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1.
Nanomaterials (Basel) ; 14(13)2024 Jul 06.
Artigo em Inglês | MEDLINE | ID: mdl-38998761

RESUMO

Sulfurized polyacrylonitrile (SPAN) is a promising cathode material for lithium-sulfur batteries owing to its reversible solid-solid conversion for high-energy-density batteries. However, the sluggish reaction kinetics of SPAN cathodes significantly limit their output capacity, especially at high cycling rates. Herein, a CNT-interpenetrating hierarchically porous SPAN electrode is developed by a simple phase-separation method. Flexible self-supporting SPAN cathodes with fast electron/ion pathways are synthesized without additional binders, and exceptional high-rate cycling performances are obtained even with substantial sulfur loading. For batteries assembled with this special cathode, an impressive initial discharge capacity of 1090 mAh g-1 and a retained capacity of 800 mAh g-1 are obtained after 1000 cycles at 1 C with a sulfur loading of 1.5 mg cm-2. Furthermore, by incorporating V2O5 anchored carbon fiber as an interlayer with adsorption and catalysis function, a high initial capacity of 614.8 mAh g-1 and a notable sustained capacity of 500 mAh g-1 after 500 cycles at 5 C are achieved, with an ultralow decay rate of 0.037% per cycle with a sulfur loading of 1.5 mg cm-2. The feasible construction of flexible SPAN electrodes with enhanced cycling performance enlists the current processing as a promising strategy for novel high-rate lithium-sulfur batteries and other emerging battery electrodes.

2.
J Colloid Interface Sci ; 674: 686-694, 2024 Jun 20.
Artigo em Inglês | MEDLINE | ID: mdl-38950467

RESUMO

The energy storage capacity of porous carbon materials is closely tied to their surface structure and chemical properties. However, developing an innovative and straightforward approach to synthesize yolk-shell carbon spheres (YCs) remains a great challenge till date. Herein, we prepared a series of porous nitrogen-doped yolk-shell carbon spheres (NYCs) via a "pyrolysis-capture" method. This method involves coating the resorcinol-formaldehyde (RF) resin sphere with a layer of compact silica shell induced by 2-methylimidazole (ME) catalysis to produce a confined nano-space. Based on the confined effect of compact silica shell, volatile gases emitted from the RF resin and ME during pyrolysis can not only diffuse into the pores of the RF resin but can also be captured to form an outer carbon shell. This results in the tunable structures of NYCs materials. As the pyrolysis temperature rises, the shell thickness of NYCs reduces, the pore size expands, the roughness increases, and the N/O content of surface elements is enhanced. Notably, as an electrode material used forsupercapacitors,the optimized NYCs-800 exhibits excellent performance with a capacitance of 301.2F g-1 at the current density of 1 A/g and outstanding cycling life stability of 96.1% after 10,000 cycles. These results signify that controlling the surface structure and chemical properties of NYCs materials is an effective approach for constructing advanced energy storage materials.

3.
J Colloid Interface Sci ; 651: 235-242, 2023 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-37542898

RESUMO

In this work, we have proposed a strategy to fabricate double-shell nanotubes as amphiphilic photoactive nanoreactors (HTTBPC) through the ordered hybridization of mesoporous organosilicon (PMO) and titanium dioxide (TiO2) nanotubes. Unlike the previous rough composite, the heterogeneous structure established between cobalt-porphyrin functionalized PMO and conventional TiO2 has a staggered matching band gap, which makes it have excellent light harvesting and high carrier separation ability. This is still unexplored. Interestingly, the prepared photocatalysts exhibited superior activity (99%) and benzaldehyde selectivity (94%) in the oxidation of styrene in water at room temperature, which was 3.8 and 2.8 times higher than that of TiO2 nanotubes and PMO functionalized with cobalt porphyrin, respectively. It was demonstrated that the strong interaction between cobalt porphyrin PMO and TiO2 improved the separation of photogenerated carriers and the amphiphilic properties of mesoporous organosilica boosted the adsorption of substrate molecules in water, contributing to the significantly enhanced photocatalytic activity. This work provides a design of high-performance photocatalysts for alkene oxidation under green conditions.

4.
J Colloid Interface Sci ; 650(Pt B): 1319-1326, 2023 Nov 15.
Artigo em Inglês | MEDLINE | ID: mdl-37478749

RESUMO

Molecularly imprinted photoelectrochemical sensors (MIPES) have gained significant attention in the detection field due to their high selectivity and accuracy. However, their sensitivity still needs improvement. Here we developed a TiO2-based MIPES (TiO2 NRs/NiOOH/rMIP) to detect ciprofloxacin (CIP). We identified the photoactive sites of TiO2 by NiOOH photo-deposition and anchored the imprinted sites on the photoactive sites by complexation between CIP and NiOOH. By regulating the imprinted sites, the photocurrent difference before and after the addition of CIP increases and the detection sensitivity of CIP is improved. Moreover, a PN heterojunction is formed between TiO2 and NiOOH, which enables rapid transfer of photoexcited holes and electrons to different semiconductors under the built-in electric field. This leads to improved photoactivity of TiO2 and further increases the sensitivity of MIPES. Compared with sensors prepared by the traditional electro-polymerization CIP and Molecularly imprinted polymers (TiO2 NRs/NiOOH/eMIP), TiO2 NRs/NiOOH/rMIP as constructed in this work displays higher sensitivity, wider linear detection range, and lower limit of detection (LOD). Additionally, TiO2 NRs/NiOOH/rMIP shows good selectivity, stability, and recovery rate, and has a promising application prospect in the actual detection of antibiotics.

5.
J Colloid Interface Sci ; 649: 223-233, 2023 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-37348342

RESUMO

Lithium-sulfur batteries (LSBs) are among the most promising next-generation high energy density energy-storage systems. However, practical application has been hindered by fundamental problems, especially shuttling by the higher-order polysulfides (PSs) and slow redox kinetics. Herein, a novel electrolyte-based strategy is proposed by adding an ultrasmall amount of the low-cost and commercially available cationic antistatic agent octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate (SN) into a routine ether electrolyte. Due to the strong cation-anion interaction and bridge-bonding with SN, rapid flocculation of the soluble polysulfide intermediates into solid-state polysulfide-SN sediments is found, which significantly inhibited the adverse shuttling effect. Moreover, a catalytic effect was also demonstrated for conversion of the polysulfide-SN intermediates, which enhanced the redox kinetics of Li-S batteries. Encouragingly, for cells with only 0.1 % added SN, an initial specific capacity of 783.6 mAh/g and a retained specific capacity of 565.7 mAh/g were found at 2C after 200 cycles, which corresponded to an ultralow capacity decay rate of only 0.014 % per cycle. This work may provide a simple and promising regulation strategy for preparing highly stable Li-S batteries.

6.
Chem Rev ; 123(11): 7025-7080, 2023 Jun 14.
Artigo em Inglês | MEDLINE | ID: mdl-37053573

RESUMO

Thermochromic energy efficient windows represent an important protocol technology for advanced architectural windows with energy-saving capabilities through the intelligent regulation of indoor solar irradiation and the modulation of window optical properties in response to real-time temperature stimuli. In this review, recent progress in some promising thermochromic systems is summarized from the aspects of structures, the micro-/mesoscale regulation of thermochromic properties, and integration with other emerging energy techniques. Furthermore, the challenges and opportunities in thermochromic energy-efficient windows are outlined to promote future scientific investigations and practical applications in building energy conservation.

7.
Nanoscale ; 14(36): 13227-13235, 2022 Sep 22.
Artigo em Inglês | MEDLINE | ID: mdl-36052550

RESUMO

The sluggish conversion reaction and the accompanying huge volume fluctuation greatly hinder the application of lithium-selenium (Li-Se) batteries. Therefore, reasonably constructing stable carbonaceous hosts with efficient electrochemically active sites is particularly essential for promoting the development of Se cathodes. Herein, a metal-organic solid derived carbon host with multiple heterogeneous NiSe2/Ni2Co/CoSe2 interfaces was fabricated via in situ selenization. The formation of multiple heterointerfaces introduced subtle atomic array distortions, which provided additional electrochemically active sites compared with single heterointerfaces. Besides, the establishment of a built-in electric field was favorable for electron transfer and the absorption of Li+, thereby accelerating the reaction kinetics. Depending on the hollow structure and the heterogeneous catalysts, Li-Se batteries with NiSe2/Ni2Co/CoSe2@Se cathodes delivered reversible capacities of 503 and 324 mA h g-1 after 900 and 2200 cycles at 1 and 12 C, respectively. This work revealed the synergistic mechanism of multiple heterostructures composed of a Ni2Co alloy and in situ derived bimetallic selenides for Se cathodes and provided new insights into the exploitation of energy storage materials.

8.
ACS Appl Mater Interfaces ; 14(33): 37716-37726, 2022 Aug 24.
Artigo em Inglês | MEDLINE | ID: mdl-35971946

RESUMO

In this study, chlorophyll-copper (ChlCu)-modified ZnO nanorods (ChlCu/ZnO) were prepared, and then sodium ethylenediamine tetraacetate (EDTA) was used to remove part of Cu2+ in ChlCu, leaving cavities with specific adsorption activity for Cu2+ in E-ChlCu/ZnO. Appropriate EDTA treatment improved the photoactivity of ChlCu/ZnO and the adsorption selectivity to Cu2+. However, excessive EDTA treatment might lead to the collapse of the ChlCu structure, resulting in a decrease in photoactivity. The E-ChlCu/ZnO sample with 8 h of ChlCu treatment and 2 h of EDTA treatment showed optimal photoactivity. The as-prepared E-ChlCu/ZnO exhibited activity as a light-activated nanozyme, which could oxidize 3,3',5,5'-tetramethylbenzidine (TMB) to blue under illumination, but when Cu2+ was present in the solution, this colorimetric reaction was inhibited; therefore, E-ChlCu/ZnO could be used for colorimetric detection of Cu2+. Because of the existence of specific cavities, E-ChlCu/ZnO showed excellent detection selectivity, a wide linear detection range (0-1 and 1-15 µM), and a low detection limit (0.024 µM) in the colorimetric detection of Cu2+.

9.
ACS Appl Mater Interfaces ; 14(28): 31782-31791, 2022 Jul 20.
Artigo em Inglês | MEDLINE | ID: mdl-35786834

RESUMO

The focus of designing and synthesizing composite catalysts with high photocatalytic efficiency is the regulation of nanostructures and optimization of heterojunctions. By increasing the contact area between the catalysts, additional reaction sites can be established and charge carriers can be transferred and reacted faster. Here, two-dimensional (2D) Mo2C is prepared via a novel approach by carbonizing precursors intercalated by low-boiling solvents, and a composite catalyst Mo2C/graphitic carbon nitride (g-C3N4) with 2D to 2D structure optimization was synthesized through the self-assembly of 2D Mo2C and 2D g-C3N4. The hydrogen production rate of the photocatalyst at the optimal ratio is 675.27 µmol g-1 h-1, which further exceeds 2D g-C3N4. It is 5.1 times that of the 7 wt % B/2D Mo2C/g-C3N4 photocatalyst and also 3.5 times that of 0.5 wt % Pt/g-C3N4. The enhanced photocatalytic activity is attributed to the fact that Mo2C as a cocatalyst can rapidly transfer the photogenerated electrons of g-C3N4 to the surface of Mo2C, and the 2D to 2D structure can provide abundant reaction sites for photogenerated electrons to prevent their recombination with holes. This study provides new ideas and techniques for the development of 2D platinum-like cocatalysts and the optimization of nanojunctions.

10.
Org Lett ; 24(17): 3302-3306, 2022 May 06.
Artigo em Inglês | MEDLINE | ID: mdl-35468280

RESUMO

Employing FeCl2 as a cheap and readily available catalyst, a facile imidization of phosphines with N-acyloxyamides is described, affording synthetically useful N-acyliminophosphoranes with high functional group tolerance. The transformation is easily performed under an air atmosphere at room temperature and could be scaled up to gram scale with a catalyst loading of 1 mol %. The iminophosphoranyl moiety in the product was further utilized as an effective directing group for controllable ortho C(sp2)-H bond amidations under Rh(III) catalysis.

11.
J Am Chem Soc ; 144(14): 6583-6593, 2022 Apr 13.
Artigo em Inglês | MEDLINE | ID: mdl-35380434

RESUMO

Morphological control of covalent organic frameworks (COFs) is particularly interesting to boost their applications; however, it remains a grand challenge to prepare hollow structured COFs (HCOFs) with high crystallinity and uniform morphology. Herein, we report a versatile and efficient strategy of amorphous-to-crystalline transformation for the general and controllable fabrication of highly crystalline HCOFs. These HCOFs exhibited ultrahigh surface areas, radially oriented nanopore channels, quite uniform morphologies, and tunable particle sizes. Mechanistic studies revealed that H2O, acetic acid, and solvent played a crucial role in manipulating the hollowing process and crystallization process by regulating the dynamic imine exchange reaction. Our approach was demonstrated to be applicable to various amines and aldehydes, producing up to 10 kinds of HCOFs. Importantly, based on this methodology, we even constructed a library of unprecedented HCOFs including HCOFs with different pore structures, bowl-like HCOFs, cross-wrinkled COF nanocapsules, grain-assembled HCOFs, and hydrangea-like HCOFs. This strategy was also successfully applied to the fabrication of COF-based yolk-shell nanostructures with various functional interior cores. Furthermore, catalytically active metal nanoparticles were implanted into the hollow cavities of HCOFs with tunable pore diameters, forming attractive size-selective nanoreactors. The obtained metal@HCOFs catalysts showed enhanced catalytic activity and outstanding size-selectivity in hydrogenation of nitroarenes. This work highlights the significance of nucleation-growth kinetics of COFs in tuning their morphologies, structures, and applications.

12.
J Colloid Interface Sci ; 605: 624-636, 2022 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-34352443

RESUMO

A 3D α-MoO3 nanostructure for high-performance triethylamine (TEA) detection was synthesized via the facial oxidation of MoS2 nanoflowers (NFs) obtained by a hydrothermal process. The influence of the time of hydrothermal process in growing MoS2 on the morphologies of the final MoO3 obtained after calcination was investigated. As-obtained MoO3 and their precursors were systematically characterized by various techniques, such as X-ray diffraction, Raman, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, and N2 adsorption-desorption isotherms. Results showed that MoO3 with a hierarchical layered nanostructure was successfully obtained. After hydrothermal treatment of the MoS2 precursor for 20 h, the typical MoO3-based sensor (called M20) exhibited a high response of 2.42 at a very low TEA concentration of only 0.1 ppm at 240 °C. The M20 sensor response to 50 ppm TEA was as high as 125 with a fast response/recovery time of 14/22 s. Moreover, the sensor had a high stability and reproducibility as well as a high selectivity against other interfering VOCs or gases. Due to the tendency of TEA to adsorb to active oxygen sites of MoO3, the enhanced sensing properties of MoO3 can be ascribed to the remarkable hierarchical structure and large surface area. MoO3 obtained after calcination of hydrothermally grown MoS2 is thus a promising sensing material for enhanced TEA gas detection.

13.
Inorg Chem ; 60(17): 13212-13221, 2021 Sep 06.
Artigo em Inglês | MEDLINE | ID: mdl-34379393

RESUMO

Due to the low solubility of BaF2, the BaTiF6:Mn4+ phosphor for whitelight-emitting diodes application has been generally synthesized by the hydrothermal route, during which process the valence of the manganese dopant is difficult to be controlled as tetravalent. In this paper, a new synthesis method that proceeded at room temperature was reported. This method uses BaTiOF4 as the precursor and allows for the control of the phase transformation rate from BaTiOF4 to BaTiF6 in the K2MnF6/HF acid solution. Benefitting from that, we successfully prepared red-emitting BaTiF6:Mn4+ elongated crystals with a single-crystal nature up to a record-breaking length of 200-300 µm. The effects of the crystallinity of the BaTiOF4 precursor on its phase transformation rate into BaTiF6 and on the optimal Mn4+ doping concentration were studied. The BaTiF6:Mn4+ single-crystal phosphor exhibits relatively excellent hydrolysis-resistant behavior after being immersed in water for 3 h, at which condition the commercial K2SiF6:Mn4+ has become brown. This study may inspire the room-temperature preparation of other hydrolysis-resistant alkali earth fluorotitanate or fluorosilicate phosphors with stable tetravalent manganese doping.

14.
ACS Appl Mater Interfaces ; 13(28): 33693-33703, 2021 Jul 21.
Artigo em Inglês | MEDLINE | ID: mdl-34235923

RESUMO

Pickering emulsifiers are significant for organic reactions in an aqueous medium because they have the ability of emulsifying water-oil biphasic systems. For this reason, 2,5-bis[(E)-2-(triethoxysilyl)vinyl]pyridine [BTOSVP] containing a pyridine bridging group was selected as a precursor to prepare a novel salt of organosilicon framework (SOF), an amphiphilic mesoporous pyridine hydrobromide nanosphere. We first synthesized a mesoporous organosilicon framework made up of organic groups containing vinyl groups, pyridine groups, and so forth. Then, hydrobromic acid was added to protonate the pyridine groups in the mesoporous organosilicon framework. Eventually, pyridine hydrobromide salt was formed on the surfaces of channels, and the SOF was successfully prepared for the first time. Pyridine hydrobromide salt can be ionized in water into protonated pyridine cations located on the SOF surfaces and free Br-anions swimming around the protonated pyridine cations because of the electrostatic interaction. In the water-oil biphasic systems, hydrophilicity of SOF originates from the protonated pyridine cations and the lipophilicity of SOF comes from organic groups in the framework; thus, this new kind of SOF can be used as a new generation of solid Pickering emulsifiers. Most importantly, the mesoporous SOF nanosphere can also be used as a catalyst for significantly improved dibromination of olefins in an aqueous medium.

15.
J Colloid Interface Sci ; 599: 849-856, 2021 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-33991801

RESUMO

Defect engineering is an important strategy to regulate electronic structure of electrocatalysts for electrochemical N2 fixation, aiming at improving the electron state density and enhancing the adsorption and activation of inert N2. In this paper, a high-temperature strategy to anneal the natural molybdenite under Ar atmosphere was developed, and the as-obtained molybdenite with S vacancies boosted a high activity for N2 reduction reaction. In 0.1 M HCl, the catalyst annealed at 800 °C exhibits a high Faradic efficiency of 17.9% and a NH3 yield of 23.38 µg h-1 mg-1cat. at -0.35 V versus reversible hydrogen electrode, two times higher than that of the pristine molybdenite. The facile one-step annealing method introduces the defects (e.g., S vacancies) in the surface of the natural molybdenite particles to prepare catalysts for generating ammonia by reducing nitrogen at room temperature under ordinary pressure, promoting the development of low-carbon economic prospect.

16.
Nanoscale ; 13(20): 9229-9235, 2021 May 27.
Artigo em Inglês | MEDLINE | ID: mdl-33978033

RESUMO

Organic reactors in a green solvent (water) is the goal of sustainable development. Green nanoreactors with excellent amphiphilicity and catalytic activity are strongly desired. Herein, a novel amphiphilic nanoreactor Pd@amZSM-5 with ultrasmall size has been successfully synthesized via a simple one-step oil bath method, subjected to the modification-etching-modification strategy and in situ reduction of Pd2+. Ultrasmall Pd@amZSM-5 nanoreactors (60 nm) with hierarchical structures showed outstanding amphiphilicity for forming Pickering emulsions with fine uniform droplets (50 µm). Fine droplets formed short diffusion distances, which can significantly improve the catalytic activity in biphasic reactions. Moroever, the ultrasmall Pd@amZSM-5 nanoreactors demonstrated excellent catalytic activity for the selective oxidation of alcohols in water using air as the oxidant. Alkali was not present in the reaction system. The hydrophilic aminopropyl groups on the surface of the Pd@amZSM-5 nanoreactors not only changed the affinity of the zeolite surface and provided targeting points for Pd nanoparticles but also provided an alkaline environment for the selective oxidation of alcohols. The ultrasmall Pd@amZSM-5 nanoreactors presented excellent universality for aromatic alcohols (with >90% conversion and >90% selectivity) and allylic alcohols (with 100% conversion and 100% selectivity).

17.
J Colloid Interface Sci ; 585: 276-286, 2021 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-33290888

RESUMO

Carbon-metal composites are promising multifunctional electrocatalysts, but it is still challenging to prepare carbon-metal composites with tunable structure and strong metal-carbon interactions. Here, we present a unique gas-foaming assembly strategy to prepare cytosine-Co chelate derived Co and N codoped carbon nanotube (Co-NCNT). The structure for Co-NCNTs could be easily controlled by regulating cytosine-Co coordination or the carbonization temperature. The optimal Co-NCNT possesses homogeneous distributed NCNTs (10 nm), CoOx (5 nm) and CoNx moieties to synergistically boost electrochemical processes, and offer mesoporous nanosheet architecture to guarantee fast mass migrate and electron transfer. As a result, Co-NCNT shows remarkable ORR performance (onset potential of 0.93 V in 0.1 M KOH electrolyte) along with significant OER and HER activity. More important, it was found that CoNx moieties are responsible for the remarkable electrocatalytic activity in Co-NCNTs, because CoNx could alter active center, enhance metal-carbon synergy, decrease interfacial resistance and reinforce the strength of composites. Therefore, this paper not just demonstrates an advanced multi-functional electrocatalyst, but could also give deep understanding on the designing of multifunctional electrocatalysts.

18.
ACS Appl Mater Interfaces ; 12(36): 40684-40691, 2020 Sep 09.
Artigo em Inglês | MEDLINE | ID: mdl-32805837

RESUMO

It is strongly desired to design and synthesize amphiphilic nanoreactors with tunable compatibility, which are stable at the biphasic interface in both acidic and alkaline environments. Herein, a novel amphiphilic R1-ZSM-5-R2 nanoreactor with adjustable hydrophilic-lipophilic balance (solid) (HLB(S)) values has been successfully synthesized by hydrophilic/lipophilic asymmetric modification of the surface of hemishell zeolites. The hemishell zeolites obtained by alkali etching have different surfaces for this asymmetric modification. Owing to the unique hemishell structures and asymmetric modification, the R1-ZSM-5-R2 nanoreactors with an optimized type and amount of modified organosilanes show excellent stability and emulsifying properties under extreme environments, which is important for cascade reactions in a biphasic system. The modified amino groups on the surface of the nanoreactors not only enhance the hydrophilicity of the hemishell zeolites and stabilize ultrasmall Pt nanoparticles (1.90 nm) but also used for the catalytic synthesis of trans-cinnamaldehyde. The Pt@R1-ZSM-5-R2 amphiphilic catalysts fabricated through a one-step reduction of Pt nanoparticles present outstanding performances in the biphasic cascade synthesis of cinnamic acid, achieving a very high turnover frequency (TOF) of 978 h-1. The TOF values of the catalysts correspond well to the HLB(S) values of the R1-ZSM-5-R2 nanoreactors.

19.
Chemistry ; 26(58): 13295-13304, 2020 Oct 15.
Artigo em Inglês | MEDLINE | ID: mdl-32627241

RESUMO

Lithium-sulfur batteries, owing to the multi-electron participation in the redox reaction, possess enormous energy density, which has aroused much attention. Nevertheless, the detrimental shuttle effect, volume expansion, and electrical insulation of sulfur, have hindered their application. To improve the cyclability, a functional host, consisting of Co nanoparticles and N-doped hollow graphitized carbon (Co-NHGC) material, is elaborated, which has the advantages of: 1) the graphitized carbon material working as an electronic matrix to improve the utilization rate of sulfur; 2) the hollow structure relieving the stress change caused by volume expansion; 3) the rich active sites catalyze the electrochemical reaction of sulfur and entrap polysulfides. These advantages significantly improve the performance of the lithium-sulfur batteries. Accordingly, the S@Co-NHGC cathode exhibits excellent initial specific capacity, high coulombic efficiency, and excellent rate performance. This work utilizes a novel method of dopamine in situ etching of a metal-organic framework to synthetize the Co-NHGC host of sulfur, which will hopefully provide inspiration for other energy materials.

20.
Dalton Trans ; 49(17): 5711-5721, 2020 May 07.
Artigo em Inglês | MEDLINE | ID: mdl-32297895

RESUMO

Blue light pumped red luminescence with broadband and high photon-energy emission is highly desired for phosphor-converted white light-emitting diodes (pc-wLEDs), to achieve a high color rendering index and high luminous efficacy. Mn4+-doped red-emitting phosphors generally exhibit sharp vibronic emissions associated with the parity- and spin-forbidden 2Eg→4A2g transitions. In this paper, two abnormal luminescence behaviors were observed for Mn4+ in the MgAl2O4:Mn4+ spinel phosphor with a short wavelength emission band peaking at 651 nm. Firstly, the Mn4+ 2Eg→4A2g transition exhibits ultrabroadband luminescence in MgAl2O4 and the large full-width at half-maximum (FWHM) is dependent both on the calcination temperature and on the partial substitution of Al3+ with Ga3+. Secondly, the thermal quenching behavior of the Mn4+ 2Eg→4A2g luminescence in MgAl2O4 shows a dependence on its thermal treatment and preparation method. The Rietveld refinement and Raman results demonstrate that the variation in the FWHM of the luminescence spectra is a sum effect of structural ordering (i.e., isotropic displacement decrease of constituent atoms) and the Mg ↔ Al anti-site disorder. A model for the observed varying thermal quenching of luminescence was tentatively proposed. The intrinsic thermal quenching temperature of Mn4+ luminescence in MgAl2O4 was found to be 390-400 K using the samples prepared by the co-precipitation and molten salt methods. The present work gives a novel perspective to understand the luminescence spectra of Mn4+ 2Eg→4A2g transition.

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