A novel white-emitting phosphor ZnWO_4:Dy^(3+)

A new white luminescent material Dy3＋ doped ZnWO4 was synthesized by hydrothermal route followed by calcining proc- ess. The phase structure, morphology and luminescent properties of as-synthesized samples were characterized by X-ray diffraction, scanning electron microscopy and fluorescence spectrophotometry, respectively. The results indicated that the sample was pure ZnWO4：Dy3＋ only when the pH value of the reaction system was 6. The ZnWOa：Dy3＋ sample was composed of spherical particles, and the particle size was about 80-130 nm. The excitation spectrum consisted of a broad band ascribed to the charge transfer transi- tion from oxygen ligand to tungsten ion. The emission spectrum of ZnWO4：Dy3＋ was composed of two major parts： the broad band attributing to the intrinsic emission of WO42- and the 4F9/2→6H15/2 transition of Dy3＋, and the sharp emission peak corresponding to the 4F9/2→61-113/2 transition of Dy3＋. The optimal emission intensity of the Zn1-xWOa：Dy3＋x phosphors was realized when x= 1.5 mol. %. Moreover, all of the ZnI_xWOa：Dy3＋ （x=0.5 mol.%, 1 mol.%, 1.5 mol.%, 2 mol.%） phosphors could exhibit white light emission, which could be potentially applied in white lighting-emitting diodes.

Properties of Self-recoverable Mechanoluminescence Phosphor Ca_(5)Ga_(6)O_(14)∶Eu^(3+) and Its Information Encryption Application

A novel self-recoverable mechanoluminescent phosphor Ca_(5)Ga_(6)O_(14)∶Eu^(3+) was developed by the high-tem-perature solid-state reaction method,and its luminescence properties were investigated.Ca_(5)Ga_(6)O_(14)∶Eu^(3+)can produce red mechanoluminescence,and importantly,it shows good repeatability.The mechanoluminescence of Ca_(5)Ga_(6)O_(14)∶Eu^(3+) results from the piezoelectric field generated inside the material under stress,rather than the charge carriers stored in the traps,which can be confirmed by the multiple cycles of mechanoluminescence tests and heat treatment tests.The mechanoluminescence color can be turned from red to green by co-doping varied concentrations of Tb^(3+),which may be meaningful for encrypted letter writing.The encryption scheme for secure communication was devised by harnessing mechanoluminescence patterns in diverse shapes and ASCII codes,which shows good encryption performance.The results suggest that the mechanoluminescence phosphor Ca_(5)Ga_(6)O_(14)∶Eu^(3+),Tb^(3+)may be applied to the optical information encryption.

Structural and Luminescent Properties of Mg_(0.25-x)Al_(2.57)O_(3.79)N_(0.21):xMn^(2+)Green-Emitting Transparent Ceramic Phosphor

A series of spinel-type Mg_(0.25-x)Al_(2.57)O_(3.79)N_(0.21):xMn^(2+)(MgAlON:xMn^(2+))phosphors were synthesized by the solid-state reaction route.The transparent ceramic phosphors were fabricated by pressureless sintering followed by hot-isostatic pressing(HIP).The crystal structure,luminescence and mechanical properties of the samples were systematically investigated.The transparent ceramic phosphors with tetrahedrally coordinated Mn^(2+)show strong green emission centered around 515 nm under blue light excitation.As the Mn^(2+)concentration increases,the crystal lattice expands slightly,resulting in a variation of crystal field and a slight red-shift of green emission peak.Six weak absorption peaks in the transmittance spectra originate from the spin-forbidden ^(4)T_(1)(^(4)G)→^(6)A_(1) transition of Mn^(2+).The decay time was found to decrease from 5.66 to 5.16 ms with the Mn^(2+)concentration.The present study contributes to the systematic understanding of crystal structure and properties of MgAlON:xMn^(2+)green-emitting transparent ceramic phosphor which has a potential application in high-power light-emitting diodes.

Pillar effect induced by ultrahigh phosphorous/nitrogen doping enables graphene/MXene film with excellent cycling stability for alkali metal ion storage

Graphene's large theoretical surface area and high conductivity make it an attractive anode material for potassium-ion batteries(PIBs).However,its practical application is hindered by small interlayer distance and long ion transfer distance.Herein,this paper aims to address the issue by introducing MXene through a simple and scalable method for assembling graphene and realizing ultrahigh P doping content.The findings reveal that MXene and P-C bonds have a "pillar effect" on the structure of graphene,and the P-C bond plays a primary role.In addition,N/P co-doping introduces abundant defects,providing more active sites for K^(+) storage and facilitating K^(+) adsorption.As expected,the developed ultrahigh phosphorous/nitrogen co-doped flexible reduced graphene oxide/MXene(NPrGM) electrode exhibits remarkable reversible discharge capacity(554 mA hg^(-1) at 0.05 A g^(-1)),impressive rate capability(178 mA h g^(-1) at 2 A g^(-1)),and robust cyclic stability(0.0005% decay per cycle after 10,000 cycles at 2 A g^(-1)).Furthermore,the assembled activated carbon‖NPrGM potassium-ion hybrid capacitor(PIHC) can deliver an impressive energy density of 131 W h kg^(-1) and stable cycling performance with 98.1% capacitance retention after5000 cycles at 1 A g^(-1).Such a new strategy will effectively promote the practical application of graphene materials in PIBs/PIHCs and open new avenues for the scalable development of flexible films based on two-dimensional materials for potential applications in energy storage,thermal interface,and electromagnetic shielding.

Achieving Narrowed Bandgaps and Blue-Light Excitability in Zero-Dimensional Hybrid Metal Halide Phosphors via Introducing Cation-Cation Bonding

Zero-dimensional(0D)hybrid metal halides,which consist of organic cations and isolated inorganic metal halide anions,have emerged as phosphors with efficient broadband emissions.However,these materials generally have too wide bandgaps and thus cannot be excited by blue light,which hinders their applications for efficient white light-emitting diodes(WLEDs).The key to achieving a blue-light-excitable 0D hybrid metal halide phosphor is to reduce the fundamental bandgap by rational chemical design.In this work,we report two designed hybrid copper(I)iodides,(Ph_(3)MeP)_(2)Cu_(4)I_(6)and(Cy_(3)MeP)_(2)Cu_(4)I_(6),as blue-light-excitable yellow phosphors with ultrabroadband emission.In these compounds,the[Cu_(4)I_(6)]^(2-)anion forms an I6 octahedron centered on a cationic Cu_(4)tetrahedron.The strong cation-cation bonding within the unique cationic Cu_(4)tetrahedra enables significantly lowered conduction band minimums and thus narrowed bandgaps,as compared to other reported hybrid copper(I)iodides.The ultrabroadband emission is attributed to the coexistence of free and self-trapped excitons.The WLED using the[Cu_(4)I_(6)]^(2-)anion-based single phosphor shows warm white light emission,with a high luminous efficiency of 65 Im W^(-1)and a high color rendering index of 88.This work provides strategies to design narrow-bandgap 0D hybrid metal halides and presents two first examples of blue-light-excitable 0D hybrid metal halide phosphors for efficient WLEDs.

Fabrication of YAG:Ce^(3+) and YAG:Ce^(3+),Sc^(3+) Phosphors by Spark Plasma Sintering Technique

In this study,a single-doped phosphors yttrium aluminum garnet(Y_(3)Al_(5)O_(12),YAG):Ce^(3+),single-doped YAG:Sc^(3+),and double-doped phosphors YAG:Ce^(3+),Sc^(3+) were prepared by spark plasma sintering(SPS)(lower than 1 200℃).The characteristics of synthesized phosphors were determined using scanning electron microscopy(SEM),X-ray diffraction(XRD),and fluorescence spectroscopy.During SPS,the lattice structure of YAG was maintained by the added Ce^(3+) and Sc^(3+).The emission wavelength of YAG:Ce^(3+) prepared from SPS(425-700 nm) was wider compared to that of YAG:Ce^(3+) prepared from high-temperature solid-state reaction(HSSR)(500-700 nm).The incorporation of low-dose Sc^(3+) in YAG:Ce^(3+) moved the emission peak towards the short wavelength.

Durable hierarchical phosphorus‐doped biphase MoS_(2)electrocatalysts with enhanced H^(*)adsorption

Phase engineering is an efficient strategy for enhancing the kinetics of electrocatalytic reactions.Herein,phase engineering was employed to prepare high‐performance phosphorous‐doped biphase(1T/2H)MoS_(2)(P‐BMS)nanoflakes for hydrogen evolution reaction(HER).The doping of MoS_(2)with P atoms modifies its electronic structure and optimizes its electrocatalytic reaction kinetics,which significantly enhances its electrical conductivity and structural stability,which are verified by various characterization tools,including X‐ray photoelectron spectroscopy,high‐resolution transmission electron microscopy,X‐ray absorption near‐edge spectroscopy,and extended X‐ray absorption fine structure.Moreover,the hierarchically formed flakes of P‐BMS provide numerous catalytic surface‐active sites,which remarkably enhance its HER activity.The optimized P‐BMS electrocatalysts exhibit low overpotentials(60 and 72 mV at 10 mA cm^(−2))in H_(2)SO_(4)(0.5 M)and KOH(1.0 M),respectively.The mechanism of improving the HER activity of the material was systematically studied using density functional theory calculations and various electrochemical characterization techniques.This study has shown that phase engineering is a promising strategy for enhancing the H*adsorption of metal sulfides.

Research on the Low-carbon Cementitious Materials:Effect of Triisopropanolamine on the Hydration of Phosphorous Slag and Steel Slag

Cement,phosphorous slag(PS),and steel slag(SS)were used to prepare low-carbon cementitious materials,and triisopropanolamine(TIPA)was used to improve the mechanical properties by controlling the hydration process.The experimental results show that,by using 0.06%TIPA,the compressive strength of cement containing 60%PS or 60%SS could be enhanced by 12%or 18%at 28 d.The presence of TIPA significantly affected the hydration process of PS and SS in cement.In the early stage,TIPA accelerated the dissolution of Al in PS,and the formation of carboaluminate hydrate was facilitated,which could induce the hydration;TIPA promoted the dissolution of Fe in SS,and the formation of Fe-monocarbonate,which was precipitated on the surface of SS,resulting in the postponement of hydration,especially for the high SS content.In the later stage,under the continuous solubilization effect of TIPA,the hydration of PS and SS could refine the pore structure.It was noted that compared with portland cement,the carbon emissions of cement-PS-TIPA and cement-SS-TIPA was reduced by 52%and 49%,respectively.

Tunable Emission and Energy Transfer of the Novel KY_(1-x)(MoO_(4))_(2-y)(WO_(4))y:xLn^(3+)(Ln^(3+)=Dy^(3+),Eu^(3+),and Tm^(3+))Single-phase White Luminescence Phosphor for White LEDs

The phosphors of KY_(1-x)(MoO_(4))_(2-y)(WO_(4))y:xLn^(3+)(Ln^(3+)=Tm^(3+),Dy^(3+),Eu^(3+))were synthesized by using a sol-gel method.Then,the crystal structure,luminescence properties,energy transfer,and white emission of the prepared materials were researched.The molar ratio of the anion group on the photoluminescence(PL)emission and excitation intensity were investigated,revealing that the optimum intensity could be obtained by using=3:1.The optimal Dy^(3+) doping concentration of KY(MoO_(4))1.5(WO4)0.5was obtained.In addition,the color-tunable emissions of Dy^(3+)/Eu^(3+)-codoped KY(MoO_(4))1.5(WO4)0.5phosphors were observed because of the effective energy transfer(ET)from Dy^(3+)to Eu^(3+)ions.Finally,by doping appropriate concentrations of Tm^(3+),Dy^(3+),and Eu^(3+)and different concentrations of(WO_(4))^(2-),white light emitting phosphors KY_(0.92)(WO_(4))2:0.01Tm^(3+),0.06Dy^(3+),0.01Eu^(3+)with excellent color-rending properties were obtained.The chromaticity coordinate was calculated as(x=0.3238,y=0.3173),closing to the artificial daylight(D65,x=0.313,y=0.329)illuminant,and which indicates the potential application of near ultraviolet White light-emitting diodes(WLEDs).

Direct observation of the distribution of impurity in phosphorous/boron co-doped Si nanocrystals

Doping in Si nanocrystals is an interesting topic and directly studying the distribution of dopants in phosphorous/boron co-doping is an important issue facing the scientific community.In this study,atom probe tomography is performed to study the structures and distribution of impurity in phosphorous/boron co-doped Si nanocrystals/SiO_(2) multilayers.Compared with phosphorous singly doped Si nanocrystals,it is interesting to find that the concentration of phosphorous in co-doped samples can be significantly improved.Theoretical simulation suggests that phosphorous-boron pairs are formed in co-doped Si nanocrystals with the lowest formation energy,which also reduces the formation energy of phosphorous in Si nanocrystals.The results indicate that co-doping can promote the entry of phosphorous impurities into the near-surface and inner sites of Si nanocrystals,which provides an interesting way to regulate the electronic and optical properties of Si nanocrystals such as the observed enhancement of conductivity and sub-band light emission.

Mn^(4+) activated phosphors in photoelectric and energy conversion devices

Owing to their high luminous efficiency and tunable emission in both red light and far-red light regions,Mn^(4+)ion-activated phosphors have appealed significant interest in photoelectric and energy conversion devices such as white light emitting diode(W-LED),plant cultivation LED,and temperature thermometer.Up to now,Mn^(4+)has been widely introduced into the lattices of various inorganic hosts for brightly redemitting phosphors.However,how to correlate the structure-activity relationship between host framework,luminescence property,and photoelectric device is urgently demanded.In this review,we thoroughly summarize the recent advances of Mn^(4+)doped phosphors.Meanwhile,several strategies like co-doping and defect passivation for improving Mn^(4+)emission are also discussed.Most importantly,the relationship between the protocols for tailoring the structures of Mn^(4+)doped phosphors,increased luminescence performance,and the targeted devices with efficient photoelectric and energy conversion efficiency is deeply correlated.Finally,the challenges and perspectives of Mn^(4+)doped phosphors for practical applications are anticipated.We cordially anticipate that this review can deliver a deep comprehension of not only Mn^(4+)luminescence mechanism but also the crystal structure tailoring strategy of phosphors,so as to spur innovative thoughts in designing advanced phosphors and deepening the applications.

Intensified reactive extraction of 4-hydroxypyridine with di(2-ethylhexyl) phosphoric acid in 1-octanol by using tributyl phosphate

The efficient separation of amphoteric organic compounds from dilute solutions is of great importance in the industrial field. In the present work, the reactive extractions of 4-hydroxypyridine(4-HP) with tributyl phosphate(TBP), di(2-ethylhexyl) phosphoric acid(D2EHPA) and TBP + D2EHPA dissolved in 1-octanol were investigated, respectively. The influences of the initial concentrations of TBP, D2EHPA and TBP + D2EHPA on distribution ratio(D) were discussed, as well as the reactive extraction mechanism were proposed. The obvious intensification effect was observed when the mixture of TBP and D2EHPA was used as extractant. The best extraction conditions were found to be of the molar ratio of D2EHPA and TBP at 2:1 and the equilibrium aqueous pH at 3.50-4.50. D values increased with the increase of the total concentration of TBP and D2EHPA in 1-octanol. Especially, the analysis on the extraction mechanisms clearly indicate(i) TBP in 1-octanol shows negligible reactive extraction toward 4-HP,(ii) D2EHPA in 1-octanol exhibits moderate extraction effect by forming 4-HP:D2EHPA(1:1) and 4-HP:2D2EHPA(1:2) type complexes, while(iii) D2EHPA in TBP/1-octanol demonstrates the maximum distribution ratio with the 4-HP:D2EHPA(1:1) type complex domination. The discussion provides new insights on the mechanism and opens a new way for the intensified extraction of amphoteric organic compounds by using the mixture of multiple extractants in the diluent.

Enhancing ammonia production rates from electrochemical nitrogen reduction by engineering three-phase boundary with phosphorus-activated Cu catalysts

Electrochemical N_(2) reduction reaction(eNRR) over Cu-based catalysts suffers from an intrinsically low activity of Cu for activation of stable N_(2) molecules and the limited supply of N_(2) to the catalyst due to its low solubility in aqueous electrolytes.Herein,we propose phosphorus-activated Cu electrocatalysts to generate electron-deficient Cu sites on the catalyst surface to promote the adsorption of N_(2) molecules.The eNRR system is further modified using a gas diffusion electrode(GDE) coated with polytetrafluoroethylene(PTFE) to form an effective three-phase boundary of liquid water-gas N_(2)-solid catalyst to facilitate easy access of N_(2) to the catalytic sites.As a result,the new catalyst in the flow-type cell records a Faradaic efficiency of 13.15% and an NH_(3) production rate of 7.69 μg h^(-1) cm^(-2) at-0.2 V_(RHE),which represent 3.56 and 59.2 times increases from those obtained with a pristine Cu electrode in a typical electrolytic cell.This work represents a successful demonstration of dual modification strategies;catalyst modification and N_(2) supplying system engineering,and the results would provide a useful platform for further developments of electrocatalysts and reaction systems.

Green Synthesis and Luminescent Properties of Mn4+ Doped Red Phosphor for WLED

Herein, the K3MoO2F5.2H2O:Mn4+ phosphor was synthesized by using low toxic NH4HF2 and HCl instead of highly toxic HF. The K3MoO2F5.2H2O:Mn4+ phosphor has a blocky structure and exhibits sharp red emission at the range of 580 to 670 nm excited by the blue light at 470 nm. The fabricated WLED device at 20 mA current has low correlation color temperature (CCT = 3608 K) and high color rendering index (Ra = 90.1), which can significantly improve the electroluminescence performance of cold WLED devices. These results indicate that the K3MoO2F5.2H2O:Mn4+ phosphor has potential application value in warm WLED excited by blue light chip. .

BaCaLa_(8)(SiO_(4))_(6)O_(2)∶Eu^(3+)荧光粉的发光性能和光温传感特性研究

合成了BaCaLa_(8)(SiO_(4))_(6)O_(2)∶Eu^(3+)荧光粉,根据其光致发光激发光谱和发射光谱研究光致发光性能。BaCaLa_(8)(SiO_(4))_(6)O_(2)晶格中,Eu^(3+)离子可能占据两种格位,能够被近紫外光或蓝光有效激发。392 nm近紫外光激发下,制备荧光粉呈现红光发射,峰值波长位于612 nm,表明其在固态照明领域具有应用价值。测试了最佳掺杂浓度下荧光粉的热性能。423 K时样品发光强度为298 K下的62.0%,呈现出对温度敏感特性,相对温度传感灵敏度最大值为1.163%K^(-1),揭示了其在光学温度传感领域的应用潜力。

红色荧光粉CaAlSiN_(3)∶Eu^(2+)的结构精修和性能

运用高温固相法合成系列掺铕(Eu)的氮化物荧光粉Ca1-xAlSiN_(3)∶xEu^(2+),对所得到的最佳样品Ca_(0.99)AlSiN_(3)∶0.01Eu^(2+)进行系列表征和结构精修.结果表明,样品Ca_(0.99)AlSiN_(3)∶0.01Eu^(2+)的晶粒尺寸为10μm左右,各元素分布均匀,其精修图与实测XRD谱图基本吻合,属于正交晶系结构.该样品的色坐标为(0.645 1, 0.354 5),落在红光区域,色纯度高达100%,相关色温为2 449 K,属于低色温.该荧光粉在298~473 K范围内表现出良好的热稳定性,活化能为0.26 eV,具有广阔的市场前景.

磷矿粉球团冷固结成型试验及机械性能的影响因素

针对磷矿粉矿无法直接入炉冶炼黄磷的问题,本文采用磷矿粉冷固结成型方法来制备磷矿粉球团,研究黏结剂用量、水分添加量、成型压力和烧结温度对磷矿粉球团落下强度和抗压强度的影响。研究结果表明:球团的抗压强度和落下强度随黏结剂用量的增加而升高,随成型压力的增加呈现先升高后降低,随水分质量分数的增加呈现先升高后降低,抗压强度随着烧结温度的升高而升高;在黏结剂用量为0.4%、水分质量分数为8%、成型压力为11 MPa条件下制备的磷矿粉生球团的抗压强度可达148.46 N/P,落下强度达46次/(0.5 m);在1200℃下烧结2 h后,磷矿球团的抗压强度可达966 N/P,且经跌落破碎后无粉化现象。本文旨在弥补富磷矿块矿资源的不足,并为进一步促进磷矿粉矿在黄磷生产中的应用提供参考。

我国甜菜土壤有效磷丰缺指标与适宜施磷量研究

【目的】甜菜是重要的糖料作物,土壤磷素供应和磷肥施用影响甜菜的产量和品质。为此,我们开展甜菜土壤有效磷丰缺指标与适宜施磷量研究。【方法】采用“零散实验数据整合法”建立我国甜菜相对产量与土壤有效磷含量回归方程。以“甜菜”“施肥”“磷”为主题词,在中国知网检索到相关论文44篇,剔除低质量试验数据后,共获得104组包含不施磷和施磷处理甜菜产量数据,及对应的土壤有效磷含量数据,建立不施磷甜菜相对产量与土壤有效磷含量之间的回归方程。参考“土壤养分丰缺分级改良方案”将土壤有效磷含量分为7级,将各节点不施磷甜菜相对产量带入建立的回归方程,计算出每个节点的土壤有效磷含量,作为甜菜土壤有效磷分级指标。采用“养分平衡—地力差减法新公式”,依据目标产量和磷肥利用率,计算了不同丰缺等级土壤的甜菜适宜施磷量。【结果】我国甜菜缺磷处理相对产量与土壤有效磷含量回归方程为:y=14.169 Ln(x)+46.679(R~2=0.3242,n=104,P<0.01)。我国甜菜土壤有效磷由高到低分为7个等级,对应的有效磷含量依次为≥44、22~44、11~22、6~11、3~6、1.5~3和<1.5 mg/kg。当甜菜目标产量为30~90 t/hm^(2)、磷肥利用率为15%~35%时,有效磷第1~7级土壤的适宜施磷量分别为0、13~90、26~180、39~270、51~360、64~450、77~540 kg/hm^(2)。【结论】鉴于收集采用的数据样本量大且来源于高质量试验,本研究建立的我国甜菜缺磷处理相对产量与土壤有效磷含量之间的回归方程具有很好的可信度,依据该方程确定了土壤有效磷丰缺指标,进而若干目标产量和磷肥利用率下不同丰缺等级土壤的甜菜适宜施磷量得以推荐。

工作场所空气中钼酸铵分光光度法测定磷酸的改进研究

为建立可行的钼酸铵分光光度法检测工作场所空气中的磷酸的方法,将样品经震荡处理,酸化、还原反应60 min后(混合酸溶液:15.0 g/L钼酸铵+4.0 mol/L硫酸;还原剂:15.0 g/L硫酸肼)进行分光光度分析,发现目标物的检测在1.74~100μg范围内线性良好(线性相关系数r=0.9998),磷酸最低检出浓度为0.02 mg/m^(3)(以采集75 L空气样品计),不同浓度样品的平均加标回收率在99.4%~102.4%之间。这表明改进后的方法灵敏度高、准确度高,适用实际样品的检测。

共掺La^(3+)和过量Sr^(2+)对荧光粉Sr_(1.96)Eu_(0.04)SiO_4发光性质的影响

采用高温固相法制备了荧光粉Sr_(1.96-x)Eu_(0.04)SiO_(4)∶xLa^(3+)(x=0、0.01、0.02、0.03、0.04、0.05)和Sr_(1.94+y)Eu_(0.04)La_(0.02)SiO_(4)∶ySr^(2+)(y=0、0.05、0.10、0.20、0.30).使用X射线粉末衍射仪、荧光分光光度计表征了荧光粉的物质结构和发光性质.结果表明:荧光粉的XRD均与Sr_(2)SiO_(4)标准卡片PDF 39-1256对应,没有杂质相产生.荧光粉Sr_(1.96)Eu_(0.04)SiO_(4)中掺入La^(3+)能增强其发光强度,且发射峰的位置不变.当La^(3+)掺杂量为2%(摩尔分数)时,荧光粉Sr_(1.94)Eu_(0.04)La_(0.02)SiO_(4)的发光强度最强.在Sr_(1.94)Eu_(0.04)La_(0.02)SiO_(4)中掺入一系列过量浓度Sr^(2+),能增强其发光强度,且不改变发射峰的位置和形状.当Sr^(2+)过量10%时,荧光粉的发光强度最强.荧光粉的宽带发射光谱可以拟合为2个独立的发射峰,对应Eu^(2+)的4f~65d~1→4f~7跃迁,2个发射峰的强度随着通气量的增大有规律变化,使得荧光粉的发光颜色从绿光区过渡到黄光区.