In this work, we have demonstrated a facile approach to synthesize donut-shaped LiMn2O4 comprising interpenetrating nanograins, and this material demonstrates excellent high-rate cycling reversibility.

Layer-by-layer self-assembled TiO2 hierarchical nanosheets with exposed {001} facets have been successfully fabricated via a simple one-step solvothermal reaction. The anatase TiO2 layer-by-layer hierarchical nanosheets (TiO2 LHNs) exhibit favorable light scattering effect and large surface area, owing to their layer-by-layer hierarchical structure. When applied to the dye-sensitized solar cells (DSSCs), the layer-by-layer hierarchical structure with exposed {001} facet could effectively enhance light harvesting and dye adsorption, followed by increasing the photocurrent of DSSCs. As a result, the photoelectric conversion efficiency (η) of 7.70% has been achieved for the DSSCs using TiO2 LHNs as the bifunctional layer, indicating 21% improvement compared to the pure Degussa P25 (6.37%) as photoanode. Such enhancement can be mainly ascribed to the better light scattering capability of TiO2 LHNs, higher dye adsorption on TiO2 LHN {001} facets, and longer lifetime of the injected electrons in TiO2 LHNs compared to P25, which are examined by UV-vis spectrophotometry and electrochemical impedance spectroscopy under the same conditions. These remarkable properties of TiO2 LHNs make it a promising candidate as a bifunctional scattering material for DSSCs.

Hierarchical fastener-like spheres assembled from anatase TiO2 nanosheets with exposed {001} facets are successfully synthesized via a facile one-pot hydrothermal process. Compared with standard commercial P25, the as-obtained hierarchical fastener-like TiO2 spheres exhibit an improved light harvesting efficiency, owing to the excellent light scattering effect of layer-by-layer hierarchical structure and superior dye adsorption capacity of the dominant {001} facets. As a consequence, the photoanode composed of TiO2 fastener-like sphere scattering layer shows an improved DSSCs conversion efficiency of 7.01% compared to that of commercial P25 (5.78%). The remarkable electrochemical performances of hierarchical fastener-like TiO2 spheres indicate their promising application as scattering materials for DSSCs.

Due to the advantages of both rapid electron transport of reduced graphene oxide (rGO) sheet and high catalytic performance of ordered mesoporous carbon (OMC), composites of OMC with rGO (G@OMC) have been prepared through the hard-template approach and used as efficient counter electrode (CE) materials for dye-sensitized solar cells (DSSCs). When compared with pure OMC, the as-obtained G@OMC composites exhibit a higher electrocatalytic activity for the reduction of triiodide, owing to the synergetic effect between rGO and OMC. As a consequence, the DSSCs assembled with this G@OMC (CE show an improved photovoltaic conversion efficiency of 6.38% compared with 5.67% for DSSCs assembled with OMC CE, which could compete with the efficiency (7.05%) produced by the Pt CE under the same conditions.

The construction of nanoporous conductive polymer membranes has potential applications in catalysts and energy-conversion devices. In this letter, we present a facile method to prepare free-standing polypyrrole (PPy) nanotube films by simply heating pulp-like homogeneous suspensions at a low temperature, which can be employed as a novel counter electrode (CE) to substitute for the expensive fluorine-doped tin oxide (FTO) glass and Pt used in dye-sensitized solar cells (DSSCs). The DSSCs assembled with these paper-like PPy membranes show an impressive conversion efficiency of 5.27%, which is about 84% of the cell with a conventional Pt/FTO CE (6.25%).

Thin titanium dioxide (TiO2) semiconductor layer with different scattering layers are investigated in dye-sensitized solar cells (DSSCs). Usually, the scattering layer is placed after the photoanode films in order to harvest more incidents light. The scattering layer based on rutile phase TiO2 is prepared, and placed in the different position of the photoanode films (on the surface of the FTO glass, between the two layers of transparent TiO2 film and after the transparent TiO2 film). We use STT, TST and TTS as marks (T and S represent the transparent TiO2 layer and the scattering layer respectively). The result of this study indicates that STT which has the lowest incident light harvesting efficiency demonstrates the highest electron collection efficiency, while TTS which has the highest incident light harvesting efficiency sacrifices the electron collection efficiency greatly. It is discovered that TST, of which the incident light harvesting efficiency basically remains unchanged compared to TTS, reveals higher electron collection efficiency and achieves the maximum photovoltaic conversion efficiency (7.0%). By applying UV-Visible and diffuse reflectance spectroscopy, electrochemical impedance spectroscopy (EIS), the effects of the incident light harvesting and electron collection efficiencies on different cells are analyzed. It makes the best use of this scattering layer and has a reference for the application of other scattering layer types.

The novel concept of introducing intermediate band into the mesoporous TiO2 backbone of dye-sensitized solar cells (DSSCs) is proposed to take full advantage of the sunlight and enhance the power conversion efficiency. Nominal trace amount W-doped TiO2 nanocrystralline films were prepared with the purpose of forming intermediate band in the bandgap of TiO2. A notable improvement of the device performance was obtained when N-type W-doped TiO2 films were applied as the photoanode of DSSCs. The short-circuit current density (Jsc) increased from 12.40 mA cm–2 to 15.10 mA cm–2, and the conversion efficiency increased from 6.64 to 7.42% when nominal 50 ppm (ppm) W-doped TiO2 was adopted.

Highly uniform core/double-shell-structured β-NaYF4:Er3+,Yb3+@SiO2@TiO2 hexagonal sub-microprisms are prepared and employed in dye-sensitized solar cells (DSCs) internally. This work paves a facile way to enable the most-efficient upconversion material (β-NaYF4:Er3+,Yb3+) to be used as scattering and upconversion centers in the photoelectrode of a DSC.

Hierarchically porous polyaniline–reduced graphene oxide hybrids have been developed via oxidative polymerization of aniline by MnO2 on reduced graphene sheets under acidic conditions (named M-PANI@rGO). The formation mechanism of the above hybrids indicates that the MnO2 undergoes oxidative disintegration and results in the porous structure of polyaniline (PANI) nanoparticle formation on the reduced graphene oxide (rGO) surface. The scanning electron microscopy (SEM) images and Brunauer–Emmett–Teller (BET) nitrogen sorption–desorption measurement clearly showed the nanoporous nature of the M-PANI@rGO hybrids. TEM-EDX confirmed the complete removal/degradation of MnO2 during the oxidative polymerization of aniline. Just for comparison, PANI–rGO hybrids have also been prepared via conventional polymerization using (NH4)2S2O8 as the oxidant (named C-PANI@rGO). When these different architectural PANI@rGO hybrids were applied as the counter electrode for dye-sensitized solar cells (DSSCs), the short-circuit current density (Jsc) and power-conversion efficiency (η) of the DSSCs with C-PANI@rGO hybrids are measured to be 11.64 mA cm−2 and 5.62%, respectively, while the corresponding values are 12.88 mA cm−2 and 6.15% for the DSSCs with M-PANI@rGO hybrids, which is comparable to 6.73% for the cell with a Pt counter electrode under the same experimental conditions. The hierarchically porous M-PANI@rGO hybrid is thus a promising candidate to replace platinum as a counter electrode for DSSCs.

Controlling over ordered porosity by self-assembly is challenging in the area of materials science. Materials with highly ordered aperture are favorable candidates in catalysis and energy conversion device. Here we describe a facile process to synthesize highly ordered mesoporous carbon (OMC) by direct tri-constituent co-assembly method, which uses resols as the carbon precursor, tri-block copolymer F127 as the soft template and tetraethoxysilane (TEOS) as the inorganic precursor. The obtained products are characterized by small-angle X-ray diffraction (SAXD), Brunauer-Emmett-Teller (BET) nitrogen sorption-desorption measurement and transmission electron microscope (TEM). The results indicate that the OMC possesses high surface areas of 1209 m(2) g(-1), homogeneous pore size of 4.6 nm and a large pore volume of 1.65 cm(3) g(-1). The advantages of high electrochemical active surface area and favorable accessible porosity of OMC benefit the catalysis of I(3)(-) to I(-). As a result, the OMC counter electrode displays a remarkable property when it was applied in dye-sensitized solar cells (DSSCs). For comparison, carbon black (CB) counter electrode and Pt counter electrode have also been prepared. When these different counter electrodes were applied for dye-sensitized solar cells (DSSCs), the power-conversion efficiency (η) of the DSSCs with CB counter electrode are measured to be 5.10%, whereas the corresponding values is 6.39% for the DSSC with OMC counter electrode, which is comparable to 6.84% of the cell with Pt counter electrode under the same experimental conditions.

The concentration of tetrabutyl titanate (TBT) and H2O influence on the reaction kinetics of TBT and acetic acid (AcOH) solvothermal system are systematically studied. It is found that TBT and H2O have greatly accelerated the hydrolysis-condensation process of the TBT-AcOH system. By adjusting those concentrations with reaction time, we prepare five kinds of sub-micron/micron precursors, which are hierarchical structures consisting of different primary building blocks. The morphology of these precursors varies from noninterlaced structures composed of flower-like microsphere and ellipsoid sphere to interlaced structures composed of flower-like microsphere interlaced nanofibers, ellipsoid spheres interlaced flower-like microsphere and nanoparticles interlaced flower-like microsphere. These interlaced structures are synthesized for the first time and are not ordinary mixtures of the noninterlaced structures. After heat treatment, these precursors are transformed to anatase TiO2. Shape-dependent photovoltaic performances of dye-sensitized solar cells (DSSCs) are also discussed. DSSCs based on these hierarchical sub-micron/micron TiO2 show 7.3%-7.9% energy conversion efficiencies, and the devices based on interlaced structures have higher efficiencies (7.4%-7.9%) than those of the devices based on noninterlaced structures (7.3%-7.6%). (C) 2013 Elsevier B.V. All rights reserved.

We demonstrate a strategy for incorporating plasmon resonant metallic nanoparticles in the construction of hierarchical TiO(2) spheres. Localized electric fields can be produced by the addition of Au nanoparticles, which can excite dye molecules more effectively than incident far-field light. The synergistic effect of surface plasmon resonance with constructed TiO(2) nanostructures has been investigated, and was confirmed by optical spectroscopy, J-V characteristics, EIS analysis and OCVD measurements. When Au nanoparticles are incorporated into the constructed TiO(2) spheres, the device achieves a power conversion efficiency of 6.62%, a 4.6% increase compared to the device based on constructed TiO(2) spheres without plasmon resonant Au nanoparticles, and a 17.4% increase compared to that without any treatment.

Submicrometer-sized monodispersed TiO2 spheres were synthesized by a controlled hydrolysis of titanium tetraisopropoxide (TTIP) and subsequent solvothermal treatment. The X-ray diffraction (XRD), scanning electron microscopy (SEM), and UV-visible spectroscopy analyses revealed that aqueous ammonia concentration and calcining temperature significantly influence the morphology, crystallization, dye loading and light scattering capacity of TiO2 microspheres. And it was found that the TiO2 microspheres prepared by this method showed a good thermal stability of phase. Bilayered dye-sensitized solar cells (DSSCs) composed of TiO2 microspheres as the scattering cover layers and TiO2 nanocrystallines as the underlayer exhibited a remarkable improvement in the power conversion efficiency (8.25%) compared with the nanocrystalline TiO2 DSSC (6.38%), owing to high light scattering efficiency and the dye-loading capacity of the microsphere cover layer. In addition, electrochemical impedance spectra (EIS) and open-circuit photo-voltage decay curves (OCVD) testing indicated that the microsphere cover layer passivated the surface states, increased the density of bulk traps, enlarged the lifetime of electrons, and promoted more efficient charge-transfer, which was also an important reason for the improved power conversion efficiency of double-layered DSSCs.

The interaction between ZnO compact layer and TiCl4 post-treatment on TiO2 photoelectrode for dye sensitized solar cell (DSSC) is investigated. Photoelectrode combined the two modifications is designated as ZnO+2l+TiCl4. It is found that after the TiCl4 treatment the ZnO compact layer transforms to a bi-functional layer, which suppresses back electrons transfer from FTO to electrolyte and reduces the FTO/TiO2 interfacial resistance. In addition, the newly formed TiO2 coating generated by TiCl4 post-treatment contains abundant and well dispersed Zn element, which further facilitates electron transfer at TiO2 layer. Meanwhile, the electron lifetime in ZnO+2l+TiCl4 is the longest. Consequently, the overall energy conversion efficiency of the cell with ZnO+2l+TiCl4 is significantly enhanced to 8.9%, which is 8.8% higher than that with pure TiCl4 post-treatment and 17.7% higher than that without any treatment. These results are verified by material characterization and corresponding opto-electrical properties measurements. Experimental results demonstrate this facile method is a more promising alternative to the conventional interface and surface modification in high efficient DSSCs.

Highly porous carbon/SnO2/TiO2 nanocomposite films that can be used as counter electrodes in dye-sensitized solar cells (DSSCs) are fabricated by coating a homogeneous and viscous carbon paste on F-doped tin oxide conducting glass. The carbon paste is prepared by ball-milling a mixture of carbon, SnO2 powder and TiO2 hydrosol in an organic solution. The composite films are characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscope, Brunauer-Emmett-Teller and Form Talysruf Profiler. The results indicate that the photovoltaic performances of the composite DSSCs are influenced by the content of SnO2. When the content is increased to 30%. SnO2 not only acts as "framework" to strengthen the mechanical stability of the composite film but also increases the specific surface area and root-mean-square roughness, which improve fill factor and short-circuit current, finally increasing power conversion efficiency from 5.12% to 6.15%. Cyclic voltammetry analysis and electronic impedance spectroscopy of the optimum composite film display higher catalytic activity for I-3(-)/I- redox reactions and much lower charge-transfer resistance compared with Pt, respectively. Dye-sensitized solar cells based on this nanocomposite counter electrode achieve efficiency as high as 6.15% which is comparable to that of the cells using sputtering Pt as counter electrode at similar conditions. (C) 2011 Elsevier B.V. All rights reserved.

A series of biodegradable amphiphilic graft copolymers with poly-alpha,beta-[N-(2-hydroxyethyl)-L-aspartamide] (PHEA) as the backbone and poly(2,2-dimethyltrimethylene carbonate) (PDTC) segments with different lengths as the grafted branches were synthesized and characterized. The in vitro degradation of the obtained PHEA-g-PDTC copolymers was studied. With particular branch lengths, PHEA-g-PDTC can form self-assembling micelles in an aqueous solution. Transmission electron microscopy (TEM) images demonstrated that the micelles were regularly spherical in shape. The particle size and distribution of the micelles were measured. Nanoparticle drug delivery systems were prepared by the direct dissolution method. The in vitro release behaviors of two drugs, prednisone acetate and tegafur, with different water solubilities were investigated.

A series of biodegradable amphiphilic graft polymers were successfully synthesized by grafting poly(glycolide) (PGA) sequences onto a water-soluble poly-α,β-[N-(2-hydroxyethyl)-L-aspartamide] (PHEA) backbone. These novel graft polymers were synthesized by the ring-opening polymerization initiated by the macroinitiator PHEA bearing hydroxyl groups without adding any catalyst. The graft polymers were characterized by Fourier transform infrared spectroscopy (FTIR), 1H nuclear magnetic resonance spectroscopy (1H NMR), combined size-exclusion chromatography (SEC) and multiangle laser light scattering (MALLS) analysis, and differential scanning calorimetry (DSC). By controlling the feed ratio of the macroinitiator to the monomer, graft polymers with different branch lengths can be obtained. The degradation behaviors of the copolymers were studied. Based on the amphiphilicity of the graft copolymers, nanoparticle drug delivery systems were prepared by the direct dissolution method and the dialysis method, and the in vitro drug release behavior was investigated. Transmission electron microscopy (TEM) images demonstrated that these nanoparticles were regularly spherical in shape. The particle size and distribution of the nanoparticles were measured.

A biodegradable amphiphilic graft polymer was successfully synthesized by grafting hydrophobic poly(1,3-trimethylene carbonate) (PTMC) sequences onto a hydrophilic poly-alpha,beta-(N-(2-hydroxyethyl)-L-aspartamide) (PHEA) backbone. The graft polymer, PHEA-g-PTMC, was synthesized by ring-opening polymerization initiated by the macroinitiator PHEA bearing hydroxyl groups without adding any catalyst. The graft polymer was characterized by Fourier transform infrared spectroscopy, 1H-nuclear magnetic resonance spectroscopy, combined size-exclusion chromatography and multiangle laser light scattering analysis. Two drugs with distinct water solubility, prednisone acetate and tegafur, were encapsulated in the PHEA-g-PTMC nanoparticles. The in vitro release of two drugs from PHEA-g-PTMC nanoparticle drug-delivery systems was investigated.

A biodegradable amphiphilic graft polymer was successfully synthesized by grafting hydrophobic poly(1,3-trimethylene carbonate) (PTMC) sequences onto a hydrophilic poly-alpha,beta-(N-(2-hydroxyethyl)-L-aspartamide) (PHEA) backbone. The graft polymer, PHEA-g-PTMC, was synthesized by ring-opening polymerization initiated by the macroinitiator PHEA bearing hydroxyl groups without adding any catalyst. The graft polymer was characterized by Fourier transform infrared spectroscopy, 1H-nuclear magnetic resonance spectroscopy, combined size-exclusion chromatography and multiangle laser light scattering analysis. Two drugs with distinct water solubility, prednisone acetate and tegafur, were encapsulated in the PHEA-g-PTMC nanoparticles. The in vitro release of two drugs from PHEA-g-PTMC nanoparticle drug-delivery systems was investigated.

The application amphiphilic biodegradable graft polymers in drug delivery system was investigated. The synthesis of a series of biodegradable amphiphilic graft polymers by grafting poly(2,2-dimethyltrimethylene carbonate) (PDTC) sequences onto poly-α,β-(N-(2-hydroxyethyl)-L-aspartamide) (PHEA) backbone was also discussed. The PHEA-g-PDTC polymers were synthesized by the ring-opening polymerization of DTC using PHEA with pendant hydroxyl groups as a macroinitiator without catalyst. The molecular weight of PHEA-2 is found to be much lower than PHEA, indicating the degradation occurred during the heating at 120 °C.