CO_2/N_2-光双重刺激响应型表面活性剂的合成及性能研究

利用7-羟基香豆素、1,10-二溴癸烷和盐酸二甲胺合成了一种双重刺激响应型的表面活性剂7-(氧-10-二甲氨基-癸基)-香豆素(7-OAC)。通入CO_2或N_2,可实现表面活性的"开"与"关",也可利用其结构中的香豆素基团在300 nm以上紫外光下进行光二聚反应。通过质谱、核磁等表征了其结构,测定了其表面性能及N_2/CO_2和双重光刺激响应性能。     

壳聚糖的接枝改性及其CO2/N2响应乳化性能研究

通过化学反应将甲基丙烯酸二甲氨基乙酯(DMAEMA)接入壳聚糖(CTS)的分子结构中,获得改性产物CTS-gDMAEMA。使用红外光谱和核磁氢谱对其进行了结构表征。向CTS-g-DMAEMA的聚集体分散液中依次通入CO_2和N_2后,其外观形态、透光率和电导率发生了明显的循环变化,证实了CTS-g-DMAEMA的CO_2/N_2刺激响应性。水-液体石蜡的乳化实验证明,与原料CTS相比,CTS-g-DMAEMA具有更好的稳定乳液的能力;并且在CO_2/N_2作用下,由CTS-g-DMAEMA制备的乳液可以发生破乳和再乳化的循环。     

11-苄硒基十一羧酸铵盐的双重刺激响应性质

合成了一种对氧化还原(Redox)和CO_2/N_2具有双重刺激响应的表面活性剂11-苄硒基十一羧酸铵盐(BSeUA),分别利用傅里叶红外光谱、核磁共振和电喷雾质谱等手段研究了BSeUA在Redox和CO_2/N_2刺激响应前后的分子结构变化特征。结果表明,在过氧化氢和水合肼交替作用下,BSeUA分子中二价硒醚基团(-Se-)与相应的四价硒亚砜基团(-Se=O)之间可以氧化还原可逆互变,在CO_2和N_2交替作用下,BSeUA分子中羧酸根(-COO-)与相应的羧酸(-COOH)之间可以可逆互变,从而实现BSeUA对Redox和CO_2/N_2具有双重刺激响应。分别在Redox和CO_2/N_2刺激作用下,由BSeUA稳定的乳液可以在破乳和再乳化2种状态下开关可逆循环至少5次,且乳液粒径和稳定性未发生明显变化。     

N_2优先渗透ZIF-8复合膜的制备及其CO_2捕集

为了获得经济节能的烟道气CO_2回收方法,制备了一种新型的N_2优先渗透ZIF-8复合膜。以柔性聚砜(PSf)多孔膜为支撑层,采用Zn~(2+)与壳聚糖的交联溶液对聚砜支撑层表面改性,使Zn~(2+)固定在PSf膜表面;然后与2-甲基咪唑(Hmim)配位得到ZIF-8晶种层;最后通过界面聚合法二次生长制得ZIF-8复合膜。采用FTIR、XRD及SEM对ZIF-8复合膜的形貌结构进行表征,结果显示成功制备了致密的ZIF-8复合膜。在进料气为纯气条件下,探究了二次生长时间、Zn~(2+)溶液的浓度、测试时间及测试压力对ZIF-8复合膜N_2/CO_2分离性能的影响,阐明其N_2优先渗透机理;并进一步考察了混合气分离性能。结果表明:在25℃和0.1 MPa下,最优ZIF-8复合膜的N_2渗透性为523 GPU,N_2/CO_2选择性为19;同条件下混合气的N_2渗透性和N_2/CO_2选择性分别为517 GPU和18。所制备的ZIF-8复合膜可以使N_2优先渗透,实现烟道气中高浓度N_2渗透,低浓度CO_2截留在膜的上游侧。原因主要是ZIF-8复合膜含有较多的CO_2强吸附位点,使CO_2被吸附在膜内不易从膜的下游侧脱附,渗透性小,而N_2优先渗透,这为N_2优先渗透膜的制备提供了一种新思路。     

叔胺基CO2开关表面活性剂的合成及性能研究

以不同碳链长度的脂肪酸(n=12,14和16)和N,N-二甲基-1,3-丙二胺为原料合成了系列长链脂肪酰胺叔胺C_nAMPM。通过核磁共振氢谱和电导率实验证实了其CO_2开关响应性能。研究发现:通入CO_2后,CnAMPM表现出表面活性剂特征,随着碳链长度增加,cmc线性降低,发泡性能、乳化正庚烷的能力和在标准帆布上的润湿性能也相应下降。通入N_2后,发泡力大幅度降低;C_(12)AMPM的乳化性能较好,润湿性能好于另外2种;而C_(14)AMPM和C_(16)AMPM的乳化能力和润湿能力均较差。     

Ce_xZr_(1-x)O_2催化CO_2和甲醇直接合成DMC的性能研究

通过水热法制备了Ce/Zr摩尔比分别为1∶19、1∶9、2∶8、3∶7的铈锆复合物,利用微型高压反应釜考察了在160℃、3. 5 MPa下4种催化剂对CO_2和甲醇直接合成碳酸二甲酯(DMC)的催化性能,并利用XRD、N_2吸附-脱附、FT-IR、NH_3-TPD和CO_2-TPD对其进行表征。结果表明,Ce的加入没有改变单斜ZrO_2的晶相,Ce/Zr摩尔比为2∶8(Ce_(0.2)ZrO_2)时表现出优异的催化性能,这与表面具有较多的酸碱位数量和较大的孔体积有关。此外,采用密度泛函理论(DFT)的计算构建了单斜ZrO_2(111)和CeO_2(110)晶面,在单斜ZrO_2上加入Ce可以提高表面的酸性,进而改变其催化性能。     

PSF-Pebax 3533复合膜的制备及其CO_2/N_2分离性能的研究

采用溶液涂膜法制备了一系列聚砜(PSF)/聚醚嵌段酰胺(Pebax 3533)复合膜,通过傅里叶变换红外光谱、X射线衍射仪、扫描电子显微镜对复合膜的结构进行了表征,并进一步研究了各组分含量和测试温度对CO_2、N_2渗透选择性能的影响。对于PSF-Pebax复合膜,随着Pebax 3533含量的增加,复合膜的CO_2和N_2渗透系数增加,PSF-Pebax(60/40)与纯PSF相比,CO_2和N_2渗透系数分别提高了196%和215%,同时CO_2/N_2选择系数依然维持在20,展现出优良的气体渗透选择性能。此外,随着温度的升高,复合膜的CO_2和N_2的渗透系数明显增加。     

可逆CO_2/N_2响应型开关聚合物的合成及性能评价

以N-(3-二甲氨基丙基)甲基丙烯酰胺(DMAPMA)和丙烯酰胺(AM)为单体,以过硫酸铵和亚硫酸氢钠为引发剂进行自由基聚合,合成了一种CO_2/N_2开关响应型聚合物P(DMAPMA-AM)。通过单因素实验得出最佳合成条件为:n(AM)∶n(DMAPMA)=4∶1、单体总质量分数为25%、n[(NH_4)_2S_2O_8]∶n(NaHSO_3)=2∶3、引发剂加入量为单体总质量的0.2%、反应温度40℃、反应时间4 h。用FTIR、1HNMR对产物进行了结构表征,测量了质量分数为0.2%的聚合物水溶液在通入CO_2/N2前后的电导率、Zeta电位和平均粒径,并对其乳化性能进行了考察。结果表明:在通入CO_2后,溶液的电导率由12.6μs/cm上升到40.7μs/cm,Zeta电位由1.25 m V上升到10.11 m V,平均粒径由708.6 nm降低到137.1 nm,而向溶液改通N2后溶液的电导率降到14.2μs/cm,Zeta电位下降到1.96 m V,平均粒径上升到589.8 nm,表明P(DMAPMA-AM)具有可逆的CO_2/N2开关响应性能。扫描电镜测试发现,通入CO_2/N_2前后聚合物线团的尺寸以及疏水颗粒的数目发生了显著变化。CO_2/N2能将聚合产物存在的油水混合体系进行有效的破乳/乳化。     

沉淀剂对Ni-Al_2O_3催化剂结构及基于浆态床的CO甲烷化性能的影响

利用行星式球磨机,以NH_4HCO_3、Na_2CO_3和(NH_4)_2CO_3为沉淀剂,采用机械化学法制备3种负载型Ni-Al_2O_3催化剂(分别记为Ni-NH4HC、Ni-Na C和Ni-NH_4C)。利用XRD、H2-TPR、N_2吸附-脱附、SEM和TPH等对催化剂进行表征,考察沉淀剂对Ni-Al_2O_3催化剂晶相结构、还原特征、孔道结构、表面形貌和浆态床CO甲烷化性能的影响。结果表明,以(NH_4)_2CO_3为沉淀剂所制备的Ni-NH_4C催化剂比表面积较大;活性组分晶粒尺寸较小。催化剂性能评价表明,CO甲烷化的"初始段"约需1 h,Ni-NH_4C和Ni-NH_4HC试样在"稳定段"的CO转化率均较高,约为77%;而Ni-NH_4C的CH_4选择性更高,在90%左右,这与催化剂活性金属的"尺寸效应"有较大关联。     

G-C_3N_4/CeO_2光催化剂的制备及其还原CO_2的性能研究

环境和能源问题是人类在21世纪面临的两个重大问题。利用有效的光催化剂将CO_2催化转化为碳氢燃料既有利于改善环境,又可以缓解能源问题。将类石墨相氮化碳(g-C_3N_4)与氧化铈(Ce O2)复合形成异质结复合材料作为光催化剂。利用XRD、TEM、FT-IR、DRS、光致发光等手段对制备的光催化剂进行表征,表征结果表明中空氧化铈纳米球分布在g-C_3N_4表面,引进氧化铈增强g-C_3N_4的光学性能;在可见光条件下进行光催化还原CO_2的实验,光催化结果表明,氧化铈的引进提高了g-C_3N_4的光催化效率。     

ZrB2质与TiB2质耐火材料

介绍了ZrB2 与TiB2 以及其他一些非氧化物高温材料的性质 ;ZrB2 与TiB2 在高温工业中的应用与预期发展 ;ZrB2 与TiB2 原料与制品的生产 ,包括自蔓延高温合成ZrB2 与TiB2 ;ZrB2 质与TiB2 质复合材料 ,如ZrB2 -SiC ,TiB2-SiC ,ZrB2 -BN ,TiB2 -BN ,ZrB2 -MoSi2 ,TiB2 -MoSi2 ,ZrB2-C ,TiB2 -C ,ZrB2 -B4C ,TiB2 -B4C等。     

Electronic Structure and Properties of the O2+2, SO2+ and S2+2 Diatomic Dications

Multiply charged ions show novel energetic features which can potentially have useful photophysical properties. In order to investigate these interesting type systems, energy interaction curves for the ground and excited electronic states of O²⁺₂, SO²⁺, and S²⁺₂ have been generated by the ab initio complete active space multiconfiguration self-consistent field (CAS-MCSCF) method. The calculations were carried out in a triple-zeta sp plus double-zeta d Gaussian function basis set using compact effective potentials to replace the core electrons. In order to gauge the accuracy of the results, analogous calculations were carried out on the valence isoelectronic N₂ and NO⁺ systems for which experimental information is available for comparison of geometric and spectroscopic properties. Diverse high energy spectroscopy experiments on O²⁺₂ are interpreted and reconciled using the calculated ground and excited state energy interaction curves. Special attention is paid to the ₃Σ₊^u state, whose location and character have been particularly puzzling. Almost all the dication molecular states studied show the characteristic avoided crossing of diabatic states which gives a trapped equilibrium structure and a barrier to dissociation. These features make the dication kinetically stable, but thermodynamically unstable with an exothermic dissociation energy. The spectroscopy experiments on O²⁺₂ show that these states are experimentally attainable.     

Eu~(2+)掺杂SrSi_2O_2N_2和Sr_(0.37)Ba_(0.60)Si_2O_2N_2荧光粉的发光性能及应用

采用高温固相法合成Sr_(0.97)Eu_(0.03)Si_2O_2N_2和Sr_(0.37)Ba_(0.60)Eu_(0.03)Si_2O_2N_2荧光粉,通过X射线衍射、激发光谱、发射光谱及转换后LED器件的性能等研究了荧光粉的结构、发光性能和稳定性。结果表明:在稀土Eu2+掺杂的Sr Si2O2N2荧光粉中,当部分Sr2+被Ba2+取代后,形成三斜晶系的Sr_(0.37)Ba_(0.60)Eu_(0.03)Si_2O_2N_2荧光粉,激发和发射光谱红移,在近紫外-蓝光区具有更高的激发效率。将2种荧光粉与Ga(N)In芯片封装,Sr0.37Ba0.60Eu0.03Si2O2N2荧光粉转换的白光LED器件,在光效、显色指数和光效维持特性方面均高于Sr_(0.97)Eu_(0.03)Si_2O_2N_2转换的LED器件。     

沉淀法白炭黑与纳米级二氧化硅

依据二氧化硅粒子的形成过程，指出传统沉淀法白炭黑并不具有科学意义上的纳米实质，研究重点侧重于改进其分散性能，同时也简介了纳米二氧化硅的制备方法及用途。     

多卤代吡啶选择性合成醚类的反应

以KOH为碱,DMSO为溶剂,在空气中,温度为50℃的条件下,多卤代吡啶和苯酚类化合物反应,形成相应的醚类化合物,该反应具有很好的收率以及区域选择性,是一种有效构建C-O键的方法;以K_2CO_3为碱,DMSO和H_2O为溶剂,在空气中,室温下,多卤代吡啶和苯硫酚类化合物反应,形成相应的的吡啶硫醚化合物,该反应也具有很好的收率以及区域选择性,是一种有效构建C-S键的方法。     

Separation and purification of aflatoxins B1, B2, G1 and G2, and comparison of semi-synthetic aflatoxins B2 and G2 with naturally-occurring aflatoxins B2 and G2

A method is described for the isolation of highly purified aflatoxins B₁, B₂, G₁ and G₂ from extracts ofAspergillus flavus. The four aflatoxins, isolated from background impurities by rapid passage of the extracts through an acid alumina column, are separated from each other by chromatography on a silica gel column. Aflatoxins B₂ and G₂ are prepared by hydrogenation of the mixture of aflatoxins B₁, B₂, G₁ and G₂ and then separated by elution from a silica gel column with chloroform containing 0.7% ethanol. A comparison of semi-synthetic aflatoxins B₂ and G₂ with naturally-occurring aflatoxins B₂ and G₂ shows no significant difference in physical properties. Presented at the AOCS-AACC Meeting, Washington, D.C. April, 1968.     

氢氧直接合成法制过氧化氢技术进展

氢气和氧气直接合成过氧化氢是典型的原子经济性反应，因过程简单、产品清洁、生产成本低而成为催化领域研究开发的一个热点。总结了该法近年来在催化剂活性组分的选取及载体方面的进展；详细介绍了溶剂的选取和反应机理；讨论了各种反应器的安全性。指出今后的研究重点是提高氢气利用率、开发新型的反应器、提高过程的安全性。     

Solubility and microstructural development of TiO2-containing 3Al2O3·2SiO2 and 2Al2O3·SiO2 mullites obtained from single-phase gels

The interdependence of the titanium oxide amount and the anisotropic growth of mullites prepared from single-phase gels were investigated. Gels with stoichiometries 3(Al_2−xTi_xO₃)·2(SiO₂) and 2(Al_2−xTi_xO₃)·(SiO₂), with 0 ≤ x ≤ 0.15 were prepared by the semialkoxide method. Gels and specimens heated at temperatures between 1200 and 1600 °C were characterized by using infrared spectroscopy (IR), X-ray diffraction (XRD) and transmission and field emission scanning electron microscopies (TEM and FESEM). Al₂TiO₅ as minor impurity was detected in both series of mullites for gel precursor compositions x = 0.10 and x = 0.15, obtained at temperatures between 1200 and 1600 °C. Variations of lattice parameters of mullite, processed at temperatures from the range between 1400 and 1600 °C, with the starting nominal amount of titanium oxide indicated that the solubility limit of titanium oxide was in ranges 3.8–4.1 and 4.1–4.4 wt% TiO₂ for 3:2 and 2:1 mullites series, respectively. The anisotropic growth of titanium-doped mullite crystalline grains was significant only when the nominal amount of titanium oxide exceeded the limit of solubility into the mullite structure (for both mullite series). Stronger anisotropy occurred for the 3:2 series specimens, i.e. for the SiO₂-richer mullites. In both series of mullites, the anisotropic grain growth was observed for the process temperatures higher than 1400 °C; the crystalline grains of mullites processed at lower temperatures were equiaxials and of almost the same size.     

生产乙炔对电石的要求及乙炔清净

目前国内外乙炔大部分仍是由电石制得。然而由于工业电石除CaC2 外还含有很多杂质 ,所以生产乙炔不仅要求电石的纯度、粒度 ,还要求水温。一般电石的块度采用 8～ 2 5mm ,发生器温度控制在 85± 5℃ ,乙炔气体中含H2 S、H3 P、NH3 等气体会使氯乙烯合成氯化催化剂活性下降。因此 ,必须对乙炔气体进行清洁。采用次氯酸钠液体的氧化性将乙炔中的杂质氧化成酸性物质而除去。