Hematite crystal growth in high-temperature lead-free multicomponent alkali borosilicate glass frit for red overglaze enamels

To elucidate the crystal growth process of hematite in high-temperature lead-free multicomponent alkali borosilicate glass, which is essentially important to control the color of red overglaze enamels, frit and hematite mixture is heat-treated and subjected to microscopic observations. Hematite particles slightly grew due to sintering at low temperature. Once the glass matrix formed near the softening point of frit, hematite dissolved into glass fluid. Hematite crystal growth concomitantly ensued with decrease in the number of hematite particles via Ostwald ripening as the temperature increased. The grown particles exhibited an anisotropic morphology with straight outlines reflecting crystal planes, the morphology of which is completely different from those grown by sintering and particles prior to heating. These results suggest that comprehensive understanding of frit and hematite from the perspectives of glass science and chemistry as well as powder technology are important to truly control the color of red overglaze enamels.     

Catalytic behavior in CH4 decomposition of catalysts derived from red mud: Impact of residual Na2O

Catalyst samples for CH₄ decomposition were prepared from red mud (RM) by an acid-leaching neutralization precipitation approach. Water-washing the resultant precipitates multiple times, followed by drying at 105 °C and calcination at 500 °C, resulted in a threshold of residual Na₂O, equivalent to 96% Na₂O removal. Drying the precipitate at a higher temperature of 200 °C, followed by repeated water washing, provided a deeper Na₂O removal of 99% and made the resultant samples more active for the targeted reaction. Subsequently, four catalyst samples with a simulated red mud composition and NaOH contents from 0 to 0.3 wt% were prepared and the catalytic test results revealed that the Na₂O remaining in the RM-derived catalysts did not only inhibit their activation in CH₄ but also lower their maximal activities for CH₄ decomposition. Finally, two catalysts with the same simulated red mud composition and their Na impregnated respectively on Fe₂O₃ and a mixture support of Al₂O₃-SiO₂-TiO₂ were prepared and tested to explore the effect of Na distribution on the activation behavior of RM-derived catalysts for CH₄ decomposition. The activity testing results showed that it was the Na residual dispersed on iron oxides in the RM-derived samples to significantly inhibit the activation of CH₄ decomposition.     

Eco-friendly and degradable red phosphorus nanoparticles for rapid microbial sterilization under visible light

Pathogens pose a serious challenge to environmental sanitation and a threat to public health.The frequent use of chemicals for sterilization in recent years has not only caused secondary damage to the environment but also increased pathogen resistance to drugs,which further threatens public health.To address this issue,the use of non-chemical antibacterial means has become a new trend for environmental disinfection.In this study,we developed red phosphorus nanoparticles(RPNPs),a safe and degradable photosensitive material with good photocatalytic and photothermal properties.The red phosphorus nanoparticles were prepared using a template method and ultrasonication.Under the irradiation of simulated sunlight for 20 min,the RPNPs exhibited an efficiency of 99.98%in killing Staphylococcus aureus due to their excellent photocatalytic and photothermal abilities.Transmission electron microscopy and ultraviolet–visible spectroscopy revealed that the RPNPs exhibited degradability within eight weeks.Both the RPNPs and their degradation products were nontoxic to fibroblast cells.Therefore,such RPNPs are expected to be used as a new type of low-cost,efficient,degradable,biocompatible,and eco-friendly photosensitive material for environmental disinfection.     

Enhanced luminescence and energy transfer performance of double perovskite structure Gd2MgTiO6:Bi3+, Mn4+ phosphor for indoor plant growth LED lighting

Deep-red light emitting phosphors are widely used in LEDs for indoor plant growth because of the critical role played by red light in plant growth. The luminescence properties of deep-red phosphors are still not well understood at present. An energy transfer strategy is a common and effective method to improve luminescence properties. In principle, the energy transfer process may occur when the sensitizer's emission spectra overlap with the activator's excitation spectra. In this work, Bi³⁺ and Mn⁴⁺ were incorporated into the matrix of Gd₂MgTiO₆ as sensitisers and activators, respectively. Mn⁴⁺ ions tend to occupy the [TiO₆] octahedral site and the Bi³⁺ ions are expected to substituted in the site of Gd³⁺. The energy transfer process from Bi³⁺ to Mn⁴⁺ was realised and the photoluminescence (PL) intensity of Mn⁴⁺ increased with the doping content of Bi³⁺. Upon excitation at 375 nm, the PL intensity of Mn⁴⁺ increased to 116.4% when the doping concentration of Bi³⁺ reached 0.3%. Finally, the pc-LED devices were prepared by a Gd₂MgTiO₆:Bi³⁺, Mn⁴⁺ phosphor. The high red luminescence indicated that this phosphor has potential applications in indoor LED lighting.     

Tuning of emission by effect of local symmetry in BaLaLiWO6:Dy3+/Eu3+ for WLEDs

The luminescence center energy transfer, crystal field strength, and covalency are limited by the crystal structure of the host and subsequently affect the luminescence efficiency, color, and intensity. Here, we report an excellent red phosphor BaLaLiWO₆:0.40Eu³⁺ and the dependence between symmetry and luminous performance. A model for changing symmetry is drawn by analyzing the Coulomb potential and structure for the application of a double-perovskite phosphor BLLWO: Dy³⁺, Eu³⁺ in white light LEDs. The addition of Dy³⁺/Eu³⁺ makes the W-O bond formed by the B-site and oxygen ion longer and the Li-O bond shorter, and the difference between the eight octahedral around the A-site is reduced, increasing the symmetry of the A-site. Local symmetry was successfully modulated by changing the Eu³⁺ concentration to control the Y/B ratio of Dy³⁺ and the R/O ratio of Eu³⁺ and smoothly achieved (0.382, 0.373) warm white light color coordinate. The phosphor has excellent thermal stability and still has 92.3% intensity at 475 K. The above results show that the wavelength composition of the luminescence is tunable by changing the symmetry of the environment in which the doped ions are located. It applies to single hosts for the regulation of white light emission.     

调控Al2O3晶型控制MgAl2O4:Mn4+荧光粉中Mn价态研究

Mn⁴⁺激活红光荧光粉是白光半导体发光二极管(wLEDs)领域当前研究热点之一。Mn⁴⁺离子²E→⁴A₂跃迁在铝酸盐中的最短发光波长是在MgAl₂O₄中实现的651 nm发光, 由于其结构中含有形成四面体或八面体配位的两种阳离子格位(Mg²⁺/Al³⁺), 易造成所掺杂锰元素存在多种价态(+2/+4/+3等)。本研究通过改变起始原料中Al₂O₃的晶型(γ/α比例)及退火处理来调控锰离子在MgAl₂O₄晶格中的占据格位, 对其主要存在价态实现调控。采用荧光光谱和紫外-可见-近红外漫反射光谱技术来表征所合成荧光粉中Mn离子的价态及其演变。研究发现, 高α/(α+γ)比铝源促进Mn²⁺形成, 而低α/(α+γ)比铝源促进Mn⁴⁺形成。通过使用高活性纳米γ-Al₂O₃为铝源, 有效抑制了锰离子在MgAl₂O₄中Mg²⁺格位的占据及Mn²⁺离子的形成, 经空气中1550 ℃保温5 h的一次高温热处理即可制备出在可见光区只有Mn⁴⁺红光发光的高纯高亮度MgAl₂O₄:Mn⁴⁺荧光粉。氧化铝晶型影响锰离子掺杂格位和掺杂价态的本质规律是: 氧化铝活性决定实际固溶掺杂反应步骤, 进而影响锰离子掺杂格位和价态。本研究提出的反应步骤调控作为反应气氛、电荷补偿剂、反应温度三种调控方法外的一种新方法, 为Mn⁴⁺激活铝酸盐荧光粉中锰离子掺杂价态调控提供了新思路。     

Y4.67Si3O13-based phosphors: Structure,morphology and upconversion luminescence for optical thermometry

How to improve the sensitivity of the temperature-sensing luminescent materials is one of the most important objects currently. In this work, to obtain high sensitivity and learn the corresponding mechanism, the rare earth (RE) ions doped Y_4.67Si₃O₁₃ (YS) phosphors were developed by solid-state reaction. The phase purity, structure, morphology and luminescence characteristics were evaluated by XRD, TEM, emission spectra, etc. The change of the optical bandgaps between the host and RE-doped phosphors was found, agreeing with the calculation results based on density-functional theory. The temperature-dependence of the upconversion (UC) luminescence revealed that a linear relationship exists between the fluorescence intensity ratio of Ho³⁺ and temperature. The theoretical resolution was evaluated. High absolute (0.083 K⁻¹) and relative (3.53% K⁻¹ at 293 K) sensitivities have been gained in the YS:1%Ho³⁺, 10%Yb³⁺. The effect of the Yb³⁺ doping concentration and pump power on the sensitivities was discussed. The pump-power–dependence of the UC luminescence indicated the main mechanism for high sensitivities in the YS:1%Ho³⁺, 10%Yb³⁺. Moreover, the decay-lifetime based temperature sensing was also evaluated. The above results imply that the present phosphors could be promising candidates for temperature sensors, and the proposed strategies are instructive in exploring other new temperature sensing luminescent materials.     

Alkali metal ion substitution induced luminescence enhancement of NaLaMgWO6:Eu3+ red phosphor for white light-emitting diodes

Alkali metal ion substitution is an effective strategy to improve the luminescence properties of phosphors. In this work, a series of red-emitting phosphors Na_1-xLi_x/2K_x/2La_0.6Eu_0.4MgWO₆ were prepared by a traditional high-temperature solid-state reaction. Their phase structure, microstructure, luminescence properties and potential application in phosphor-converted white light-emitting diodes (pc-WLEDs) were investigated in detail. X-ray diffraction (XRD) result revealed the formation of a solid solution when x?≤?0.3, which kept monoclinic structure of NaLaMgWO₆. Photoluminescence investigation indicated that the partial substitution of Li⁺/K⁺ ions for Na⁺ ions improved largely the red emission of Eu³⁺. Based on the optimized Na_0.7Li_0.15K_0.15La_0.6Eu_0.4MgWO₆ sample with relatively good thermal stability, a WLED device was fabricated by combining a near-ultraviolet (NUV) chip (~400?nm) with the phosphor mixture of commercial green/blue phosphors and the optimized red phosphor. The results indicated that the optimized red phosphor in this work could be a potential candidate for WLEDs pumped by NUV chips.     

Hydrocracking and hydrodesulfurization of diesel over zeolite beta-containing NiMo supported on activated red mud

NiMo nanocatalysts supported on activated red mud with different zeolite beta contents were successfully prepared by impregnation technique. Their hydrocracking and hydrodesulfurization activities were evaluated with two different kinds of diesel feed (iso diesel and heavy diesel) in a fixed bed reactor at ambient pressure and 500 °C. Physico-chemical properties of synthesized samples were characterized using the methods of XRF, XRD, FESEM, BET, FTIR and NH₃-TPD. The results indicated that zeolite incorporation resulted in a significant increase in specific surface area (BET result) and acidic strength (TPD result) of nanocatalysts. FESEM analysis confirmed that the particles size of zeolite-containing NiMo/ARM was less than 100 nm and the average size of particles was about 30 nm. Hydrocracking results illustrated that incorporation of zeolite beta improved cracking activity considerably. In addition, NiMo nanocatalyst containing 37.5 wt% of zeolite had the highest yields of desirable products (naphtha, kerosene and diesel) and the highest conversion. Moreover, the flash point and viscosity of the liquid product decreased notably the nanocatalysts with 37.5 wt% and 12.5 wt% of zeolite were able to remove approximately 96% and 72% of the sulfur content of iso diesel and heavy diesel, respectively.     

基于深度学习的彩色以及近红外图像去马赛克

单传感器捕获的彩色-近红外（RGB-NIR）图像存在光谱干扰，从而导致重建出的标准彩色图像（RGB）图像与近红外（NIR）图像存在色彩失真以及细节信息模糊。针对这个问题提出一种基于深度学习的去马赛克方法，通过引入跳远连接与稠密连接解决了梯度消失和梯度弥散问题，使得网络更容易训练，并且提升了网络的拟合能力。首先，用浅层特征提取层提取了马赛克图像的像素相关性以及通道相关性等低级特征；然后，将得到的浅层特征图输入到连续多个的残差稠密块以提取专门针对去马赛克的高级语义特征；其次，为充分利用低级特征与高级特征，将多个残差稠密块提取到的特征进行组合；最后，通过全局跳远连接恢复最终的RGB-NIR图像。在深度学习框架Tensorflow上使用公共的图像与视觉表示组（IVRG）数据集、有植被的户外多光谱图像（OMSIV）数据集和森林（Forest）三个公开数据集进行实验。实验结果表明，所提方法优于基于多级自适应残差插值、基于卷积卷积和神经神经网络以及基于深度残差U型网络的主流的RGB-NIR图像去马赛克方法。