基于铝离子敏化牡丹提取物(丹皮酚)荧光法定量分析Al^(3+)的研究

饮用水是人体铝元素的主要摄入来源.微量铝离子可对人体健康造成很大危害.WHO(世界卫生组织)规定,饮用水中允许的最高铝离子浓度为200μg/L(7.41μmol/L).因此铝离子的高灵敏检测显得尤为重要.目前常用的铝离子检测方法存在操作麻烦,周期长等缺点,所以构建一种简便、快捷的铝离子检测方法尤为重要.丹皮酚是一种提取自牡丹皮的有机化合物,其与Al^(3+)结合后荧光会数倍增强.基于丹皮酚与铝离子结合产生荧光增强现象,建立了一种检测铝离子的荧光分析方法.此方法只需常温反应5 min,并且检测限为0.5μmol/L(线性范围:0~100μmol/L),构建的检测方法具有快速、低成本、简单、高特异性和高灵敏等优点,有很好的应用前景.

基于新绿原酸的紫外吸收和电化学双信号响应的Al^(3+)分析新方法研究

目的 利用新绿原酸(NCGA)与Al^(3+)的相互作用,建立一种基于NCGA的紫外吸收和电化学双信号响应的Al^(3+)分析新方法。方法 基于NCGA与单壁碳纳米管(CNTs)之间的π-π堆积作用,构建了NCGA/CNTs/GC电极。利用差分脉冲(DPV)技术和修饰电极在+0.23 V的氧化电流的下降对Al^(3+)进行定量分析。基于NCGA对Al^(3+)在325 nm处的吸收降低同时伴随365 nm新峰生成的紫外光谱响应,并且在277和340 nm处出现等吸收点,利用365 nm和325nm处的吸光度值之比(A_(365)/A_(325))对Al^(3+)进行定量分析。结果 基于NCGA的分析方法对Al^(3+)的紫外吸收在0.1~100μmol·L^(-1)呈现出良好的线性关系,检测限为0.034μmol·L^(-1);基于NCGA的修饰电极对Al^(3+)的电流响应在0.01~0.1,0.1~10和10~100μmol·L^(-1)呈现良好的线性关系,检测限为0.45 nmol·L^(-1)。生理浓度的其他金属离子和生理活性物质对两种信号测定方法均无明显干扰。在NCGA的紫外分析方法和电化学分析方法下,大鼠血清的加标回收率分别为97.4%~101%(n=3)和98.5%~99.4%(n=3)。结论 本方法具有良好的线性、选择性和准确度,并被成功用于大鼠中Al^(3+)的准确定量。该方法有望应用于Al^(3+)相关的生理和病理事件研究。

A ratiometric fluorescent probe for hypoxanthine detection in aquatic products based on the enzyme mimics and fluorescence of cobalt-doped carbon nitride

A ratiometric fluorescent probe for hypoxanthine(Hx)detection was established based on the mimic enzyme and fluorescence characteristics of cobalt-doped graphite-phase carbon nitride(Co doped g-C_(3)N_(4)).In addition to emitting strong fluorescence,the peroxidase activity of Co doped g-C_(3)N_(4)can catalyze the reaction of O-phenylenediamine and H_(2)O_(2)to produce diallyl phthalate which can emit yellow fluorescence at 570 nm.Through the decomposition of Hx by xanthine oxidase,Hx can be indirectly detected by the generating hydrogen peroxide based on the measurement of fluorescent ratio I(F_(570)/F_(370)).The linear range was 1.7-272.2 mg/kg(R^(2)=0.997),and the detection limit was 1.52 mg/kg(3σ/K,n=9).The established method was applied to Hx detection in bass,grass carp,and shrimp,and the data were verified by HPLC.The result shows that the established probe is sensitive,accurate,and reliable,and can be used for Hx detection in aquatic products.

Oxygen vacancy defects engineering on Cu-doped Co_(3)O_(4) for promoting effective COS hydrolysis

The activation of H_(2)O is a key step of the COS hydrolysis,which may be tuned by oxygen vacancy defects in the catalysts.Herein,we have introduced Cu into Co_(3)O_(4) to regulate the oxygen vacancy defect content of the catalysts.In situ DRIFTS and XPS spectra reveal that COS and H_(2)O are adsorbed and activated by oxygen vacancy.The 10 at%Cu doped Co_(3)O_(4) sample(10Cu-Co_(3)O_(4))exhibits the optimal activity,100%of COS conversion at 70℃.The improved oxygen vacancies of CueCo_(3)O_(4) accelerate the activation of H_(2)O to form active -OH.COS binds with hydroxyl to form the intermediate HSCO^(-)_(2),and then the activated-OH on the oxygen vacancy reacts with HSCO^(-)_(2) to form HCO^(-)_(3).Meanwhile,the catalyst exhibits high catalytic stability because copper species(Cu+/Cu^(2+))redox cycle mitigate the sulfation of Co_(3)O_(4)(Co^(2+)/Co^(3+)).Our work offers a promising approach for the rational design of cobalt-related catalysts in the highly efficient hydrolysis COS process.

Preparation of Sn-doped Ga_(2)O_(3) thin films and their solar-blind photoelectric detection performance

Sn doping is an effective way to improve the response rate of Ga_(2)O_(3) film based solar-blind detectors. In this paper,Sn-doped Ga_(2)O_(3) films were prepared on a sapphire substrate by radio frequency magnetron sputtering. The films were characterized by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy and ultraviolet visible spectroscopy, and the effect of annealing atmosphere on the properties of films was studied. The Ga_(2)O_(3) films changed from amorphous to β-Ga_(2)O_(3) after annealing at 900 °C. The films were composed of micro crystalline particles with a diameter of about 5–20 nm.The β-Ga_(2)O_(3) had high transmittance for wavelengths above 300 nm, and obvious absorption for solar-blind signals at 200–280 nm.The metal semiconductor metal type solar-blind detectors were prepared. The detector based on Sn-doped β-Ga_(2)O_(3) thin film annealed in N_2 has the best response performance to 254 nm light. The photo-current is 10 μA at 20 V, the dark-current is 5.76 pA,the photo dark current ratio is 1.7 × 10~6, the response rate is 12.47 A/W, the external quantum efficiency is 6.09 × 10~3%, the specific detection rate is 2.61 × 10~(12) Jones, the response time and recovery time are 378 and 90 ms, respectively.

Al^(3+)离子掺杂δ-MnO_(2)的制备和电化学性能

采用水热法合成了不同比例Al^(3+)离子掺杂的δ-MnO_(2)纳米粉体.通过X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、 X射线光电子能谱(XPS)、循环伏安(CV)曲线、电化学阻抗谱(EIS)和恒电流充放电(GCD)曲线等手段对材料的结构和电化学性能进行了表征.结果表明, Al^(3+)离子进入δ-MnO_(2)的晶格替代部分Mn^(3+)和Mn^(4+)离子,使得δ-MnO_(2)电极的性能明显提升.当反应物中Al^(3+)/Mn^(2+)摩尔比为0.45时,所得样品(A0.45M)的性能最好;其在1 A/g电流密度下的比电容为207.61 F/g,是纯相δ-MnO_(2)(A0M)的2.4倍;其在10 A/g电流密度下循环10000次后的比电容为100.81 F/g,容量保持率为81.33%.

Al^(3+)掺杂对Ca_(3)(Zr,Ti)Si_(2)O_(9):Bi^(3+)蓝色荧光粉发光性能的影响

文章通过高温固相法成功制备出了Ca_(3)(Zr,Ti)Si_(2)O_(9):Bi^(3+),Al^(3+)系列荧光粉,其发射峰位于420 nm,对应Bi^(3+)离子的6s→6p跃迁。采用Al3+离子替代的实验策略,优化了荧光粉的发光性能。发现Al3+离子的掺入使晶体颗粒分布均匀,荧光粉的发射强度增强,量子效率有效提高、荧光寿命减小。通过高斯拟合分析Bi^(3+)离子在该荧光粉中的格位占据情况发现Bi^(3+)离子占据两种不同Ca^(2+)的格位,而Al^(3+)离子的掺入,减小Bi3+离子发光中心之间的临界距离,以及促进Bi^(3+)离子格位-格位之间的能量转移,导致荧光粉的临界浓度减小。通过色坐标计算表明荧光粉的色纯度也有效提高。研究表明,阳离子替代的实验策略能够成功优化荧光粉的发光性能,在促进植物光合作用的LED照明器件中具有潜在应用价值。

CuO掺杂C_(3)N对C_(5)F_(10)O分解组分吸附性能的第一性原理研究

全氟五碳酮(C_(5)F_(10)O)作为可替代SF_(6)的新型环保绝缘气体已被投入到实际应用中.当绝缘设备内部发生局部放电等故障时,C_(5)F_(10)O会分解产生弱绝缘性的CF_(4)、C_(2)F_(6)以及剧毒的CF_(2)O、HF等有害组分,为保证绝缘设备的安全运行,需有选择地通过吸附去除这些分解组分.新型类石墨烯C_(3)N材料在气体吸附领域具有良好的应用前景,文中基于第一性原理计算了CuO分子掺杂C_(3)N对主要分解组分CF_(4)、C_(2)F_(6)及剧毒产物CF_(2)O、HF的吸附过程,计算并分析了各分解组分吸附时的吸附能、态密度、电荷转移量、差分电荷密度以及不同环境温度下的恢复时间.结果表明,CuO-C_(3)N对HF表现出良好的吸附性,CF_(2)O次之,但其无法吸附CF_(4)与C_(2)F_(6),因此CuO-C_(3)N可以作为一种高性能的气体吸附剂对C_(5)F_(10)O绝缘设备内的剧毒分解组分HF进行吸附去除.

Al^(3+)对污泥自热高温微氧消化产酸及有机物释放的影响

为开发利用剩余污泥消化液中的有机物,向污泥自热高温微氧消化(ATMAD)体系投加不同量的AlCl_(3)·6H_(2)O,研究Al^(3+)对该体系内有机物、挥发性脂肪酸(VFA)及氨氮、磷酸盐释放的影响.结果表明,消化体系内存在的Al^(3+)抑制了有机物的分解转化,改变了污泥消化液中有机组分的含量与构成.对照组中VFA的最大产量是Al^(3+)浓度为1.0g/L的实验组VFA产量的6.9倍.消化结束后Al^(3+)浓度为1.0g/L的体系内NH_(4)^(+)-N浓度为502.06mg/L,而对照组中NH_(4)^(+)-N浓度仅为334.41mg/L.Al^(3+)也降低了体系内微生物活性.消化体系中存在的Al^(3+)不利于活性污泥ATMAD体系的产酸与稳定化,在污泥ATMAD体系中应避免引入过多的Al^(3+),以保证消化体系能够充分产酸,释放有机物,为污水处理生物脱氮提供优质碳源.

缺陷MOF-74的合成以及其对Al^(3+)和Sn^(2+)荧光传感能力的研究

在发光金属有机骨架中引入适度缺陷可以调节材料的荧光性能,增强其对分析物的荧光检测能力。本文以三乙胺作为调节剂,通过配位调制的方法得到了缺陷金属有机骨架MOF-74-TEA,借助XRD、IR和SEM等表征手段对结构和形貌进行了详细表征,用荧光光谱法研究了其对Al^(3+)和Sn^(2+)的识别能力。与无缺陷MOF-74-1相比,MOF-74-TEA提高了对Al^(3+)和Sn^(2+)的检测灵敏度,并且提高了其对Al^(3+)检测的线性范围。其原因可能是缺陷的引入增强了分析物在材料中的扩散和传质,材料活性作用位点的增多使其与金属离子作用力更强,配体-金属电荷转移效率更高。

Al^(3+)改性骨胶的性能及其胶接工艺

用NaOH对骨胶进行降解,然后用Al^(3+)对其进行配位改性,制得室温下呈液态的骨胶,探讨了改性机制。对骨胶改性前后的结构和性能进行表征和测试,并优选出改性骨胶压制胶合板的最佳工艺参数。结果表明:Al^(3+)与N、O以配位键结合,形成稳定的五元环结构;骨胶经改性后,胶膜表面更为规整,没有明显缺陷,断裂面整体呈现海藻状结构,热稳定性无明显变化,耐水性明显提高。当热压的温度为110℃,时间为20 min,压力为4 MPa,存放时间为48 h时,胶合板具有相对最大的胶接强度。

Mn^(2+)掺杂对YAG∶Ce^(3+)荧光陶瓷发光性能的影响

过渡族金属Mn^(2+)掺杂的石榴石荧光陶瓷被认为是实现高显色激光照明的候选材料。然而,由于Mn^(2+)在不同配位环境下离子半径的多样性,Mn^(2+)掺杂石榴石陶瓷体系设计方案尚不明确。本文采用真空烧结技术制备得到不同浓度Mn^(2+)掺杂的YAG∶Ce^(3+)荧光陶瓷,并将Mn^(2+)分别设计进入八面体(OC)和十二面体(DO)格位。通过表征样品物相和显微结构、光致发光、荧光寿命、量子效率等,并通过LD激光器激发对荧光陶瓷的发光性能进行研究。实验结果表明,在添加电荷与体积补偿剂SiO_(2)的前提下,相比Mn^(2+)进入十二面体格位,Mn^(2+)进入八面体后石榴石的晶体结构更加稳定。因此,当Mn^(2+)的浓度控制在0.5%^(6)%(at)范围内,OC系列样品的量子效率高于DO系列样品。此外,OC系列样品的PL谱中位于588 nm和725 nm处的发射峰分别对应于Mn^(2+)占据八面体和十二面体格位的^(4)T_(1)→^(6)A_(1)电子跃迁,而DO系列样品中位于572 nm处的发射峰则源于Mn^(2+)占据扭曲的十二面体格位产生的电子跃迁。得益于Ce^(3+)→Mn^(2+)间高效的能量传递,将浓度为6%(at)的Mn^(2+)设计进入YAG∶Ce^(3+)中八面体格位制得荧光陶瓷,封装得到的激光白光光源的显色指数为70.8,相对色温为5117 K。本文对于Mn^(2+)掺杂的石榴石发光材料的开发研究是有力补充,也为提升YAG∶Ce^(3+)荧光陶瓷光谱中的红光成分,进而提高医疗、显示等领域的激光光源的显色性能提供借鉴。

Pr掺杂Sm_(0.5)Sr_(0.5)CoO_(3)阴极的性能研究

固体氧化物燃料电池(SOFC)因能量转换效率高,绿色无污染而备受关注。研究发现,钙钛矿结构的Sm_(0.5)Sr_(0.5)CoO_(3-δ)(SSC)是电子-离子混合导体,具有良好的氧还原活性,以及电导率高、极化电阻低等优点。为了探究镧系元素Pr掺杂对SSC阴极性能的影响,采用溶胶-凝胶法制备Pr_(x)Sm_(0.5-x)Sr_(0.5)CoO_(3)(x=0.1,0.2,0.3,0.4,0.5)阴极粉体,对其进行一系列表征和电化学性能测试。电化学阻抗谱(EIS)测试表明,当Pr掺杂量为0.3时,PSSC-30阴极在550~750℃范围内的极化电阻均小于其他掺杂量;在700℃时,全电池的功率密度达到最大,为311.06mW/cm^(2)。

Preparation and Characterization of Fe^(3+)-doped Nanometer TiO_2 Photocatalysts

Fe^3＋ -doped nanometer TiO2 photocatalysts were prepared by sol-gel technique. TiO2 powders with different Fe^3＋ / Ti^4 ＋ molar ratios ranging from 0. 05% to 25% were synthesized by calcinating the gels in the temperature range of 200-600 ℃ . The effects of the content of iron ions and calcination temperature on the physical properties of the powders and their photocatalytic activities were examined by the photodecorapositon of methyl orange in sunlight. The results show that Fe dopant can decrease the temperature of nanatase-ratile transformation. The ideal photocatalytic property was achieved when the sample with an Fe^3＋ / Ti^4＋ ratio of 20 at% was calcined at about 300 ℃ for an hour, which is superior to that of commercial Degussa P-25. The optimum microstructure of the Fe-doped TiO2 for a high photocatalytic activity in sunlight is consisted of nanatase and ratile.

Al掺杂Fe_(2)(MoO_(4))_(3)的热致变色性能研究

通过溶胶凝胶法制备了单斜Fe_(2)(MoO_(4))_(3)到单斜Al_(2)(MoO_(4))_(3)固溶体系列的Fe_(2-x)Al_(x)(MoO_(4))_(3)(x=0,0.2,0.4,0.6,0.8,1.0,1.2,1.4,1.6,1.8,2.0)粉末样品。通过X射线衍射发现所有样品都具有相同的单斜相结构,没有发生相分离,成功做到不同比例下的Fe_(2-x)Al_(x)(MoO_(4))_(3)共存。单斜Fe_(2)(MoO_(4))_(3)的晶胞体积随铝含量增加而减小,这与Al^(3+)取代Fe^(3+)的进入有关。在600℃下烧制的x=1.6的组合物表现出最好的可逆热致变色性能。基于电荷转移机理的无机可逆热致变色材料具有随温度连续变色的特性,本研究将对钼酸盐基质中的发色团离子之间相互作用的理论机理进行解释,进一步提升新型热致变色材料的可控调节制备及应用。

Structure and Luminescence Properties of Eu^(3+) Doped SiO_2 Glass Synthesized by Sol-Gel Process

Under different annealing temperatures, Eu 3+ doped SiO 2 gel and glass were prepared by sol gel method, and the structure and luminescent properties were studied with excitation spectra, emission spectra, IR and DTA TG. The results show that the fluorescent intensity tends to get stable when concentration of Eu 3+ doped is above 1 86 % (mass fraction) most water absorbed by the gel was removed at 300 ℃, and that the emission spectrum of Eu 3+ , with peaks at 614, 588, 577 nm, is due to 5D 0→ 7F 2, 5D 0→ 7F 1, 5D 0→ 7F 0 transitions, and the excitation peaks at 318, 362, 380, 393, 412 and 462 nm were observed. These results illustrate that the temperature range of 300～500 ℃ is critical for the structure conversion from gel to glass, and the fluorescence is strongly quenched by water.

Bi_(2)(SnO_(3))3掺杂(Ba,Sr)TiO_(3)介电陶瓷介电性能的研究

通过传统固相法制备Bi_(2)(SnO_(3))_(3)(BSO)掺杂(Ba_(0.79)Sr_(0.21))TiO_(3)((Ba,Sr)TiO_(3),BST)陶瓷。采用XRD、SEM等研究了Bi_(2)(SnO_(3))_(3)(BSO)掺杂对BST陶瓷的物相和微观结构及介电的性能影响。实验结果表明:随着BSO掺杂量增加,BST基介电陶瓷的介电常数开始增大而后减小然后再增大随后再减小,陶瓷的介质损耗首先增大然后减小。当掺杂BSO的量是2 wt%的时候,BST基介电陶瓷具有较好的介电性能:介电常数是5430;介质损耗是0.0145,电容温度变化率是+20.64%,-45.58%。BSO掺杂的BST基介电陶瓷仍为钙钛矿结构。BSO的掺杂起到移峰和压峰的作用。

β-Ga_(2)O_(3)的p型掺杂研究进展

β-Ga_(2)O_(3)具有超宽禁带宽度、高击穿场强、较高的巴利加优值等优点使其成为一种新兴半导体材料,在高功率电子器件、气体传感器、日盲紫外探测器等方面有着极大的应用潜力,但p型掺杂难的问题成为了β-Ga_(2)O_(3)发展的巨大障碍。本文首先简要概述了β-Ga_(2)O_(3)的优点,并介绍了其晶体结构和基本性质。其次,说明了β-Ga_(2)O_(3)的本征缺陷,尤其是氧空位对导电性能的影响。然后,详细讨论了β-Ga_(2)O_(3) p型掺杂的研究现状,包括p型掺杂困难的原因和N掺杂、Mg掺杂、Zn掺杂、其他受主元素掺杂、两种元素共掺杂以及其他方法。最后,总结并对β-Ga_(2)O_(3)未来的发展进行了展望。

MgGa_(2)O_(4)∶Cr^(3+),Al^(3+)近红外发光长余辉纳米粒子的制备及发光性能研究

利用乙二醇辅助共沉淀法,制备了小尺寸近红外发光Al^(3+)共掺杂镓酸镁(MgGa_(2)O_(4))∶0.3%Cr^(3+)(MGO∶0.3%Cr^(3+),Al^(3+))长余辉发光纳米粒子(PLNP),考察了Al^(3+)掺杂对MGO∶0.3%Cr^(3+)晶体结构和光学性质的影响。研究结果表明,Al^(3+)掺杂对MGO∶0.3%Cr^(3+)的晶体结构无影响,但能提高MGO∶0.3%Cr^(3+)的发光强度。当Al^(3+)掺杂量为0.4%(摩尔分数)时,MGO∶0.3%Cr^(3+),0.4%Al^(3+)(Al^(3+)、Cr^(3+)相对于Ga^(3+)的物质的量比,摩尔分数)PLNP发光强度最强,余辉平均发光寿命从46.98s(MGO∶0.3%Cr^(3+))增大至78.75s(MGO∶0.3%Cr^(3+),0.4%Al^(3+)),平均粒径为(6.53±1.79)nm。本研究为制备小尺寸和高发光强度的PLNP提供了一种有效的方法。此外,高发光强度和长余辉寿命的MGO∶0.3%Cr^(3+),0.4%Al^(3+) PLNP为光学传感、成像和治疗等提供了材料支撑。

基于N掺杂Ti_(3)C_(2)MXene量子点的荧光探针用于Hg2+和S2-的传感检测

基于N掺杂Ti_(3)C_(2) MXene量子点(N-Ti_(3)C_(2) MQDs)荧光探针和配位相互作用,构建了一种检测Hg^(2+)和S^(2-)的“开-关-开”型荧光传感新方法.研究发现,制备的N-Ti_(3)C_(2) MQDs发射蓝色荧光(λem=440 nm),荧光量子产率为15.7%.Hg^(2+)与N-Ti_(3)C_(2) MQDs表面的—NH2,—COOH,—OH等官能团产生选择性配位作用,导致N-Ti_(3)C_(2) MQDs体系荧光猝灭.当加入S^(2-)后,由于S^(2-)与Hg^(2+)之间强的结合力,形成HgS沉淀,从而使N-Ti_(3)C_(2) MQDs体系荧光恢复.基于该原理,构建了一种“开-关-开”型荧光传感方法,实现了对Hg^(2+)和S^(2-)的定量检测.N-Ti_(3)C_(2) MQDs探针的荧光强度与Hg^(2+)浓度在0.02~200μmol/L范围内呈良好线性关系,检出限为10 nmol/L(S/N=3);与S^(2-)浓度在0.07~150μmol/L范围内呈良好线性关系,检出限为30 nmol/L(S/N=3).该方法具有成本低、操作简单、灵敏度高和选择性好等特点,并可用于水样中Hg^(2+)和S^(2-)的检测.