Multi‐Shell Porous TiO2 Hollow Nanoparticles for Enhanced Light Harvesting in Dye‐sensitized Solar Cells

An optimized configuration for nanomaterials in working electrodes is vital to the high performance of dye‐sensitized solar cells (DSSCs). Here, a fabrication method is introduced for multi‐shell TiO₂ hollow nanoparticles (MS‐TiO₂‐HNPs) via a sol–gel reaction, calcination, and an etching process. The prepared uniform MS‐HNPs have a high surface area (ca. 171 m² g^?1), multireflection, and facile electrolyte circulation and diffusion. During the MS‐HNP fabrication process, the amount of SiO₂ precursor and H₂O under reaction has a significant effect on aggregation and side reactions. The etching process to obtain pure TiO₂ is influenced by anatase crystallinity. Additionally, single‐shell (SS)‐TiO₂‐HNPs and double‐shell (DS)‐TiO₂‐HNPs are synthesized as a control. The MS‐TiO₂‐HNPs exhibit a high surface area and enhance light reflectance, compared with the SS‐ and DS‐TiO₂‐HNPs of the same size. The power conversion efficiency of the optimized MS‐TiO₂‐HNP‐based DSSCs is 9.4%, compared with the 8.0% efficiency demonstrated by SS‐TiO₂‐HNP‐DSSCs (a 17.5% improvement). These results enable the utilization of multifunctional MS‐HNPs in energy material applications, such as lithium ion batteries, photocatalysts, water‐splitting, and supercapacitors.     

Mesoporous Anatase Titania Hollow Nanostructures though Silica‐Protected Calcination

The crystallization of nanometer‐scale materials during high‐temperature calcination can be controlled by a thin layer of surface coating. Here, a novel silica‐protected calcination process for preparing mesoporous hollow TiO₂ nanostructures with a high surface area and a controllable crystallinity is presented. This method involves the preparation of uniform silica colloidal templates, sequential deposition of TiO₂ and then SiO₂ layers through sol–gel processes, calcination to transform amorphous TiO₂ to crystalline anatase, and finally etching of the inner and outer silica to produce mesoporous anatase TiO₂ shells. The silica‐protected calcination step allows crystallization of the amorphous TiO₂ layer into anatase nanocrystals, while simultaneously limiting the growth of anatase grains to within several nanometers, eventually producing mesoporous anatase shells with a high surface area (～311 m² g^?1) and good water dispersibility upon chemical etching of the silica. When used as photocatalysts for the degradation of Rhodamine B under UV irradiation, the as‐synthesized mesoporous anatase shells show significantly enhanced photocatalytic activity with greater enhancement for samples calcined at higher temperatures thanks to their improved crystallinity.     

Hierarchical Double‐Shell Nanostructures of TiO2 Nanosheets on SnO2 Hollow Spheres for High‐Efficiency,Solid‐State,Dye‐Sensitized Solar Cells

A high‐energy conversion efficiency of 8.2% at 100 mW cm^?2 is reported, one of the highest values for N719‐based, solid‐state, dye‐sensitized solar cells (ssDSSCs). The solar cells are based on hierarchical double‐shell nanostructures consisting of inner SnO₂ hollow spheres (SHS) surrounded by outer TiO₂ nanosheets (TNSs). Deposition of the TNS on the SHS outer surface is performed via solvothermal reactions in order to generate a double‐shell SHS@TNS nanostructure that provides a large surface area and suppresses recombination of photogenerated electrons. An organized mesoporous (OM)‐TiO₂ film with high porosity, large pores, and good interconnectivity is also prepared via a sol‐gel process using a poly(vinyl chloride)‐g‐poly(oxyethylene methacrylate) (PVC‐g‐POEM) graft copolymer template. This film is utilized as a matrix to disperse the double‐shell nanostructures. Such nanostructures provide good pore‐filling for solid polymer electrolytes, faster electron transfer, and enhanced light scattering, as confirmed by reflectance spectroscopy, incident photon‐to‐electron conversion efficiency (IPCE), and intensity‐modulated photocurrent spectroscopy (IMPS)/intensity‐modulated photovoltage spectroscopy (IMVS).     

MS2 (M = Co and Ni) Hollow Spheres with Tunable Interiors for High‐Performance Supercapacitors and Photovoltaics

We demonstrate in this paper facile synthesis of CoS₂ and NiS₂ hollow spheres with various interiors through a solution‐based route. The obtained CoS₂ microspheres constructed by nanosheets display a three‐dimensional architecture with solid, yolk‐shell, double‐shell, and hollow interiors respectively, with continuous changes in specific surface areas and pore‐size distributions. Especially, the CoS₂ hollow spheres demonstrate excellent supercapacitive performance including high specific capacitance, good charge/discharge stability and long‐term cycling life, owing to the greatly improved faradaic redox reaction and mass transfer. Furthermore, CoS₂ hollow spheres exhibit superior electrocatalytic activity for disulfide/thiolate (T₂/T^?) redox electrolyte in dye‐sensitized solar cells (DSCs). Therefore, this work provides a promising approach for the design and synthesis of structure tunable materials with largely enhanced supercapacitor behavior, which can be potentially applied in energy storage devices.     

Wet‐milled anatase titanium oxide nanoparticles as a buffer layer for air‐stable bulk heterojunction solar cells

In this study, an air‐stable bulk heterojunction organic solar cell demonstrated by utilization of titanium oxide (TiO₂) nanoparticles as a hole blocking layer was prepared through high‐energy grinding method. The large clumps of the anatase TiO₂ underwent deaggregation to form a stable dispersed solution during the grinding process. The resultant suspension can form a uniform and smooth TiO₂ film through spin coating on various substrates. Because of substantial oxygen and water protection effect of TiO₂ thin film, the bulk heterojunction solar cells exhibit a significant long‐term stability. It is also found that the cell performance can be promoted dramatically after ultraviolet activation. The mechanism responsible for the enhanced cell efficiency was also investigated. This solution‐based method does not require surfactants, thus preserving the intrinsic electronic and optical properties of TiO₂ that makes these proposed buffer layers quite attractive for next‐generation flexible devices appealing high conductivity and transparency. Copyright © 2014 John Wiley & Sons, Ltd.     

Conformal Nano‐Sized Inorganic Coatings on Mesoporous TiO2 Films for Low‐Temperature Dye‐Sensitized Solar Cell Fabrication

Here, a new method based on sol–gel electrophoretic deposition to produce uniform high‐quality inorganic conformal coatings on mesoporous nano‐particulate films is presented. This novel sol preparation method allows for very fine control of the coating properties, thus inducing new adjustable functionalities to these electrodes. It is shown that the deposition of an amorphous TiO₂ and/or MgO shell onto photoanodes used in dye‐sensitized solar cells (DSSCs) improves their light‐to‐electric‐power conversion efficiency without the need for sintering. It is proposed that the amorphous TiO₂ coating improves the electronic inter‐particle connection and passivates the surface states. The insulating MgO coating further reduces the electron transfer from the conduction band into the electrolyte while the electron injection from the excited dye state remains unperturbed for thin coatings. Using a low‐temperature method for DSSC production on plastic substrates, a maximum efficiency of 6.2% applying pressure together with an optimized TiO₂ coating is achieved. For systems that cannot be pressed a conversion efficiency of 5.1% is achieved using a double shell TiO₂/MgO coating.     

A Unique Disintegration–Reassembly Route to Mesoporous Titania Nanocrystalline Hollow Spheres with Enhanced Photocatalytic Activity

A novel disintegration–reassembly route is reported for the synthesis of mesoporous TiO₂ nanocrystalline hollow spheres with controlled crystallinity and enhanced photocatalytic activity. In this unique synthesis strategy, it is demonstrated that sol–gel‐derived mesoporous TiO₂ colloidal spheres can be disintegrated into discrete small nanoparticles that are uniformly embedded in the polymer (polystyrene, PS) matrix by surface‐induced photocatalytic polymerization. Subsequent reassembly of these TiO₂ nanoparticles can be induced by an annealing process after further coating of a resorcinol–formaldehyde (RF) resin, which forms self‐supported hollow spheres of TiO₂ at the PS/RF interface. The abundant phenolic groups on the RF resin serve as anchoring sites for the TiO₂ nanoparticles, thus enable the reassembly of the TiO₂ nanoparticles and prevent their sintering during the thermal crystallization process. This unique disintegration–reassembly process leads to the formation of self‐supported TiO₂ hollow spheres with relatively large surface area, high crystallinity, and superior photocatalytic activity in dye degradation under UV light irradiation.     

Titanium Containing γ‐MnO2 (TM) Hollow Spheres: One‐Step Synthesis and Catalytic Activities in Li/Air Batteries and Oxidative Chemical Reactions

Titanium containing γ‐MnO₂ octahedral molecular sieves having hollow sphere structures are successfully prepared for the first time using a one‐step synthesis method. Titanium cations are used as structure‐directing agents in the synthesis process. The assembly of the hollow spheres is carried out at the beginning of the process. Various techniques including XRD, N₂ adsorption, SEM, EDX, RAMAN, TEM, XPS, and TGA are employed for the materials characterization. Ti is incorporated into the MnO₂ framework in isolated sites, and TiO₂ phases (anatase and rutile) are not observed. When introduced in medium‐sized lithium‐air batteries, the materials give very high specific capacity (up to 2.3 A h g^?1). These materials are also catalytically tested in the oxidation of toluene with molecular oxygen at atmospheric pressure, showing significant oxidative catalytic activities in this difficult chemical reaction.     

TiO2@Layered Double Hydroxide Core–Shell Nanospheres with Largely Enhanced Photocatalytic Activity Toward O2 Generation

TiO₂@CoAl‐layered double hydroxide (LDH) core–shell nanospheres are fabricated via hydrothermal synthesis of TiO₂ hollow nanospheres followed by in situ growth of CoAl‐LDH shell, which exhibit an extraordinarily high photocatalytic activity toward oxygen evolution from water oxidation. The O₂ generation rates of 2.34 and 2.24 mmol h^?1 g^?1 are achieved under full sunlight (>200 nm) and visible light (>420 nm), respectively, which are among the highest photocatalytic activities for oxygen production to date. The reason is attributed to the desirable incorporation of visible‐ light‐active LDH shell with UV light‐responsive TiO₂ core for promoted solar energy utilization. Most importantly, the combined experimental results and computational simulations reveal that the strong donor–acceptor coupling and suitable band matching between TiO₂ core and LDH shell facilitate the separation of photoinduced electron‐hole pairs, accounting for the highly efficient photocatalytic performance. Therefore, this work provides a facile and cost‐effective strategy for the design and fabrication of hierarchical semiconductor materials, which can be applied as photocatalyst toward water splitting and solar energy conversion.     

Hybrid Templated Synthesis of Crack‐Free,Organized Mesoporous TiO2 Electrodes for High Efficiency Solid‐State Dye‐Sensitized Solar Cells

Organic/inorganic hybrid templates, i.e., aluminium oxide (Al₂O₃) nanoparticles grafted with poly(oxyethylene) methacrylate, Al₂O₃‐POEM, are synthesized via surface‐initiated atom transfer radical polymerization (ATRP), as confirmed by Fourier transform‐infrared spectroscopy (FT‐IR) and thermogravimetric analysis (TGA). Upon combining the Al₂O₃‐POEM with titanium(IV) isopropoxide (TTIP), hydrophilic TTIP is selectively confined in the hydrophilic POEM chains through hydrogen bonding interactions. Following the calcination at 450 °C and the selective etching of Al₂O₃ with NaOH, the OM‐TiO₂ films with high surface areas, good interconnectivity, and anatase phase are obtained. The solid‐state dye‐sensitized solar cells (ssDSSCs) fabricated with OM‐TiO₂ photoelectrodes and a polymerized ionic liquid (PIL) show a high energy conversion efficiency of 7.3% at 100 mW cm^?2, which is one of the highest values for ssDSSCs. The high cell performance is due to the well‐organized structure, resulting in improved dye loading, excellent pore filling of electrolyte, enhanced light harvesting, and reduced charge recombination.     

Core/Shell PbSe/PbS QDs TiO2 Heterojunction Solar Cell

Quasi type‐II PbSe/PbS quantum dots (QDs) are employed in a solid state high efficiency QD/TiO₂ heterojunction solar cell. The QDs are deposited using layer‐by‐layer deposition on a half‐micrometer‐thick anatase TiO₂ nanosheet film with (001) exposed facets. Theoretical calculations show that the carriers in PbSe/PbS quasi type‐II QDs are delocalized over the entire core/shell structure, which results in better QD film conductivity compared to PbSe QDs. Moreover, PbS shell permits better stability and facile electron injection from the QDs to the TiO₂ nanosheets. To complete the electrical circuit of the solar cell, a Au film is evaporated as a back contact on top of the QDs. This PbSe/PbS QD/TiO₂ heterojunction solar cell produces a light to electric power conversion efficiency (η) of 4% with short circuit photocurrent (J_sc) of 17.3 mA/cm². This report demonstrates highly efficient core/shell near infrared QDs in a QD/TiO₂ heterojunction solar cell.     

Battery Performance and Photocatalytic Activity of Mesoporous Anatase TiO2 Nanospheres/Graphene Composites by Template‐Free Self‐Assembly

Nanosized mesoporous anatase TiO₂ particles have important applications in high‐performance lithium ion batteries and efficient photocatalysis. In contrast to the conventional synthesis routes where various soft or hard templates are usually employed, the direct growth of uniform mesoporous anatase TiO₂ nanospheres on graphene sheets by a template‐free self‐assembly process is presented. Compared to the conventional mesoporous anatase particles consisting of polycrystalline TiO₂, the microstructure of obtained mesoporous anatase nanospheres on graphene sheets is single‐crystal‐like. The growth mechanism, lithium ion battery performance, and photocatalytic activity of the resultant mesoporous anatase TiO₂ nanospheres/graphene composites are thoroughly investigated. In comparison to the reference TiO₂, the composite shows substantial improvement in lithium specific capacity from 1 C to 50 C, and photocatalytic removing organic pollutant and hydrogen evolution. More strikingly, the specific capacity of the composite at the rate of 50 C is as high as 97 mA h g^?1, 6 times higher than that of the reference TiO₂.     

Yolk‐like Micro/Nanoparticles with Superparamagnetic Iron Oxide Cores and Hierarchical Nickel Silicate Shells

Yolk‐like nano/microparticles with superparamagnetic iron oxide (SPIO) cores and hierarchical nickel silicate (NS) shells, designated yolk SPIO@NS, are fabricated by combining the versatile sol–gel process and the hydrothermal reaction, involving the coating of SPIO particles with SiO₂ and transformation of the SiO₂ shells into NS hollow spheres with hierarchical nanostructures. Various yolk/shell nanostructures with tunable NS shell thicknesses and SPIO core sizes are successfully prepared by controlling the experimental para­meters. Au nanoparticles can be impregnated into the yolk‐like microspheres in situ to form SPIO@NS/Au composite particles and the as‐prepared magnetic nanocatalysts show good catalytic activity, using the catalytic reduction of RhB as a model reaction. This facile method can be extended to the synthesis of other encapsulated particles with yolk‐like nanostructure.     

3D Hierarchical Co3O4 Twin‐Spheres with an Urchin‐Like Structure: Large‐Scale Synthesis,Multistep‐Splitting Growth,and Electrochemical Pseudocapacitors

Novel, 3D hierarchical Co₃O₄ twin‐spheres with an urchin‐like structure are produced successfully on the large scale for the first time by a solvothermal synthesis of cobalt carbonate hydroxide hydrate, Co(CO₃)_0.5(OH)·0.11H₂O, and its subsequent calcination. The morphology of the precursor, which dominates the structure of the final product, evolves from nanorods to sheaf‐like bundles, to flower‐like structures, to dumbbell‐like particles, and eventually to twin‐spheres, accompanying a prolonged reaction time. A multistep‐splitting growth mechanism is proposed to understand the formation of the 3D hierarchical twin‐spheres of the precursor, based on the time effect on the morphologies of the precursor. The 3D hierarchical Co₃O₄ twin‐spheres are further used as electrode materials to fabricate supercapacitors with high specific capacitances of 781, 754, 700, 670, and 611 F g^?1 at current densities of 0.5, 1, 2, 4, and 8 A g^?1, respectively. The devices also show high charge‐discharge reversibility with an efficiency of 97.8% after cycling 1000 times at a current density of 4 A g^?1.     

High Reversible Pseudocapacity in Mesoporous Yolk–Shell Anatase TiO2/TiO2(B) Microspheres Used as Anodes for Li‐Ion Batteries

As an anode material for lithium‐ion batteries, titanium dioxide (TiO₂) shows good gravimetric performance (336 mAh g^?1 for LiTiO₂) and excellent cyclability. To address the poor rate behavior, slow lithium‐ion (Li⁺) diffusion, and high irreversible capacity decay, TiO₂ nanomaterials with tuned phase compositions and morphologies are being investigated. Here, a promising material is prepared that comprises a mesoporous “yolk–shell” spherical morphology in which the core is anatase TiO₂ and the shell is TiO₂(B). The preparation employs a NaCl‐assisted solvothermal process and the electrochemical results indicate that the mesoporous yolk–shell microspheres have high specific reversible capacity at moderate current (330.0 mAh g^?1 at C/5), excellent rate performance (181.8 mAh g^?1 at 40C), and impressive cyclability (98% capacity retention after 500 cycles). The superior properties are attributed to the TiO₂(B) nanosheet shell, which provides additional active area to stabilize the pseudocapacity. In addition, the open mesoporous morphology improves diffusion of electrolyte throughout the electrode, thereby contributing directly to greatly improved rate capacity.     

Dye‐sensitized TiO2 solar cells based on nanocomposite photoanode containing plasma‐modified multi‐walled carbon nanotubes

A series of anatase TiO₂‐based nanocomposite incorporated with plasma‐modified multi‐walled carbon nanotubes (MWNTs) was prepared by physical blending and shows its capability for efficient electron transport when used as photoanode in dye‐sensitized solar cells (DSSCs). These MWNTs characterized with good dispersal performance were obtained by functionalization technique via in situ plasma treatment and subsequent grafting with maleic anhydride (MA) onto the external walls reported previously. Compared with the conventional DSSCs, the TiO₂ film with 1D carbon nanotubes possesses more outstanding ability to transport electrons injected from the excited dye within the device under illumination. As a result, at an optimum addition of 0.3 wt% MWNTs‐MA in TiO₂ matrix, the photocurrent–voltage (J–V) characteristics showed a significant increase in the short‐circuit photocurrent (J_sc) of 50%, leading to an increase in overall solar conversion efficiency by a factor of 1.5. Electrochemical impedance spectroscopy analyses reveal that the MWNTs‐MA/TiO₂ incur smaller resistances at the photoanode in assembled DSSCs when compared with those in the anatase titania DSSCs. These features suggest that the conducting properties of the MWNTs‐MA within the anodes are crucial for achieving a higher transport rate for photo‐induced electrons in TiO₂ layer by exhibiting lower resistance in the porous network and hence retard charge recombination that could result in poor conversion efficiency. Copyright © 2012 John Wiley & Sons, Ltd.     

Tailoring Amino‐Functionalized Graphitic Carbon‐Encapsulated Gold Core/Shell Nanostructures for the Sensitive and Selective Detection of Copper Ions

The effective transfer of strong electromagnetic field from the gold core through the coating shell represents the most significant challenge for the applications of plasmonic nanoparticles. This study applies a one‐step arc discharge method to synthesize graphitic carbon‐encapsulated gold nanoparticles (Au@G NPs) functionalized with amino groups uniformly via adding NH₃ into He background gas. By tailoring the coating shell into few‐layered graphene, a strong localized surface plasmon resonance (LSPR) absorption band is achieved. The NH₃ introduces H radicals to strengthen the LSPR characteristic by etching the coating graphitic shell, as well as provides dissociated NH or NH₂ species to functionalize the surfaces with amino groups. With an LSPR‐based colorimetric method, it is demonstrated that trace Cu²⁺ ions can be detected rapidly with excellent sensitivity (as low as 10 × 10^‐9m linearly) and selectivity against other metal ions (Na⁺, K⁺, Mg²⁺, Ca²⁺, Co²⁺, Fe²⁺, Cd²⁺, Pb²⁺, and Hg²⁺ ions) by amino‐functionalized Au@G NPs in water samples.     

Enhanced Omnidirectional Photovoltaic Performance of Solar Cells Using Multiple‐Discrete‐Layer Tailored‐ and Low‐Refractive Index Anti‐Reflection Coatings

An optimized four‐layer tailored‐ and low‐refractive index anti‐reflection (AR) coating on an inverted metamorphic (IMM) triple‐junction solar cell device is demonstrated. Due to an excellent refractive index matching with the ambient air by using tailored‐ and low‐refractive index nanoporous SiO₂ layers and owing to a multiple‐discrete‐layer design of the AR coating optimized by a genetic algorithm, such a four‐layer AR coating shows excellent broadband and omnidirectional AR characteristics and significantly enhances the omnidirectional photovoltaic performance of IMM solar cell devices. Comparing the photovoltaic performance of an IMM solar cell device with the four‐layer AR coating and an IMM solar cell with the conventional SiO₂/TiO₂ double layer AR coating, the four‐layer AR coating achieves an angle‐of‐incidence (AOI) averaged short‐circuit current density, J_SC, enhancement of 34.4%, whereas the conventional double layer AR coating only achieves an AOI‐averaged J_SC enhancement of 25.3%. The measured reflectance reduction and omnidirectional photovoltaic performance enhancement of the four‐layer AR coating are to our knowledge, the largest ever reported in the literature of solar cell devices.     

Template‐Assisted Formation of Rattle‐type V2O5 Hollow Microspheres with Enhanced Lithium Storage Properties

In this work, rattle‐type ball‐in‐ball V₂O₅ hollow microspheres are controllably synthesized with the assistance of carbon colloidal spheres as hard templates. Carbon spheres@vanadium‐precursor (CS@V) core–shell composite microspheres are first prepared through a one‐step solvothermal method. The composition of solvent for the solvothermal synthesis has great influence on the morphology and structure of the vanadium‐precursor shells. V₂O₅ hollow microspheres with various shell architectures can be obtained after removing the carbon microspheres by calcination in air. Moreover, the interior hollow shell can be tailored by varying the temperature ramping rate and calcination temperature. The rattle‐type V₂O₅ hollow microspheres are evaluated as a cathode material for lithium‐ion batteries, which manifest high specific discharge capacity, good cycling stability and rate capability.     

Honeycomb‐Like Organized TiO2 Photoanodes with Dual Pores for Solid‐State Dye‐Sensitized Solar Cells

A solid‐state dye‐sensitized solar cell (ssDSSC) with 7.4% efficiency at 100 mW/cm² is reported. This efficiency is one of the highest observed for N719 dye. High performance is achieved via a honeycomb‐like, organized mesoporous TiO₂ photoanode with dual pores, high porosity, good interconnectivity, and excellent light scattering properties. The TiO₂ photoanodes are prepared without any TiCl₄ treatment via a one‐step, direct self‐assembly of hydrophilically preformed TiO₂ nanocrystals and poly(vinyl chloride)‐g‐poly(oxyethylene methacrylate) (PVC‐g‐POEM) graft copolymer as a titania source and a structure‐directing agent, respectively. Upon controlling the secondary forces between the polymer/TiO₂ hybrid and the solvent by varying the amounts of HCl/H₂O mixture or toluene, honeycomb‐like structures are generated to improve light scattering properties. Such multifunctional nanostructures with dual pores provide good pore‐filling of solid polymer electrolyte with large volume, enhanced light harvesting and reduced charge recombination, as confirmed by reflectance spectroscopy, incident photon‐to‐electron conversion efficiency (IPCE), and electrochemical impedance spectroscopy (EIS) analysis.