The possibility of controlling the photocatalytic activity of TiO2 nanoparticles by tailoring their crystalline structure and morphology is a current topic of great interest. In this study, a broad variety of well-faceted particles with different phase compositions, sizes, and shapes have been obtained from concentrated TiOCl2 solutions by systematically changing temperature, pH, and duration of the hydrothermal treatment. The guide to select the suitable experimental conditions was provided by thermodynamic modeling based on available thermochemical data. By combining the results of TEM, HRTEM, XRD, density, and specific surface area measurements, a complete structural and morphological characterization of the particles was performed. Correlation between the photocatalytic activity in the UV photodegradation of phenol solutions and the particle size was established. Prismatic rutile particles with length/width ratio around 5 and breadth of 60-100 nm showed the highest activity. The surface chemistry of the particles was also investigated. Treatments that decrease the surface acidity, such as washing the powders with ammonia solution and/or calcining at 400 degrees C, have detrimental effect on photocatalytic activity. The overall results suggest correlation between particle morphology and photocatalytic activity and indicate that both electron-hole recombination and adsorption at the surface can be rate-controlling processes. The systematic approach presented in this study demonstrates that a substantial improvement of the photocatalytic activity of TiO2 can be achieved by a careful design of the particle morphology and the control of the surface chemistry.

The promising properties of anatase TiO2 nanocrystals exposing specific surfaces have been investigated in depth both theoretically and experimentally. However, a clear assessment of the role of the crystal faces in photocatalytic processes is still under debate. In order to clarify this issue, we have comprehensively explored the properties of the photogenerated defects and in particular their dependence on the exposed crystal faces in shape-controlled anatase. Nanocrystals were synthesized by solvothermal reaction of titanium butoxide in the presence of oleic acid and oleylamine as morphology-directing agents, and their photocatalytic performances were evaluated in the phenol mineralization in aqueous media, using O2 as the oxidizing agent. The charge-trapping centers, Ti3+, O–, and O2 –, formed by UV irradiation of the catalyst were detected by electron spin resonance, and their abundance and reactivity were related to the exposed crystal faces and to the photoefficiency of the nanocrystals. In vacuum conditions, the concentration of trapped holes (O– centers) increases with increasing {001} surface area and photoactivity, while the amount of Ti3+ centers increases with the specific surface area of {101} facets, and the highest value occurs for the sample with the worst photooxidative efficacy. These results suggest that {001} surfaces can be considered essentially as oxidation sites with a key role in the photoxidation, while {101} surfaces provide reductive sites which do not directly assist the oxidative processes. Photoexcitation experiments in O2 atmosphere led to the formation of Ti4+–O2 – oxidant species mainly located on {101} faces, confirming the indirect contribution of these surfaces to the photooxidative processes. Although this work focuses on the properties of TiO2, we expect that the presented quantitative investigation may provide a new methodological tool for a more effective evaluation of the role of metal oxide crystal faces in photocatalytic processes.

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Macroporous materials 1,2 based on metal oxides have become strategic for various applications like photonic crystals, 3À5 catalysts, 6À8 and sensor devices, 9À13 mainly due to their lightweight, their high surface area, and the well-defined porous architecture with a limited agglomerated morphology. 2 In sensing research the improvement in selectivity, reproducibility, and stability expected for the gas sensors based on macroporous metal oxides is still a challenge for pollutant detection. 14 Unfortunately, the delicate method needed to prepare macroporous materials still limits their wide employment in effective devices. 1,2 Macroporous metal oxides are typically synthesized by alkoxidebased solÀgel processes, employing two steps: 11,15À20 (i) the selfassembling of an ordered array of colloidal microspheres of polystyrene, polymethyl methacrylate, or silica, acting as template; (ii) the filling of interstices of the structure by metal alkoxide solution, followed by solÀgel hydrolysis and densification.The subsequent thermal treatment which removes the template leads to the macroporous structure called inverted opal, where the macropores are interconnected through holes resulting from the contact between the template spheres. 2 The application of this synthetic method becomes particularly tricky wherein highly reactive metal alkoxides are used as oxide precursors, 21,22 or if the oxide needs to be doped by sensitizing centers, 11 for example, by transition metal atoms. Moreover, when the preparation of films is required, such as in the case of semiconductor oxide-based gas sensors, the two-step approach appears unsuitable to produce metal oxide thin films having high reproducible morphology, homogeneously embedding dopants, like transition metal centers.To easily obtain macroporous metal oxides with high surface area and homogeneous dopant distribution, our group recently developed a novel one-step preparation of SnO 2 and Pt-doped SnO 2 as inverse opal thin films by dip-coating deposition of solÀgel precursors. 23 The procedure enables the self-assembled formation of the closely packed polystyrene (PS) microsphere array and the simultaneous infiltration of the precursors into the voids of the structure. Thus, the oxide solid skeleton around the spheres was obtained in one-step, unlike the conventional Received: October 22, 2010 ABSTRACT: Macroporous WO 3 films with inverted opal structure were synthesized by one-step procedure, which involves the self-assembly of the spherical templating agents and the simultaneous solÀgel condensation of the semiconductor alkoxide precursor. Transition metal doping, aimed to enhance the WO 3 electrical response, was carried out by including Cr(III) and Pt(IV) centers in the oxide matrix. It turned out that Cr remains as homogeneously dispersed Cr(III) centers inside the WO 3 host, while Pt undergoes reduction and aggregation to form nanoclusters located at the oxide surface. Upon interaction with NH 3 , the electrical conductivity of transition metal doped-WO 3 increase...

Rechargeable sodium-ion batteries are becoming a viable alternative to lithium-based technology in energy storage strategies, due to the wide abundance of sodium raw material. In the past decade, this has generated a boom of research interest in such systems. Notwithstanding the large number of research papers concerning sodium-ion battery electrodes, the development of a low-cost, well-performing anode material remains the largest obstacle to overcome. Although the well-known anatase, one of the allotropic forms of natural TiO, was recently proposed for such applications, the material generally suffers from reduced cyclability and limited power, due to kinetic drawbacks and to its poor charge transport properties. A systematic approach in the morphological tuning of the anatase nanocrystals is needed, to optimize its structural features toward the electrochemical properties and to promote the material interaction with the conductive network and the electrolyte. Aiming to face with these issues, we were able to obtain a fine tuning of the nanoparticle morphology and to expose the most favorable nanocrystal facets to the electrolyte and to the conductive wrapping agent (graphene), thus overcoming the intrinsic limits of anatase transport properties. The result is a TiO-based composite electrode able to deliver an outstandingly stability over cycles (150 mA h g for more than 600 cycles in the 1.5-0.1 V potential range) never achieved with such a low content of carbonaceous substrate (5%). Moreover, it has been demonstrated for the first time than these outstanding performances are not simply related to the overall surface area of the different morphologies but have to be directly related to the peculiar surface characteristics of the crystals.

The present study reports on the synthesis and the electrochemical behavior of Na 0.71 CoO 2 , a promising candidate as cathode for Na-based batteries. The material was obtained in two different morphologies by a double-step route, which is cheap and easy to scale up: the hydrothermal synthesis to produce Co 3 O 4 with tailored and nanometric morphology, followed by the solid-state reaction with NaOH, or alternatively with Na 2 CO 3 , to promote Na intercalation. Both products are highly crystalline and have the P2-Na 0.71 CoO 2 crystal phase, but differ in the respective morphologies. The material obtained from Na 2 CO 3 have a narrow particle length (edge to edge) distribution and 2D platelet morphology, while those from NaOH exhibit large microcrystals, irregular in shape, with broad particle length distribution and undefined exposed surfaces. Electrochemical analysis shows the good performances of these materials as a positive electrode for Na-ion half cells. In particular, Na 0.71 CoO 2 thin microplatelets exhibit the best behavior with stable discharge specific capacities of 120 and 80 mAh g À1 at 5 and 40 mA g À1 , respectively, in the range 2.0-3.9 V vs. Na + /Na. These outstanding properties make this material a promising candidate to construct viable and high-performance Na-based batteries.

Silica-styrene butadiene rubber (SBR) nanocomposites were prepared by using shape-controlled spherical and rod-like silica nanoparticles (NPs) with different aspect ratios (AR = 1-5), obtained by a sol-gel route assisted by a structure directing agent. The nanocomposites were used as models to study the influence of the particle shape on the formation of nanoscale immobilized rubber at the silica-rubber interface and its effect on the dynamic-mechanical behavior. TEM and AFM tapping mode analyses of nanocomposites demonstrated that the silica particles are surrounded by a rubber layer immobilized at the particle surface. The spherical filler showed small contact zones between neighboring particles in contact with thin rubber layers, while anisotropic particles (AR > 2) formed domains of rods preferentially aligned along the main axis. A detailed analysis of the polymer chain mobility by different time domain nuclear magnetic resonance (TD-NMR) techniques evidenced a population of rigid rubber chains surrounding particles, whose amount increases with the particle anisotropy, even in the absence of significant differences in terms of chemical crosslinking. Dynamic measurements demonstrate that rod-like particles induce stronger reinforcement of rubber, increasing with the AR. This was related to the self-alignment of the anisotropic silica particles in domains able to immobilize rubber.

The sol-gel synthesis of TiO 2 from TiCl 4 assisted by the triblock copolymer EO 20 -PO 70 -EO 20 (EO ) -CH 2 CH 2 O-, PO ) -CH 2 (CH 3 )CHO-) as templating agent was carried out by systematically changing H 2 O:Ti (r w ) and HCl:Ti (r a ) molar ratios. Mesoporous and nanocrystalline TiO 2 samples with well-defined and controlled phase composition (anatase, rutile, and mixed phase) were obtained after calcination at 400 °C and characterized for the morphology, particle size, and shape using TEM, HRTEM, XRD, and surface area measurements. The role of r w and r a and influence of the copolymer in determining the phase composition was demonstrated. Rutile becomes the main phase by increasing r w . In fact, the decrease of Ti concentration slows down the condensation rate, favoring formation of rutile seeds in the gel. The photocatalytic activity of TiO 2 in the UV photomineralization of phenol depends on the phase composition and oxidizing agent, H 2 O 2 or O 2 . When the oxidation is performed by H 2 O 2 , rutile, formed by large crystalline rods with high aspect ratios (size 15-20 × 100-120 nm), shows higher catalytic activity with respect to the small, almost cubic, anatase particles (5-15 nm). If O 2 is used, the catalytic activity generally decreases and the behavior of polymorphous species is reverse. EPR investigation of the paramagnetic charge carriers, formed under UV irradiation at 10 K, showed the resonance lines of holes trapped at Olattice sites and electrons trapped at Ti 3+ and O 2 sites. The rutile crystalline rods present the largest quantity of Oand Ti 3+ centers. The overall results suggest correlation between TiO 2 particle size and shape and the photocatalytic activity and indicate that electron-hole recombination is the most probable rate-controlling process.