溶胶-凝胶法制备TiO_2-Al_2O_3复合光催化剂及其表征

以钛酸四正丁酯为钛源,异丙醇铝为铝源,采用溶胶-凝胶法制备了TiO2-Al2O3复合光催化剂,考察其对甲基橙的吸附性能和在紫外光照射下的光催化活性。采用X射线衍射(XRD)、X射线光电子能谱(XPS)、傅里叶变换红外光谱(FT-IR)、N2吸附-脱附等对催化剂的晶相结构、化学组成及BET比表面积和孔径分布等进行了表征。结果表明TiO2-Al2O3复合光催化剂由TiO2和Al2O3组成,其中TiO2为单一的锐钛矿晶相,Al2O3为非晶态,Al2O3的存在可抑制TiO2晶粒的生长。在n(Ti)/n(Al)=12,500℃煅烧3h制得的TiO2-Al2O3复合光催化剂比表面积达99.21m2/g,平均孔径为22.39nm,累计孔容积为0.4493cm3/g。在500℃煅烧制得的复合光催化剂具有最佳的光催化活性和吸附性能。与纯TiO2相比,相同条件下TiO2-Al2O3复合光催化剂的光催化活性和吸附性能都有较大提高。     

地聚合物混凝土抗冻性影响因素

通过调整地聚合物的氧化物SiO2/Al2 O3、Na2 O/Al2 O3和H2 O/Na2 O的物质的量比,利用碱激发偏高岭土制备不同强度等级的地聚合物混凝土.同时,用相同强度等级的普通硅酸盐水泥(OPC)混凝土作对比,评价地聚合物混凝土的抗冻性.结果表明:随着n(Na2O)/n(Al2O3)和n(H2 O)/n(Na2 O)增大,地聚合物混凝土的抗冻性降低;当n(SiO2)/n(Al2 O3)=3.3时,地聚合物混凝土的抗冻性最佳,冻融循环次数可达200.当地聚合物混凝土达到冻融极限时,相对动弹性模量损失较小,说明其冻融破坏的主要形式是表面脱落,而其内部结构破坏速率较OPC混凝土更慢.当抗压强度为30～50 MPa时,地聚合物混凝土抗冻性略优于OPC混凝土的抗冻性;但抗压强度在50～70 MPa时,OPC混凝土抗冻性远优于地聚合物混凝土抗冻性.此外,地聚合物混凝土具有较高水饱和系数,值均在0.85～0.95,说明地聚合物混凝土孔结构以开口孔为主.     

SiO2-Al2O3干凝胶的制备与性能研究

采用二步酸碱催化溶胶-凝胶和常压干燥法,制备了低密度多孔xSiO2-(1-x)Al2O3干凝胶,其中摩尔比x分别取0.9、0.8、0.7和0.6.SiO2凝胶按照n(正硅酸乙酯(TEOS)):n(H2O):n(无水乙醇):n(HCl):n(氨水)=1: 4:7:7.5×10-4:0.0375制备,主要作为二元复合氧化物的网络骨架.Al2O3由廉价的Al(NO3)3·9H2O与NH4OH反应制得.采用BET、XRD、IR、SEM和TEM等实验手段,对xSiO2-(1-x)Al2O3干凝胶在300、600、900、1200℃4个热处理温度下的组织结构进行了对比和分析.结果表明,最终的二元干凝胶是由纳米颗粒组成的非晶网络与Al2O3晶体共同构成的纳米多孔结构,具有高的比表面积和窄的孔径分布.该复合干凝胶中,Al2O3进入SiO2骨架中,形成一定数量的Si-O-Al键,并随着Al含量的增加而增多.其中的Al2O3随着温度的升高,经历γ-AlOOH、γ-Al2O3,最终完全转化成α-Al2O3,SiO2则始终以非晶态形式存在.由于干凝胶中Al2O3的存在,大大提高了材料的热稳定性.     

纳米TiO2/SiO2复合催化剂的制备与表征

以钛酸四丁酯、正硅酸乙酯作为前驱体,冰醋酸作为水解抑制剂,用溶胶-凝胶法制备了纳米TiO2/SiO2复合物.讨论了加水量、稳定剂、催化剂、乙醇用量、反应温度等工艺因素对制备过程的影响.用X射线衍射、红外光谱、比表面积仪等测试手段对纳米TiO2/SiO2复合粒子进行了表征.结果表明,用溶胶-凝胶法制备TiO2/SO2复合光催化粒子,整个反应采用滴加方式;各反应组分用量为n(TEOS+TBOT) :n(EtOH) :n(HCl) :n(H2O)=1 :16 :0.06 :4,n(TBOT) :n(HAc)=1 :0.6;反应温度为室温.制备得到的纳米TiO2/SiO2复合粒子主要以锐钛矿型存在;SiO进入TiO2晶体结构中,两者以化学键相结合;TiO2/SiO2复合粒子的比表面积要比纯TiO2粒子的比表面积大得多,当xTi :xsi=3时,TiO2/SiO2复合粒子比表面积达389.11 m2/g.     

双层包覆对铝粉耐腐蚀性能的影响

为了提高铝粉的耐腐蚀性能,在铝粉表面进行了无机-有机、有机-无机双层包覆,研究了反应温度、反应时间、引发剂偶氮二异丁腈(AIBN)用量、分散剂聚乙烯基吡咯烷酮(PVP)用量、n(SiO2)/n(Al)、n(H2O)/n(SiO2)对包覆效果的影响.结果表明,无机-有机包覆的最优条件是:反应温度65℃;反应时间1h;引发剂用量0.030 g,分散剂用量为0.500 g.而有机-无机双层包覆的最优条件是:n(SiO2)/n(Al)=20%,反应温度为30℃,n(H2O)/n(SiO2)=10.与原料铝粉相比,无机、有机单层包覆的缓蚀效率分别为66.1%、80.0%,而无机-有机双层包覆与有机-无机双层包覆铝粉的缓蚀效率分别可达96.4%、97.9%,即通过在铝粉表面进行双层包覆可有效地提高其耐腐蚀性能.     

TiO2-SiO2纳米多孔材料常压干燥制备

以廉价的TiCl4和工业水玻璃为原料,通过溶胶-凝胶法制得了TiO2-SiO2复合湿凝胶,用三甲基氯硅(TMCS)/乙醇(EtOH)/己烷(Hexane)溶液对湿凝胶进行改性,再经常压干燥制备了TiO2-SiO2纳米多孔材料.利用扫描电子显微镜(SEM)、红外吸收光谱(FTIR)和N2吸附/解吸法对纳米多孔材料的形貌和性质进行了分析.结果表明,所制备的TiO2-SiO2纳米多孔材料为轻质块状固体,具有连续多孔结构,密度为0.14～O.25g/cm3,孔隙率为88.6%～93.6%,比表面积为716.8～802.7m2/g.吸附和光催化降解罗丹明B的结果表明,n(Ti):n(Si)=1:3的样品吸附率最高,20h时达到86%,n(Ti):n(Si)=1:2的样品光催化降解率最高,10h时可达到94%.     

颜料铝粉包覆SiO2的研究

以硅酸钠(Na2SiO3)为原料在颜料铝粉表面包覆SiO2,研究了SiO2/Al质量比(m(SiO2)/m(Al))、温度和pH值对铝粉析氢的影响,研究表明,最佳包覆条件为:m(SiO2)/m(Al)=7.5%,T=75℃,pH=9.5.并运用光学显微镜、SEM、IR和XRD对包覆样品进行了分析与表征.     

SiO2对Al2O3凝胶纤维相变的影响

以尿素催化硅酸乙酯水解制得SiO2溶胶。采用29Si NMR、27 Al NMR、FT-IR、TEM、DTA、XRD和SEM等对SiO2溶胶、Al2O3凝胶纤维化学结构和微观结构研究结果表明,该SiO2溶胶稳定性好,含有大量的单硅酸Si(OH)4,能和Al2O3表面的Al—OH反应生成Al—O—Si键而有效地将其包裹,从而阻止了过渡态Al2O3微晶的相互接触,抑制了α-Al2O3的成核和生长。     

水滑石除磷的吸附动力学研究

采用共沉淀法制备了Mg/Al水滑石,研究了不同Mg/Al物质的量比、材料用量、不同pH条件下Mg/Al水滑石吸附除磷的动力学特征,从而对吸附速率的控制过程进行分析。结果表明水滑石对磷的吸附能较好地符合准二级动力学方程、Elovich动力学方程和内扩散模型。n(Mg)/n(Al)=3是水滑石最理想配比,水滑石投加量越大,外扩散过程越慢;一定范围内pH的升高能促进水滑石对磷吸附速率和吸附容量的提升。     

P(AA/IA/MA)凝胶的制备及对铜离子吸附性能研究

通过以丙烯酸(AA),衣康酸(IA),马来酸酐(MA)为单体,N,N-亚甲基双丙烯酰胺(MBA)为交联剂,采用水溶液聚合制备了三元共聚P(AA/IA/MA)水凝胶,并采用FTIR对凝胶结构进行表征。针对不同组成凝胶的溶胀动力学、平衡吸附能力及铜离子饱和吸附容量的研究,结果表明:最佳投料比为n(AA):n(IA):n(MA)=6:3:1,其最大饱和吸附容量可达到224.5mg/g,P(AA/IA/MA)凝胶材料的等温吸附动力学可归属为准二级动力学。考察了体系pH值及吸附材料用量对Cu2+吸附性能的影响,结果表明:P(AA/IA/MA)凝胶吸附材料的Cu2+饱和吸附容量强烈依赖于体系pH值和吸附材料用量。当P(AA/IA/MA)凝胶吸附材料添加量为0.5g/50mL时,体系内Cu2+去除率接近100%。     

新型铝改性硅胶吸附材料的制备与性能

陶瓷纤维纸经水玻璃、酸性铝盐溶液顺次浸渍得到新型铝改性硅胶吸附材料．反应的优化条件为：水玻璃浓度26．6wt％、铝盐浓度10wt％、溶液pH值1．8．^29Si和^27AlMAS NMR谱显示：铝替代硅进入SiO4硅氧四面体结构单元，但并不影响其骨架结构；红外光谱显示Si—OH对称伸缩振动峰由968cm^-1移至Si(Al)-OH的954cm^-1；扫描电镜图表明铝改性硅胶能较好地分散在瓦楞陶瓷纤维表面及其孔隙中；X射线能谱(EDS)揭示材料表面微区Al^3 的存在与含量,孔隙分析显示材料起吸附作用的主要为中孔；由于铝离子改性，新型吸附材料的吸附性能、耐热性能及机械强度等均优于同等条件下反应生成的硅胶．     

Improvement of metakaolin on radioactive Sr and Cs immobilization of alkali-activated slag matrix

Effects of metakaolin on simulated radioactive Sr or Cs immobilizing behavior of alkali-activated slag (AAS) matrix were evaluated by cation exchange capacity (CEC), distribution ratio of selective adsorption, leaching test and porosity analyses. The results revealed that the additions of metakaolin into the AAS matrixes largely enhanced their distribution ratios K(d) of selective adsorption on Sr and Cs ions. Meanwhile, this new immobilizing matrix M-AAS showed the lowest leaching rate. Hydration product analyzes by XRD, DTA, FTIR and SEM demonstrated that (Na+Al)-substituted calcium silicate hydrate (CSH) and self-generated zeolite were major hydration products in the M-AAS matrix. These products have better Sr and Cs selective adsorption as compared to C-S-H without any substitution and natural zeolite minerals.     

Uptake properties of Ni2+ by nCaO.Al2O3.2SiO2 (n=1-4) prepared from solid-state reaction of kaolinite and calcite

A series of nCaO.Al2O3.2SiO2 samples (n=1-4) were prepared by solid-state reaction of mechanochemically treated mixtures of kaolinite and calcite fired at 600-1000 degrees C for 24 h. All the samples were X-ray amorphous after firing at 600-800 degrees C but had crystallized by 900 degrees C. The main crystalline phases were anorthite (n=1), gehlenite (n=2 and 3) and larnite (n=4). The uptake of Ni2+ by nCaO.Al2O3.2SiO2 samples fired at 800 and 900 degrees C was investigated at room temperature using solutions with initial Ni2+ concentrations of 0.1-50 mmol/l. Amorphous samples (fired at 800 degrees C) showed a higher Ni2+ uptake capacity than crystalline samples (fired at 900 degrees C). Ni2+ uptake was found to increase with increasing of CaO content. Amorphous 4CaO.Al2O3.2SiO2 showed the highest Ni2+ uptake capacity (about 9 mmol/g). The Ni2+ uptake abilities of the present samples are higher than those of other materials reported in the literature. Since the sorbed Ni2+/released Ca2+ ratios of these samples are close to unity, ion replacement of Ni2+ for Ca2+ is thought to be the principal mechanism of Ni2+ uptake by the present samples.     

Photocatalytic reduction of Cr(VI) on the new hetero-system CuAl2O4/TiO2

A magnetic adsorbent, amine-functionalized silica magnetite (NH(2)/SiO(2)/Fe(3)O(4)), has been synthesized to behave as an anionic or cationic adsorbent by adjusting the pH value of the aqueous solution to make amino groups protonic or neutral. NH(2)/SiO(2)/Fe(3)O(4) were used to adsorb copper ions (metal cation) and Reactive Black 5 (RB5, anionic dye) in an aqueous solution in a batch system, and the maximum adsorption were found to occur at pH 5.5 and 3.0, respectively. The adsorption equilibrium data were all fitted the Langmuir isotherm equation reasonably well, with a maximum adsorption capacity of 10.41 mg g(-1) for copper ions and of 217 m g g(-1) for RB5. A pseudo-second-order model also could best describe the adsorption kinetics, and the derived activation energy for copper ions and RB5 were 26.92 kJ mol(-1) and 12.06 kJ mol(-1), respectively. The optimum conditions to desorb cationic and anionic adsorbates from NH(2)/SiO(2)/Fe(3)O(4) were provided by a solution with 0.1M HNO(3) for copper ions and with 0.05 M NaOH for RB5.     

Molecular modification of a novel macroporous silica-based impregnated polymeric composite by tri-n-butyl phosphate and its application in the adsorption for some metals contained in a typical simulated HLLW

Using tri-n-butyl phosphate (TBP) as a molecular modifier, a novel macroporous silica-based 4,4',(5')-di-(tert-butylcyclohexano)-18-crown-6 (DtBuCH18C6) polymeric composite (DtBuCH18C6+TBP/SiO2-P) was synthesized. It was done by impregnating and immobilizing DtBuCH18C6 and TBP molecules into the pores of SiO2-P particles utilizing an advanced vacuum sucking technique. The adsorption of 10 fission and non-fission products Sr(II), Ba(II), Ru(III), Mo(VI), Na(I), K(I), Pd(II), La(III), Cs(I), and Y(III) onto (DtBuCH18C6+TBP)/SiO2-P was investigated by examining the influence of contact time and the HNO3 concentration in a range of 0.1-5.0M at 298 K. It was found that at the optimum concentration of 2.0M HNO3 (DtBuCH18C6+TBP)/SiO2-P exhibited strong adsorption ability and high selectivity for Sr(II) over all of the tested elements, which showed very weak or almost no adsorption except Ba(II). Moreover, the quantity of DtBuCH18C6 leaked from (DtBuCH18C6+TBP)/SiO2-P in 2.0M HNO3, 326.2 ppm, was obviously lower than 658.4 ppm that leaked from DtBuCH18C6/SiO2-P. This was ascribed to the effective association of DtBuCH18C6 and TBP through intermolecular interaction, i.e., hydrogen bonding. The significant reduction of DtBuCH18C6 leakage by molecular modification with TBP was achieved. It was of great benefit to application of the (DtBuCH18C6+TBP)/SiO2-P polymeric composite in chromatographic partitioning of Sr(II), one of the main heat generators, from high level liquid waste (HLLW) in reprocessing of nuclear spent fuel in MAREC process developed recently.     

纳米Al2O3与SiO2的制备及在陶瓷釉料中的应用

以普通无机盐为原料采用沉淀法制备了纳米Al2O3和SiO2.XRD分析表明样品为无定形结构,SEM分析表明得到的纳米Al2O3和SiO2均为球形颗粒,直径分别为90m和300nm.将合成的纳米材料添加至陶瓷面釉进行烧结测试,结果表明,添加纳米材料釉料的烧结温度比普通釉料的烧结温度降低了30℃,釉层性能明显得到改善,釉料良好的性能源于纳米材料较大的表面积及高的烧结活性.     

EG/Na X型沸石复合材料的制备及其对苯气体的吸附

采用水热合成方法, 在膨胀石墨(EG)的孔壁内部和表面合成沸石, 制备EG/Na-X型沸石复合材料, 研究了SiO₂/Al₂O₃摩尔比对沸石类型的影响。采用XRD、FE-SEM、FTIR、N₂吸附-脱附等温线及静态保干器法对制得的复合材料进行表征。结果表明: 沸石类型受SiO₂/Al₂O₃摩尔比影响较大, 随SiO₂/Al₂O₃摩尔比的增加, 沸石类型逐渐由Na-A型向Na-X型转变, 在摩尔比SiO₂/Al₂O₃=7.9时, Na-A型沸石全部转变为呈八面体形状的Na-X型沸石。吸附温度为25 ℃时, EG/Na-X型沸石复合材料对苯气体的静态饱和吸附量可达340 mg/g。      

Fe~(3+)/Ti~(4+)赋存状态对钛酸铝/莫来石复合材料结构的影响

借助XRD、SEM和能谱分析仪等手段,研究了1 600℃煅烧中低品位矾土制备的钛酸铝/莫来石(Al_2TiO_5ss/3Al_2O_3·2SiO_2ss)复合材料经1 200℃保温12h后结构的稳定性。结果表明:高温煅烧中低品位矾土后,其合成材料的结晶物相组成为3Al_2O_3·2SiO_2ss、Al_2TiO_5ss和少量残存的方石英;Fe~(3+)或Ti~(4+)离子以不同形态赋存于结晶相(3Al_2O_3·2SiO_2ss和Al_2TiO_5ss)和非晶相。含Fe~(3+)/Ti~(4+)离子的3Al_2O_3·2SiO_2ss将Al_2TiO_5ss结晶相分割,使其蜷缩其间,并抑制Al_2TiO_5ss的分解;高温下,二者因组成元素相近而致使晶界融合,进而共同构建了体系牢固的致密骨架结构。由3Al_2O_3·2SiO_2ss和Al_2TiO_5ss等高温物相构成的致密结构将非晶相挤压于空隙结构的3Al_2O_3·2SiO_2ss晶间,避免了低熔点相富集带来的不利影响,进而赋予该Al_2TiO_5ss/3Al_2O_3·2SiO_2ss复合材料良好的结构稳定性。     

Corrosion Resistance of Plasma Sprayed Ceramic CompositeCoatings on Q235 Substrate

The corrosion resistance of SiO2/Al2O3, TiO2/Al2O3 and (SiO2+TiO2)/Al2O3 ceramic composite coatings on Q235 substrate fabricated by means of plasma spraying was investigated. The results show that Al2O3+13 wt pct TiO2 ceramic coating has the highest density, the lowest connected porosity and the best corrosion resistance. The corrosion mechanism of Q235 with ceramic coating has also been studied.     

Influence of ionic strength in the adsorption and during photocatalysis of reactive black 5 azo dye on TiO2 coated on non woven paper with SiO2 as a binder

Reactive black 5 (RB5), an azo dye, was degraded by using UV-irradiated TiO(2) coated on non woven paper with SiO(2) as a binder. The adsorption capacity of the photocatalyst was studied at natural pH, superior to pH(pzc) of the binder, for various ionic strengths. Different salts such as NaCl, KCl, CaCl(2), LiCl, Ca(NO(3))(2) were used to increase the ionic strength. The presence of salt increased the adsorption capacity. The electrostatic interactions between dye and oxide surface charges (TiO(2)/SiO(2)) is very important in the adsorption phenomena. The effect of the ionic strength of the solution on photocatalyst degradation was studied. The rate of degradation was increased by the presence of salts in the range of the experimental conditions. The increase of the initial decolorization rate was observed in the following order: Ca(2+)>K(+)>Na(+)>Li(+). Experiments with different anions (Cl(-), NO(3)(-)) had shown that nitrate was an indifferent electrolyte for the adsorption and photodegradation of the dye on SiO(2)/TiO(2).