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.     

Inside Front Cover: Nanocrystalline TiO2 Photocatalytic Membranes with a Hierarchical Mesoporous Multilayer Structure: Synthesis,Characterization, and Multifunction (Adv. Funct. Mater. 8/2006)

The inside cover shows a hierarchical, mesoporous, multilayer TiO2 photocatalytic membrane synthesized via a novel sol–gel dip‐coating process employing surfactant templates reported by Dionysiou and co‐workers on p. 1067. The resulting asymmetric mesoporous TiO2 membrane supported onto a porous Al2O3 substrate exhibited hierarchical changes in pore diameter and materials porosity from the top to the bottom layer. The TiO2 membrane has multiple simultaneous functions, including photocatalysis, disinfection, separation, and anti‐biofouling. A novel sol–gel dip‐coating process to fabricate nanocrystalline TiO₂ photocatalytic membranes with a robust hierarchical mesoporous multilayer and improved performance has been studied. Various titania sols containing poly(oxyethylenesorbitan monooleate) (Tween 80) surfactant as a pore‐directing agent to tailor‐design the porous structure of TiO₂ materials at different molar ratios of Tween 80/isopropyl alcohol/acetic acid/titanium tetraisopropoxide = R:45:6:1 have been synthesized. The sols are dip‐coated on top of a homemade porous alumina substrate to fabricate TiO₂/Al₂O₃ composite membranes, dried, and calcined, and this procedure is repeated with varying sols in succession. The resulting asymmetric mesoporous TiO₂ membrane with a thickness of 0.9 μm exhibits a hierarchical change in pore diameter from 2–6, through 3–8, to 5–11 nm from the top to the bottom layer. Moreover, the corresponding porosity is incremented from 46.2, through 56.7, to 69.3 %. Compared to a repeated‐coating process using a single sol, the hierarchical multilayer process improves water permeability significantly without sacrificing the organic retention and photocatalytic activity of the TiO₂ membranes. The prepared TiO₂ photocatalytic membrane has great potential in developing highly efficient water treatment and reuse systems, for example, decomposition of organic pollutants, inactivation of pathogenic microorganisms, physical separation of contaminants, and self‐antifouling action because of its multifunctional capability.     

Large‐scale Synthesis of Urchin‐like Mesoporous TiO2 Hollow Spheres by Targeted Etching and Their Photoelectrochemical Properties

A versatile targeted etching strategy is developed for the large‐scale synthesis of urchin‐like mesoporous TiO₂ hollow spheres (UMTHS) with tunable particle size. Its key feature is the use of a low‐temperature hydrothermal reaction of surface‐fluorinated, amorphous, hydrous TiO₂ solid spheres (AHTSS) under the protection of a polyvinylpyrrolidone (PVP) coating. With the confinement of PVP and water penetration, the highly porous AHTSS are selectively etched and hollowed by fluoride without destroying their spherical morphology. Meanwhile TiO₂ hydrates are gradually crystallized and their growth is preferentially along anatase (101) planes, reconstructing an urchin‐like shell consisting of numerous radially arranged single‐crystal anatase nanothorns. Complex hollow structures, such as core–shell and yolk–shell structures, can also be easily synthesized via additional protection of the interior by pre‐filling AHTSS with polyethylene glycol (PEG). The hollowing transformation is elucidated by the synergetic effect of etching, PVP coating, low hydrothermal reaction temperature, and the unique microstructure of AHTSS. The synthesized UMTHS with a large surface area of up to 128.6 m² g^‐1 show excellent light‐harvesting properties and present superior performances in photocatalytic removal of gaseous nitric oxide (NO) and photoelectrochemical solar energy conversion as photoanodes for dye‐sensitized mesoscopic solar cells.     

Controllable Synthesis of Mesoporous TiO2 Hollow Shells: Toward an Efficient Photocatalyst

TiO₂ hollow shells with well‐controlled crystallinity, phase, and porosity are desirable in many applications. In photocatalysis in particular, they can provide high active surface area, reduced diffusion resistance, and improved accessibility to reactants. Here, the results from studies of the causes for the failure of a prior etching and calcination scheme to make such shells and on a newly‐developed simple yet robust process for producing uniform mesoporous TiO₂ shells with precisely controllable crystallinity and phase are reported. The key finding is that base etching of the SiO₂@TiO₂ core‐shell particles leads to the formation of sodium titanate species, which, if not removed, promote substantial crystal growth during calcination and destroy the structural integrity of the TiO₂ shells. A simple acid treatment of the base‐etched samples may convert the sodium titanates into protonated titanates, which not only prevent the formation of the impurity phases, but also help to maintain the structural integrity of the shell and allow precise control of the TiO₂ phase and crystallinity. This new development affords convenient optimization of the structure of the hollow TiO₂ shells toward efficient photocatalysts, which outperform the commercial P25‐TiO₂ in the photocatalytic decomposition of organic dye molecules.     

Nanocrystalline TiO2 Photocatalytic Membranes with a Hierarchical Mesoporous Multilayer Structure: Synthesis,Characterization, and Multifunction

A novel sol–gel dip‐coating process to fabricate nanocrystalline TiO₂ photocatalytic membranes with a robust hierarchical mesoporous multilayer and improved performance has been studied. Various titania sols containing poly(oxyethylenesorbitan monooleate) (Tween 80) surfactant as a pore‐directing agent to tailor‐design the porous structure of TiO₂ materials at different molar ratios of Tween 80/isopropyl alcohol/acetic acid/titanium tetraisopropoxide = R:45:6:1 have been synthesized. The sols are dip‐coated on top of a homemade porous alumina substrate to fabricate TiO₂/Al₂O₃ composite membranes, dried, and calcined, and this procedure is repeated with varying sols in succession. The resulting asymmetric mesoporous TiO₂ membrane with a thickness of 0.9 μm exhibits a hierarchical change in pore diameter from 2–6, through 3–8, to 5–11 nm from the top to the bottom layer. Moreover, the corresponding porosity is incremented from 46.2, through 56.7, to 69.3 %. Compared to a repeated‐coating process using a single sol, the hierarchical multilayer process improves water permeability significantly without sacrificing the organic retention and photocatalytic activity of the TiO₂ membranes. The prepared TiO₂ photocatalytic membrane has great potential in developing highly efficient water treatment and reuse systems, for example, decomposition of organic pollutants, inactivation of pathogenic microorganisms, physical separation of contaminants, and self‐antifouling action because of its multifunctional capability.     

Well‐Ordered Large‐Pore Mesoporous Anatase TiO2 with Remarkably High Thermal Stability and Improved Crystallinity: Preparation,Characterization, and Photocatalytic Performance

Thermally‐stable, ordered mesoporous anatase TiO₂ with large pore size and high crystallinity has been successfully synthesized through an evaporation‐induced self‐assembly technique, combined with encircling ethylenediamine (EN) protectors to maintain the liquid crystal mesophase structure of TiO₂ primary particles, followed by calcination at higher temperature. The structures of the prepared mesoporous TiO₂ are characterized in detail by small‐angle and wide‐angle X‐ray diffraction, Raman spectra, N₂ adsorption/desorption isotherms, and transmission electron microscopy. Experimental results indicate that the well‐ordered mesoporous structure could be maintained up to 700 °C (M700) and also possesses large pore size (10 nm), high specific BET surface area (122 m² g^?1), and high total pore volumes (0.20 cm³ g^?1), which is attributed to encircling EN protectors for maintaining the mesoporous framework against collapsing, inhibiting undesirable grain growth and phase transformation during the calcination process. A possible formation mechanism for the highly stable large‐pore mesoporous anatase TiO₂ is also proposed here, which could be further confirmed by TG/FT‐IR in site analysis and X‐ray photoelectron spectroscopy. The obtained mesoporous TiO₂ of M700 exhibit better photocatalytic activity than that of Degussa P25 TiO₂ for degradation of highly toxic 2,4‐dichlorophenol under UV irradiation. This enhancement is attributed to the well‐ordered large‐pore mesoporous structure, which facilitates mass transport, the large surface area offering more active sites, and high crystallinity that favors the separation of photogenerated electron‐hole pairs, confirmed by surface photovoltage spectra.     

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.     

Black Titania with Nanoscale Helicity

The fabrication of mesoporous black titanium dioxide (TiO_2?x ) with a chiral nematic organization of core–shell nanorods is reported. Chiral templating of TiO₂ nanoparticles onto gelatin‐functionalized cellulose nanocrystals (CNCs) followed by calcination yields carbonized TiO₂/CNC helical materials that recover white TiO₂ replicas after carbon removal. The hydrothermal surface reduction of the traditional white TiO₂ by ascorbic acid affords freestanding chiral nematic black TiO_2?x. The black TiO_2?x is a visible light active semiconducting mesoporous structure constructed by chiral nematic crystalline–amorphous TiO₂ core–shell nanorods. The chiral black TiO_2?x nanoparticles supported on mesoporous nanocarbon networks are evaluated as lithium‐ion battery anode electrodes. Beyond the current efforts, these black TiO_2?x materials and their composites may be useful in the fields of energy storage and catalysis.     

ZnO–SnO2 Hollow Spheres and Hierarchical Nanosheets: Hydrothermal Preparation,Formation Mechanism,and Photocatalytic Properties

ZnO–SnO₂ hollow spheres and hierarchical nanosheets are successfully synthesized using an aqueous solution containing ZnO rods, SnCl₄, and NaOH by using a simple hydrothermal method. The effects of hydrothermal temperature and time on the morphology of ZnO–SnO₂ are investigated. The formation process of ZnO–SnO₂ hollow spheres and nanosheets is discussed. The samples are characterized using X‐ray powder diffraction, transmission electron microscopy, scanning electron microscopy, and UV‐vis absorption spectroscopy. Both hollow spheres and hierarchical nanosheets show higher photocatalytic activities in the degradation of methyl orange than that of ZnO rods or SnO₂.     

Robust Hollow Spheres Consisting of Alternating Titania Nanosheets and Graphene Nanosheets with High Photocatalytic Activity for CO2 Conversion into Renewable Fuels

Robust hollow spheres consisting of molecular‐scale alternating titania (Ti_0.91O₂) nanosheets and graphene (G) nanosheets are successfully fabricated by a layer‐by‐layer assembly technique with polymer beads as sacrificial templates using a microwave irradiation technique to simultaneously remove the template and reduce graphene oxide into graphene. The molecular scale, 2D contact of Ti_0.91O₂ nanosheets and G nanosheets in the hollow spheres is distinctly different from the prevenient G‐based TiO₂ nanocomposites prepared by simple integration of TiO₂ and G nanosheets. The nine times increase of the photocatalytic activity of G‐Ti_0.91O₂ hollow spheres relative to commercial P25 TiO₂ is confirmed with photoreduction of CO₂ into renewable fuels (CO and CH₄). The large enhancement in the photocatalytic activity benefits from: 1) the ultrathin nature of Ti_0.91O₂ nanosheets allowing charge carriers to move rapidly onto the surface to participate in the photoreduction reaction; 2) the sufficiently compact stacking of ultrathin Ti_0.91O₂ nanosheets with G nanosheets allowing the photogenerated electron to transfer fast from the Ti_0.91O₂ nanosheets to G to enhance lifetime of the charge carriers; and 3) the hollow structure potentially acting as a photon trap‐well to allow the multiscattering of incident light for the enhancement of light absorption.     

A Cocatalytic Electron‐Transfer Cascade Site‐Selectively Placed on TiO2 Nanotubes Yields Enhanced Photocatalytic H2 Evolution

Separation and transfer of photogenerated charge carriers are key elements in designing photocatalysts. TiO₂ in numerous geometries has been for many years the most studied photocatalyst. To overcome kinetic limitations and achieve swift charge transfer, TiO₂ has been widely investigated with cocatalysts that are commonly randomly placed nanoparticles on a TiO₂ surface. The poor control over cocatalyst placement in powder technology approaches can drastically hamper the photocatalytic efficiencies. Here in contrast it is shown that the site‐selective placement of suitable charge‐separation and charge‐transfer cocatalysts on a defined TiO₂ nanotube morphology can provide an enhancement of the photocatalytic reactivity. A TiO₂–WO₃–Au electron‐transfer cascade photocatalyst is designed with nanoscale precision for H₂ production on TiO₂ nanotube arrays. Key aspects in the construction are the placement of the WO₃/Au element at the nanotube top by site‐selective deposition and self‐ordered thermal dewetting of Au. In the ideal configuration, WO₃ acts as a buffer layer for TiO₂ conduction band electrons, allowing for their efficient transfer to the Au nanoparticles and then to a suitable environment for H₂ generation, while TiO₂ holes due to intrinsic upward band bending in the nanotube walls and short diffusion length undergo a facilitated transfer to the electrolyte where oxidation of hole‐scavenger molecules takes place. These photocatalytic structures can achieve H₂ generation rates significantly higher than any individual cocatalyst–TiO₂ combination, including a classic noble metal–TiO₂ configuration.     

Template‐Free Preparation of Hollow Sb2S3 Microspheres as Supports for Ag Nanoparticles and Photocatalytic Properties of the Constructed Metal–Semiconductor Nanostructures

A simple and convenient Ostwald ripening route to the morphology‐ and phase‐controlled preparation of hollow Sb₂S₃ microspheres is developed. The hollow spheres are clusters of smaller microspheres if orange amorphous Sb₂S₃ colloid is used as the precursor, whereas, if starting from the yellow precursor, the products are regular hollow spheres. By selecting appropriate experimental conditions for ripening, the phase of the hollow Sb₂S₃ microspheres can be controlled. Amorphous and orthorhombic hollow spheres are prepared by ripening the colloidal precursors at ambient temperature and in an autoclave, respectively. The closed shell of hollow Sb₂S₃ spheres can be easily eroded by hydrochloric acid to form an open structure. By the in situ reduction of adsorbed Ag⁺ on the surface and interior of the hollow spheres, Ag nanoparticles are introduced into them, to form functional metal–semiconductor composites, the weight content of which is controlled by regulating the concentration of the Ag⁺ source and the adsorption time. The composite structures composed of Ag nanoparticles and hollow Sb₂S₃ spheres exhibit a remarkably enhanced absorption covering the UV and visible regions of the electromagnetic spectrum. A study of the photocatalytic properties of the composite structures demonstrates that exposure to both UV and visible light enables them to induce the rapid decomposition of 2‐chlorophenol. The degradation rate increases with a larger weight content of Ag in the composite structure.     

Transparent Mesoporous Nanocomposite Films for Self‐Cleaning Applications

A versatile approach is studied for the elaboration of TiO₂ based photocatalytic coatings for self‐cleaning applications on transparent substrates. The basic principle of the synthesis relies on the use of preformed TiO₂ colloidal particles that are further dispersed within a transparent silica binder with a mesoporous structure. Film porosity in the nanometer range is controlled by achieving the sol–gel silica condensation around self‐organized micellar assemblies of a templating copolymer surfactant. The latter also acts as a stabilizer for the TiO₂ particles, thus preserving their high dispersion within the film so that excellent optical properties are maintained even for high TiO₂ loading (up to 50 %). Studies of photodegradation kinetics show that such mesoporous films are at least 15 times more active than films synthesized with a usual microporous silica binder. Moreover, the measured quantum‐yield efficiency (1.1 %) is found to be among the highest reported up to now. Improved photoactivity of the films is discussed as resulting from the closer proximity between the organic molecules and the surface of the TiO₂ crystallites as well as the improved diffusion rate of water and oxygen through the interconnected pore network.     

Self‐Assembling TiO2 Nanorods on Large Graphene Oxide Sheets at a Two‐Phase Interface and Their Anti‐Recombination in Photocatalytic Applications

TiO₂ nanorods are self‐assembled on the graphene oxide (GO) sheets at the water/toluene interface. The self‐assembled GO–TiO₂ nanorod composites (GO–TiO₂ NRCs) can be dispersed in water. The effective anchoring of TiO₂ nanorods on the whole GO sheets is confirmed by transmission electron microscopy (TEM), X‐ray diffraction (XRD), Fourier transform IR spectroscopy (FTIR), and thermogravimetric analysis (TGA). The significant increase of photocatalytic activity is confirmed by the degradation of methylene blue (MB) under UV light irridiation. The large enhancement of photocatalytic activity is caused by the effective charge anti‐recombination and the effective absorption of MB on GO. The effective charge transfer from TiO₂ to GO sheets is confirmed by the significant photoluminescence quenching of TiO₂ nanorods, which can effectively prevent the charge recombination during photocatalytic process. The effective absorption of MB on GO is confirmed by the UV‐vis spectra. The degradation rate of MB in the second cycle is faster than that in the first cycle because of the reduction of GO under UV light irradiation.     

Rapid Fabrication of an Inverse Opal TiO2 Photoelectrode for DSSC Using a Binary Mixture of TiO2 Nanoparticles and Polymer Microspheres

A rapid fabrication method of highly reflective TiO₂ inverse opal (IO) film exhibiting controllable thickness, high TiO₂ content, and excellent interfacial contact with glass substrate is presented. By inducing accelerated solvent evaporation during the colloidal self‐assembly process, a composite film of polystyrene (PS)/TiO₂ has been directly fabricated on a fluorine doped tin oxide (FTO) glass substrate, which exhibits the highly ordered opaline structure of PS embedded into the TiO₂ matrix. This hybrid fabrication path leads to the formation of layers with the preferred {111} face‐centered cubic (FCC) orientation parallel to the substrate and to produce a 1 cm²‐wide well‐ordered composite colloidal crystal film in less than 30 min. The film showed highly ordered FCC structure, particularly at the upper region, due to the induced solvent evaporation and exhibited a reliable light modulation at a reflectance mode. Regardless of the size of sacrificial PS microspheres, TiO₂ IO films of controllable thickness were successfully formed by varying the moving speed of the fabrication cell. The binary aqueous dispersion of tailor‐made anatase TiO₂ nanoparticles and monodisperse PS microspheres showed a high degree of dispersion stability under basic conditions. Hydrothermal treatment of the TiO₂ dispersion favored the crystallinity of the coated film and provided small volume contraction after thermal calcinations. The high degree of dispersion stability enabled to increase TiO₂ content in a binary mixture, which is more favorable toward the robust and large‐area IO film. The calcined films exhibited excellent mechanical robustness and intimate interfacial contact with the glass substrate. which in turn resulted in higher TiO₂ content near the glass substrate. The TiO₂ IO film was tested as a dye‐sensitized solar cell (DSSC) photoelectrode, and a single cell showed a relatively high photon‐to‐current conversion efficiency of 4.2%. The high TiO₂ content of IO film and its good adhesion to the FTO subratrate remarkably improved in the performance of the solar cell compared to the previous investigations where post‐infiltration of TiO₂ had been employed.     

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.     

Plasmonic Janus‐Composite Photocatalyst Comprising Au and C–TiO2 for Enhanced Aerobic Oxidation over a Broad Visible‐Light Range

Asymmetric Janus nanostructures containing a gold nanocage (NC) and a carbon–titania hybrid nanocrystal (AuNC/(C–TiO₂)) are prepared using a novel and facile microemulsion‐based approach that involves the assistance of ethanol. The localized surface plasmon resonance of the Au NC with a hollow interior and porous walls induce broadband visible‐light harvesting in the Janus AuNC/(C–TiO₂). An acetone evolution rate of 6.3 μmol h^?1 g^?1 is obtained when the Janus nanostructure is used for the photocatalytic aerobic oxidation of iso‐propanol under visible light (λ = 480–910 nm); the rate is 3.2 times the value of that obtained with C–TiO₂, and in photo‐electrochemical investigations an approximately fivefold enhancement is obtained. Moreover, when compared with the core–shell structure (AuNC@(C–TiO₂) and a gold–carbon–titania system where Au sphere nanoparticles act as light‐harvesting antenna, Janus AuNC/(C–TiO₂) exhibit superior plasmonic enhancement. Electromagnetic field simulation and electron paramagnetic resonance results suggest that the plasmon–photon coupling effect is dramatically amplified at the interface between the Au NC and C–TiO₂, leading to enhanced generation of energetic hot electrons for photocatalysis.     

Trifunctional TiO2 Nanoparticles with Exposed {001} Facets as Additives in Cobalt‐Based Porphyrin‐Sensitized Solar Cells

In this study, highly mesoporous TiO₂ composite photoanodes composed of functional {001}‐faceted TiO₂ nanoparticles (NPs) and commercially available 20 nm TiO₂ NPs are employed in efficient porphyrin‐sensitized solar cells together with cobalt polypyridyl‐based mediators. Large TiO₂ NPs (approximately 50 nm) with exposed {001} facets are prepared using a fast microwave‐assisted hydrothermal (FMAH) method. These unique composite photoanodes favorably mitigate the aggregation of porphyrin on the surface of TiO₂ NPs and strongly facilitate the mass transport of cobalt‐polypyridyl‐based electrolytes in the mesoporous structure. Linear sweep voltammetry reveals that the transportation of Co(polypyridyl) redox is a diffusion‐controlled process, which is highly dependent on the porosity of TiO₂ films. Electrochemical impedance spectroscopy confirms that the FMAH TiO₂ NPs effectively suppress the interfacial charge recombination toward [Co(bpy)₃]³⁺ because of their oxidative {001} facets. In an optimal condition of 40 wt% addition of FMAH TiO₂ NPs in the final formula, the power conversion efficiency of the dye‐sensitized cells improves from 8.28% to 9.53% under AM1.5 (1 sun) conditions.     

Enzymatic Micromotors as a Mobile Photosensitizer Platform for Highly Efficient On‐Chip Targeted Antibacteria Photodynamic Therapy

Photodynamic therapy (PDT) functions when the light‐excited photosensitizers transfer energy to oxygen molecules (³O₂) to produce cytotoxic singlet oxygen (¹O₂) that can effectively kill cells or bacteria. However, the PDT efficacy is often reduced by the limited availability of ³O₂ surrounding the photosensitizer and extremely short diffusion range of the photoactivated ¹O₂. Herein, an enzymatic micromotor based on hollow mesoporous SiO₂ (mSiO₂) microspheres is constructed as a mobile and highly efficient photosensitizer platform. Carboxylated magnetic nanoparticles are connected with both hollow spheres and 5,10,15,20‐tetrakis(4‐aminophenyl)porphyrin molecules through covalent linkage between amino and carboxylic groups within a one‐step reaction. Due to the intrinsic asymmetry of the mSiO₂ spheres, the micromotors can be propelled by ionic diffusiophoresis induced by the enzymatic decomposition of urea. Via numerical simulation, the self‐propulsion mechanism is clarified and the movement direction is identified. By virtue of active self‐propulsion, the current system can overcome the long‐standing shortcomings of PDT and significantly enhance the PDT efficacy by improving the accessibility of the photosensitizer to ³O₂ and enlarging the diffusing range of ¹O₂. Therefore, by proposing a new solution to the bottleneck problems of PDT, this work provides insightful perspectives to the biomedical application of multifunctional micro/nanomotors.     

Highly Organized Mesoporous TiO2 Films with Controlled Crystallinity: A Li‐Insertion Study

A study of electrochemical Li insertion combined with structural and textural analysis enabled the identification and quantification of individual crystalline and amorphous phases in mesoporous TiO₂ films prepared by the evaporation‐induced self‐assembly procedure. It was found that the properties of the amphiphilic block copolymers used as templates, namely those of a novel poly(ethylene‐co‐butylene)‐b‐poly(ethylene oxide) polymer (KLE) and commercial Pluronic P123 (HO(CH₂CH₂O)₂₀(CH₂CH(CH₃)O)₇₀(CH₂CH₂O)₂₀H), decisively influence the physicochemical properties of the resulting films. The KLE‐templated films possess a 3D cubic mesoporous structure and are practically amorphous when calcined at temperatures below 450 °C, but treatment at 550–700 °C provides a pure‐phase (anatase), fully crystalline material with intact mesoporous architecture. The electrochemically determined fraction of crystalline anatase increases from 85 to 100 % for films calcined at 550 and 700 °C, respectively. In contrast, the films prepared using Pluronic P123, which also show a 3D cubic pore arrangement, exhibit almost 50 % crystallinity even at a calcination temperature of 400 °C, and their transformation into a fully crystalline material is accompanied by collapse of the mesoporous texture. Therefore, our study revealed the significance of using suitable block‐copolymer templates for the generation of mesoporous metal oxide films. Coupling of both electrochemical and X‐ray diffraction methods has shown to be highly advisable for the correct interpretation of structure properties, in particular the crystallinity, of such sol–gel derived films.