Bi2WO6量子点(QDs)修饰Bi2MoO6-xF2x异质结的构筑及其催化活性增强机理

采用简单沉积-沉淀法合成了Bi₂WO₆@Bi₂MoO_6-xF_2x（BWO/BMO6-xF2x）异质结,借助XRD、XPS、TEM、SEM、EDS、UV-Vis-DRS、PC和EIS等测试技术对其组成、形貌、光吸收特性和光电化学性能等进行系统表征,并以模型污染物罗丹明B（RhB）的光催化降解作为探针反应来评价Bi₂WO₆@Bi₂MoO_6-xF_2x异质结的光催化活性增强机制。形貌分析表明,所得Bi₂MoO₆微球由大量厚度为20~50 nm的纳米片组成;FE-SEM和HR-TEM分析表明,尺寸约为10 nm的Bi₂WO₆量子点均匀沉积在Bi₂MoO_6-xF_2x微球表面,形成新颖的Bi₂WO₆@Bi₂MoO_6-xF_2x异质结;与纯Bi₂MoO₆或者Bi₂WO₆相比,1∶1Bi₂WO₆@Bi₂MoO_6-xF_2x异质结表现出更好的光催化活性和光电流性质,其对RhB光催化降解的表观速率常数分别为纯BMO和BWO的6.4和11.6倍。PC和EIS图谱分析表明,Bi₂WO₆量子点表面沉积显著提高Bi₂MoO_6-xF_2x光生电子/空穴的分离效率和迁移速率;活性物种捕获实验证明了·O₂^-和h⁺是主要的活性物种。根据实验结果,探讨了F^-掺杂和Bi₂WO₆量子点之间的协同效应对Bi₂MoO₆的光催化活性的影响机制。     

溴代烷烃与活性氮的反应发光研究

在流动余辉装置上, 利用N₂空心阴极放电制备活性氮, 研究了活性氮与溴代烷烃(CHBr₃、CH₂Br₂、C₂H₅Br、C₄H₉Br) 反应的化学发光.上述所有反应中, 在550～750 nm波段均观察到了较强的NBr (b¹Σ+→X³Σ^-)跃迁发射谱. 同时在活性氮与CHBr₃和CH₂Br₂的反应中, 在流动管下游还观察到了CN (A²π, B²π→X²Σ⁺)的发射谱. 验证性的实验表明, 激发态NBr (b¹Σ⁺)是由二步过程形成: N(⁴S)与溴代烷烃反应生成NBr (X³Σ^-), 再通过N₂ (A ³Σ_u⁺)分子能量转移到激发态NBr (b¹Σ⁺); 而激发态的CN是通过N(⁴S) + CBr→CN(A, B) + Br过程形成的.     

三元体系YCl3-CdCl2-H2O和四元体系YCl3-CdCl2-HCl(～8.8%)-H2O (25 ℃)的相平衡及其固相新化合物的研究

The equilibrium solubilities of the ternary system YCl₃-CdCl₂-H₂O, the quaternary system YCl₃-CdCl₂-HCl(～8.8%)-H₂O were determined at 25 ℃ and the phase diagrams were constructed. The results show that the ternary system was complicated with six equilibrim solid phases CdCl₂·2.5H₂O, CdCl₂·H₂O, 8CdCl₂·YCl₃·15H₂O (8∶1 type), 4CdCl₂·YCl₃·13H₂O(4∶1 type), 5CdCl₂·2YCl₃·26H₂O (5∶2 type) and YCl₃·6H₂O. The quaternary system was also complicated with four equilibrim solid phase CdCl₂·H₂O, 4CdCl₂·YCl₃·13H₂O (4∶1 type), 5CdCl₂·2YCl₃·26H₂O(5∶2 type) and YCl₃·6H₂O. Among the three new compounds 8CdCl₂·YCl₃·15H₂O, 4CdCl₂·YCl₃·13H₂O and 5CdCl₂·2YCl₃·26H₂O, 8CdCl₂·YCl₃·15H₂O was a kind of metastable compound only in ternary system, and it was changed into 4CdCl₂·YCl₃·13H₂O with time. Both 4∶1 type and 5∶2 type existed in ternary and quaternary system, but they were also congruently soluble compounds in quaternary system. They have been prepared from the system and have been characterized by XRD, TC-DTG and DSC.     

钙钛矿型LaxSr1－xNi1－yCoyO3光电催化活性研究

用甘氨酸-硝酸盐燃烧合成法, 制备La_xSr_1－xNi_1－yCo_yO₃复合氧化物的陶瓷粉末, 对钙钛矿氧化物进行了XRD结构分析. 在通氧或不通氧下测试氧还原和氧析出的循环伏安曲线. 结果表明: 该氧电极具有双功能催化特性, 但不完全可逆. 利用汞灯作为激发光源, 进行几种水溶性染料和五种混合染料光解实验, 利用紫外-可见、红外以及人工神经网络光度法研究La_xSr_1－xNi_1－yCo_yO₃的催化性能. 结果表明: La_xSr_1－xNi_1－yCo_yO₃ (x＝0.7, 0.9, 1; y＝0.3, 0.75)复合氧化物都具有较强光催化特性; La_xSr_1－xNi_1－yCo_yO₃的光催化活性高于La_xSr_1－xNiO₃, 这与B位离子(Ni^2—, Co^2－)的电子构型有关; Co^2＋的加入可使La_xSr_1－xNiO₃的光催化活性有所提高.     

纳米Mn-Zn铁氧体的制备和研究

Nanosize manganese zinc ferrites were fabricated by hydrothermal precipitation route using Fe₂(SO₄)₃, ZnSO₄·7H₂O, MnSO₄·H₂O as material, then some calcinated at 500 ℃ and studied by XRD, TEM, IR and VSM. The results showed that the products were spinel crystal structure and uniformly sized nanoparticles (15～25 nm) with little aggregation. The analysis of IR showed that the superficial water can be eliminated, but that was embedded in crystal lattice can not be removed by calcinating. The effect Zn content x on the lattice (a) of nanosize Mn_1-xZn_xFe₂O₄ was also discussed. The lattice of nanosize Mn_1-xZn_xFe₂O₄ decreases with x increasing; and its value deviated the standard lattice (a₀) of normal size manganese zinc ferrites. A lot of water was absorbed during the hydrothermal process owing to the large surface of nanosize particles. The change of magnetic properties of Mn_xZn_1-xFe₂O₄ with x increasing was studied: nanosize Mn_xZn_1-xFe₂O₄ particles synthesized by us exhibited peculiar magnetic properties curve with Zn content (x) increasing, Superparamagnetic behaviors of the synthesized ZnFe₂O₄ samples were confirmed by magnetic characterization, which can be explained by the difference between the distribution of the metal ions (Mn²⁺, Zn²⁺ and Fe³⁺) among the tetrahedral (A) and the octahedral (B) sites of nanosize ferrite and that of bulk ferrite.     

新半金属Fe2LaO4磁电性能的第一性原理计算

利用基于密度泛函理论的第一性原理赝势法设计并优化了含稀土元素的新半金属Fe₂LaO₄。详细计算了其电荷分布,分子磁矩等磁电性能，并结合配位场理论分析了其电子结构。结果表明，Fe₂LaO₄是一种含稀土元素的铁磁性的新ⅡB型半金属；它的稳定相晶格常数约为0.623 nm，分子磁矩约为1.0μ_B；Fe₂LaO₄属软铁磁性半金属；La较多的外层电子增强了Fe₂LaO₄内部的库仑斥力,导致了配合物ML₄和ML₆均受强场作用,从而使Fe₂LaO₄具有软铁磁性；考虑自旋分布后ML₄和ML₆的电子结构分别为a_1g¹↑a_1g¹↓t_1u³↑t_1u³↓e_g²↑e_g²↓t_2g³↑t_2g³↓和a_1g¹↑a_1g¹↓t_1u³↑t_1u³↓t_2g³↑t_2g³↓e_g²↑e_g²↓e_g^*1↑,这些电子属于分子轨道。     

不同温度下VUV光激发的Pr3+离子的发光性质

The luminescent properties of Pr³⁺-doped LaB₃O₆, SrAl₁₂O₁₉, SrB₄O₇ and NaYF₄ in the vaccum ultraviol-et (VUV) range at different temperatures were investigated under the excitation of high-energetic synchrotron radiation. For Pr³⁺ ions in LaB₃O₆, SrAl₁₂O₁₉ and SrB₄O₇, only the parity-forbidden ¹S₀→4f² transitions were observ-ed in the emission spectra at relatively low temperature; but the parity-allowed 4f5d→4f² transitions appeared simultaneously when the temperature was high enough. And the intensity of broad 4f5d→4f² emission increased relative to the intensity of ¹S₀→4f² emissions with increasing temperature. Then the thermal equilibrium model of energy levels was employed to the lowest 4f5d state and ¹S₀ state of Pr³⁺ in the three hosts. The calculated curves were in good agreement with the experimental values, indicating the occurrence of the thermal excitation from ¹S₀ state to 4f5d states at high temperatures when the lowest 4f5d state lies higher than ¹S₀ state and the photon energy is high enough.     

空气中合成固溶体荧光粉Ba2(Zn, Mg)Si2O7:Ce3+,Eu2+,Eu3+及其发光特性

采用高温固相法在空气中合成了Ba_1.97-yZn_1-xMg_xSi₂O₇:0.03Eu,yCe³⁺系列荧光粉。分别采用X-射线衍射和荧光光谱对所合成荧光粉的物相和发光性质进行了表征。在紫外光330~360 nm激发下,固溶体荧光粉Ba_1.97-yZn_1-xMg_xSi₂O₇:0.03Eu的发射光谱在350~725 nm范围内呈现多谱峰发射,360和500 nm处有强的宽带发射属于Eu²⁺离子的4f⁶5d¹-4f⁷跃迁,590~725 nm红光区窄带谱源于Eu³⁺的⁵D₀-⁷F_J (J=1,2,3,4)跃迁,这表明,在空气气氛中,部分Eu³⁺在Ba_1.97-yZn_1-xMg_xSi₂O₇基质中被还原成了Eu²⁺;当x=0.1时,荧光粉Ba_1.97Zn_0.9Mg_0.1Si₂O₇:0.03Eu的绿色发光最强,表明Eu³⁺被还原成Eu²⁺离子的程度最大。当共掺入Ce³⁺离子后,形成Ba_1.97-yZn_0.9Mg_0.1Si₂O₇:0.03Eu,yCe³⁺荧光粉体系,其发光随着Ce³⁺离子浓度的增大由蓝绿区经白光区到达橙红区;发现名义组成为Ba_1.96Zn_0.9Mg_0.1Si₂O₇:0.01Ce³⁺,0.03Eu的荧光粉的色坐标为(0.323,0.311),接近理想白光,是一种有潜在应用价值的白光荧光粉。讨论了稀土离子在Ba₂Zn_0.9Mg_0.1Si₂O₇基质中的能量传递与发光机理。     

白光LED用Sr0.955Al2Si2-xTixO8：Eu2+荧光粉的晶体结构和光谱特性

由高温固相反应制得Sr_0.955Al₂Si_2-xTi_xO₈：Eu²⁺（x=0~1.0）系列试样,研究了Ti⁴⁺置换Si⁴⁺对其晶体结构和光谱特性的影响。Ti⁴⁺以类质同相替代Si⁴⁺进入晶体晶格中,形成了连续固溶体,其晶胞参数a,b,c,β和晶胞体积V随Ti⁴⁺置换量呈线性递增。Ti⁴⁺置换Si⁴⁺对晶胞参数c的影响显著,b其次,a最小。荧光激发谱为宽带,位于230~400nm,由267nm、305nm、350nm和375nm 4个峰拟合成,表观峰值位于351nm;随着Ti⁴⁺置换量的增加,半高宽（FWHM）从105nm减小到93nm。发射光谱位于380~600nm,表观峰值位于407nm,可由406nm和441nm两峰拟合而成并且随Ti⁴⁺置换量增加线性红移,Ti⁴⁺进入晶格对长波长发射中心影响较少;Ti⁴⁺置换量为1.0时,表观发射峰位从407nm红移至417nm;利用试样荧光光谱和VanUitert经验公式,得出SrAl₂Si₂O₈：Eu²⁺中Sr²⁺的配位数为9。随着Ti⁴⁺置换量Si⁴⁺进入基质晶格,造成Eu-O距离变小,使得Eu²⁺所处的晶体场强度增强,发光中心Eu²⁺的5d能级分裂增大,造成Eu²⁺最低发射能级重心下移,两拟合谱峰峰位均呈线性红移。     

CeCl3-CdCl2-H2O和CeCl3-CdCl2-HCl-H2O的相平衡

测定了三元系CeCl₃-CdCl₂-H₂O (25 ℃)和四元系CeCl₃-CdCl₂-HCl(～8.4％)-H₂O(25 ℃) 的相平衡溶度数据,绘制了相应的溶度图.该三元系是由5个固相区CdCl₂&;#8226;2.5H₂O(原始盐)、CdCl₂&;#8226;H₂O(原始盐)、6CdCl₂&;#8226;CeCl₃&;#8226;14H₂O、4CdCl₂&;#8226;CeCl₃&;#8226;12H₂O、CeCl₃&;#8226;7H₂O(原始盐)组成的复杂体系.该四元系是由5个固相区CdCl₂&;#8226;H₂O(原始盐)、9CdCl₂&;#8226;CeCl₃&;#8226;19H₂O、6CdCl₂&;#8226;CeCl₃&;#8226;14H₂O、4CdCl₂&;#8226;CeCl₃&;#8226;12H₂O、CeCl₃&;#8226;7H₂O(原始盐)组成的复杂体系.其中6CdCl₂&;#8226;CeCl₃&;#8226;14H₂O在该三元系是介稳化合物.9CdCl₂&;#8226;CeCl₃&;#8226;19H₂O 、6CdCl₂&;#8226;CeCl₃&;#8226;14H₂O和4CdCl₂&;#8226;CeCl₃&;#8226;12H₂O用X射线粉末衍射及TG-DTG和DSC等方法进行了研究,并对X射线粉末衍射进行了指标化.     

阴离子交换离子色谱法测定乳酸催化制备的丙烯酸

通过乳酸催化脱水制备丙烯酸具有良好的应用前景。为了对其中的催化过程进行有效、及时的监控,建立了一种同时测定乳酸及丙烯酸的阴离子交换色谱法(AEC)。选择Metrohm A Supp 5阴离子交换柱(150 mm×4.0 mm),以2 mmol/L Na2CO3+2 mmol/L NaHCO3混合水溶液为流动相,采用化学抑制电导检测技术,乳酸和丙烯酸在6 min内即可实现完全分离。乳酸和丙烯酸工作曲线的线性范围分别为0.1～500 mg/L和0.1～200 mg/L,检出限分别为0.030 mg/L和0.035 mg/L,加标回收率分别为100.7%～106%和99.6%～103%,相对标准偏差分别为2.16%~2.49%和2.42%~2.48%。该方法准确、快速、灵敏、重现性好。     

辉光放电电解等离子体引发合成聚丙烯酸钠/腐植酸复合高吸水性树脂

以丙烯酸和腐植酸为原料,N,N-亚甲基双丙烯酰胺为交联剂,在水溶液中采用辉光放电电解等离子体引发聚合反应制备聚丙烯酸钠/腐植酸复合高吸水性树脂。 考察了放电电压、交联剂、丙烯酸中和度、后聚合温度、腐植酸钠和丙烯酸的含量对树脂吸水率的影响,讨论了树脂在0.9%氯化钠溶液中的溶胀速率和不同pH值溶液中的溶胀行为。 用红外光谱和热重分析分别对产物进行了结构表征和稳定性测试,结果表明,最佳的合成条件为：放电电压470 V、交联剂质量分数为0.6%、腐植酸钠质量分数为4%、丙烯酸质量分数为10%、中和度60%、后聚合温度70 ℃。 所得复合树脂对蒸馏水的吸水率为1152 g/g,对0.9%NaCl溶液的吸水率为89 g/g,800 ℃后复合树脂残留率为44.3%。     

焦磷酸盐-磷酸盐复合催化剂高效催化乳酸脱水制丙烯酸

利用沉淀法制得焦磷酸盐与磷酸盐在浆状态下复配制备成复合催化剂,并用于催化乳酸脱水制丙烯酸.实验发现催化剂的组成对乳酸的转化率及丙烯酸的选择性有着重要的影响,当磷酸盐/焦磷酸盐质量比在30∶70～50∶50范围内,可以获得较高的乳酸的转化率和丙烯酸的选择性.催化反应条件如反应温度,乳酸进料浓度,液空速也被详细地进行了考察.此外,考察了该复合催化剂的稳定性.当催化剂连续运行56 h后,乳酸的转化率保持在96%以上,丙烯酸的选择性也高达57%.为了进一步揭示催化剂的结构与催化性能之间的关系,利用X射线粉末衍射、热重、扫描电镜和傅立叶红外等对催化剂进行了表征.     

Synthesis,characterization and water absorbency properties of poly(acrylic acid)/sodium humate superabsorbent composite

A novel poly(acrylic acid)/sodium humate superabsorbent composite was synthesized by aqueous solution polymerization of acrylic acid using N, N′‐methylenebisacrylamide as a crosslinker and ammonium persulfate as an initiator in the presence of sodium humate. The effects on water absorbency such as initial monomer concentration, degree of neutralization of acrylic acid, amount of crosslinker, initiator and sodium humate, etc. were investigated. The water absorbency of the superabsorbent composite synthesized under optimal synthesis conditions with a sodium humate content of 20% exhibited an absorption of 1268 g H₂O/g sample and 93 g H₂O/g sample in distilled water and in 0.9 wt% NaCl solution, respectively. Swelling rate and water retention tests were also carried out. The results show that sodium humate, as a kind of functional filler, can enhance comprehensive properties of superabsorbent composite and reduce the product cost significantly. Copyright © 2005 John Wiley & Sons, Ltd.     

丙烯酸/2-丙烯酰胺基-2-甲基丙磺酸高吸水树脂的反相悬浮聚合及其性能

采用反相悬浮聚合法,通过均匀实验设计,制备了聚(丙烯酸(AA)/2-丙烯酰胺基-2-甲基丙磺酸(AMPS)）(PAAMPS)高吸水树脂,探讨了单体摩尔分数及其中和度、引发剂及交联剂摩尔分数（相对于单体总量）对蒸馏水、质量分数0.9%NaCl水溶液中吸液性能的影响,并经实验数据拟合,得到了二次回归方程,比较了优化配方、单因素实验的模拟值和实验值,结果表明,模拟值与优化值基本接近,其优化工艺参数为：AMPS占单体的摩尔分数8%,中和度为75%,交联剂、引发剂用量与单体的摩尔分数分别为0.035%和0.17%,单体总质量浓度为30%,分散剂用量为单体质量分数的0.5%,反应温度70 ℃,反应时间1.5 h。 此条件下合成的PAAMPS在蒸馏水、0.9%NaCl水溶液中的吸液倍率分别为1.600和130 g/g。     

Graft Copolymerization of Artemisia Seed Gum with Acrylic Acid under Microwave and its Water Absorbency

A super‐absorbent polymer was prepared by grafting copolymerization of acrylic acid onto Artemisia seed gum, using microwave irradiation and ammonium persulfate as an initiator. The effect of various preparation conditions on its water absorbency, such as the ratio of acrylic acid to Artemisia seed gum, degree of acrylic acid neutralization, amount of initiator and microwave irradiation time, was investigated by orthogonal tests. The optimal reaction conditions were 3 min (irradiation time), 70% neutralization degree of acrylic acid and 2% initiator on the basis of the mass of acrylic acid used. When the mass ratio of acrylic acid to Artemisia seed gum is 5:0.5, the product has a water absorbency close to 400 times at room temperature in distilled water, this indicated that is has a high water absorbency. The structure of the graft copolymer was confirmed by Fourier transform infrared spectrometer (FT‐IR) and thermogravimetric analysis (TGA). Further more, this microwave irradiation processing method to prepare water absorbent materials has no industrial cast off produced, that is to say, this method is environmentally friendly.     

Preparation of AgBiVMoO/-Al2O3 Catalysts for the Partial Oxidation of Propane

A novel mixed sol method was developed for the preparation of supported catalysts. Analyses by means of XRD and BET show that a 40%AgBiVMoO/γ-Al2O3 catalyst prepared by this method possessed high specific surface area and high dispersion of the active phase. As a result, high acrylic acid selectivity of 8.5% was obtained when the catalyst was used in the reaction of propane partial oxidation to acrylic acid in a fixed-bed reactor.     

高比表面介孔MoVTeNbO催化剂的制备及其催化性能

采用水热法添加模板剂十六烷基三甲基溴化铵(CTAB)和配合剂柠檬酸(CA)制备了Mo VTe Nb O系列催化剂,并将其应用于丙烯一步氧化制备丙烯酸的反应.结果表明,CA的添加量对催化剂的形貌、孔结构、比表面积及催化性能具有明显的影响.当n(CA)/n(Mo)=0.36时,Mo VTe Nb O催化剂为介孔纳米催化剂,其平均孔径为4.9 nm,具有较高的比表面积(37.8 m2/g)和较小的催化剂晶粒(粒径范围为10~16 nm),与常规水热法制备的催化剂相比,Mo VTe Nb O介孔纳米催化剂的晶粒变小、催化性能得到了显著提高,丙烯一步氧化制丙烯酸的转化率可由53.9%提高至71.2%,丙烯酸收率可提高到45.8%.     

离子色谱法测定水中4种有机酸

建立了水样中甲酸、乙酸、丙烯酸和甲基丙烯酸的离子色谱测定方法,采用IonPac AS11-HC阴离子分离柱,以KOH为淋洗液,采用浓度梯度洗脱,可同时测定上述4种有机酸。方法对实际水样中甲酸、乙酸、丙烯酸和甲基丙烯酸的平均加标回收率在80.2%~103.3%,相对标准偏差在5.8%之内,检出限分别为:0.005,0.003,0.005和0.004mg/L;定量下限分别为:0.020,0.012,0.020和0.016mg/L。方法准确、简便、环保,能够满足实际水样的测定需要,且水样中常见的阴离子不会对目标污染物的测定产生影响。     

Selective oxidation of propane to acrylic acid over mixed metal oxide catalysts

The effects of metal atomic ratio, water content, oxygen content, and calcination temperature on the catalytic performances of MoVTeNbO mixed oxide catalyst system for the selective oxidation of propane to acrylic acid have been investigated and discussed. Among the catalysts studied, it was found that the MoVTeNbO catalyst calcined at a temperature of 600 ℃ showed the best performance in terms of propane conversion and selectivity for acrylic acid under an atmosphere of nitrogen. An effective MoVTeNbO oxide catalyst for propane selective oxidation to acrylic acid was obtained with a combination of a preferred metal atomic ratio （Mo1V0.31Te0.23Nb0.12）. The optimum reaction condition for the selective oxidation of propane was the molar ratio of C3H8 ：O2 ： H2O ： N2 = 4.4： 12.8 ： 15.3 ： 36.9. Under such conditions, the conversion of propane and the maximum yield of acrylic acid reached about 50% and 21%, respectively.