arXiv subjects

A. J. Silvestre

Publications and source records attributed to A. J. Silvestre.

At least 19 recordsLinked to original sources

arXiv2022

Novel C-dots/titanate nanotubular hybrid materials with enhanced optical and photocatalytic properties

Advanced nanomaterials with enhanced optical and photocatalytic properties for the photodegradation of organic pollutants, in particular pharmaceuticals and personal care products (PPCPs), were successfully prepared by a swift one-pot synthesis. Nanostructured materials were synthesized through an integrated hydrothermal procedure which generates titanate nanotubes (TNTs) with different carbon dots (C-dots) contents, from an amorphous titanium oxide-based source and cork industry wastewaters (CIWWs) as carbon source. Their structural, microstructural, morphological, and optical properties were studied by XRD, TEM, UV-Vis diffuse reflectance and photoluminescence spectroscopies. As aimed, the hybrid C-dots/TNT nanomaterials extend their light absorption towards the red, in comparison to pristine TNTs, prompting them for a more efficient use of light in photocatalysis by widening the TNTs energy uptake range. The decrease of bandgap energy with increasing sample's C-dots content seems to be originated from energy intermediate states formed within the TNTs forbidden band resulting from Ti-O-C bonds established between the TNTs and the C-dots that form tails of states. The as-synthesized C-dots/TNT samples were tested in the photodegradation of caffeine as a pollutant model. Rewarding results were obtained, with the hybrid C-dots/TNT nanomaterials showing significant enhanced photocatalytic ability toward caffeine degradation in comparison to pristine TNTs. Photocatalysis assays in the presence of scavengers and/or in the absence of oxygen were also performed aiming to characterize the most reactive species formed during the semiconductor photo-activation process and thus assessing to possible reactive pathways underpinning the photocatalytic activity of the hybrid C-dots/TNT nanomaterials.

physics.app-ph↗

arXiv2016

Argon assisted chemical vapor deposition of CrO$_2$: an efficient process leading to high quality epitaxial films

A comparative study of the structural, microstructural and magnetic properties of CrO$_2$ thin films grown onto (110) and (100) TiO$_2$ rutile single crystal substrates by chemical vapor deposition (CVD), using CrO$_3$ as chromium precursor and either oxygen or argon as carrier gas is presented. Our results show that growth under argon carrier gas leads to high quality CrO$_2$ epilayers with structural and magnetic properties similar to those obtained using the more standard oxygen carrier gas. Furthermore, we interpret the larger magnetic coercivity observed for the (110) oriented films in terms of their microstructure, in particular of the highest strain and edge roughness of the building structures of the CrO$_2$ epilayers, which are settled by the substrate crystallographic orientation.

cond-mat.mtrl-sci↗

arXiv2015

Synthesis of titanate nanofibers co-sensitized with ZnS and Bi2S3 nanocrystallites and their application on pollutants removal

The synthesis of nanocomposite materials combining titanate nanofibers (TNF) with nanocrystalline ZnS and Bi2S3 semiconductors is described in this work. The TNF were produced via hydrothermal synthesis and sensitized with the semiconductor nanoparticles, through a single-source precursor decomposition method. ZnS and Bi2S3 nanoparticles were successfully grown onto the TNF's surface and Bi2S3-ZnS/TNF nanocomposite materials with different layouts were obtained using either a layer-by-layer or a co-sensitization approach. The samples' photocatalytic performance was first evaluated through the production of the hydroxyl radical using terephthalic acid as probe molecule. All the tested samples show photocatalytic ability for the production of this oxidizing species. Afterwards, the samples were investigated for the removal of methylene blue. The nanocomposite materials with best adsorption ability for the organic dye were the ZnS/TNF and Bi2S3ZnS/TNF. The removal of the methylene blue was systematically studied, and the most promising results were obtained considering a sequential combination of an adsorption-photocatalytic degradation process using the Bi2S3ZnS/TNF powder as a highly adsorbent and photocatalyst material.

cond-mat.mtrl-sci↗

arXiv2013

Synthesis of sub-5 nm Co-doped SnO$_2$ nanoparticles and their structural, microstructural, optical and photocatalytic properties

A swift chemical route to synthesize Co-doped SnO$_2$ nanopowders is described. Pure and highly stable Sn$_{1-x}$Co$_x$O$_{2-δ}$ (0 $\le$ x $\le$ 0.15) crystalline nanoparticles were synthesized, with mean grain sizes < 5 nm and the dopant element homogeneously distributed in substitutional sites of the SnO$_2$ matrix. The UV-visible diffuse reflectance spectra of the Sn$_{1-x}$Co$_x$O$_{2-δ}$ samples reveal red shifts, the optical bandgap energies decreasing with increasing Co concentration. The Urbach energies of the samples were calculated and correlated with their bandgap energies. The photocatalytic activity of the Sn$_{1-x}$Co$_x$O$_{2-δ}$ samples was investigated for the 4-hydroxylbenzoic acid (4-HBA) degradation process. A complete photodegradation of a 10 ppm 4-HBA solution was achieved using 0.02% (w/w) of Sn$_{0.95}$Co$_{0.05}$O$_{2-δ}$ nanoparticles in 60 min of irradiation.

cond-mat.mtrl-sci↗

arXiv2013

Synthesis and properties of Co-doped titanate nanotubes and their optical sensitization with methylene blue

Here we report on a novel chemical route to synthesize homogenous cobalt doped titanate nanotubes (CoTNT), using an amorphous Co-doped precursor. The influence of the synthesis temperature, autoclave dwell time and metal doping on the structural and microstructural as well as on the optical properties of the synthesized titanate nanotubes is studied and discussed. The optical band gaps of the CoTNT samples are red shifted in comparison with the values determined for the undoped samples, such red shifts bringing the absorption edge of the CoTNT samples into the visible region. CoTNT materials also demonstrate particular high adsorption ability for methylene blue, the amount of the adsorbed dye being higher than the one predictable for a monolayer formation. This suggests the possibility of intercalation of the dye molecule between the TiO6 layers of the TNT structure. It is also shown that the methylene blue sensitized Co-doped nanostructures are highly stable under UV radiation and present a strong and broad absorption in the visible region.

cond-mat.mtrl-sci↗

arXiv2013

Structural, electrical and magnetic studies of Co:SnO2 and (Co,Mo):SnO2 films prepared by pulsed laser deposition

Here we report on the structural, optical, electrical and magnetic properties of Co-doped and (Co,Mo)-codoped SnO2 thin films deposited on r-cut sapphire substrates by pulsed laser deposition. Substrate temperature during deposition was kept at 500 C. X-ray diffraction analysis showed that the undoped and doped films are crystalline with predominant orientation along the [101] direction regardless of the doping concentration and doping element. Optical studies revealed that the presence of Mo reverts the blue shift trend observed for the Co-doped films. For the Co and Mo doping concentrations studied, the incorporation of Mo did not contribute to increase the conductivity of the films or to enhance the ferromagnetic order of the Co-doped films.

cond-mat.mtrl-sci↗

arXiv2013

Phase growth control in low temperature PLD Co:TiO2 films by pressure

This paper reports on the structural and optical properties of Co-doped TiO2 thin films grown onto (0001) Al2O3 substrates by non-reactive pulsed laser deposition (PLD) using argon as buffer gas. It is shown that by keeping constant the substrate temperature at as low as 310 C and varying only the background gas pressure between 7 Pa and 70 Pa, it is possible to grow either epitaxial rutile or pure anatase thin films, as well as films with a mixture of both polymorphs. The optical band gaps of the films are red shifted in comparison to the values usually reported for undoped TiO2, which is consistent with n-type doping of the TiO2 matrix. Such band gap red shift brings the absorption edge of the Co-doped TiO2 films into the visible region, which might favour their photocatalytic activity. Furthermore, the band gap red shift depends on the films phase composition, increasing with the increase of the Urbach energy for increasing rutile content.

cond-mat.mtrl-sci↗

arXiv2012

Influence of the sodium/proton replacement on the structural, morphological and photocatalytic properties of titanate nanotubes

Titanate nanotubes (TNT) with different sodium contents have been synthesised using a hydrothermal approach and a swift and highly controllable post-washing processes. The influence of the sodium/proton replacement on the structural and morphological characteristics of the prepared materials was analysed. Different optical behaviour was observed depending on the Na+/H+ samples' content. A band gap energy of 3.27\pm0.03 eV was estimated for the material with higher sodium content while a value of 2.81\pm0.02 eV was inferred for the most protonated material, which therefore exhibits an absorption edge in the near visible region. The point of zero charge of the materials was determined and the influence of the sodium content on the adsorption of both cationic and anionic organic dyes was studied. The photocatalytic performance of the TNT samples was evaluated in the rhodamine 6G degradation process. Best photodegradation results were obtained when using the most protonated material as catalyst, although this material has shown the lowest R6G adsorption capability.

cond-mat.mtrl-sci↗

arXiv2012

Synthesis of titanate nanostructures using amorphous precursor material and their adsorption/photocatalytic properties

This paper reports on a new and swift hydrothermal chemical route to prepare titanate nanostructures (TNS) avoiding the use of crystalline TiO2 as starting material. The synthesis approach uses a commercial solution of TiCl3 as titanium source to prepare an amorphous precursor, circumventing the use of hazardous chemical compounds. The influence of the reaction temperature and dwell autoclave time on the structure and morphology of the synthesised materials was studied. Homogeneous titanate nanotubes with a high length/diameter aspect ratio were synthesised at 160^{\circ}C and 24 h. A band gap of 3.06\pm0.03 eV was determined for the TNS samples prepared in these experimental conditions. This value is red shifted by 0.14 eV compared to the band gap value usually reported for the TiO2 anatase. Moreover, such samples show better adsorption capacity and photocatalytic performance on the dye rhodamine 6G (R6G) photodegradation process than TiO2 nanoparticles. A 98% reduction of the R6G concentration was achieved after 45 minutes of irradiation of a 10 ppm dye aqueous solution and 1 g/L of TNS catalyst.

cond-mat.mtrl-sci↗

arXiv2011

Cr2O3 thin films grown at room temperature by low pressure laser chemical vapour deposition

Chromia (Cr2O3) has been extensively explored for the purpose of developing widespread industrial applications, owing to the convergence of a variety of mechanical, physical and chemical properties in one single oxide material. Various methods have been used for large area synthesis of Cr2O3 films. However, for selective area growth and growth on thermally sensitive materials, laser-assisted chemical vapour deposition (LCVD) can be applied advantageously. Here we report on the growth of single layers of pure Cr2O3 onto sapphire substrates at room temperature by low pressure photolytic LCVD, using UV laser radiation and Cr(CO)6 as chromium precursor. The feasibility of the LCVD technique to access selective area deposition of chromia thin films is demonstrated. Best results were obtained for a laser fluence of 120 mJ cm-2 and a partial pressure ratio of O2 to Cr(CO)6 of 1.0. Samples grown with these experimental parameters are polycrystalline and their microstructure is characterised by a high density of particles whose size follows a lognormal distribution. Deposition rates of 0.1 nm s-1 and mean particle sizes of 1.85 μm were measured for these films.

cond-mat.mtrl-sci↗

arXiv2010

Ferromagnetic order in aged Co-doped TiO2 anatase nanopowders

Oxide based diluted magnetic semiconductor (DMS) materials have been a subject of increasing interest due to reports of room temperature ferromagnetism in several systems and their potential use in the development of spintronic devices. However, concerns on the stability of the magnetic properties of different DMS systems have been raised. Their magnetic moment is often unstable, vanishing with a characteristic decay time of weeks or months, which precludes the development of real applications. This paper reports on the ferromagnetic properties of two-year-aged Ti1-xCoxO2-δ reduced anatase nanopowders with different Co contents (0.03<x<0.10). Aged samples retain rather high values of magnetization, remanence and coercivity which provide strong evidence for a quite preserved long-range ferromagnetic order. In what concern Co segregation, some degree of metastability of the diluted Co doped anatase structure could be inferred in the case of the sample with the higher Co content.

cond-mat.mtrl-sci↗

arXiv2009

Magnetic properties of Co-doped TiO2 anatase nanopowders

This letter reports on the magnetic properties of Ti1-xCoxO2 anatase phase nanopowders with different Co contents. It is shown that oxygen vacancies play a fundamental role in promoting the long-range ferromagnetic order in the material studied, in addition to the transition-metal doping. Furthermore, the results allow ruling out the premise of a strict connection between Co clustering and the ferromagnetism observed in the Co:TiO2 anatase system.

cond-mat.mtrl-sci↗

arXiv2007

CVD of CrO2: towards a lower temperature deposition process

We report on the synthesis of highly oriented a-axis CrO2 films onto (0001) sapphire by atmospheric pressure CVD from CrO3 precursor, at growth temperatures down to 330 degree Celsius, i.e. close to 70 degrees lower than in published data for the same chemical system. The films keep the high quality magnetic behaviour as those deposited at higher temperature, which can be looked as a promising result in view of their use with thermally sensitive materials, e.g. narrow band gap semiconductors.

cond-mat.mtrl-sci↗

arXiv2006

CVD of CrO2 Thin Films: Influence of the Deposition Parameters on their Structural and Magnetic Properties

This work reports on the synthesis of CrO2 thin films by atmospheric pressure CVD using chromium trioxide (CrO3) and oxygen. Highly oriented (100) CrO2 films containing highly oriented (0001) Cr2O3 were grown onto Al2O3(0001) substrates. Films display a sharp magnetic transition at 375 K and a saturation magnetization of 1.92 Bohr magnetons per f.u., close to the bulk value of 2 Bohr magnetons per f.u. for the CrO2. Keywords: Chromium dioxide (CrO2), Atmospheric pressure CVD, Spintronics.

cond-mat.mtrl-sci↗

arXiv2006

KrF pulsed laser deposition of chromium oxide thin films from Cr8O21 targets

Chromium oxides, CrxOy, are of great interest due to the wide variety of their technological applications. Among them, CrO2 has been extensively investigated in recent years because it is an attractive compound to be used in spintronic heterostructures. However, its synthesis at low temperatures has been a difficult task due to the metastable nature of this oxide. This is indeed essential to ensure interface quality and the ability to coat thermal-sensitive materials such as those envisaged in spintronic devices. Pulsed Laser Deposition (PLD) is a technique that has the potential to meet the requirements stated above. In this work, we describe our efforts to grow chromium oxide thin films by PLD from Cr8O21 targets, using a KrF excimer laser. The as-deposited films were investigated by X-ray diffraction and Rutherford backscattering spectrometry. Structural and chemical composition studies showed that the films consist of a mixture of amorphous chromium oxides exhibiting different stoichiometries depending on the processing parameters, where nanocrystals of mainly Cr2O3 are dispersed. The analyses do not exclude the possibility of co-deposition of Cr2O3 and a low fraction of CrO2. PACS: 81.15.Fg, 75.50.Dd

cond-mat.mtrl-sci↗

arXiv2006

Morphological and Structural Characterization of Cro2/Cr2o3 Films Grown by Laser-CVD

This work reports on the synthesis of chromium (III, IV) oxides films by KrF laser-assisted CVD. Films were deposited onto sapphire substrates at room temperature by photodissociation of Cr(CO)6 in dynamic atmospheres containing oxygen and argon. A study of the processing parameters has shown that partial pressure ratio of O2 to Cr(CO)6 and laser fluence are the prominent parameters that have to be accurately controlled in order to co-deposit both crystalline oxide phases. Films consistent with such a two-phase system were synthesised for a laser fluence of 75 mJ cm-2 and a partial pressure ratio about 1. PACS: 81.15.Fg, 81.15.Kk, 81.05.Je

cond-mat.mtrl-sci↗

arXiv2006

Comparing a current-carrying circular wire with polygons of equal perimeter; Magnetic field versus magnetic flux

We compare the magnetic field at the center of and the self-magnetic flux through a current-carrying circular loop, with those obtained for current-carrying polygons with the same perimeter. As the magnetic field diverges at the position of the wires, we compare the self-fluxes utilizing several regularization procedures. The calculation is best performed utilizing the vector potential, thus highlighting its usefulness in practical applications. Our analysis answers some of the intuition challenges students face when they encounter a related simple textbook example. These results can be applied directly to the determination of mutual inductances in a variety of situations.

physics.ed-ph↗

arXiv2002

TiN Films Deposited by Laser CVD: A Growth Kinetics Study

Results on the chemical composition, structure and growth kinetics of titanium nitride (TiN) films deposited on mild steel substrates by pyrolytic laser-induced chemical vapour deposition (LCVD) are presented. Golden coloured lines of TiN were deposited from a reactive gas mixture of TiCl4, N2 and H2 using a continuous wave TEM00 CO2 laser beam as heat source. The chemical composition and structure of the films were determined by electron probe microanalysis (EPMA) and glancing incidence X-ray diffraction (GIXRD). A non-contact laser profilometer was used to measure the thickness profiles of the films. Using the data obtained in the steady-state region of the TiN laser-written lines, growth rates in the range 3.7 to 6.9 micrometers per second were deduced. The Arrhenius relation between the deposition rate and the deposition temperature yields an apparent activation energy of 46.9(+-)3.8 kJ.mol-1. This result enabled us to conclude that under our deposition conditions the LCVD of TiN is controlled by mass transport in the vapour phase. Keywords: Coatings; Titanium nitride (TiN); Laser chemical vapour deposition (LCVD); Growth mechanisms.

cond-mat.mtrl-sci↗