M2+(M=Cu、Cd、Ag、Fe)掺杂氧化锌纳米粉晶的抗菌性能

采用柠檬酸溶胶-凝胶法制备了ZnO及M²⁺掺杂ZnO纳米粉晶(M=Cu、Cd、Ag、Fe),用现代测试技术表征了样品的组成、结构和形貌,以大肠杆菌(Escherichia coli)、金黄色葡萄球菌(Staphylococcus aureus)和白色念珠菌(Candida albicans)为测试菌株,用抑菌圈、最小抑菌浓度和最小杀菌浓度等方法研究了样品在日光照射下的抗菌活性。结果表明,与母体ZnO相比,Cu、Ag、Cd掺杂样品的抗菌性能明显地增强,这可能是由于掺杂金属离子置换Zn²⁺生成了晶格缺陷和电荷缺陷,阻止了光生电子和光生空穴对的复合从而增强了光催化活性和抗菌活性。     

Ag掺杂对n-ZnO纳米棒/p-GaN异质结结构和发光性能的影响

利用简单的水热合成法在p-GaN薄膜上制备了Ag掺杂的一维ZnO纳米棒(ZnO NRs),并且研究了Ag掺杂对于ZnO NRs结构和形貌以及n-ZnO NRs/p-GaN异质结发光特性的影响。结果表明,不同Ag掺杂浓度的ZnO纳米棒截面均呈六边形的棒状结构,且纳米棒的取向垂直于衬底;XRD分析结果表明,随着Ag掺杂浓度的增加,ZnO纳米棒(0002)晶面的峰位向衍射角减小的方向移动,表明Ag+置换了ZnO晶格中的部分Zn2+后使其晶格常数略增加;随着Ag掺杂浓度的增加,ZnO纳米棒近带边发光峰发生一定的红移并且强度逐渐减弱,黄带发光峰逐渐增强,n-ZnO NRs/p-GaN异质结具有更好的传输效率。     

助剂对于Cu/ZnO催化剂结构特征及催化草酸二甲酯加氢合成乙二醇反应性能的影响

采用共沉淀法合成了掺杂不同助剂的Cu-M/ZnO (Cu:ZnO 物质的量比=5∶4,M=Zr⁴⁺、Al³⁺、Mg²⁺，助剂含量为4.0%)用于催化草酸二甲酯(Dimethyl oxalate, DMO)选择加氢反应催化剂。结果表明，微量掺杂Al³⁺、Mg²⁺助剂嵌入于ZnO 晶相，Zr⁴⁺助剂嵌入Cu晶相均能显著促进Cu/ZnO 催化剂中铜分散；其中，Mg²⁺助剂能够有效增强Cu、ZnO 物相间相互作用，Zr⁴⁺助剂能够有效增强Cu、ZrO₂物相间相互作用。催化DMO加氢选择加氢反应，Cu/ZnO 催化剂乙二醇(Ethylene glycol,EG)收率仅为75.0%,Cu-Al/ZnO 、Cu-Zr/ZnO 和Cu-Mg/ZnO 催化剂的EG收率分别为90.0%、85.0%、95.0%。相比Cu/ZnO 和Cu-Al/ZnO 催化剂催化DMO选择加氢反应易于失活，Cu-Zr/ZnO 和C...     

Cu2+掺杂CdS纳米晶的制备与表征

以巯基乙酸为稳定剂,采用水相合成法制备了Cu2+掺杂的CdS纳米晶. 分别用电感耦合等离子体发射光谱仪、原子力显微镜测试技术对样品的化学成分及形状进行分析表征,研究了掺杂CdS纳米晶的荧光激发与发射光谱. 实验结果表明,在样品制备过程的溶液中回流2 h后,组成为Cd0.99Cu0.01S的样品形状有棒状和粒状2种,Cu2+的掺入使得CdS纳米晶的荧光发射光谱红移,没有掺杂的样品在回流前的最大发射波长在520 nm处,而组成为Cd0.99Cu0.01S和Cd0.98Cu0.02S的样品在回流前的最大发射波长分别为595和610 nm,通过改变Cu与Cd摩尔比可调控CdS纳米晶的发射波长范围.     

Ag掺杂对n-ZnO纳米棒/p-GaN异质结结构和发光性能的影响

利用简单的水热合成法在p-GaN薄膜上制备了Ag掺杂的一维ZnO纳米棒（ZnO NRs）,并且研究了Ag掺杂对于ZnO NRs结构和形貌以及n-ZnO NRs/p-GaN异质结发光特性的影响。结果表明,不同Ag掺杂浓度的ZnO纳米棒截面均呈六边形的棒状结构,且纳米棒的取向垂直于衬底;XRD分析结果表明,随着Ag掺杂浓度的增加,ZnO纳米棒（0002）晶面的峰位向衍射角减小的方向移动,表明Ag⁺置换了ZnO晶格中的部分Zn²⁺后使其晶格常数略增加;随着Ag掺杂浓度的增加,ZnO纳米棒近带边发光峰发生一定的红移并且强度逐渐减弱,黄带发光峰逐渐增强,n-ZnO NRs/p-GaN异质结具有更好的传输效率。     

SbxZn1-xO1+x/2及其壳聚糖复配物的制备和抗菌性能

采用溶胶-凝胶法制备了SbxZn1-xO1+x/2及其壳聚糖的复配物,通过X-射线衍射仪(XRD)、傅里叶变换红外光谱仪(FTIR)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)等表征了样品的物相结构、组成和微观形貌。以大肠杆菌、白色念珠菌和金黄色葡萄球菌为测试菌种,研究了样品的抗菌性能。结果表明,SbxZn1-xO1+x/2的抗菌活性优于纯ZnO,其中x=0.05的样品活性最好;复配物的抗菌活性明显优于单一组分,当Sb0.05Zn0.95O1.025和壳聚糖质量比mSZ/mCS=2时,样品抗菌性能最佳。     

Cu掺杂TiO_2作为SERS基底的研究

本文采用溶胶-水热法制备了TiO2及Cu掺杂的TiO2纳米粒子作为表面增强拉曼光谱(SERS)活性基底,观察到当4-巯基苯甲酸吸附在3%Cu掺杂的TiO2表面上时,其SERS信号得到了最大程度的增强.Cu离子掺杂进TiO2晶格时会使TiO2表面的缺陷浓度(表面态)得到增加,一定量的缺陷浓度对TiO2-to-Molecule的电荷转移机理起到促进作用,进一步证明了化学增强机理在SERS现象的贡献.     

Y-Cu共掺杂ZnO电子结构与光学性质的第一性原理计算

采用基于密度泛函理论(DFT)的第一性原理平面波赝势法研究了本征ZnO、Y和Cu单掺杂ZnO、Y-Cu共掺杂ZnO的电子结构和光学性质. 计算结果表明, 在本文的掺杂浓度下, Y和Cu单掺杂可以提高ZnO的载流子浓度, 从而改善ZnO的导电性, Y-Cu共掺时ZnO半导体进入简并状态, 呈现金属性. Y 掺杂ZnO可以提高体系在紫外区域的吸收, 而Cu掺杂ZnO在可见光和近紫外区域发生吸收增强现象, 其中由于Y离子和Cu离子之间的协同效应, Y-Cu共掺杂ZnO时体系对可见光和近紫外区域的光子能量吸收大幅增加, 因此Y-Cu共掺杂ZnO可以用于制作光电感应器件.     

多元金属掺杂改性ZnO/ZSM-5紫外光降解罗丹明B印染废水研究

运用溶胶-凝胶法将纳米ZnO负载于ZSM-5制光催化剂,用Ag、Fe、Cu掺杂改性ZnO/ZSM-5光催化性能并探究光催化剂ZnO/ZSM-5降解罗丹明B(RhB)模拟印染废水性能。以SEM和XRD分析手段对材料进行表征;探究溶液pH、底物初始浓度、光催化剂的用量及光强等因素对ZnO/ZSM-5降解RhB效果的影响。结果表明:ZnO/ZSM-5降解RhB印染废水最佳条件:ZnO/ZSM-5用量0.1 g·L~(-1)、初始浓度5 mg·L~(-1)、pH为7的RhB溶液、在紫外光源20 W的条件下降解RhB速率高达98.8%;Ag、Fe、Cu掺杂量分别:5%Ag-ZnO/ZSM-5、3%Fe-ZnO/ZSM-5、0.01%Cu-ZnO/ZSM-5时RhB的降解率分别高达97.52%、90.07%、87.12%;Ag、Fe、Cu共同掺杂的3%Fe-0.1%Cu-5%Ag-ZnO/ZSM-5催化效果优于单种金属元素掺杂改性材料。     

水热合成Fe3+掺杂ZnO复合材料及其光催化活性

以Zn(Ac)2·2H2O、Fe(NO3)3·9H2O和NaOH为原料,采用水热法合成了Fe3+掺杂ZnO复合材料. 并用X射线衍射和扫描电子显微镜测试技术对合成样品的结构和形貌进行了表征. 结果表明,Fe3+掺杂ZnO合成产物为直棒状,直径为500 nm,长度为3 μm左右. 样品的紫外可见漫反射分析结果表明,在300～500 nm紫外可见光区域均有强的吸收. Fe3+掺杂ZnO作为光催化剂降解有机染料性能优于纯ZnO材料.     

Gd2O3:Yb3+,Nd3+,Tm3+/SiO2/Ag纳米复合材料的合成及上转换发光性质

通过多步骤的化学法合成了Gd_2O_3:Yb~(3+),Nd~(3+),Tm~(3+)/SiO_2/Ag纳米复合材料。利用XRD,TEM,EDS,XPS,CLSM等方法对样品进行表征。实验结果表明,具有低声子能、稳定的化学性质的Gd2O3作为上转换发光的基质,当掺杂的敏化剂Nd3+离子浓度为1.0%(n/n),激活剂离子Tm3+浓度为0.5%(n/n)时,上转换发光强度达到最大值。此外,表面吸附的Ag纳米颗粒,由于表面等离激元共振耦合作用,使得上转换发光蓝光波段的强度增强1.70倍。     

CaWO_4∶xEu~(3+),ySm~(3+),zLi~+红色荧光粉的制备及光学性能

采用微波固相法制备了CaWO_4∶xEu~(3+),ySm~(3+),zLi~+红色荧光粉。测量样品的XRD图、激发谱、发射谱及发光衰减曲线,研究并分析了Eu~(3+)、Sm~(3+)、Li~+的掺杂浓度,对样品微结构、光致发光特性、能量传递及能级寿命的影响。结果表明,Eu~(3+)、Sm~(3+)、Li~+掺杂并未引起合成粉体改变晶相,仍为CaWO_4单一四方晶系结构。Eu~(3+)、Sm~(3+)共掺样品中,Sm~(3+)掺杂为3%时,Sm~(3+)对Eu~(3+)的能量传递最有效。Li~+掺杂起到了助熔剂和敏化剂的作用,使样品发光更强。在394 nm激发下,与CaWO_4∶3%Eu~(3+)样品比较,3%Eu~(3+)、3%Sm~(3+)共掺CaWO_4及3%Eu~(3+)、3%Sm~(3+)、1%Li~+共掺CaWO_4样品的发光分别增强2倍及2.4倍。同一激发波长下,单掺Eu~(3+)样品寿命最短,Sm~(3+)、Eu~(3+)共掺样品随Sm~(3+)浓度增加,寿命先减小后增加,且掺杂了Li~+的样品比不掺Li~+的样品~5D_0能级寿命有所增加。     

Thermodynamic exploitation of the liquidus curves in the MIPO3–Pb(PO3)2, MIPO3–Cu(PO3)2 and MIPO3–Ce(PO3)3 systems (M I=Li, Na, K, Rb, Cs, Ag, Tl)

The thermodynamic exploitation of the solid–liquid equilibria in the M^IPO₃–Pb(PO₃)₂, M^IPO₃–Cu(PO₃)₂ and M^IPO₃–Ce(PO₃)₃ systems (with M ^I=Li, Na, K, Rb, Cs, Ag, Tl) is carried out using a semi-empirical equation of the liquidus curves already used with success for similar binary systems. The enthalpy of fusion is calculated for each pure polyphosphate on the assumption that the liquid solution is ideal and only formed by M^IPO₃ and M(PO₃)_q entities (q=2 for Pb and Cu, q=3 for M=Ce). In the most binary systems, a wide difference between the calculated values of the melting enthalpies of these polyphosphates and the measured ones determined from the DTA curves, was observed. This difference is probably due to the existence of some molecular associations in the liquid phase.     

Solvothermal Synthesis of M‐doped TiO2 Nanoparticles for Sonocatalysis of Methylene Blue and Methyl Orange (M = Cd,Ag, Fe,Ce, and Cu)

M‐doped TiO₂ nanoparticles were synthesized by a sol–gel‐assisted solvothermal method. X‐ray diffraction (XRD) , transmission electron microscopy (TEM) , and diffuse reflection spectroscopy (DRS) were used to characterize the as‐synthesized samples. The sonocatalytic performance of the specimens for methylene blue and methyl orange degradation was evaluated. XRD confirmed the formation of anatase as the unique phase in all samples. TEM showed that Cd, Cu, and Ce led to increased particle size in comparison to TiO₂ nanoparticles, whereas Fe and Ag had no considerable influence on this parameter. DRS confirmed the change in the absorption edge, and E _g values decreased in the range 4.6–1.2% by Cd, Ce, Fe, Cu, and Ag doping, respectively. Among the different dopants, only Cd and Ag improved the absorbance of UV –visible light, and only these samples induced sonodegradation of the dye models. It can be concluded that the improvement in the dye removal efficiency is not related to an increase in the crystallinity and/or a decrease in E _g, but only related to the increase in absorbance.     

载银羟基磷灰石抗菌粉体和陶瓷的制备及抗菌性能

采用水热法一步合成载银羟基磷灰石抗菌粉体(Ag-HA),并将其应用于抗菌陶瓷的制备。研究结果表明水热条件下HA实际载银量与AgNO₃加入量存在较好的线性关系。XRD和TEM分析结果显示Ag-HA与HA具有相同的晶体结构,水热条件下Ag⁺取代Ca²⁺在HA晶体中的位置,生成Ag_xCa_10-x(PO₄)₆(OH)₂。Ag-HA长度随Ag⁺掺入量的增加而增大,当Ag⁺掺入量增加至1.50%时,Ag-HA由棒状生长为晶须状。选择4.50% Ag-HA作为抗菌粉体,其掺入量为9wt%时,陶瓷的抗菌率>99.9%,此时釉料中Ag₃PO₄含量为0.56%,低于目前研究中釉料中Ag₃PO₄添加量(2wt%~4wt%),不但在一定程度上解决了抗菌陶瓷产品成本较高的问题,而且满足JC/T 897-2002(抗菌陶瓷制品抗菌性能)对抗菌陶瓷抗菌性能的要求。     

LiBa0.95-yBO3∶0.05Tb3+,yBi3+荧光粉的制备及荧光性质

以硼酸和碳酸盐为原料,用高温固相法制备了可被(近)紫外光(369、254 nm)有效激发的Tb³⁺单掺杂Li Ba1-xBO3∶xTb³⁺(物质的量分数x=0.02、0.03、0.04、0.05、0.06、0.07)及Bi³⁺和Tb³⁺共掺杂LiBa_0.95-yBO₃∶0.05Tb³⁺,y Bi³⁺(物质的量分数y=0.02、0.03、0.04、0.05、0.06、0.07)的2个系列荧光粉,产物的结构和形貌分别用粉末X射线衍射(PXRD)和扫描电子显微镜进行表征。PXRD测定结果表明2个系列的产物均为纯相LiBaBO3。通过对第一系列产物荧光光谱的测定,筛选出发光强度最好的产物,据此确定铽离子的最佳掺杂量;在此基础上制备出铋离子掺杂量不同的第二系列荧光粉。荧光光谱测定的实验结果表明,Tb³⁺/Bi³⁺共掺杂的荧光粉的发光强度好于Tb³⁺单掺杂的荧光粉,这说明Bi³⁺对Tb³⁺有敏化作用;而且随着Bi³⁺掺杂量的增加,产物的荧光强度表现出先增加后减小的趋势,当Bi³⁺的掺杂量y=0.03时,产物的荧光强度达到最大。Bi³⁺和Tb³⁺之间存在偶极-四极相互作用而进行能量传递。系列荧光粉的CIE坐标显示其发光颜色在一定程度上呈现出由绿色光到白光的渐变趋势。     

Cu、N共掺杂TiO2纳米管光催化重整甘油制备合成气

通过碱性水热-离子交换法制备了Cu、N共掺杂TiO₂纳米管(Cu/N-TNT),对其光催化重整甘油制备合成气性能进行了研究。结果表明,Cu/N-TNT具有富含氧空位(O_v)的管状结构,N以Ti-N形式取代部分O形成杂质能级,Cu以Cu²⁺形式掺杂在催化剂晶格间隙和表面,Cu、N共掺杂促进TiO₂表面电荷有效分离,有利于其光催化重整甘油制备合成气活性和选择性的提高。紫外光照射8h时,掺Cu量为0.15%的Cu/N-TNT催化剂上CO和H₂产量分别为7.3和8.5 mmol·g^-1,是原始TiO₂的9.1和70.8倍,n_H2/n_CO从0.52提高为1.18,n_CO/n_CO2从0.21提高至0.42。Cu/N-TNT表面N和O_V为醛类脱羰和甲酸脱水生成CO提供反应活性位点,Cu作为浅势阱提...     

Divalent transition metal complexes of 3,5-pyrazoledicarboxylate

New divalent transition metal 3,5-pyrazoledicarboxylate hydrates of empirical formula Mpz(COO)₂(H₂O)₂, where M=Mn, Co, Ni, Cu, Zn and Cd (pz(COO)₂=3,5-pyrazoledicarboxylate), metal hydrazine complexes of the type Mpz(COO)₂N₂H₄ where M=Co, Zn or Cd and Mpz(COO)₂nN₂H₄·H₂O, where n=1 for M=Ni and n=0.5 for M=Cu have been prepared and characterized by physico-chemical methods. Electronic spectroscopic data suggest that Co and Ni complexes adopt an octahedral geometry. The IR spectra confirm the presence of unidentate carboxylate anion (Δν=ν_asy(COO^–)–ν_sym(COO^–)>215 cm^–1) in all the complexes and bidentate bridging hydrazine (ν_N–N=985–950 cm^–1) in the metal hydrazine complexes. Both metal carboxylate and metal hydrazine carboxylate complexes undergo endothermic dehydration and/or dehydrazination followed by exothermic decomposition of organic moiety to give the respective metal oxides as the end products except manganese pyrazoledicarboxylate hydrate, which leaves manganese carbonate. X-ray powder diffraction patterns reveal that the metal carboxylate hydrates are isomorphous as are those of metal hydrazine complexes of cobalt, zinc and cadmium.     

The development of a method for the determination of trace elements in fuel alcohol by ETV-ICP-MS using isotope dilution calibration

A method for the determination of Ag, Cd, Cu, Pb and Tl in fuel alcohol by isotope dilution electrothermal vaporization inductively coupled plasma mass spectrometry (ID ETV-ICP-MS) is proposed. The analytes were separated in two groups: Ag and Cu were determined without modifier and Cd, Pb and Tl with the use of Pd as chemical modifier. The employed ETV operational conditions were pyrolysis temperature of 800 °C for Cd, Pb and Tl and of 900 °C for Ag and Cu and vaporization temperature of 2400 °C for both groups. Seven common, one with additive and one anhydrous fuel ethanol samples were analyzed. The spiked and reference isotopes were, respectively, ¹⁰⁹Ag and ¹⁰⁷Ag, ¹¹²Cd and ¹¹¹Cd, ⁶³Cu and ⁶⁵Cu, ²⁰⁶Pb and ²⁰⁸Pb and ²⁰³Tl and ²⁰⁵Tl. The added amounts of the enriched isotope material were the same for all samples: 4.6 ng of ¹⁰⁹Ag, 5 ng of ¹¹²Cd, 21.1 ng of ⁶³Cu, 9 ng of ²⁰⁶Pb and 0.21 ng of ²⁰³Tl. The blank was bi-distilled ethanol, acidified with 0.3% (v/v) nitric acid, as the samples. The limits of detection (LODs) were calculated as three times the standard deviation of the concentrations in the blank (n = 10) and were, in μg L⁻¹, for Ag: 0.02, for Cd: 0.08, for Cu: 0.1, for Pb: 0.05 and for Tl: 0.001. The obtained concentrations in the samples were in agreement with those obtained by external calibration (EC), according to the paired t-test. The isotope dilution (ID) showed to be a robust, fast and simple calibration technique for the analysis of fuel ethanol.