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1.
J Phys Condens Matter ; 32(1): 014001, 2020 Jan 01.
Artigo em Inglês | MEDLINE | ID: mdl-31514175

RESUMO

The PEC performance of WO3/BiVO4 heterojunction photoanodes with a fixed BiVO4 thick top layer and different WO3 layer thicknesses was investigated under backside irradiation, in comparison with the performance of the same electrodes without a top BiVO4 layer. While the performance of these latter increase with increasing WO3 thickness, the presence of a BiVO4 layer, besides leading to an effective sensitization up to 520 nm, leads to a decrease of incident photon to current efficiency in the short wavelength's range. After having excluded major WO3 filter effects, this has been attributed to charge carrier recombination effects occurring when both oxides get excited and becoming more relevant with increasing WO3 thickness and decreasing excitation wavelength.

2.
J Am Chem Soc ; 140(43): 14042-14045, 2018 Oct 31.
Artigo em Inglês | MEDLINE | ID: mdl-30296074

RESUMO

The dynamics of photopromoted electrons in BiVO4, WO3, and WO3/BiVO4 heterojunction electrodes has been directly probed by transient absorption (TA) midinfrared (mid-IR) spectroscopy in the picosecond to microsecond time range. By comparison of the dynamics recorded with the two individual oxides at 2050 cm-1 with that of the heterojunction system after excitation at different wavelengths, electron-transfer processes between selectively excited BiVO4 and WO3 have been directly tracked for the first time. These results support the charge carrier interactions which were previously hypothesized by probing the BiVO4 hole dynamics through TA spectroscopy in the visible range. Nanosecond mid-IR TA experiments confirmed that charge carrier separation occurs in WO3/BiVO4 electrodes under visible-light excitation, persisting up to the microsecond time scale.

3.
ACS Appl Mater Interfaces ; 10(33): 27745-27756, 2018 Aug 22.
Artigo em Inglês | MEDLINE | ID: mdl-30048108

RESUMO

In the present work, two H2 evolution photocatalysts were prepared by employing two different oxides, TiO2 and zirconium titanate (ZrTiO4), as the support of various copper phases. For both the supports the same Cu loading (0.5% w/w) was adopted, but two different impregnation procedures have been followed, leading to different forms of Cu in the final composite material that are: (i) Cu(II) species dispersed on the oxide surface and (ii) Cu2O particles dispersed on the oxide surface. The present paper based on the parallel use of photocatalytic test and spectroscopic analysis performed in catalytic conditions illustrates the evolution of photocatalytic systems occurring during the H2 evolution reaction tests, pointing out that the as-prepared materials represent a pre-catalyst and they are modified during irradiation leading to the real working systems different from the starting ones. The herein presented spectroscopic analysis aims to contribute to the living debate on the oxidation state of copper in mixed Cu/oxide materials and on its role in hydrogen evolution under photocatalytic conditions.

4.
Zebrafish ; 14(5): 411-421, 2017 10.
Artigo em Inglês | MEDLINE | ID: mdl-28678643

RESUMO

The accumulation of nitrogen compounds represents a pivotal problem in the management of fish culture. Several methods were investigated in the last decades for treatment of waste waters, and the use of photocatalytic materials has received increasing attention. The photocatalytic degradation (PCD) process with titanium dioxide (TiO2) represents the most promising single-step method to promote the removal of nitrogen compounds from water. The present study compares for the first time the effects on fish culture of a classical mechanical, biological, and ultraviolet purification system to a TiO2-PCD one, with particular emphasis on water chemistry and on physiological responses in zebrafish. Fish were exposed for 14 days to the two different purification systems and samplings were performed 7 and 14 days after the experiment beginning. The photocatalytic system showed excellent efficiency in removing nitrogen compounds from water with no significant adverse effects on fish. Physiological analysis on fish samples included histological analysis of gills and gut, TUNEL assay of the gills, and real-time polymerase chain reaction (liver) of genes involved in stress response and growth. No significant biological alterations were detectable on the cultured fish.


Assuntos
Compostos de Nitrogênio/química , Fármacos Fotossensibilizantes/química , Titânio/química , Poluentes Químicos da Água/química , Purificação da Água/métodos , Peixe-Zebra/crescimento & desenvolvimento , Animais , Concentração de Íons de Hidrogênio , Oxirredução , Estresse Oxidativo/efeitos da radiação , Fotólise
6.
PLoS One ; 11(10): e0164670, 2016.
Artigo em Inglês | MEDLINE | ID: mdl-27741313

RESUMO

A series of 14 mesoporous titania materials has been synthesized using the simple alcothermal template-free method and various alcohols, such as methanol, propanols and butanols, as solvents. All materials were characterized by both wide and small angle XRD, which exhibited the anatase phase with short-range ordered mesoporous structure that is still forming during post synthetic temperature treatment in most of the investigated materials. Nitrogen adsorption-desorption isotherms confirmed the mesoporous structure with surface area ranging from 241 to 383 m2g- 1 and pore volumes from 0.162 to 0.473 m3g-1, UV-Vis diffuse reflectance showed the redshift of the absorption edge and the bandgap decrease after post synthetic calcination of the materials presented. The TEM, FT-IR, DTA and TG measurements have been made to well characterize the materials synthesized. The mesoporous samples obtained were applied as anode materials for dye-sensitized solar cells and showed good activity in photon-to-current conversion process with efficiency values ranging from 0.54% to 4.6% and fill factors in the 52% to 67% range. The photovoltaic performances were not as high as those obtained for the materials synthesized by us earlier employing ethanol as a solvent. The differences in the electron lifetime, calculated from electrochemical impedance spectroscopy results and varying between 4.3 to 17.5 ms, were found as a main factor determining the efficiency of the investigated photovoltaic cells.


Assuntos
Energia Solar , Solventes/química , Titânio/química , Adsorção , Álcoois/química , Corantes/química , Microscopia Eletrônica de Transmissão , Nitrogênio/química , Porosidade , Espectroscopia de Infravermelho com Transformada de Fourier , Termogravimetria , Difração de Raios X
7.
ACS Appl Mater Interfaces ; 8(15): 9745-54, 2016 Apr 20.
Artigo em Inglês | MEDLINE | ID: mdl-27019104

RESUMO

Crystal shape control on a series of anatase photocatalysts was achieved by varying the amount of HF employed as a capping agent in their hydrothermal synthesis. A systematic comparison between their physicochemical properties, determined by several complementary surface and bulk techniques before and after thermal treatment at 500 °C, allowed one to discern the influence of the relative amount of exposed {001} crystal facets among a series of effects simultaneously affecting their oxidative photocatalytic activity. The results of both formic acid and terephthalic acid photo-oxidation test reactions point to the primary role played by calcination in making {001} facets effectively photoactive. Annealing not only removes most of the residual fluorine capping agent from the photocatalyst surface, thus favoring substrate adsorption, but also produces morphological modifications to a crystal packing that makes accessible a larger portion of surface {001} facets due to the unpiling of platelike crystals. The photocatalyst bearing the highest amount of exposed {001} facets (60%) shows the highest photoactivity in both the direct and the (•)OH-radical-mediated photocatalytic test reaction.

8.
Materials (Basel) ; 9(4)2016 Apr 08.
Artigo em Inglês | MEDLINE | ID: mdl-28773404

RESUMO

Evolution of pure hydrogen and oxygen by photocatalytic water splitting was attained from the opposite sides of a composite Pt/Ti/TiO2 photoelectrode. The TiO2 films were prepared by radio frequency (RF)-Magnetron Sputtering at different deposition time ranging from 1 up to 8 h and then characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and ultraviolet-visible-near infrared (UV-vis-NIR) diffuse reflectance spectroscopy. The photocatalytic activity was evaluated by incident photon to current efficiency (IPCE) measurements and by photocatalytic water splitting measurements in a two-compartment cell. The highest H2 production rate was attained with the photoelectrode prepared by 6 h-long TiO2 deposition thanks to its high content in the rutile polymorph, which is active under visible light. By contrast, the photoactivity dropped for longer deposition time, because of the increased probability of electron-hole recombination due to the longer electron transfer path.

9.
J Am Chem Soc ; 137(17): 5646-9, 2015 May 06.
Artigo em Inglês | MEDLINE | ID: mdl-25884483

RESUMO

We introduce the use of pure molten ortho-phosphoric acid (o-H3PO4) as an electrolyte for self-organizing electrochemistry. This electrolyte allows for the formation of self-organized oxide architectures (one-dimensional nanotubes, nanochannels, nanopores) on metals such as tungsten that up to now were regarded as very difficult to grow self-ordered anodic oxide structures. In this work, we show particularly the fabrication of thick, vertically aligned tungsten oxide nanochannel layers, with pore diameter of ca. 10 nm and illustrate their potential use in some typical applications.

10.
Phys Chem Chem Phys ; 17(7): 4864-9, 2015 Feb 21.
Artigo em Inglês | MEDLINE | ID: mdl-25607570

RESUMO

Cathodoluminescence spectroscopy is profitably exploited to study energy transfer mechanisms in Au and Pt/black TiO2 heterostructures. While Pt nanoparticles absorb light in the UV region, Au nanoparticles absorb light by surface plasmon resonance and interband transitions, both of them occurring in the visible region. The intra-bandgap states (oxygen vacancies) of black TiO2 play a key role in promoting both hot electron transfer and plasmonic resonant energy transfer from Au nanoparticles to the TiO2 semiconductor with a consequent photocatalytic H2 production increase. An innovative criterion is introduced for the design of plasmonic composites with increased efficiency under visible light.

11.
J Phys Chem A ; 119(19): 4433-8, 2015 May 14.
Artigo em Inglês | MEDLINE | ID: mdl-25390039

RESUMO

We report that 1-hydropyridinyl radicals (1-PyH(•)) photogenerated in solution react with dissolved CO2 en route to its 2e(-) reduction into carboxylic acids. The 254 nm excitation of pyridine (Py) in deaerated 2-PrOH/H2O mixtures saturated with 1 atm of CO2 yields a suite of products, among which we identified Na(HCOO)2(-) (m/z(-) = 113), C5H6NCOO(-) (m/z(-) = 124), and C5H10O2NCOO(-) (m/z(-) = 160) species by electrospray ionization mass spectrometry. These products demonstrably contain carboxylate functionalities that split CO2 neutrals via collisionally induced dissociation. We infer that 1-PyH(•) [from (1) (3)Py* + 2-PrOH → 1-PyH(•) + (•)PrOH] adds to CO2, in competition with radical-radical reactions, leading to intermediates that are in turn reduced by (•)PrOH into the observed species. The formation of carboxylates in this system, which is shown to require CO2, Py, 2-PrOH, and actinic radiation, amounts to the homogeneous 2e(-) reduction of CO2 by 2-PrOH initiated by Py*. We evaluate a rate constant (2) k2(1-PyH(•) + CO2 → (•)Py-1-COOH) ≈ O (10) M(-1) s(-1) and an activation energy E2 ≥ 9 kcal mol(-1) that are compatible with thermochemical estimates for this reaction.


Assuntos
Dióxido de Carbono/química , Radicais Livres/química , Processos Fotoquímicos , Piridinas/química , Ácidos Carboxílicos/química , Espectrometria de Massas por Ionização por Electrospray , Água/química
12.
Adv Mater ; 25(42): 6133-7, 2013 Nov 13.
Artigo em Inglês | MEDLINE | ID: mdl-23963835

RESUMO

Electrochemical anodization of low-concentration (0.02-0.2 at% Au) TiAu alloys in a fluoride electrolyte leads to self-organized TiO2 nanotubes that show a controllable, regular in situ decoration with elemental Au nanoclusters of ≈5 nm in diameter. The degree of self-decoration can be adjusted by the Au concentration in the alloy and the anodization time. Such Au particle decorated tubes show a high activity for photocatalytic H2 production from ethanol solutions.


Assuntos
Ouro/química , Hidrogênio/química , Nanotubos/química , Titânio/química , Ligas/química , Catálise , Etanol/química , Fluoretos/química , Raios Ultravioleta
13.
Angew Chem Int Ed Engl ; 52(29): 7514-7, 2013 Jul 15.
Artigo em Inglês | MEDLINE | ID: mdl-23765440

RESUMO

Peas in a pod: A highly aligned Au(np)@TiO2 photocatalyst was formed by self-organizing anodization of a Ti substrate followed by dewetting of a gold thin film. This leads to exactly one Au nanoparticle (np) per TiO2 nanocavity. Such arrays are highly efficient photocatalysts for hydrogen generation from ethanol.

14.
Chemistry ; 19(19): 5841-4, 2013 May 03.
Artigo em Inglês | MEDLINE | ID: mdl-23519978

RESUMO

A little dopey: Ta-doped titania (TiO2) nanotube (NT) arrays can be grown by electrochemical anodization onto low-Ta-concentration (0.03-0.4 at % Ta) Ti-Ta alloys. Under optimized conditions (0.1 at % Ta, annealing at 650 °C and 7 µm thickness), Ta-doped TiO2 NT arrays show a significantly enhanced activity in photoelectrochemical water splitting under simulated sunlight conditions (see figure).

15.
Photochem Photobiol Sci ; 12(4): 595-601, 2013 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-22930393

RESUMO

The effect of noble metal (Pt and Au) nanoparticle photodeposition on a series of NH4F-doped TiO2 photocatalysts calcined at 700 °C was investigated both in a thermodynamically down-hill reaction, i.e. the degradation of formic acid in aqueous suspension, and in an up-hill reaction, i.e. hydrogen production from methanol-water vapour mixtures. All photocatalysts were characterized by BET, XRD, UV-vis absorption and HRTEM analysis. Intriguing synergistic effects of simultaneous bulk and surface TiO2 modification were evidenced in both photocatalytic reactions, which can be interpreted in relation to the structural features of the materials. On one hand NH4F doping guarantees that the most active TiO2 anatase phase is stabilised up to high calcination temperature, ensuring high crystallinity and good photoinduced charge carriers production, on the other hand noble metal nanoparticles contribute in increasing the separation of photoproduced charge carriers, resulting in enhanced photocatalytic performances of the surface- and bulk-modified photocatalyst systems.

16.
J Environ Manage ; 96(1): 86-90, 2012 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-22208401

RESUMO

The beneficial effect of a TiO2-based photocatalytic treatment on the indoor air purification of a swine farm has been evaluated in a trial performed in two identical mechanically ventilated traditional weaning units, with 391 animals lodged in each of them. One unit was used as reference, whereas the walls of the second unit (260 m2) were coated with ca. 70 g m(-2) of TiO2 and irradiated with ten UV-A lamps. The environmental parameters (i.e. the ventilation rate, the internal and external temperature and relative humidity), together with NH3, CH4, CO2 and N2O concentrations in the exhaust ducts and PM10 emissions, were monitored in the two units throughout all of the production cycle (75 days). Significant decreases in CH4 concentration (ca. 27%, P < 0.05) and PM10 emission (ca. 17%, P < 0.01) were observed, together with an increase of the piglets' productive performance in the treated unit with respect to the reference one. Indeed, the ADG (Average Daily Gain of piglets) was 424 g vs. 414 g for the piglets lodged in the two units, respectively, with a significantly better feed conversion ratio (FCR, ratio between the food ingested by the animals and their weight gain) of 2.18 vs. 2.44 (P < 0.001). Therefore, the photocatalytic treatment with TiO2 coating had positive effects not only on methane concentration and particulate matter concentration and emission, but also significantly improved the feed conversion ratio of growing piglets, very likely due to the increased quality of indoor air, with positive economic repercussions for the farmer. Internal photocatalytic treatment in swine husbandry could thus be considered as a potential Best Available Technology (BAT).


Assuntos
Poluentes Ocupacionais do Ar/análise , Criação de Animais Domésticos/métodos , Pintura , Sus scrofa/crescimento & desenvolvimento , Titânio , Poluição do Ar em Ambientes Fechados , Amônia/análise , Ração Animal , Animais , Dióxido de Carbono/análise , Metano/análise , Material Particulado , Suínos , Temperatura , Desmame , Ganho de Peso
17.
J Hazard Mater ; 211-212: 188-95, 2012 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-21959186

RESUMO

Commercial TiO(2) samples with different phase composition and surface area were tested as photocatalysts in the photoinduced reduction of Cr(VI) in aqueous suspensions at pH 3.7 under UV-visible light irradiation. This reaction was also coupled with the simultaneous photocatalytic oxidation of the pollutant azo dye Acid Orange 8 (AO8) and of formic acid, acting as hole scavengers. The co-presence of oxidizable and reducible species ensured better separation of photogenerated charge carriers, resulting in a higher rate of both organics' oxidation and Cr(VI) reduction, especially in the case of high surface area anatase TiO(2), having the strongest affinity for Cr(VI) and AO8, as demonstrated by competitive adsorption tests. The effects on Cr(VI) photocatalytic reduction of gold nanoparticles photodeposited on TiO(2) and of the Au loading were also investigated, aiming at ascertaining if this noble metal plays a role in the electron transfer processes involved in Cr(VI) reduction.


Assuntos
Cromo/química , Ouro/química , Nanopartículas Metálicas/química , Titânio/química , Poluentes Químicos da Água/química , Compostos Azo/química , Compostos Azo/efeitos da radiação , Catálise , Cromo/efeitos da radiação , Corantes/química , Corantes/efeitos da radiação , Luz , Oxirredução , Processos Fotoquímicos , Poluentes Químicos da Água/efeitos da radiação
18.
J Hazard Mater ; 211-212: 203-7, 2012 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-22119301

RESUMO

The importance of the choice of a suitable substrate as supporting material for photoactive TiO(2), either in the form of powders or thin films or in photoactive paints, is frequently disregarded. In this paper four different supports (stainless steel, sand-blasted stainless steel, Teflon and glass) are object of investigation. The final aim is to verify the presence of interactions between the photocatalyst (AEROXIDE(®) TiO(2) P25 by Evonik Degussa Corporation) and the support, directly involved in the photocatalytic activity in the NO(x) abatement. The characterization results have been correlated with the photoactivity of the different samples. In particular, a coating of about 6-9 µm seems to allow a photocatalytic result free from any positive or negative interference with the supporting material, therefore giving reliable results about the photoactivity of the TiO(2) under investigation.


Assuntos
Poluentes Atmosféricos/química , Óxidos de Nitrogênio/química , Titânio/química , Poluentes Atmosféricos/efeitos da radiação , Catálise , Luz , Óxidos de Nitrogênio/efeitos da radiação , Fotólise
19.
Phys Chem Chem Phys ; 13(40): 18217-27, 2011 Oct 28.
Artigo em Inglês | MEDLINE | ID: mdl-21909553

RESUMO

The photocatalytic behaviour of a series of ammonium fluoride (NH(4)F)-doped titania (TiO(2)) photocatalysts was investigated in the decomposition of acetic acid in aqueous suspensions and in the gas phase mineralization of acetaldehyde. Very similar photocatalytic activity trends, usually increasing with increasing the calcination temperature for a given nominal dopant amount, were obtained for the two test reactions. Moderately doped TiO(2) calcined at 700 °C, consisting of pure anatase, was the best performing photocatalyst in both reactions. The photocatalytic oxidation of acetic acid was investigated systematically as a function of irradiation wavelength, by collecting so-called action spectra. By comparing the shapes of the action spectra with those of the absorption spectra of the investigated photocatalysts a model is proposed, based on spectral features deconvolution, which allows a clear distinction between inactive light absorption and effective photoactivity in acetic acid decomposition.

20.
Photochem Photobiol Sci ; 10(3): 355-60, 2011 Mar 02.
Artigo em Inglês | MEDLINE | ID: mdl-20820674

RESUMO

The effect of the crystalline phase of TiO(2) (anatase, rutile and brookite) on its photocatalytic activity in hydrogen production from methanol-water vapours has been investigated by testing a series of both home-made and commercial TiO(2) photocatalysts, either bare or surface-modified by deposition of a fixed amount, i.e. 1 wt%, of platinum as co-catalyst. For all of the TiO(2) samples the rate of hydrogen production increased by one order of magnitude upon Pt deposition, because of the ability of Pt to enhance the separation of photoproduced electron-hole pairs. Under irradiation in the 350-450 nm wavelength range, brookite and anatase showed similar photoactivities, both superior to that of rutile. By contrast, rutile, possessing a narrower band gap, was active also under visible light (λ > 400 nm), whereas no hydrogen evolution was observed with anatase and brookite under such conditions. Surface area proved to be a key parameter, strongly influencing photoactivity. However, as the particle size became ultra-small, the semiconductor absorption edge was blue-shifted because of size quantisation effects, with a consequent decrease in hydrogen production rate due to the smaller portion of incident photons absorbed by the photocatalyst.

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