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.     

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.     

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。     

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。     

VB2n-(n=8~12)团簇几何结构、电子及热力学特性的理论研究

基于卡里普索结构预测程序和密度泛函理论的第一性原理计算,搜索确定了VB_2n^-（n=8~12）团簇的基态和亚稳态结构。结果发现,V原子的掺杂完全改变了原硼团簇的结构并提高了原体系的稳定性。掺杂体系基态结构分别呈现高对称性的鼓状（VB₁₆^-：C_2v）、管状（VB₁₈^-：C_2v和VB₂₀^-：C_s）及笼状（VB₂₂^-：C₂和VB₂₄^-：D_3h）结构。基于基态结构,研究了体系的电荷转移和极化率,拟合出了光电子能谱、红外和拉曼谱图,分析了流变键和芳香特性。最后,研究了体系的热力学特性,讨论了温度对热力学参数的影响。     

Ni-Co双金属催化剂上沼气重整制氢机理

用传统湿式浸渍法制备了La₂O₃掺杂的商业γ-Al₂O₃负载的沼气重整催化剂Ni-Co/La₂O₃-γ-Al₂O₃, 并用程序升温加氢(TPH)、程序升温氧化(TPO)、程序升温表面反应(TPSR)、程序升温脱附(TPD)及脉冲实验对催化剂进行了表征. 结果表明, 沼气重整过程中Ni-Co/La₂O₃-γ-Al₂O₃催化剂上的表面碳物种主要来源于CH₄的裂解, CO₂的贡献很小. CH₄裂解能够产生三种活性不同的碳物种, 即C_α、C_β与C_γ. 随着反应的进行, C_α物种减小而C_β与C_γ物种增加, 且C_γ物种能够转变为惰性的石墨碳. 重整反应过程中CH₄与CO₂的活化能相互促进. 催化剂表面的O物种与C反应生成CO或与CH_x反应生成CH_xO再分解为CO与吸附态的H物种, 可能是Ni-Co/La₂O₃-γ-Al₂O₃催化剂上沼气重整的速率控制步骤.     

(Zn1-xMnx)C2O4·2H2O在空气中的热分解动力学研究

用热分析（TG-DTG/DTA）、X射线衍射（XRD）技术和透射电镜（TEM）研究了固态物质Zn_1-xMn_xC₂O₄•2H₂O在空气中热分解的过程。热分析结果表明，Zn_1-xMn_xC₂O₄•2H₂O在空气中分两步分解，其失重率与理论计算失重率相吻合。 XRD和TEM结果表明，Zn_1-xMn_xC₂O₄•2H₂O分解的最终产物为Zn_1-xMn_xO,其颗粒大小约为10-13 nm。在非等温条件下对Zn_1-xMn_xC₂O₄•2H₂O的热分解动力学进行了分析。用Friedman法和Flynn-Wall-Ozawa(FWO)法求取了分解过程的活化能E，并用多元线性回归给出了可能的机理函数。Zn_1-xMn_xC₂O₄•2H₂O两步热分解的活化能分别为155.7513 kJ/mol 和215.9397 kJ/mol。     

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。     

Tm3+/Er3+/Ho3+共掺SiO2-Bi2O3-AlF3-BaF2玻璃发光性能

采用高温熔融法制备了Tm³⁺/Er³⁺/Ho³⁺共掺的铋硅酸盐50SiO₂-40Bi₂O₃-5AlF₃-5BaF₂玻璃。研究了在808 nm激光器（Laser Diode）激发下Tm³⁺/Er³⁺/Ho³⁺共掺的铋硅酸盐在2 060 nm处的发光性能,同时测试及分析了该铋硅酸盐玻璃的差热特性、吸收光谱及荧光光谱。根据吸收光谱以及Judd-Oflet理论,计算了Ho³⁺的Judd-Oflet强度参数Ω_t（t=2,4,6）以及Tm³⁺/Er³⁺/Ho³⁺相应的吸收截面。铋硅酸盐玻璃中,Tm₂O₃、Er₂O₃和Ho2O3掺杂浓度分别为0.75%、1.0%和0.5%时,2 060 nm处Ho³⁺∶⁵I₇→⁵I₈发射峰强度达到最大。对Tm³⁺/Er³⁺/Ho³⁺ 3种离子的光谱性质和离子间可能存在的能量传递也做了分析。Ho³⁺在1 953 nm处的最大吸收截面σ_abs为9.08×10^-21 cm²,在2 060 nm处的最大发射截面σem为11.68×10^-21 cm²,辐射寿命τ_mea为2.75 ms,具有良好的增益效应σ_emτ（3.212×10^-20 cm^-2·ms）。     

Eu3+离子在Ca2PbO4一维结构基质中的发光研究

A Eu³⁺-doped Ca₂PbO₄ with one-dimensional structure was prepared with a solid-state reaction method and its characteristics were investigated. The XRD results show that the substitution of Ca²⁺ by Eu³⁺ has no influence on the structure of Ca₂PbO₄. Under the excitation of ultraviolet light， the Ca₂PbO₄:Eu³⁺ phosphor exhibits strong red emission at about 618 nm which is assigned to the ⁵D₀- ⁷F₂ electric-dipole transition. The compounds Sr₂CeO₄ and Ca₂SnO₄ have the same crystal symmetry as that of Ca₂PbO₄ and it is found that the emission intensity of Ca₂PbO₄∶Eu³⁺ is higher than that of Sr₂CeO₄∶Eu³⁺ and lower than that of Ca₂SnO₄∶Eu³⁺. The excitation spectrum of Ca₂PbO₄∶Eu³⁺ appears to be a broad band with two peaks at about 289 nm and 340 nm. The former peak is attributed to the Eu³⁺-O₂- charge transfer transition， while the latter one may be related to the absorption of Ca₂PbO₄ host or its crystal defects.     

Preparation of Cu (II)/PEI–QPEI/SiO2 nanopowder as antibacterial material

The silica nanoparticles were prepared by the sol–gel process, and then twice modified and grafted by polyethylenimine (PEI) on their surface. After quaternary ammonium reaction and chelated copper reaction, the PEI/SiO₂, QPEI/SiO₂, PEI–QPEI/SiO₂ and Cu (II)/PEI–QPEI/SiO₂ nanopowders were obtained in turn. The morphology and structure of the products were characterized through SEM, EDX, HRTEM, FTIR and element analysis. At the same time, the antibacterial activity of the products to E. coli and Candida were evaluated through quantification and qualitative ways, e.g. microcalorimetric method and culture dish method. The results suggested that the Cu (II)/PEI–QPEI/SiO₂, a novel three-component functional nanopowder, presented the best antibacterial activity to both E. coli and Candida duo to the synergistic sterilization capability of the ammonium salt and copper ions, compared with other products. It indicated that the Cu (II)/PEI–QPEI/SiO₂ nanopowder could be a novel antibacterial nanomaterial to widely application in preventing and minimizing bacteria of the organism and environment in future.     

原位制备PEI/SiO2复合材料及其改性环氧树脂的研究

在N,N-二甲基乙酰胺/四氢呋喃(DMAc/THF)混合溶剂中,在正硅酸乙酯(TEOS)存在条件下,通过溶胶-凝胶法原位制备了聚醚酰亚胺(PEI)/SiO2复合材料.在该复合材料中,当SiO2含量低于20 wt％时,透射电镜(TEM)和扫描电镜(SEM)的观察表明,SiO2纳米粒子可以均匀分散,粒径可在80～300 n...     

固定化青霉素酰化酶新型载体PEI/SiO2的制备及其特性

通过γ-氯丙基三甲氧基硅烷的媒介, 将聚乙烯亚胺(PEI)化学偶联在硅胶微粒表面, 制备了固定化青霉素酰化酶的新型复合载体PEI/SiO2, 最终制得了活性高且稳定性好的固定化青霉素酰化酶. 通过测定复合载体表面PEI的偶合量, 考察了各种反应条件对复合载体制备的影响规律; 通过红外光谱与电导滴定法测定, 对复合载体表面的化学结构与组成进行了表征; 为探索复合载体PEI/SiO2固定化酶的作用机理, 测定了复合载体在固定化酶前的ζ电位. 研究结果表明, 通过氯丙基硅烷偶联剂的媒介, 聚胺大分子PEI可以充分地被化学偶联在SiO2表面, 键合量可达到15%. 偶联反应的适宜条件: 反应温度90-94 ℃; 反应时间5h; PEI的质量浓度0.45-0.50 g/mL. 由于PEI分子链中含有大量氨基, 少量的共价键联与大量的物理吸附相结合, 既可使青霉素酰化酶被快速稳定地固定化, 又能很好地保持酶的构象, 使其具有较高的催化活性与活力回收率, 而且具有良好的连续操作稳定性, 重复使用15次, 固定化酶的活性可稳定地保持在初活性的87.5%水平上.     

Efficient CO2 capture on low-cost silica gel modified by polyethyleneimine

In this work,a series of polyethyleneimine(PEI) functionalized commercial silica gel were prepared by wet impregnation method and used as CO 2 sorbent.The as-prepared sorbents were characterized by N 2 adsorption,FT-IR and SEM techniques.CO 2 capture was tested in a fixed bed reactor using a simulated flue gas containing 15.1% CO 2 in a temperature range of 25-100 C.The effects of sorption temperature and amine content on CO 2 uptake of the adsorbents were investigated.The silica gel with a 30 wt% PEI loading manifested the largest CO 2 uptake of 93.4 mg CO 2 /g adsorbent(equal to 311.3 mg CO 2 /g PEI) among the tested sorbents under the conditions of 15.1%(v/v) CO 2 in N 2 at 75 C and atmospheric pressure.Moreover,it was rather low-cost.In addition,the PEI-impregnated silica gel exhibited stable adsorption-desorption behavior during 5 consecutive test cycles.These results suggest that the PEI-impregnated silica gel is a promising and cost-effective sorbent for CO 2 capture from flue gas and other stationary sources with low CO 2 concentration.     

Layer-by-layer surface modification of functional nanoparticles for dispersion in organic solvents

In order to prepare SiO(2) nanoparticles that are dispersible in various organic solvents, an anionic surfactant 1, which branches into a hydrophobic chain and a hydrophilic chain, was adsorbed on to SiO(2) nanoparticles through a layer-by-layer surface modification route using polyethyleneimine (PEI). First, the relationship among the additive content of PEI, adsorbed content of PEI, and the redispersion stability of the SiO(2) nanoparticles in water was investigated. While almost the entire PEI was adsorbed when the additive PEI content was lower than 67 mg/g of SiO(2), the adsorbed content of PEI became saturated when the additive content was increased above 90 mg/g of SiO(2). SiO(2) nanoparticles that were saturated with PEI could be redispersed into water at sizes close to their primary particle size without the large-scale formation of aggregates. Next, the anionic surfactant 1 was adsorbed on the SiO(2) nanoparticles by using a SiO(2) aqueous suspension saturated with adsorbed PEI. It was found that the adsorbed content of 1 increased almost linearly as the additive content was increased when the additive condition was below 1400 mg/g of SiO(2). Furthermore, SiO(2) nanoparticles adsorbed with 80 mg/g of SiO(2) of PEI and 810 mg/g of SiO(2) of 1 could be dispersed into various organic solvents with different polarities. This layer-by-layer modification technique can also be applied to Ag nanoparticles in order to prepare Ag nanoparticles that can be dispersed in various organic solvents.     

构建巯基-Ce(Ⅳ)盐氧化还原引发体系实现丙烯腈在硅胶微粒表面的高效接枝聚合

使用偶联剂γ-巯丙基三甲氧基硅烷(MPMS,KH-590),对微米级硅胶微粒进行了表面化学改性,将巯基引入硅胶微粒表面(SiO2-MPMS),构成巯基-Ce(Ⅳ)盐氧化-还原引发体系,探索研究了丙烯腈在硅胶微粒表面的引发接枝聚合,制得了高接枝度(30 g/100g)的接枝微粒SiO2-MPMS-g-PAN.采用红外光谱(FTIR)、扫描电镜(SEM)及热重分析(TGA)等方法对接枝微粒SiO2-MPMS-g-PAN进行了表征.在此基础上,重点研究了主要因素对巯基-Ce(Ⅳ)盐体系引发AN接枝聚合的影响.研究结果表明,类似于羟基-Ce(Ⅳ)盐体系,巯基-Ce(Ⅳ)盐体系也可以有效地引发乙烯基单体在固体微粒表面接枝聚合.与在固体微粒表面引入可聚合双键的"grafting through"接枝聚合法相比,铈盐引发的接枝聚合,由于活性位点居于载体表面,故具有高的接枝度,是一种高效率的表面引发接枝法.为制得高接枝度的接枝微粒SiO2-MPMS-g-PAN,本研究体系适宜的酸浓度为0.25 mol/L;Ce(Ⅳ)盐浓度为5.0×10-3 mol/L;接枝聚合宜在50℃下进行.     

接枝型三相转移催化剂的制备及其催化作用

将苯乙烯(St)接枝聚合在微米级硅胶表面,制备了接枝微粒PSt/SiO2;使用新型氯甲基化试剂1,4-二氯甲氧基丁烷,对接枝在硅胶表面的聚苯乙烯进行了氯甲基化(CM)反应,制得了氯甲基聚苯乙烯/硅胶(CMPS/SiO2)接枝微粒;使三乙胺与CMPS分子链上的苄氯基团发生季铵化反应,制得了固载有季铵盐(Quaternary salt)的接枝微粒QPSt/SiO2,即制得了接枝型三相相转移催化剂.将此相转移催化剂用于氯化苄与乙酸钠合成乙酸苄酯的相转移催化反应,考察了催化活性、各种因素对相转移催化反应的影响及催化剂的重复使用性能.实验结果表明,接枝型三相相转移催化剂QPSt/SiO2对乙酸苄酯的合成具有较高的催化活性,在液-固-液之间即可有效地实现反应物种乙酸根的转移,在60℃的较低温度下反应7 h,氯化苄的转化率可达66.1%;研究发现,固体催化剂QPSt/SiO2表面接枝聚合物PSt的季铵化程度对其催化活性有很大的影响,季铵化程度过大与过小催化活性都较低,当季铵化程度为20%左右时,催化剂的活性最高.     

表面引发接枝聚合法制备抗蚜威分子表面印迹材料及其分子识别与结合特性研究

基于表面引发接枝聚合,设计与建立了一种新的分子表面印迹(MIP)方法.先使用偶联剂γ-氨丙基三甲氧基硅烷(AMPS)对微米级硅胶微粒进行表面改性,制得改性硅胶AMPS-SiO2;在酸性水溶液体系中,凭借强静电相互作用,阴离子单体对苯乙烯磺酸钠(PSSS)被结合在模板分子抗蚜威周围;改性硅胶AMPS-SiO2表面的氨基与溶液中的过硫酸盐构成氧化还原引发体系,在硅胶微粒表面产生自由基,引发结合在模板分子周围的SSS及交联剂甲基双丙烯酰胺(MBA)在硅胶微粒表面发生接枝交联聚合,从而实现了抗蚜威分子的表面印迹,制得了抗蚜威分子表面印迹材料MIP-PSSS/SiO2.以残杀威为对比物,采用静态与动态两种方法,考察研究了分子表面印迹材料MIP-PSSS/SiO2对抗蚜威的分子识别特性与结合性能.研究结果表明,印迹材料MIP-PSSS/SiO2对抗蚜威分子具有特异的识别选择性与优良的结合亲和性,相对于残杀威分子,MIP-PSSS/SiO2对抗蚜威分子的识别选择性系数为9.373,显示出高的分子识别选择性.     

New synthetic methods for the formation of basic,polyvalent, hyperbranched grafts

A practical synthetic route to polybasic, polyamine, hyperbranched grafts using commercially available polyethyleneimine (PEI) and cyanuric chloride as a coupling agent is described. The grafting process was followed by XPS spectroscopy, TGA analysis, ATR‐IR spectroscopy, acid–base titration, and by ¹³C CP‐MAS NMR spectroscopy. In the case of silica gel, thermal gravimetric analyses showed that a 35 wt % loading of graft could be obtained. Acid–base titration of hyperbranched PEI grafts on silica gel and oxidized polyethylene powder showed the ion‐exchange capacities of these PEI‐grafted substrates were 1.00 and 0.17 mmol of base/g of solid, respectively. Although the focus of the paper is on grafting on silica gel, the influence of the kind of support and solvent on the grafting process and the ion‐exchange capacity was examined. Water was a good solvent for PEI grafting onto silica gel, but a more hydrophobic polyethylene support required the use of dichloromethane as a solvent for PEI graft synthesis. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4654–4665. 2005     

动态多孔海绵结构多层膜负载溶菌酶用于抗菌涂层的研究

以聚丙烯酸(PAA)和聚乙烯亚胺(PEI)为构筑单元,运用层层自组装技术制备了聚电解质多层膜.该多层膜具有独特的动态特点——经酸处理后膜内部形成海绵状通孔结构,该海绵结构在饱和水蒸气的处理下,多孔结构能够闭合,重新回到致密的膜结构.借助该种动态多层膜平台,能够简单有效地通过毛细作用力将溶菌酶负载并固定于多层膜中,为制备基于抗菌蛋白的抗菌涂层提供了新的方法.扫描电镜表征了多层膜动态变化过程,激光共聚焦显微镜表征了溶菌酶在膜内的分布情况,并测定了溶菌酶载入量及其释放动力学.进一步的抗菌测试表明该种抗菌涂层在溶菌酶和PEI的共同作用下可以有效地抑制金黄色葡萄球菌.将多层膜同时负载溶菌酶和乳铁蛋白,提升了涂层对大肠杆菌的杀菌效果.