Sr2+含量对红色荧光粉Ca0.85-xSrxMoO4:Eu3+0.075,Li+0.075发光性能的影响

采用溶胶-凝胶法制备了Ca0.85-xSrxMoO4:Eu3+0.075,Li+0.075(x=0,0.05,0.1,0.15,0.2,0.3,0.4)系列红色荧光粉.对样品前驱体的热重分析表明:温度升高到540℃后样品质量基本上保持稳定,不再发生失重现象;此外,还对样品的结构和发光性能进行表征,实验结果表明:适量Sr2+取代部分的Ca2+不但没有改变Ca0.85MoO4:Eu3+,Li+的物相结构,而且明显提高了荧光粉Ca0.85MoO4:Eu3+,Li+的相对发光强度,其主要是由于加入少量的Sr2+使晶体发生了畸变,从而导致发光强度的增加.实验结果表明,Sr2+的最佳掺杂量为15%(原子分数).     

Ca掺杂的Ba2Al2Si10N14O4∶Eu2+荧光粉发光性能

通过固相反应制备了系列Ca掺杂的Ba2Al2Si10N14O4∶Eu2+绿色荧光粉,发现当半径较大的Ba被Ca取代后导致了晶格的收缩,通过X射线衍射(XRD)测量和Unitcell软件计算发现Ca的最大掺杂量在20%。Ca掺入Eu0.4Ba1.6Al2Si10N14O4荧光粉后,可有效地提高光转换性能,并使激发光谱发生一定程度的红移和宽化,从而被近紫外宽波段光有效激发,与近紫外LED的发射光谱匹配。同时Ca的掺杂也使发射光谱发生了可控的红移,可以由520 nm的绿光红移至548 nm的黄光区域。进一步发现Eu2+的淬灭浓度随着20%Ca的掺入而降低,这是由于Ca掺入导致的晶格收缩使Eu2+离子间距离减小。最后在CIE色度图中对不同Ca,Eu浓度的荧光粉的色坐标位置进行比较,发现可通过Ca,Eu浓度的变化在很大范围内调制荧光粉的发光性能。     

Ca掺杂的Ba2Al2Si10N14O4:Eu2+荧光粉发光性能

通过固相反应制备了系列Ca掺杂的Ba2Al2Si10M14O4:Eu2+色荧光粉,发现当半径较大的Ba被Ca取代后导致了晶格的收缩,通过X射线衍射(XRD)测量和Unitcell软件计算发现Ca的最大掺杂量在20％.Ca掺人Eu0.4Ba1.6Al2Si10N14O4荧光粉后,可有效地提高光转换性能,并使激发光谱发生一定程度的红移和宽化,从而被近紫外宽波段光有效激发,与近紫外LED的发射光谱匹配.同时Ca的掺杂也使发射光谱发生了可控的红移,可以由520 nm的绿光红移至548 nm的黄光区域.进一步发现Eu2+的淬灭浓度随着20％ Ca的掺入而降低,这是由于Ca掺入导致的晶格收缩使Eu2+离子间距离减小.最后在CIE色度图中对不同Ca,Eu浓度的荧光粉的色坐标位置进行比较,发现可通过Ca,Eu浓度的变化在很大范围内调制荧光粉的发光性能.     

Ca,Sr共掺杂铈氧化物及其在甲烷氧化偶联反应中的应用

采用柠檬酸法制备了Ca,Sr共掺杂的CeO_2催化剂,发现共掺杂催化剂较单掺杂或未掺杂催化剂呈现出更好的催化甲烷氧化偶联(OCM)反应性能.通过表征可知,Ca,Sr共掺杂催化剂的物相为CeO_2和SrCO_3,Ca高度分散或掺杂于CeO_2之中;CeO_2的粒径明显变小;表面呈中等程度碱性;Ce基催化剂上的亲电氧物种数量随着碱土金属的掺杂而增大,亲电氧物种与晶格氧摩尔比(O_2-2+O-2)/O-2的大小顺序(CeSrCaCe SrCeO_2)与C2选择性一致;且SrCO_3相的存在有助于Ce基氧化物催化甲烷氧化偶联反应(OCM)性能的改善.     

Eu3+掺杂双钙钛矿Sr2CaMoO6橙红色荧光粉的结构特征及其发光性能

采用EDTA-柠檬酸联合配位法制备一系列组成的(Sr1-xEux)2CaMoO6橙红色荧光粉。通过X射线衍射、拉曼光谱、扫描电镜及荧光光谱研究不同Eu3+离子掺杂浓度下Sr2CaMoO6∶Eu3+荧光粉的晶体结构、掺杂位置、形貌及其光致发光性能。Rietveld全谱拟合结果表明:掺杂后样品为(Ca/Mo)O6八面体少量倾斜的空间群为P21/n的正交双钙钛矿结构,随着Eu3+离子共掺杂浓度的增加,样品的晶胞体积减小;Eu3+离子取代八面体间隙的Sr2+位置致使双钙钛矿的T2g(1)拉曼振动模发生蓝移;在近紫外区宽而强电荷迁移带和蓝光激发下,该荧光粉分别发射以Eu3+离子5D0-7F1磁偶极跃迁为主的橙光和以5D0-7F2电偶极跃迁为主的红光,组成为(Sr0.98Eu0.02)2CaMoO6的荧光粉具有最强的橙红光发射强度,是一种潜在的适用于近紫外LED芯片的光转换红光材料。     

钨钼酸盐荧光粉基质组成及其退火过程对荧光性能的影响

采用高温固相法合成了一系列Eu3+掺杂的钨钼酸盐红色荧光粉CaxSr0.88-x(WO4)y(MoO4)1-y:0.08Eu3+。对其晶体结构和荧光性能进行了X射线衍射(XRD)、荧光光谱(PL)的表征,研究了不同Sr/Ca和WO4/MoO4比例对荧光粉光谱性能的影响,初步研究了不同退火过程对其发光性能的影响。所合成的Ca0.70Sr0.18(MoO4)0.5(WO4)0.5:0.08Eu3+荧光粉发光强度较好,可以被近紫外光(395 nm)和蓝光(465nm)有效激发,发射峰位于616 nm(Eu3+的5 D0→7 F2跃迁)。     

(Ca,Me)La4Si3O13:Eu3+(Me=Sr,Ba)荧光粉的结构和发光特性

采用高温固相法制备了(Ca,Me)La4Si3O13∶Eu3+(Me=Sr,Ba)系列红色荧光体,考察了Eu3+掺杂浓度和Sr2+,Ba2+置换对荧光体结构和发光特性的影响。Eu3+最佳掺杂浓度为nEu3+∶nLa3+=1∶7,5D0-7F2与5D0-7F1跃迁发射强度比为2.55。Eu3+掺杂使晶胞参数a和c呈线性变小,对c的影响大于a,使a/c比增大。Sr2+和Ba2+分别置换基质中的Ca2+可以形成完全固溶体,晶胞参数随Sr2+或Ba2+的置换量增加呈线性增大,使a/c比减小。各发射峰强度在Sr2+置换量为0.4 mol时出现极大值,但随Ba2+置换量的增加而不断增强,全置换后荧光强度最大。荧光体的色坐标为(0.638 5,0.353 0)。     

Ca、Ba掺杂Sm0.5Sr0.5CoO3作为中低温固体氧化物燃料电池阴极的结构与性能

通过X射线衍射(XRD)、热重、热膨胀、电导率以及电化学交流阻抗等测试技术研究了SmSr1-xAexCo2O6(x=0, 0.2, 0.4, 0.6, 0.8, 1; Ae=Ca, Ba)作为中低温固体氧化物燃料电池(IT-SOFC)阴极的结构与性能. 研究表明, 固相法合成的SmSr0.8Ae0.2Co2O6(Ae=Ca, Sr, Ba; 简写为SSAC)随着Ca、Ba掺杂量的增大晶体结构发生变化. 其中, 空间群为Pnma晶体结构的电极SSAC中, 晶胞参数随着Sr、Ca、Ba的顺序增大; SSAC晶体中的氧空位浓度随着Ca、Sr、Ba的顺序增大, SSAC热膨胀系数与Ae元素关系不大, 氧催化性能随着Ca、Sr、Ba的顺序降低. 由于载流子浓度降低, 使得Ba 掺杂Sm0.5Sr0.5CoO3(SSC)后电极的电导率降低. 由于导电活化能增大, 使得Ca掺杂SSC后电极的电导率也降低.     

Sr/Ca比变化对红色荧光粉Cal-xSrxS:Eu2+的影响

在CO气氛下采用固相反应法合成了发红光的Ca1-xSrxS:Eu2 荧光粉,研究了基质阳离子Sr/Ca比变化对其晶体性质及发光性能的影响.结果表明,随着Sr/Ca比的减少,荧光粉的晶胞参数逐渐降低;同时,由于受电子云膨胀效应和晶体场影响,发射主峰向长波方向移动,红色比逐渐增大,色纯度提高.     

Sr／Ca比变化对红色荧光粉Ca1-xSrxS：Eu^2＋的影响

在CO气氛下采用固相反应法合成了发红光的Ca1-xSrxS:Eu^2 荧光粉，研究了基质阳离子Sr／Ca比变化对其晶体性质及发光性能的影响。结果表明，随着Sr／Ca比的减少，荧光粉的晶胞参数逐渐降低；同时，由于受电子云膨胀效应和晶体场影响，发射主峰向长波方向移动，红色比逐渐增大，色纯度提高。     

MF2-MgF2(M=Ca,Sr,Ba)体系中钐离子的价态及光谱

高温固相反应合成了钐离子激活的MF_2-MgF_2磷光体,考察了合成条件及基质组成对钐离子价态的影响,并讨论了荧光光谱与基质及钐离子价态间的关系.     

Mn2+在铝酸盐中的发光

用金属硝酸盐、稀土氧化物和乙酸锰为原料,用燃烧法合成了Ce³⁺、Tb³⁺、Mn²⁺共激活的铝酸盐绿色荧光粉,在Ce³⁺和Tb³⁺共激活的铝酸盐体系中掺入Mn²⁺后,发射峰中出现锰的特征峰.通过对其结构的分析,对Mn²⁺发光和最佳掺杂量给出了合理的解释.同时研究了不同碱金属和碱土金属离子代替Mg²⁺时,对Mn²⁺发光的影响.     

New SrAl2B2O7:Eu2+, Mn2+ phosphors for white light-emitting diodes

A series of Eu(2+) and Mn(2+) co-doped SrAl(2)B(2)O(7) phosphors were prepared by solid-state reaction method. X-ray powder diffraction (XRD) and photoluminescence excitation and emission were employed to characterize the phosphors. The results show that energy transfers between Eu(2+)and Mn(2+) ions. As the content of Ca(2+) ions in Ca(x)Sr(0.92-x)Al(2)B(2)O(7):Eu(2+)(0.06), Mn(2+)(0.02) phosphors increased, the CIE coordinates decreased and close to the white color standard mandated by the National Television Standard Committee (NTSC). Meanwhile, a white LED (light-emitting diode) was fabricated by combining the Ca(0.5)Sr(0.42)Al(2)B(2)O(7):Eu(2+)(0.06), Mn(2+)(0.02) phosphors with a 370 nm InGaN chip. The color coordinate of the fabricated white LED was also close to the white color standard, indicating that the Ca(0.5)Sr(0.42)Al(2)B(2)O(7):Eu(2+)(0.06), Mn(2+)(0.02) phosphor is a promising single-host phosphor that can be used in white LEDs.     

单一基质白光荧光粉Ca0.955-xAl2Si2O8:0.045Eu2+,xMn2+的晶胞参数变化和光谱特性

利用高温固相反应制备了Ca_(0.955-x)Al_2Si_2O_8∶0.045Eu~(2+),xMn~(2+)(x=0,0.05,0.10,0.15,0.20,0.25,0.30,0.325,0.35,0.375,0.40,0.425)一系列试样,系统研究了Mn~(2+)取代基质中Ca~(2+)进入晶格中对其晶胞参数和光谱特性影响。Mn~(2+)以类质同相替代Ca~(2+)进入晶体晶格中,形成了连续固溶体,试样均为三斜晶系,P空间群。随着Mn~(2+)掺杂量增加,晶胞参数(a,b,c,γ)和晶胞体积V均呈线性递减,且a轴减幅最大,b轴最小,晶面夹角(α,β)呈线性递增。在357 nm激发下,获得的Ca_(0.955-x)Al_2Si_2O_8∶0.045Eu~(2+),xMn~(2+)发射光谱均有Eu~(2+)的4f→5d跃迁产生的433 nm和Mn~(2+)的~4T_1(~4G)→~6A_1(~6S)跃迁产生的567 nm两个宽带谱组成。在荧光粉Ca_(0.955-x)Al_2Si_2O_8∶0.045Eu~(2+),xMn~(2+)中,Eu~(2+)与Mn~(2+)间存在能量传递,Eu~(2+)→Mn~(2+)间能量传递的临界距离R_(Eu-Mn)=0.947 1 nm,Eu~(2+)→Mn~(2+)能量传递过程为电四极-电四极的多极矩相互作用。通过改变Mn~(2+)掺杂量,在紫外芯片的有效激发下,荧光粉的发射光颜色可从蓝光区(0.158 2,0.086 0)逐渐移至近白光区(0.295 3,0.298 9),可获得一种紫外激发适用于白光LED的单一组分白色荧光粉。     

在空气中合成MBPO5:Eu2+和MBPO5:Yb2+(M=Ca,Sr,Ba)荧光体

以含RE₂O₃(RE=Eu, Yb)为起始物, 在空气中成功地合成了MBPO5:RE(²⁺)(M=Ca, Sr, Ba;RE(²⁺)=Eu(²⁺), Yb(²⁺))荧光体, 测定了它们的激发和发射光谱峰位以及发射半高宽.     

Systematic study of compositional and synthetic control of vacancy and magnetic ordering in oxygen-deficient perovskites Ca2Fe(2-x)Mn(x)O(5+y)and CaSrFe(2-x)Mn(x)O(5+y) (x = 1/2, 2/3, and 1; y = 0-1/2)

Ten compounds belonging to the series of oxygen-deficient perovskite oxides Ca(2)Fe(2-x)Mn(x)O(5) and CaSrFe(2-x)Mn(x)O(5+y), where x = 1/2, 2/3, and 1 and y ≈ 0-0.5, were synthesized and investigated with respect to the ordering of oxygen vacancies on both local and long-range length scales and the effect on crystal structure and magnetic properties. For the set with y ≈ 0 the oxygen vacancies always order in the long-range sense to form the brownmillerite structure containing alternating layers of octahedrally and tetrahedrally coordinated cations. However, there is a change in symmetry from Pnma to Icmm upon substitution of Sr for one Ca for all x, indicating local T(d) chain (vacancy) disorder. In the special case of CaSrFeMnO(5) the neutron diffraction peaks broaden, indicating only short-range structural order on a length scale of ~160 ?. This reveals a systematic progression from Ca(2)FeMnO(5) (Pnma, well-ordered tetrahedral chains) to CaSrFeMnO(5) (Icmm, disordered tetrahedral chains, overall short-range order) to Sr(2)FeMnO(5) (Pm3m, destruction of tetrahedral chains in a long-range sense). Systematic changes occur in the magnetic properties as well. While long-range antiferromagnetic order is preserved, the magnetic transition temperature, T(c), decreases for the same x when Sr substitutes for one Ca. A review of the changes in T(c) for the series Ca(2)Fe(2-x)M(x)O(5), taking into account the tetrahedral/octahedral site preferences for the various M(3+) ions, leads to a partial understanding of the origin of magnetic order in these materials in terms of a layered antiferromagnetic model. While in all cases the preferred magnetic moment direction is (010) at low temperatures, there is a cross over for x = 0.5 to (100) with increasing temperature for both the Ca(2)Fe(2-x)Mn(x)O(5) and the CaSrFe(2-x)Mn(x)O(5) series. For the y > 0 phases, while a brownmillerite ordering of oxygen vacancies is preserved for the Ca(2) phases, a disordered Pm3m cubic perovskite structure is always found when Sr is substituted for one Ca. Long-range magnetic order is also lost, giving way to spin glass or cluster-glass-like behavior below ~50 K. For the x = 0.5 phase, neutron pair distribution function (NPDF) studies show a local structure related to brownmillerite ordering of oxygen vacancies. Neutron diffraction data at 3.8 K show a broad magnetic feature, incommensurate with any multiple of the chemical lattice, and with a correlation length (magnetic domain) of 6.7(4) ?.     

(CH3)2NH(CH2)2NH(CH3)2][(UO2)2F2(HPO4)2]: a new organically templated layered uranium phosphate fluoride--synthesis, structure, characterization, and ion-exchange reactions

A new organically templated layered uranium phosphate fluoride, [(CH(3))(2)NH(CH(2))(2)NH(CH(3))(2)][(UO(2))(2)F(2)(HPO(4))(2)] has been synthesized by hydrothermal reaction of UO(3), H(3)PO(4), HF, and (CH(3))(2)NCH(2)CH(2)N(CH(3))(2) at 140 degrees C. [(CH(3))(2)NH(CH(2))(2)NH(CH(3))(2)][(UO(2))(2)F(2)(HPO(4))(2)] has a layered crystal structure consisting of seven-coordinated UO(5)F(2) pentagonal bipyramids and four-coordinated HPO(4) tetrahedra. Each anionic layer containing three-, four-, and six-membered rings is separated by [(CH(3))(2)NH(CH(2))(2)NH(CH(3))(2)](2+) cations. The [(CH(3))(2)NH(CH(2))(2)NH(CH(3))(2)](2+) cations may be readily exchanged with the M(2+) ions (M = Ba, Sr and Ca) in water to give high crystalline AE(UO(2))(2)(PO(4))(2).6H(2)O (AE = Ca, Sr, Ba).     

Growth and Spectral Characterization of Nd3+∶(Sr0.7Ca0.3)3Y(BO3)3 Crystal

A Nd3+ :(Sr0.7Ca0.3)3Y(BO3)3 crystal with dimensions of 17×23 mm3 has been grown by the Czochralski method. The spectroscopic characterization of Nd3+ :(Sr0.7Ca0.3)3Y(BO3)3 crystal was investigated. The polarized absorption cross-sections of Nd3+ :(Sr0.7Ca0.3)3Y(BO3)3 crystal are 2.81×10-20 cm2 with full width at half maximum (FWHM) of 14 nm at 808 nm for σ-polarization and 2.04×10 -20 cm 2 with FWHM of 19 nm at 807 nm for σ-polarization, respectively. The polarized emission cross-sections of Nd3+ :(Sr0.7Ca0.3)3Y(BO3)3 crystal are 12.2×10-20 cm2 at 1062 nm for the π-polarization and 13.6×10-20 cm2 at 1061 nm for the σ-polarization, respectively. After the Ca 2+ ion partly substitutes for Sr2+ ion in the Sr3Y(BO3)3 crystal to form the (Sr0.7Ca0.3)3Y(BO3)3 solid solution, it can improve the quantum efficiency of Nd3+ :(Sr0.7Ca0.3)3Y(BO3)3 crystal. The quantum efficiency is 31.7%. These results may be regarded Nd3+ :(Sr0.7Ca0.3)3Y(BO3)3 crystal as a potential solid-state laser material.     

V2O5/MO-Al2O3（M = Mg，Ca，Sr，Ba）催化剂用于正丁烷催化氧化脱氢反应

采用浸渍法制备了不同V2O5担载量的V2O5/MO-Al2O3(M = Mg, Ca, Sr, Ba)催化剂,钒物种的前驱体为偏钒酸铵.对制备的催化剂进行了一系列表征,并对催化剂上正丁烷选择性氧化脱氢制取丁烯进行了反应研究.表征结果(包括比表面积、X射线衍射、傅里叶红外光谱、氢气程序升温还原和拉曼光谱)显示,不同碱土金属元素掺杂的催化剂显示不同的钒价态信息和催化性能.其中掺杂Ca, Sr, Ba的催化剂,正钒酸盐相很难被还原,因此催化剂的氧化还原循环难以建立,导致以上三种催化剂在正丁烷氧化脱氢反应中活性较低.然而, Mg掺杂的催化剂却显示出较高的催化活性和选择性.实验结果表明：在Mg掺杂的载体上担载5% V2O5的催化剂上600°C时可获得高达30.3%的正丁烷转化率和64.3%的烯烃总选择性.这与V2O5担载量为5%时,在获得高度分散的钒氧化合物物种时可使MgO晶相稳定存在密切相关.