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1.
ACS Appl Mater Interfaces ; 16(26): 34303-34312, 2024 Jul 03.
Artigo em Inglês | MEDLINE | ID: mdl-38885089

RESUMO

Perovskite nanocrystals hold significant promise for a wide range of applications, including solar cells, LEDs, photocatalysts, humidity and temperature sensors, memory devices, and low-cost photodetectors. Such technological potential stems from their exceptional quantum efficiency and charge carrier conduction capability. Nevertheless, the underlying mechanisms of photoexcitation, such as phase segregation, annealing, and ionic diffusion, remain insufficiently understood. In this context, we harnessed hyperspectral fluorescence microspectroscopy to advance our comprehension of fluorescence enhancement triggered by UV continuous-wave (cw) laser irradiation of CsPbBr3 colloidal nanocrystal thin films. Initially, we explored the kinetics of fluorescence enhancement and observed that its efficiency (φph) correlates with the laser power (P), following the relationship φph = 7.7⟨P⟩0.47±0.02. Subsequently, we estimated the local temperature induced by the laser, utilizing the finite-difference method framework, and calculated the activation energy (Ea) required for fluorescence enhancement to occur. Our findings revealed a very low activation energy, Ea ∼ 9 kJ/mol. Moreover, we mapped the fluorescence photoenhancement by spatial scanning and real-time static mode to determine its microscale length. Below a laser power of 60 µW, the photothermal diffusion length exhibited nearly constant values of approximately (22 ± 5) µm, while a significant increase was observed at higher laser power levels. These results were ascribed to the formation of nanocrystal superclusters within the film, which involves the interparticle spacing reduction, creating the so-called quantum dot solid configuration along with laser-induced annealing for higher laser powers.

2.
Environ Sci Pollut Res Int ; 30(46): 102986-103000, 2023 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-37674070

RESUMO

The photocatalytic efficiency of some semiconductors depends mainly on their morphological, optical, and structural properties, which can be modified by varying the calcination temperature. In order to evaluate how these properties change, as a function of temperature in a AA'BB'O3 perovskite material, La0.9Sr0.1Fe0.8Co0.2O3±Î´ (LSFC) was synthesized by the Pechini method and calcined at different temperatures (600 °C, 700 °C, 800 °C, and 900 °C). All the samples were characterized structurally, morphologically, and optically by XRD, SEM, and UV-Vis spectroscopy. Additionally, specific surface area and pore size distribution were calculated by BET and BHJ methods. LSFC was evaluated as photocatalyst material, estimating the degradation of reactive black 5 (RB5), employing as irradiation source UV light and sunlight. The obtained results display a clear tendency between the photoactivity and the heat treatment: degradation percentage decreases as the calcination temperature increases mainly due to the crystal and grain size and, furthermore, loss of porosity and the decrease in surface area, affecting the photocatalytic activity (98%, 95%, 74%, and 50% degradation, respectively). All the ceramic samples follow a pseudo-first-order reaction.

3.
J Mol Model ; 29(9): 285, 2023 Aug 23.
Artigo em Inglês | MEDLINE | ID: mdl-37608185

RESUMO

CONTEXT: BaTiO3 is one of the most important ferroelectric oxides in electronic applications. Also, it has attractive properties for catalysis that could be used for reducing contamination levels, especially carbon monoxide, CO. CO is one of the main gaseous pollutants generally released from the combustion of fossil fuel. In this work, the CO transformation on pristine and Au-modified BaTiO3 perovskite for H2CO obtention is studied. The CO adsorption and hydrogenation on pristine BaTiO3 leads to formaldehyde synthesis as the most stable product through two possible routes. Furthermore, hydrogenation stages are less probable on pristine BaTiO3. On Au-modified BaTiO3 formaldehyde is the principal product too but Au adatom generates H2CO competition with HCOH. After BaTiO3 modification with Au unpaired electrons were generated. These unpaired electrons are related to the adatom reactivity. According to the obtained results, pristine and Au-modified BaTiO3 can adsorb and hydrogenate CO generating formaldehyde as the principal product. BaTiO3 modifications with Au increase the reactivity of the perovskite in the CO hydrogenation reactions. CO hydrogenation process on Au suggests that further hydrogenation stages beyond formaldehyde are possible. METHODS: The study was performed through ab initio calculations using the periodic spin-polarized Density Functional Theory (DFT) as implemented in Quantum ESPRESSO. DFT calculations were carried out using the Plane Wave self-consistent field (PWscf). Spin density difference allows us to identify reactive regions related to dangling bonds and unpaired electrons. A plane wave basis set was used to represent the electron states. Vanderbilt pseudopotentials with nonlinear core correction were used to model the ionic cores and valence electrons interaction. Exchange-correlation energies were treated within the generalized gradient approximation (GGA) with the Perdew-Burke-Ernzerhof (PBE) parameterization.

4.
J Phys Condens Matter ; 35(49)2023 Sep 13.
Artigo em Inglês | MEDLINE | ID: mdl-37643624

RESUMO

Large two-photon absorption (2PA) cross-section combined with high emission quantum efficiency and size-tunable bandgap energy has put colloidal semiconductor nanocrystals (NCs) on the vanguard of nonlinear optical materials. After nearly two decades of intense studies on the nonlinear optical response in quantum-confined semiconductors, this is still a vibrant field, as novel nanomaterials are being developed and new applications are being proposed. In this review, we examine the progress of 2PA research in NCs, highlighting the impact of quantum confinement on the magnitude and spectral characteristics of this nonlinear response in semiconductor materials. We show that for NCs with three-dimensional quantum confinement, the so-called quantum dots, 2PA cross-section grows linearly with the nanoparticle volume, following a universal volume scaling. We overview strategies used to gain further control over the nonlinear optical response in these structures by shape and heterostructure engineering and some applications that might take advantage of the series of unique properties of these nanostructures.

5.
Chemistry ; 29(4): e202202518, 2023 Jan 18.
Artigo em Inglês | MEDLINE | ID: mdl-36206198

RESUMO

Lead (Pb) halide perovskite nanocrystals, with the general formula APbX3 , where A=CH3 NH3+ , CH(NH2 )2+ , or Cs+ and X=Cl- , Br- , or I- , have emerged as a class of materials with promising properties due to their remarkable optical properties and solar cell performance. However, important issues still need to be addressed to enable practical applications of these materials, such as instability, mass production, and Pb toxicity. Recent studies have carried out the replacement of Pb by various less-toxic cations as Sn, Ge, Sb, and Bi. This variety of chemical compositions provide Pb-free perovskite and metal halide nanostructures with a wide spectral range, in addition to being considered less toxic, therefore having greater practical applicability. Highlighting the necessity to address and solve the toxicity problems related to Pb-containing perovskite, this review considers the prospects of the Pb-free perovskite, involving synthesis methods, and properties of them, including advantages, disadvantages, and applications.

6.
Environ Sci Pollut Res Int ; 30(7): 19111-19119, 2023 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-36223012

RESUMO

In this work, we studied the effect of CO2 in the feed stream of the TRM process performance of nickel supported on LaFeO3 perovskite for hydrogen production compared to the POM reaction. The perovskite and nickel supported on LaFeO3 were synthesized and characterized by thermogravimetric analysis (TGA/DTA), X-ray diffraction (XRD), transmission electron microscopy (TEM), and programmed reduction temperature (TPR). The catalytic tests were carried out in temperatures varying from 700 to 800 °C with feed flow of 350 cm3/min and 200 cm3/min for TRM and POM, respectively. The hydrogen selectivity for the tri-reforming was 78%, while for the partial oxidation reaction, only 55% H2 at 700 °C. Results showed that the hydrogen selectivity for the Ni/LaFeO3 catalyst is significantly higher for the tri-reforming process, suggesting that CO2 enhanced the hydrogen selectivity compared to the partial oxidation of methane. Analyses by Raman spectroscopy and thermogravimetric calculations showed structural modifications of the catalysts after the reaction. The Raman spectrum showed segregated NiO and Fe3O4 and low carbon formation at 700 °C. The proposed mechanism suggests methane and oxygen adsorption, lattice oxygen and CO2 on surface active sites, and vacancies for both reactions.


Assuntos
Dióxido de Carbono , Metano , Dióxido de Carbono/química , Metano/química , Níquel/química , Hidrogênio/química , Oxigênio/química
7.
Environ Res ; 212(Pt A): 113149, 2022 09.
Artigo em Inglês | MEDLINE | ID: mdl-35378122

RESUMO

Recently, halides (silver halides, AgX; perosvkite halides, ABX3) and oxyhalides (bismuth oxyhalides, BiOX) based nanomaterials are noticeable photocatalysts in the degradation of organic water pollutants. Therefore, we review the recent reports to explore improvement strategies adopted in AgX, ABX3 and BiOX (X = Cl, Br and I)-based photocatalysts in water pollution remediation. Herein, the photocatalytic degradation performances of each type of these photocatalysts were discussed. Strategies such as tailoring the morphology, crystallographic facet exposure, surface area, band structure, and creation of surface defects to improve photocatalytic activities of pure halides and BiOCl photocatalysts are emphasized. Other strategies like metal ion and/or non-metal doping and construction of composites, adopted in these photocatalysts were also reviewed. Furthermore, the way of production of active radicals by these photocatalysts under ultraviolet/visible light source is highlighted. The deciding factors such as structure of pollutant, light sources and other parameters on the photocatalytic performances of these materials were also explored. Based on this literature survey, the need of further research on AgX, ABX3 and BiOX-based photocatalysts were suggested. This review might be beneficial for researchers who are working in halides and oxyhalides-based photocatalysis for water treatment.


Assuntos
Bismuto , Nanoestruturas , Bismuto/química , Catálise , Luz , Nanoestruturas/química , Prata/química
8.
Materials (Basel) ; 15(7)2022 Mar 25.
Artigo em Inglês | MEDLINE | ID: mdl-35407744

RESUMO

In the present work, LaNi0.5Ti0.5O3 and La2NiTiO6 nanoparticles were synthesized by the modified Pechini method. LaNi0.5Ti0.5O3 was calcined at 1073 K for 17 h or 100 h, while La2NiTiO6 was calcined at 1273 K for 135 h. The double perovskite calcined at 1073 K for 17 h presented orthorhombic symmetry with Pbnm space group, mean particle size was 31.9 ± 1 nm, random ordering of Ni2+ and Ti4+ cations, Néel temperature close to 15 K, and magnetic moment of 1.29 µB. By increasing the calcination time, this material showed the same symmetry and space group, a mean particle size of 50.7 ± 2 nm, short-range ordering of Ni2+ and Ti4+ cations, Néel temperature around 12 K, and magnetic moment of 0.96 µB. La2NiTiO6 presented a monoclinic crystal structure, with P21/n space group, mean particle size of 80.0 ± 5 nm, rock salt ordering of Ni2+ and Ti4+, Néel temperature of approximately 23 K, and magnetic moment of 2.75 µB.

9.
Nanomaterials (Basel) ; 12(5)2022 Feb 28.
Artigo em Inglês | MEDLINE | ID: mdl-35269311

RESUMO

Zinc oxide (ZnO) has interesting optoelectronic properties, but suffers from chemical instability when in contact with perovskite interfaces; hence, the perovskite deposited on the top degrades promptly. Surface passivation strategies alleviate this instability issue; however, synthesis to passivate ZnO nanoparticles (NPs) in situ has received less attention. Here, a new synthesis at low temperatures with an ethanolamine post treatment has been developed. By using ZnO NPs prepared with ethanolamine and butanol (BuOH), (E-ZnO), the stability of the FA0.9Cs0.1PbI3 (FACsPI)−ZnO interface was achieved, with a photoconversion efficiency of >18%. Impedance spectroscopy demonstrates that the recombination at the interface was reduced in the system with E-ZnO/perovskite compared to common SnO2/perovskite and that the quality of the perovskite on the top is clearly due to the ZnO in situ passivation with ethanolamine. This work extends the use of E-ZnO as an n-type charge extraction layer and demonstrates its feasibility with methylammonium perovskite. Moreover, this study paves the way for other in situ passivation methods with different target molecules, along with new insights regarding the perovskite interface rearrangement when in contact with the modified electron transport layer (ETL).

10.
Molecules ; 28(1)2022 Dec 28.
Artigo em Inglês | MEDLINE | ID: mdl-36615449

RESUMO

Since the beginning of the 21st century, triazine-based molecules have been employed to construct different organic materials due to their unique optoelectronic properties. Among their applications, photovoltaics stands out because of the current need to develop efficient, economic, and green alternatives to energy generation based mainly on fossil fuels. Here, we review all the development of triazine-based organic materials for solar cell applications, including organic solar cells, dye-sensitized solar cells, and perovskite solar cells. Firstly, we attempt to illustrate the main synthetic routes to prepare triazine derivatives. Then, we introduce the main aspects associated with solar cells and their performance. Afterward, we discuss different works focused on the preparation, characterization, and evaluation of triazine derivatives in solar cells, distinguishing the type of photovoltaics and the role of the triazine-based material in their performance (e.g., as a donor, acceptor, hole-transporting material, electron-transporting material, among others). Throughout this review, the progress, drawbacks, and main issues of the performance of the mentioned solar cells are exposed and discussed. Finally, some conclusions and perspectives about this research topic are mentioned.


Assuntos
Combustíveis Fósseis , Doadores de Tecidos , Humanos , Transporte Biológico , Transporte de Elétrons , Triazinas
11.
Polymers (Basel) ; 13(23)2021 Nov 28.
Artigo em Inglês | MEDLINE | ID: mdl-34883665

RESUMO

The atomic layer deposition (ALD) of Al2O3 between perovskite and the hole transporting material (HTM) PEDOT:PSS has previously been shown to improve the efficiency of perovskite solar cells. However, the costs associated with this technique make it unaffordable. In this work, the deposition of an organic-inorganic PEDOT:PSS-Cl-Al2O3 bilayer is performed by a simple electrochemical technique with a final annealing step, and the performance of this material as HTM in inverted perovskite solar cells is studied. It was found that this material (PEDOT:PSS-Al2O3) improves the solar cell performance by the same mechanisms as Al2O3 obtained by ALD: formation of an additional energy barrier, perovskite passivation, and increase in the open-circuit voltage (Voc) due to suppressed recombination. As a result, the incorporation of the electrochemical Al2O3 increased the cell efficiency from 12.1% to 14.3%. Remarkably, this material led to higher steady-state power conversion efficiency, improving a recurring problem in solar cells.

12.
ACS Appl Mater Interfaces ; 13(49): 59252-59262, 2021 Dec 15.
Artigo em Inglês | MEDLINE | ID: mdl-34851611

RESUMO

The excellent performance of hybrid metal-halide perovskite nanocrystals (NCs) contrasts with their unsatisfactory stability in a high-humidity environment or water. Herein, polymer composite lead-halide perovskites (LHPs) NCs were prepared by casting or spin-coating to produce a high fluorescence yield and a fully water-resistant material. Poly(l-lactide) (PLla), polypropylene glycol (PPGly), and polysulfone (PSU) commercial polymers were used to prepare suspensions of MAPbBr3-HDA NCs (MA: CH3NH3; HDA: hexadecylamine). The MAPbBr3-HDA@PLla suspension exhibited a maximum fluorescence quantum yield of 93% compared to 43% for the pristine MAPbBr3-HDA NCs. Strong emissions around 528 nm were also observed, with the same full width at half maximum value of 20 nm, demonstrating the successful fabrication of brightly luminescent LHP NCs@polymer combinations. Time-resolved photoluminescence measurements directly observed the enhanced spontaneous emission of the NCs induced by the polymeric environment. However, the cast films of MAPbBr3-HDA NCs mixed with PLla or PPGly did not resist water immersion. On the contrary, MAPbBr3-HDA@PPGly/PSU films containing well-dispersed ∼10 nm LHP NCs retained a bright green fluorescence emission even after 18 months under air conditions or water immersion up to 45 °C. From water contact angle measurements, profilometry, and X-ray photoelectron spectroscopy data, it could be assumed that the slightly hydrophobic PSU polymer is responsible for the high water stability of the fluorescent films, which avoids MAPbBr3-HDA NC degradation. This work shows that the LHP NC dispersion in dissolved commodity polymers holds great promise toward the long-term stability of LHP NC composites for the future development of wearable electronic devices and other waterproof applications.

13.
Nanotechnology ; 33(9)2021 Dec 07.
Artigo em Inglês | MEDLINE | ID: mdl-34808612

RESUMO

A systematic study of the synthetic procedure to improve quantum efficiency of luminescent hybrid perovskite QDs through ligand-assisted precipitation method is presented. Particularly, the influence of the dielectric constant and dipole moment of the antisolvent on the reaction time and the photophysical properties of the QDs is highlighted. After evaluating the influence of antisolvents and optimizing experimental parameters such as reaction time and Pb excess of the precursor, colloidal crystalline MAPbBr3QDs with exceptionally high absolute quantum yield up to 97.7% in solution and 69.1% in solid film were obtained. Finally, MAPbBr3QDs precipitated from anisole were processed like UV-curable nanocomposite as efficient down conversion layer resulting in very narrow green emission light-emitting diode.

14.
ChemistryOpen ; 10(8): 790-797, 2021 08.
Artigo em Inglês | MEDLINE | ID: mdl-34352155

RESUMO

The catalytic performance of a perovskite-type lanthanum ferrite LaFeO3 to remove arsenic from water has been investigates for the first time. LaFeO3 was prepared by citrate auto-combustion of dry gel obtained from a solution of the corresponding nitrates poured into citric acid solution. Kinetic studies were performed in the dark with As(V) and in the dark and under UV-C irradiation at pH 6-7 with As(III) (both 1 mg L-1 ), and As : Fe molar ratios (MR) of 1 : 10 and 1 : 100 using the LaFeO3 catalyst. As(V) was removed from solution after 60 min in the dark in 7 % and in 47 % for MR=1 : 10 and MR=1 : 100, respectively, indicating the importance of the amount of the iron material on the removal. Oxidation of As(III) in the dark was negligible after 60 min in contact with the solid sample, but complete removal of As(III) was observed within 60 min of irradiation at 254 nm, due to As(III) photooxidation to As(V) and to As(III) sorption to a minor extent. Morphological and microstructural studies of the catalyst complement the catalytic testing. This work demonstrates that LaFeO3 can be used for the removal of As(III) from highly arsenic contaminated water.

15.
Chempluschem ; 86(7): 1006-1013, 2021 Jun 24.
Artigo em Inglês | MEDLINE | ID: mdl-34260160

RESUMO

Two novel and simple donor-π-bridge-donor (D-π-D) hole-transporting materials (HTMs) containing two units of the p-methoxytriphenylamine (TPA) electron donor group covalently bridged by means of the 3,4-dimethoxyselenophene spacer through single and triple bonds are reported. The optoelectronic and thermal properties of the new selenium-containing HTMs have been determined using standard experimental techniques and theoretical density functional theory (DFT) calculations. The selenium-based HTMs have been incorporated in mesoporous perovskite solar cells (PSCs) in combination with the triple-cation perovskite [(FAPbI3 )0.87 (MAPbBr3 )0.13 ]0.92 [CsPbI3 ]0.08 . Limited values of power conversion efficiencies, up to 13.4 %, in comparison with the archetype spiro-OMeTAD (17.8 %), were obtained. The reduced efficiencies showed by the new HTMs are attributed to their poor film-forming ability, which constrains their photovoltaic performance due to the appearance of structural defects (pinholes).

16.
Rev. colomb. quím. (Bogotá) ; 50(1): 86-97, ene.-abr. 2021. tab, graf
Artigo em Inglês | LILACS-Express | LILACS | ID: biblio-1289325

RESUMO

Abstract We report on the synthesis of C60 and C70 monoadducts at room temperature through the Bingel reaction; employing acetylacetone as ligand; in presence of DBU (1,8-Diazabicyclo [5.4.0] undec-7-ene), carbon tetrabromide (CBr4), and o-dichlorobenzene. Diacetylmethane-[C60-Ih]-fullerene-[5,6] and diacetylmethane-[C70-D5h]-fullerene-[5,6] monoadducts were obtained with yields of 69% and 44%, respectively. The products were purified by column chromatography (CC, on silica gel, using hexane, carbon disulfide, and chloroform as eluents at room temperature) and characterized by Nuclear Magnetic Resonance ('H and 13C), Fourier-Transform Infrared (FT-IR) and UV-Visible spectroscopies, Matrix-assisted Laser Desorption/Ionization-Time of Flight (MALDI-TOF) Mass spectrometry, Cyclic Voltammetry (CV), and Osteryoung Square Wave Voltammetry (OSWV). Both compounds showed irreversible reduction peaks controlled by diffusion, with LUMO energy levels of -3.09 eV, -3.13 eV for C60, and C70 monoadducts, respectively. These values are comparable with the -3.99 eV of PC61BM. The synthetized adducts were incorporated into inverted-type perovskite solar cells and were used as electron transporting materials (ETM) obtaining power conversion efficiencies (PCE) of 8.5% and 14.0% for the C60 and C70 monoadducts, respectively. When C60 is replaced by a lower symmetrical fullerene such as C70 an improved light absorption in the visible region is observed.


Resumen Reportamos la síntesis de monoadductos de C60 y C70 a temperatura ambiente a través de la reacción de Bingel, empleando acetilacetona como ligando, en presencia de DBU (1,8-diazabiciclo [5.4.0] undec-7-eno), tetrabromuro de carbono (CBr4) y o-diclorobenceno. Se obtuvieron monoadductos de diacetilmetano-[C -I.]-fullereno-[5,6] y diacetilmetano-[C70-D5h]-fullereno-[5,6] con rendimientos del 69% y 44%, respectivamente. Los productos se purificaron por cromatografía en columna (CC, usando silica gel, hexano, disulfuro de carbono y cloroformo como fase móvil, a temperatura ambiente) y se caracterizaron por resonancia magnética nuclear (1H y 13C), infrarrojo con transformada de Fourier (FT-IR), espectroscopia UV-Visible, espectrometría de masas, desorción/ionización láser asistida por matriz - tiempo de vuelo (MALDI-TOF), voltametría cíclica (CV) y voltametría de onda cuadrada de Osteryoung (OSWV). Ambos compuestos mostraron picos de reducción irreversibles controlados por difusión, con niveles de energía LUMO de -3,09 eV y -3,13 eV para los monoadductos C60 y C70, respectivamente. Estos valores son comparables con el -3,99 eV de PC61BM. Los aductos sintetizados se incorporaron a las células solares de perovskita de tipo inversa y se usaron como materiales de transporte de electrones (ETM) obteniendo eficiencias de conversión de energía (PCE) de 8,5% y 14,0% para los monoaductos C60 y C70, respectivamente. Cuando el C60 se reemplaza por un fullereno menos simétrico como el C70, se observa una absorción de luz mejorada en la región visible.


Resumo Reportamos a sínteses de monoadutos de C60 e C70 a temperatura ambiente através da reação de Bingel, utilizando acetilacetona como ligando, na presença de DBU (1,8-diazabiciclo [5.4.0] undec-7-eno), tetrabromuro de carbono (CBr4) e o-diclorobenzeno. Foram obtidos monoadutos de diacetilmetano-[C60-IJ-fulereno-[5,6] e diacetilmetano-[C70-D5J-fulereno-[5,6] com rendimentos de 69% e 44%, respectivamente. Os produtos se purificaram por cromatografia em coluna (CC, usando sílica gel, hexano, dissulfeto de carbono e clorofórmio como fase móvel à temperatura ambiente ) e se caracterizaram por ressonância magnética nuclear OH e 13C), infra-vermelho com transformada de Fourier (FT-IR), espectroscopia UV-Visível, espectrometria de massas, ionização e dessorção a laser assistida por matriz-tempo de voo (MALDI-TOF), voltametria cíclica (CV) e voltametria de onda quadrada de Osteryoung (OSWV). Ambos compostos mostraram picos de redução irreversíveis controlados por difusão, com níveis de energia LUMO de -3,09 eV, -3,13 eV para os monoadutos C60 e C70, respectivamente. Estos valores são comparáveis com -3,99 eV de PC61BM. Os adutos sintetizados se incorporaram nas células solares de perovskita de tipo inversa e se usaram como materiais de transporte de eletrões (ETM) obtendo eficiências de conversão de energia (PCE) de 8,5% e 14,0% para os monoadutos C60 e C70, respectivamente. Quando o C60 se substitui por um fulereno menos simétrico como o C70, se observa uma absorção de luz melhorado na região visível.

17.
Molecules ; 25(20)2020 Oct 16.
Artigo em Inglês | MEDLINE | ID: mdl-33081238

RESUMO

Temperature-dependent Raman scattering and differential scanning calorimetry were applied to the study of the hybrid organic-inorganic azide-perovskite [(CH3)4N][Cd(N3)3], a compound with multiple structural phase transitions as a function of temperature. A significant entropy variation was observed associated to such phase transitions, |∆S| ~ 62.09 J·kg-1 K-1, together with both a positive high barocaloric (BC) coefficient |δTt/δP| ~ 12.39 K kbar-1 and an inverse barocaloric (BC) coefficient |δTt/δP| ~ -6.52 kbar-1, features that render this compound interesting for barocaloric applications. As for the obtained Raman spectra, they revealed that molecular vibrations associated to the NC4, N3- and CH3 molecular groups exhibit clear anomalies during the phase transitions, which include splits and discontinuity in the phonon wavenumber and lifetime. Furthermore, variation of the TMA+ and N3- modes with temperature revealed that while some modes follow the conventional red shift upon heating, others exhibit an unconventional blue shift, a result which was related to the weakening of the intermolecular interactions between the TMA (tetramethylammonium) cations and the azide ligands and the concomitant strengthening of the intramolecular bondings. Therefore, these studies show that Raman spectroscopy is a powerful tool to gain information about phase transitions, structures and intermolecular interactions between the A-cation and the framework, even in complex hybrid organic-inorganic perovskites with highly disordered phases.


Assuntos
Azidas/química , Compostos de Cálcio/química , Varredura Diferencial de Calorimetria/métodos , Óxidos/química , Análise Espectral Raman/métodos , Titânio/química , Cádmio/química , Cátions/química , Transição de Fase , Temperatura , Vibração
18.
Materials (Basel) ; 13(3)2020 Feb 07.
Artigo em Inglês | MEDLINE | ID: mdl-32046065

RESUMO

The search for catalysts with features that can improve coke resistance and decrease byproduct formation is a current goal in H2 production from renewable sources. In this work, the effect of the presence of Ni nanoparticles over Co/La-Ce oxides on the ethanol decomposition reaction was studied. Catalysts were synthetized using as precursor a La0.8Ce0.2NixCo1-xO3 perovskite-type material to ensure a low segregation of phases and a high dispersion of metals. After reduction at 873 K, the perovskite structure was destroyed, and metal Co-Ni particles were supported over a lanthanum-cerium oxide. The materials were characterized by different techniques before and after reaction. Solids exhibited metal particle sizes between 5 and 15 nm demonstrating the advantages of the preparation method to obtain Ni-Co alloys. Although the results of adsorption of ethanol followed by diffuse reflectance infrared fourier transformed spectroscopy (DRIFTS) showed acetate species strongly adsorbed on the catalyst's surface, the material (Ni0.7Co0.3/La0.8Ce0.2) with the lowest particle size was the most stable system leading to the lowest amount of carbon deposits during ethanol decomposition. This catalyst showed the better performance, with a higher ethanol conversion (98.4%) and hydrogen selectivity (75%). All catalysts exhibited carbonaceous deposits, which were an ordered and disordered carbon phase mixture.

19.
J Mater Res Technol ; 9(6): 12795-12803, 2020.
Artigo em Inglês | MEDLINE | ID: mdl-38620721

RESUMO

The present situation of COVID-19 diverted our focus towards utilizing the degraded solar cells for sensor application, this will help in global energy harvesting. So, here is our successful effort to reuse already degraded solar cells as ultraviolet (UV) and infrared (IR) sensor. The spin-coated perovskite (CH3NH3PbI3-XClX) has been already tested for visible light spectrum, as an extension to that now it is utilized as UV and IR intensity sensors to cover the whole spectrum. The employed CH3NH3PbI3-XClX material was used after its efficiency loss has been reached to a saturation point in photovoltaic devices. Each deposited layer was investigated from UV to the IR absorption spectrum for deepening study through UV-vis spectroscopy. In the sandwiched architecture possessing FTO/PEDOT: PSS/Perovskite/PC61BM/CdS/Au symmetry, the perovskite film has been employed as an absorbent layer, however, other layers participation also plays a key role. The resultant device yielded very good sensing performance because of the enhanced excitons generation which is attributed to the precise selection of the interfacial materials, e.g. CdS and PC61BM as an ETM and PEDOT: PSS as HTM. The impedance and capacitance of the devices within 0.01-200 kHz under varied UV and IR illumination intensities were investigated. Measurements showed that as the intensity of the light increased i.e., UV (0-200 W/m2) and IR (0-5800 W/m2), impedance decreased while capacitance increased. The current results are attributed to the increase in the concentration of charges i.e., electron-hole pairs generation depending on the built-in capacitance and frequency of the charges.

20.
Appl Radiat Isot ; 153: 108815, 2019 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-31344649

RESUMO

In this paper, luminescent properties of Europium trivalent ion in the matrix with unbalanced charge of barium hafnate under UV radiation, with special emphasis on the 5D0 → 7F0 transition are reported. The synthesis was conducted by the hydrothermal route at 200 °C with a reaction time of 90 min using chlorides as raw materials. In order to determinate the luminescent quenching concentration, the samples were doped with different amounts of Europium trivalent ions being the sample doped with 1 and 3% at of Eu3+ which shows the highest luminescent emission. X-ray diffraction analysis showed that the material crystallize in the cubic perovskite structure with space group Pm-3m. The Energy Dispersive Spectroscopy (EDS) shows there are not elements other those that Ba, Hf, O and Eu in the synthesized material. Photoluminescent emission spectra show peaks of emission associated with the 5D0 → 7FJ (J = 0,1,2,3,4) transitions, characteristics of europium ion. The 5D0 → 7F0 transition centered at 580 nm showed an unusual great intensity when it was excited with the wavelength associated with the charge transfer band (272 nm). Finally the decay time was measured in the 5D0 → 7FJ (J = 0,1,2,3,4) transitions using the sample doped with Eu3+ (3% at).

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