Alberto Naldoni

Effect of Nature and Location of Defects on Bandgap Narrowing in Black TiO2 Nanoparticles

The increasing need for new materials capable of solar fuel generation is central in the development of a green energy economy. In this contribution, we demonstrate that black TiO(2) nanoparticles obtained through a one-step reduction/crystallization process exhibit a bandgap of only 1.85 eV, which matches well with visible light absorption. The electronic structure of black TiO(2) nanoparticles is determined by the unique crystalline and defective core/disordered shell morphology. We introduce new insights that will be useful for the design of nanostructured photocatalysts for energy applications.

Surface enamel remineralization: biomimetic apatite nanocrystals and fluoride ions different effects

A new method for altered enamel surface remineralization has been proposed. To this aim carbonate-hydroxyapatite nanocrystals which mimic for composition, structure, nanodimensions, and morphology dentine apatite crystals and resemble closely natural apatite chemical-physical properties have been used The results underline the differences induced by the use of fluoride ions and hydroxyapatite nanocrystals in contrasting the mechanical abrasions and acid attacks to which tooth enamel is exposed. Fluoride ions generate a surface modification of the natural enamel apatite crystals increasing their crystallinity degree and relative mechanical and acid resistance. On the other hand, the remineralization produced by carbonate-hydroxyapatite consists in a deposition of a new apatitic mineral into the eroded enamel surface scratches. A new biomimetic mineral coating, which progressively fills and shadows surface scratches, covers and safeguards the enamel structure by contrasting the acid and bacteria attacks.

Photodegradation of Pollutants in Air: Enhanced Properties of Nano-TiO2Prepared by Ultrasound

Nanocrystalline TiO2samples were prepared by promoting the growth of a sol–gel precursor, in the presence of water, under continuous (CW), or pulsed (PW) ultrasound. All the samples turned out to be made of both anatase and brookite polymorphs. Pulsed US treatments determine an increase in the sample surface area and a decrease of the crystallite size, that is also accompanied by a more ordered crystalline structure and the samples appear to be more regular and can be considered to contain a relatively low concentration of lattice defects. These features result in a lower recombination rate between electrons and holes and, therefore, in a good photocatalytic performance toward the degradation of NOxin air. The continuous mode induces, instead, the formation of surface defects (two components are present in XPS Ti 2p3/2region) and consequently yields the best photocatalyst. The analysis of all the characterization data seems to suggest that the relevant parameter imposing the final features of the oxides is the ultrasound total energyper volume (Etot/V) and not the acoustic intensity or the pulsed/continuous mode.

Alkaline phosphatase grafting on bioactive glasses and glass ceramics.

Bone integration of orthopaedic or dental implants and regeneration of damaged bone at the surgical site are still unresolved problems in prosthetic surgery. For this reason, biomimetic surfaces (i.e. both inorganic and biological bioactive surfaces) represent a challenge for bone implantation. In this research work a hydrolase enzyme (alkaline phosphatase) was covalently grafted to inorganic bioactive glass and glass ceramic surfaces, in order to impart biological bioactivity. The functionalized samples were analysed by means of X-ray photoelectron spectroscopy in order to verify enzyme presence on the surface. Enzyme activity was measured by means of UV-visual spectroscopy after reaction with the natural substrate. Scanning electron microscopy-energy-dispersive spectroscopy observations allowed monitoring of the morphological and chemical modification of the materials during the different steps of functionalization. In vitro inorganic bioactivity was investigated by soaking samples in simulated body fluid. Enzymatic activity of the samples was tested and compared before and after soaking. Enzymatic activity of the solution was monitored at different experimental times. This study demonstrates that alkaline phosphatase could be successfully grafted onto different bioactive surfaces while maintaining its activity. Presence of the enzyme in vitro enhances the inorganic bioactivity of the materials tested.

Hierarchical Hematite Nanoplatelets for Photoelectrochemical Water Splitting

A new nanostructured α-Fe2O3 photoelectrode synthesized through plasma-enhanced chemical vapor deposition (PE-CVD) is presented. The α-Fe2O3 films consist of nanoplatelets with (001) crystallographic planes strongly oriented perpendicular to the conductive glass surface. This hematite morphology was never obtained before and is strictly linked to the method being used for its production. Structural, electronic, and photocurrent measurements are employed to disclose the nanoscale features of the photoanodes and their relationships with the generated photocurrent. α-Fe2O3 films have a hierarchical morphology consisting of nanobranches (width ∼10 nm, length ∼50 nm) that self-organize in plume-like nanoplatelets (350-700 nm in length). The amount of precursor used in the PE-CVD process mainly affects the nanoplatelets dimension, the platelets density, the roughness, and the photoelectrochemical (PEC) activity. The highest photocurrent (j = 1.39 mA/cm(2) at 1.55 VRHE) is shown by the photoanodes with the best balance between the platelets density and roughness. The so obtained hematite hierarchical morphology assures good photocurrent performance and appears to be an ideal platform for the construction of customized multilayer architecture for PEC water splitting.

Probing Long‐Lived Plasmonic‐Generated Charges in TiO2/Au by High‐Resolution X‐ray Absorption Spectroscopy

Exploiting plasmonic Au nanoparticles to sensitize TiO2 to visible light is a widely employed route to produce efficient photocatalysts. However, a description of the atomic and electronic structure of the semiconductor sites in which charges are injected is still not available. Such a description is of great importance in understanding the underlying physical mechanisms and to improve the design of catalysts with enhanced photoactivity. We investigated changes in the local electronic structure of Ti in pure and N-doped nanostructured TiO2 loaded with Au nanoparticles during continuous selective excitation of the Au localized surface plasmon resonance with X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS). Spectral variations strongly support the presence of long-lived charges localized on Ti states at the semiconductor surface, giving rise to new laser-induced low-coordinated Ti sites.

Porous TiO2 microspheres with tunable properties for photocatalytic air purification

The synthesis of highly-crystalline porous TiO(2) microspheres is reported using ultrasonic spray pyrolysis (USP) in the presence of colloidal silica as a template. We have exploited the interactions between hot SiO(2) template particles surface and TiO(2) precursor that occur during reaction inside the droplets, to control the physical and chemical properties of the resulting particles. Varying the SiO(2) to titanium precursor molar ratio and the colloidal silica dimension, we obtained porous titania microspheres with tunable morphology, porosity, BET surface area, crystallite size, band-gap, and phase composition. In this regard, we have also observed the preferential formation of anatase vs. rutile with increasing initial surface area of the silica template. The porous TiO(2) microspheres were tested in the photocatalytic degradation of nitrogen oxides (NO(x)) in the gas phase. USP prepared nanostructured titania samples were found to have significantly superior specific activity per surface area compared to a commercial reference sample (P25 by Evonik-Degussa).

Solar-Powered Plasmon-Enhanced Heterogeneous Catalysis

Abstract Photocatalysis uses semiconductors to convert sunlight into chemical energy. Recent reports have shown that plasmonic nanostructures can be used to extend semiconductor light absorption or to drive direct photocatalysis with visible light at their surface. In this review, we discuss the fundamental decay pathway of localized surface plasmons in the context of driving solar-powered chemical reactions. We also review different nanophotonic approaches demonstrated for increasing solar-to-hydrogen conversion in photoelectrochemical water splitting, including experimental observations of enhanced reaction selectivity for reactions occurring at the metalsemiconductor interface. The enhanced reaction selectivity is highly dependent on the morphology, electronic properties, and spatial arrangement of composite nanostructures and their elements. In addition, we report on the particular features of photocatalytic reactions evolving at plasmonic metal surfaces and discuss the possibility of manipulating the reaction selectivity through the activation of targeted molecular bonds. Finally, using solar-to-hydrogen conversion techniques as an example, we quantify the efficacy metrics achievable in plasmon-driven photoelectrochemical systems and highlight some of the new directions that could lead to the practical implementation of solar-powered plasmon-based catalytic devices.

Enhanced electrocatalytic activity of gold nanoparticles on hydroxyapatite nanorods for sensitive hydrazine sensors

Well-designed noble metals and ceramic nanoarchitectures are significantly important for the development of high performance, selective, sensitive and cost effective electrochemical sensors. Here, we report gold (Au) nanoparticles (NPs) uniformly dispersed on hydroxyapatite (HAp) nanorods forming particles on rod nanoarchitectures for sensitive hydrazine sensors. The Au/HAp nanocomposites were prepared by a versatile hydrothermal precipitation method. The precipitated citrate-stabilized Au NPs were 6–8 nm in size and strongly anchored onto rod-shaped HAp with a diameter of 10 nm and length of 65 nm. The structural, chemical, and electrochemical properties and growth mechanism of the Au nanoparticles on the HAp nanorods (NRs) are presented. Progress toward the application of hybrid nanocomposites in electrochemical oxidation of hydrazine is reviewed. Compared to Au NPs, the incorporation of Au NPs into HAp NRs favored the adsorption of hydrazine, thus bringing hydrazine much closer to the catalytic sites of Au NPs and then increasing the efficiency of hydrazine oxidation in neutral solution. The amperometric (i–t) hydrazine sensor, using the as-prepared Au/HAp as the electrochemical catalyst, shows a wide linear response range of 0.5–1429 μM, a lower detection limit (0.017 μM) and very high sensitivity of 0.5 μA μM−1 cm−2. Furthermore, the Au/HAp nanocomposites showed an excellent anti-interference property towards the various organic and inorganic electroactive compounds, and good inter-electrode and intra-electrode reproducibility. Our present technique shows both qualitative and quantitative measurement of hydrazine in various water samples with high sensitivity, cost effectiveness and rapid analysis time.

Influence of TiO2 electronic structure and strong metal–support interaction on plasmonic Au photocatalytic oxidations

Aiming at understanding how plasmonic reactions depend on important parameters such as metal loading and strong metal–support interaction (SMSI), we report the plasmonic photodegradation of formic acid (FA) under green LED irradiation employing three TiO2 supports (stoichiometric TiO2, N-doped TiO2, black TiO2) modified with Au nanoparticles (NPs) 3–6 nm in size. The rate of FA photooxidation follows different trends depending on Au loading for stoichiometric and doped Au/TiO2 materials. In the first case, the only contribution of hot electron transfer produces a volcano-shaped curve of photoreaction rates with increasing Au loading. When TiO2 contains intra-bandgap states the photoactivity increases linearly with the amount of Au NPs due to the concomitant enhancement produced by hot electron transfer and plasmon resonant energy transfer (PRET). The role of PRET is supported by finite element method simulations, which show that the increase in both Au NP inter-distance and SMSI enhances the probability of charge carrier generation at the Au/TiO2 interface.