstructure of the stretched films were studied. Water vapor permeability (WVP) results showed a significant decrease in permeability of the films stretched at temperatures higher than 60 °C. Porosity, pore size and water vapor transmission rate in the porous nanocomposite films had a direct relation with nanoparticle content, extension rate and stretching ratio. Study of the morphology of the stretched films, using SEM, revealed that the pores form due to PP/TiO₂ interfacial debonding at low stretching ratios. Higher stretching ratios cause an enlargement of the pores and the formation of a PP fibril structure parallel to the stretching direction. Quantification of dye adsorption revealed that the quantity of adsorbed dye increased with porosity and surface area of the pores. © 2014 Society of Chemical Industry     

Excellent antimicrobial properties of mesoporous anatase TiO2 and Ag/TiO2 composite films

Optically transparent, crack-free, mesoporous anatase TiO₂ thin films were fabricated. The Ag/TiO₂ composite films were prepared by incorporating Ag in the pores of TiO₂ films with an impregnation method via photoreduction. The as-prepared composite films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectronic spectra (XPS) and N₂ adsorption. The release behavior of silver ions in the mesoporous composite film was also studied. Moreover, the antimicrobial behaviors of the mesoporous film were also investigated by confocal laser scanning microscopy. The antibacterial activities of the composite films were studied by a fluorescence label method using Escherichia coli (E. coli) as a model. The as-prepared mesoporous TiO₂ films showed much higher antimicrobial efficiency than that of glass and commercial P25 TiO₂ spinning film. The facts would result from the high surface area, small crystal size and more active sites for the mesoporous catalysis. After the doping of Ag, a significant improvement for the antimicrobial ability was obtained. To elucidate the roles of the membrane photocatalyst and the doped silver in the antimicrobial activity, cells from a silver-resistant E. coli were used. These results indicated that Ag nanoparticles in the mesoporous were not only an antimicrobial but also an intensifier for photocatalysis. The as-prepared mesoporous composite film is promising in application of photocatalysis, antimicrobial and self-clean technologies.     

Phase inversion process to prepare quasi-solid-state electrolyte for the dye-sensitized solar cells

A quasi-solid-state electrolyte for the dye-sensitized solar cells was prepared following the phase inversion process. The microporous polymer electrolyte based on poly(vinylidene fluoride-co-hexafluoropropylene) (P(VDF-HFP)) hybrid with different amount of TiO₂ nanoparticles were prepared. The surface morphologies, the differential scanning calorimetry, and the ionic conductivity of the microporous polymer electrolyte were tested and analyzed. The results indicated that the microporous polymer electrolyte with TiO₂ nanoparticles modification exhibited better ionic conductivity compared with the original P(VDF-HFP) polymer electrolyte. The optimal ionic conductivity of 0.8 mS cm⁻¹ is obtained with the 30 wt % TiO₂ nanoparticles modification. When assembled with the 30 wt % TiO₂ nanoparticles modified quasi-solid-state electrolyte, the dye-sensitized TiO₂ nanocrystalline solar cell exhibited the light to electricity conversion efficiency of 2.465% at light intensity of 42.6 mW cm⁻², much better than the performance of original P(VDF-HFP) microporous polymer electrolyte DSSC. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Influence of functionalized reduced graphene oxide and compatibilizer on mechanical,thermal and morphological properties of polypropylene/polybutene-1 (PP/PB-1) blends

Polypropylene/Polybutene-1 (PP/PB-1) blends and nanocomposites containing pristine partially reduced graphene oxide (rGO) and chemically functionalized rGO (FrGO) with silane, and silane grafted with 1,12-dodecanediamine and 1,12-dodecanediol were studied. The effects of the chemical treatments on structure and thermal stability of rGO were first thoroughly investigated. Attenuated total reflectance Fourier infrared (ATR-FTIR) spectroscopy analyses of FrGO evidenced the existence of functional groups on rGO after each chemical treatment, while X-ray diffraction (XRD) results confirmed the effectiveness of the interlayer grafting process through shifting of the basal spacings as witnessed by increased d₀₀₂ values. Furthermore, thermogravimetric analysis (TGA) revealed that the functionalization of rGO resulted in improved thermal stability of rGO demonstrated by its increased thermal degradation temperature. The PP/PB-1 blends and their rGO and FrGO based nanocomposites were prepared by melt blending masterbatch process in the presence of an acrylic acid modified polypropylene compatibilizer (PP-g-AA). Mechanical testing showed that Young’s modulus and tensile strength of the PP/PB-1 blends significantly improved after co-addition of FrGO and PP-g-AA to form the nanocomposites, but it also endowed a drastic decrease in their elongation at break and especially in their impact strength. XRD analyses attested the successful formation of intercalated nanocomposites, and scanning electron microscopy (SEM) examinations disclosed a two-phase morphology consisting of PB-1 dispersed droplets in the PP matrix. SEM also indicated that the incorporation of PP-g-AA into the blends and the nanocomposites contributed to enhanced adhesion and dispersion of PB-1 phase and FrGO nanoparticles within the polymer matrix.     

Photocatalytic properties of TiO2 sol-gel modified nanocomposite films

TiO₂ nanocomposite films with different concentrations of TiO₂ MT-150A nanoparticles were immobilized on glass substrates using a dip coating process. The crystalline structure and surface chemical state of nanocomposite film properties were examined by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), respectively. The specific surface area and morphology of TiO₂ MT-150A nanoparticles were evaluated by the BET method and Field Emission Scanning Electron Microscopy (FE-SEM). The photocatalytic activities of films were evaluated by the methyl orange decoloring rate. XPS measurements showed that the oxygen amount (%) was related to the film composition. The composite film with 10 g/L MT-150A loading yielded the highest amount of surface oxygen (26.82%) and TiO₂ rutile showed the lowest amount of surface oxygen (13.67%) in the form of surface hydroxyl groups. The remaining oxygen was identified as lattice oxygen. In addition, the nanocomposite film with 10 g/L MT-150A loading yielded the highest photocatalytic activity.     

P(VDF-HFP)-based micro-porous composite polymer electrolyte prepared by in situ hydrolysis of titanium tetrabutoxide

A micro-porous composite polymer electrolyte (MCPE) was prepared in situ by adding TiO₂ nanoparticles from the hydrolysis of titanium tetrabutoxide to a solution of poly(vinylidenefluoride-co-hexafluoropropylene) [P(VDF-HFP)] copolymer. The prepared microporous polymer films (MCPFs) were characterized by scanning electronic microscopy, X-ray diffraction, thermogravimetric analysis, FT-IR and electrochemical interface resistance. After the addition of TiO₂ nanoparticles the polarity of CF₂ groups in the polymer chains and the crystallinity of the MCPFs decreased. When the composite polymer film contained 8.5 wt% of TiO₂ nanoparticles the MCPE exhibited excellent electrochemical properties such as high ionic conductivity, up to 2.40 × 10⁻³ S cm⁻¹ at room temperature.     

Enhanced photoresponse and photocatalytic activities of graphene quantum dots sensitized Ag/TiO2 thin film

TiO₂ thin films were fabricated through hydrothermal method. Silver nanoparticles were loaded on TiO₂ thin films via photoreduction technique. Subsequently, the graphene quantum dots (GQDs) were spin‐coated on the Ag/TiO₂ nanocomposites thin films. The crystal structure, surface morphology and UV‐vis absorbance were tested by XRD, SEM and ultraviolet‐visible spectrophotometer. These results indicated that Ag nanoparticles and GQDs are anchored on the TiO₂ nanorods. Absorbance of Ag/TiO₂ and GQDs/Ag/TiO₂ nanocomposite thin films have been extended into the visible region. Visible‐light response of the samples were investigated by electrochemical workstation. The photoresponse of the sample can be enhanced by sensitization of the Ag nanoparticles and GQDs. The enhanced visible‐light response may be due to the surface plasmon resonance of silver nanoparticles and visible absorbance of GQDs. The highest photocatalytic activity has been observed in the 9‐GQDs/Ag/TiO₂ composite thin film. The efficient charge separation and transportation can be achieved by introducing the Ag nanoparticles and GQDs in the TiO₂ thin film.     

Surface modification of TiO2 nanoparticles with silane coupling agent for nanocomposite with poly(butyl acrylate)

Abstract

In order to enhance the compatibility of TiO₂ nanoparticles in poly(butyl acrylate) (PBA) matrix, surface modification of TiO₂ was conducted using 3-methacryloxypropyl-trimethoxysilane (MPS). To improve the effect of surface modification, TiO₂ was predispersed in ethanol via ultrasonic waves. The process was investigated in detail to obtain the optimum condition of ultrasonic dispersion. The dispersion of TiO₂ in ethanol was evaluated via sedimentation rate. Fourier transform infrared spectroscopy and thermogravimetric analysis were performed to investigate the effect of surface modification. It was found that the organic functional groups of MPS had been successfully grafted onto the surface of TiO₂ nanoparticles. Finally, both neat PBA film and TiO₂/PBA composite film were prepared and characterised. The modified TiO₂ presented good compatibility in PBA matrix.     

Dye sensitized CO<Subscript>2</Subscript> reduction over pure and platinized TiO<Subscript>2</Subscript>

TiO₂ thin and thick films promoted with platinum and organic sensitizers including novel perylene diimide dyes (PDI) were prepared and tested for carbon dioxide reduction with water under visible light. TiO₂ films were prepared by a dip coating sol–gel technique. Pt was incorporated on TiO₂ surface by wet impregnation [Pt(on).TiO₂], or in the TiO₂ film [Pt(in).TiO₂] by adding the precursor in the sol. When tris (2,2′-bipyridyl) ruthenium(II) chloride hexahydrate was used as sensitizer, in addition to visible light activity towards methane production, H₂ evolution was also observed. Perylene diimide derivatives used in this study have shown light harvesting capability similar to the tris (2,2′-bipyridyl) ruthenium(II) chloride hexahydrate.     

pH Sensitive polypropylene porous membrane prepared by grafting acrylic acid in supercritical carbon dioxide

pH sensitive membrane was prepared by grafting acrylic acid (AA) on the porous polypropylene (PP) membrane using supercritical (SC) CO₂ as a solvent. The monomer (AA) and the initiator (benzyl peroxide, BPO) were impregnated into the PP substrate with the aid of SC CO₂, and were grafted onto the microporous PP substrate. The grafted membranes were characterized by Fourier transform infrared spectroscopy (FTIR), field emission scanning electron microscopy (FE-SEM), and the water permeability of the virgin and grafted membranes were determined at different pH values. It was demonstrated that the grafting degree (Dg) could be easily controlled by varying operating conditions, such as the monomer concentration, pressure, and temperature during the soaking process. The water permeation of the virgin membrane is nearly independent of pH. However, the water permeation of grafted membranes decreases dramatically with pH as the pH varies from 3 to 6 because the conformation of the PAA changes significantly with the pH of the contacting solution.     

Impact of different die draw ratio on crystalline and oriented properties of polypropylene cast films and annealed films

Four kinds of polypropylene (PP) cast films with different die draw ratios (DDR) were prepared. The impact of different DDR on the crystalline and oriented properties of PP cast films and annealed films was explored herein. Wide angle X-ray diffraction (WAXD) and fourier transform infrared (FTIR) methods were adopted to examine the orientation degree of crystalline and amorphous phases. Long period distance (L_p) of the crystalline structure was tested by small angle X-ray scattering (SAXS). Crystallization was determined by differential scanning calorimeter (DSC). The oriented and crystalline behaviors of the samples were carried out by the elastic recovery (ER) testing. Then, samples after being annealed were examined by the same methods. The influence of annealing process on the films’ structures and properties was explored. Besides, the final stretched microporous membranes manufactured via stretching the annealed films along machine direction were examined by scanning electronic microscope (SEM). No matter for cast films or for annealed films, it is found that the films’ orientation degree of crystalline and amorphous phases, as well as L_p and crystallinity are larger at higher DDR and relatively lower at lower DDR. When the DDR is overly high (DDR?=?170), both the oriented and crystalline properties will decline. Elastic recovery testing indicates that a film with better orientation of the crystalline and the amorphous phases as well as with higher crystallinity can be obtained at an appropriate DDR. SEM images show that stretched membranes with better microporous structure can be obtained when the precursor film is prepared at a proper DDR.     

Location of functionalized-TiO<Subscript>2</Subscript> nanoparticle in an immiscible PP/PA6 blends and its effect on the compatibility of the components

Nanocomposites based on 70/30 (w/w) polypropylene (PP)/polyamide 6 (PA6) immiscible blends and functionalized-TiO₂ nanoparticles were prepared via melt compounding. The influences of TiO₂ on the morphology of nanocomposites were investigated. Scanning electron microscopy results revealed the domain size of the dispersed PA6 phase decreased in presence of functionalized-TiO₂ and the TiO₂ nanoparticles were preferentially located at the PA6 phase and at the interfacial region between PP and PA6, which were ascertained by differential scanning calorimetry. The functionalized-TiO₂ nanoparticles played the compatibilizer for the immiscible PP/PA6 blends, increasing the interaction of the two phases in certain extent. Therefore, a clear compatibiliting effect was induced by the TiO₂ in the immiscible PP/PA6 blends.