聚酰亚胺/SnO_2杂化膜的制备和表征及其气体渗透性测定

杂化材料作为一种新型材料结合了有机无机材料的优异特性，具有较高的热稳定性、机械强度和某些特殊的化学性质，在微电子、光电设备、传感器和分离膜等诸多领域得到应用与研究．溶胶凝胶法作为合成杂化材料的主要手段，具有反应条件温和，可通过调配反应参数来控制杂化材料的微观形态和性质等优点．     

溶胶凝胶法合成聚酰亚胺二氧化钛杂化膜

溶胶凝胶法制备了负载型聚酰亚胺 二氧化钛杂化膜 ,采用扫描电镜、红外光谱、TG DTA、压汞法和气体渗透性能测试装置对膜材料的表面形貌、表面结构、热性能、孔径分布和气体渗透性能进行了表征 .结果表明 ,杂化膜材料形成了有机相包裹无机相的交联结构 ;聚酰亚胺与二氧化钛粒子形成了新型键联结构 ;其热分解温度随二氧化钛含量的增加而降低 ,在 4 5 0℃以下热稳定性优于聚酰亚胺膜材料 ;平均孔径随二氧化钛含量增大而增大 ,孔径分布趋于弥散 ;N2 、H2 和CO2 在膜内渗透由Knudsen扩散控制 ,H2 O N2 分离因子均大于Knudsen扩散值 ,表现出良好的亲水性 .     

Low-temperature CO oxidation over CuO-CeO2/SiO2 catalysts：Effect of CeO2 content and carrier porosity

The effects of CeO2 contents and silica carder porosity with their pore diameters ranging from 5.2 nm to 12.5 nm of CuO-CeO2/SiO2 catalysts in CO oxidation were investigated. The catalysts were characterized by N2 adsorption/desorption at low temperature, X-ray diffraction (XRD), temperature-programmed reduction by H2 (H2-TPR), oxygen temperature programmed desorption (O2-TPD) and X-ray photoelectron spectroscopy (XPS). The results suggested that, the ceria content and the porosity of SiO2 carder possessed great impacts on the structures and catalytic performances of CuO-CeO2/SiO2 catalysts. When appropriate content of CeO2(Ce content ≤8 wt%) was added, the catalytic activity was greatly enhanced. In the catalyst supported on silica carrier with larger pore diameter, higher dispersion of CuO was observed, better agglomeration-resistant capacity was displayed and more lattice oxygen could be found, thus the CuO-CeO2 supported on Si-1 showed higher catalytic activity for low-temperature CO oxidation.     

Physicochemical aspects of novel surfactantless, self-templated mesoporous SnO2 thin films

A novel method of synthesis consisting of the production of ordered arrangements of tubular pores distributed inside SnO2 annealed thin films, which are prepared from a rotating disk process carried out at 2000-3500 rpm, is herein described. The main novelty is that no surfactant molecules are required in order to create these ordered pore structures; the templating entities are supramolecular assemblies of oligomeric chains formed during the extra-long aging allowed to the sol-gel processing of tin(IV) tetra-tert-amiloxide, Sn(OAm(t))4, chelated with acetylacetone molecules. Low angle X-ray diffraction peaks of SnO2 thin films calcined at 500 degrees C clearly certify the existence of ordered mesostructures when employing the right H2O/Sn(OAm(t))4 molar ratio during the SnO2 sol-gel synthesis. The final SnO2 ordered mesostructures are reminiscent of those linked to MCM-41 and SBA-15 substrates. Pore-size distribution analyses proceeding from N2 sorption isotherms at 76 K on the SnO2 thin films calcined at 500 degrees C unequivocally confirm the presence of tubular mesopores (mode pore sizes ranging from 5 to 7 nm). The thicknesses of the SnO2 films range from 80 to 150 nm after performing a drying process at 100 degrees C and from 70 to 125 nm after calcining in air at 500 degrees C; these film thicknesses show, in general, decreasing trends when either the spinning rate or the H2O/(Sn(OAm(t))4 ratio is increased.     

Low-temperature CO oxidation over CuO-CeO_2/SiO_2 catalysts:Effect of CeO_2 content and carrier porosity

The effects of CeO2 contents and silica carrier porosity with their pore diameters ranging from 5.2 nm to 12.5 nm of CuO-CeO2/SiO2 cata-lysts in CO oxidation were investigated.The catalysts were characterized by N2 adsorption/desorption at low temperature,X-ray diffraction (XRD),temperature-programmed reduction by H2 (H2-TPR),oxygen temperature programmed desorption (O2-TPD) and X-ray photoelectron spectroscopy (XPS).The results suggested that,the ceria content and the porosity of SiO2 carrier possessed great impacts on the structures and catalytic performances of CuO-CeO2/SiO2 catalysts.When appropriate content of CeO2 (Ce content 8 wt%) was added,the catalytic activity was greatly enhanced.In the catalyst supported on silica carrier with larger pore diameter,higher dispersion of CuO was observed,better agglomeration-resistant capacity was displayed and more lattice oxygen could be found,thus the CuO-CeO2 supported on Si-1 showed higher catalytic activity for low-temperature CO oxidation.     

金催化一氧化碳氧化反应中锌锡复合氧化物的载体效应

氧化物负载的纳米金催化剂对CO氧化反应具有极高的活性,这不仅依赖于金的结构特性,也取决于氧化物载体的结构.近年来,除了氧化硅、氧化铝等惰性载体以及氧化钛、氧化铈、氧化铁等可还原性载体外,人们还致力于探索各类新型氧化物载体.另一方面,锡酸锌是具有反尖晶石结构的化合物,并且在透明导电氧化物、锂离子电池阳极材料、光电转换装置以及传感器等方面应用广泛.然而,迄今为止,锡酸锌仍未被用于负载纳米金催化剂,因此相关的构效关系作用研究也十分有限.基于此,本文采用氮气吸附-脱附实验、电感耦合等离子体原子发射光谱(ICP-AES)、X射线衍射(XRD)、X射线光电子能谱(XPS)、透射电子显微镜(TEM)和高分辨电镜(HRTEM)、高角环形暗场像-扫描透射电子显微镜(HAADF-STEM)、X射线吸收精细结构谱(XAFS)和氢气程序升温脱附(H2-TPD)等手段,系统研究了锡酸锌负载的纳米金催化剂在CO氧化反应中催化性能差异的原因.首先,利用水热法制备了锡酸锌(ZTO)载体,而其织构性质可由碱(N2H4·H2O)与金属离子(Zn2+)的比例在4/1(ZTO_1)、8/1(ZTO_2)和16/1(ZTO_3)之间进行调节.结果发现, ZTO_2具有最大的孔体积(0.223 cm3/g)和最窄的孔径分布.再采用沉积沉淀法将0.7 wt% Au负载于其上,得到金-锡酸锌(Au_ZTO)催化剂. ICP-AES测得样品中Au含量在0.57-0.59 wt%,与投料比接近. CO氧化反应结果显示, Au_ZTO_1和Au_ZTO_2的表观活化能相同,但后者的活性更高;而Au_ZTO_3在220°C以下没有活性,催化性能最差,与纯锡酸锌载体相当. XRD结果显示,反应过程中ZTO晶相、晶胞参数及晶粒尺寸变化不明显; TEM和HRTEM分析表明,载体ZTO在反应前后均为多面体形貌,平均颗粒尺寸在12-16 nm; XPS结果验证了Zn2+和Sn4+离子是新鲜和反应后样品中载体金属的存在形式; HAADF-STEM探测到所有样品中均含有1-2 nm的Au粒子; XAFS结果表明, Au以Au0形式存在,并且在Au_ZTO_3中Au平均粒径大于4 nm,而其它两样品约为2 nm. H2-TPR结果表明,金的引入对ZTO载体耗氢量影响不大,但还原峰温度向低温移动;金属-载体相互作用强弱与催化活性高低具有正相关性,即Au_ZTO_2> Au_ZTO_1>> Au_ZTO_3.这是由于不同织构性质的锡酸锌载体对于纳米金活性物种的稳定作用不同所致,具有最大孔体积和最窄孔径分布的ZTO_2负载的金纳米颗粒表现出最高活性.     

定向含硼MFI型沸石膜对纯气体的渗透性以及对乙醇/水体系的分离选择性

研究定向含硼MFI型沸石膜和原多孔玻璃基材对纯气体的渗透性以及对乙醇/水体系的分离选择性.原多孔玻璃基材对纯气体的透过表现出诺森扩散选择性,表明气体以诺森扩散通过.纯气体透过焙烧后的B-A1-ZSM-5沸石膜,H₂,He,Ne,Ar,O₂,CO₂对N₂的理想选择性分别为16.8,15.6,12.6,9.41,8.60,5.32;CO和SO₂对N₂的理想选择性分别为0.135和0.0179;O₂对CO和SO₂的理想选择性分别为63.7和480.2.这表明该类沸石膜对纯气体的透过不仅具有良好的理想选择性,而且可能为新型防毒面具提供一种很好的可选材料.渗透汽化实验表明,在测定温度范围内原多孔玻璃基材对三种不同浓度的乙醇/水体系几乎没有分离性能.焙烧后的B-A1-ZSM-5沸石膜对5 wt%,50wt%和95wt%乙醇/水体系的分离,水的最大分离系数分别为28.2,135.7和518.5,且温度均为303 K.表明该MFI型沸石膜具有强的亲水性.     

Membrane formation mechanism and permeation properties of a novel porous polyimide membrane

The transport properties of a novel porous fluorinated polyimide membrane fabricated by a wet phase inversion process were studied with a stirred dead‐end filtration cell. The porous membrane‐forming solvents were tetrahydrofuran (THF), acetone, N,N‐dimethylacetamide (DMAc), N‐methylpyrrolidone (NMP), N,N‐dimethylformamide (DMF), and dimethylsulfoxide (DMSO). The phase separation phenomena in a ternary system of polyimide/solvent/water were investigated from cloud point curves by a titration method and binary interaction parameters. Solvent–water demixing in the system has been found to play very important roles in determining the structure and surface morphology of the polyimide membrane. The porous fluorinated polyimide membranes showed pore sizes from 4 to 500 nm and permeation properties from ultrafiltration to a microfiltration range. In this study, we particularly focused on fouling of the polyimide membranes, because fouling decreases the flux and increases the resistance. Interestingly, the porous polyimide membrane showed excellent water flux recovery after water cleaning compared with that of the polyethersulfone (PSf) membrane, which suggest that for a 6FDA‐6FAP membrane, the protein–membrane and protein–protein interaction was not so strong compared with those in a PSf membrane. Copyright © 2002 John Wiley & Sons, Ltd.     

表面修饰的有机-无机杂化微孔SiO2膜的制备及氢气分离性能

采用苯基三乙氧基硅烷(PTES)和1,2-双(三乙氧基硅基)乙烷(BTESE)为前驱体, 通过溶胶-凝胶法制备了苯基修饰的有机-无机杂化SiO2 膜材料. 通过N2吸附、视频光学接触角测量、热重分析和红外光谱对膜材料的孔结构和疏水性能进行了表征, 并深入研究了膜材料的氢气渗透和分离性能. 结果表明, 修饰后的膜材料具有微孔结构, 孔径集中分布在0.4~0.6 nm. 在温度为40 ℃, 湿度为70%~80%的水热环境下陈化30 d后, 膜材料仍保持微孔结构. 苯基修饰后膜材料具有疏水性, 当n(PTES)/n(BTESE)=0.6时, 膜材料对水的接触角达到(125±0.4)°. 氢气在膜材料中的输运遵循活化扩散机理, 300 ℃时, 膜材料的H2渗透率达到8.71×10-7mol·m-2·Pa-1·s-1, H2/CO2的理想分离系数达到5.53.     

几种芳杂环高分子膜对气体分离性能的研究

聚苯基-1,2,4-三嗪(PPT)、聚苯基单醚喹嗯啉(PPQ(E))、聚苯基喹哑心啉(PPQ(B))、聚酰亚胺(PI)和聚苯并咪唑吡咯酮(PY)均是耐高温高分子。本文制备了这些高聚物的均质膜(除PI外),研完了它们对O_2、N_2和H_2、N_2、CO、CH_4的分离性。     

Effect of O2 and H2O on the tri-reforming of the simulated biogas to syngas over Ni-based SBA-15 catalysts

A series of Ni/SBA-15 catalysts with Ni contents from 7.5 wt% to 15 wt% were prepared by impregnation method. The effect of O2 and H2O on the combined reforming of the simulated biogas to syngas was investigated in a continuous flow fixed-bed micro-reactor. The stability of the catalyst was tested at 800 ℃. The results indicated that 10 wt%Ni/SBA-15 catalyst exhibited the highest catalytic activities for the combined reforming of the simulated biogas to syngas. Under the reaction conditions of the feed gas molar ratios CH4/CO2/O2/H2O = 2/1/0.6/0.6, GHSV = 24000 ml•g{cat}-1\cdoth-1 and the reaction temperatureT = 800 ℃, the conversions of CH4 and CO2 were 92.8% and 76.3%, respectively, and the yields of CO and H2 were 99.0% and 82.0%, respectively. The catalytic activities of the catalyst did not decrease obviously after 100 h reaction time on stream.     

金属有机化学气相沉积法制备SnO2/MCM-41半导体传感器及其性能研究

采用金属有机化学气相沉积(MOCVD)法制备了SnO2/MCM-41半导体传感器, 考察了沉积时间和沉积温度对SnO2/MCM-41半导体传感器的SnO2沉积量、比表面积和孔径的影响; 研究发现, 随着SnO2沉积量的增加, 孔径有规律地下降, 说明SnO2较均匀地沉积在介孔分子筛MCM-41的孔道之中. SnO2/MCM-41半导体传感器对CO和H2具有较高的传感性能, 其传感性能的大小与CO和H2的浓度成正比.     

Effect of O_2 and H_2O on the tri-reforming of the simulated biogas to syngas over Ni-based SBA-15 catalysts

A series of Ni/SBA-15 catalysts with Ni contents from 7.5 wt% to 15 wt% were prepared by impregnation method.The effect of O2 and H2O on the combined reforming of the simulated biogas to syngas was investigated in a continuous flow fixed-bed micro-reactor.The stability of the catalyst was tested at 800 ?C.The results indicated that 10wt%Ni/SBA-15 catalyst exhibited the highest catalytic activities for the combined reforming of the simulated biogas to syngas.Under the reaction conditions of the feed gas molar ratios CH4/CO2/O2/H2O = 2/1/0.6/0.6,GHSV = 24000 ml gc?a1t h?1 and the reaction temperature T = 800 ?C,the conversions of CH4 and CO2 were 92.8% and 76.3%,respectively,and the yields of CO and H2 were 99.0% and 82.0%,respectively.The catalytic activities of the catalyst did not decrease obviously after 100 h reaction time on stream.     

H2 separation using defect-free, inorganic composite membranes

Defect-free, microporous Al(2)O(3)/SAPO-34 zeolite composite membranes were prepared by coating hydrothermally grown zeolite membranes with microporous alumina using molecular layer deposition. These inorganic composite membranes are highly efficient for H(2) separation: their highest H(2)/N(2) mixture selectivity was 1040, in contrast with selectivities of 8 for SAPO-34 membranes. The composite membranes were selective for H(2) for temperatures up to at least 473 K and feed pressures up to at least 1.5 MPa; at 473 K and 1.5 MPa, the H(2)/N(2) separation selectivity was 750. The H(2)/CO(2) separation selectivity was lower than the H(2)/N(2) selectivity and decreased slightly with increasing pressure; the selectivity was 20 at 473 K and 1.5 MPa. The high H(2) selectivity resulted either because most of the pores in the Al(2)O(3) layer were slightly smaller than 0.36 nm (the kinetic diameter of N(2)) or because the Al(2)O(3) layer slightly narrowed the SAPO-34 pore entrance. These composite membranes may represent a new class of inorganic membranes for gas separation.     

Synthesis and characterization of uniform alumina-mesoporous silica hybrid membranes

The synthesis and characterization of alumina-mesoporous silica (alumina-MS) hybrid membranes are reported. The hybrids are formed using a variation of the evaporative-induced self-assembly (EISA) process reported by Hayward et al. (Langmuir 2004, 20, 5998) based on dip coating of an Anopore 200 nm membrane with a Brij-56/TEOS/HCl/H2O solution. Numerous analytical methods are used to probe both the hybrid material and the silica phase after dissolution of the Anopore substrate. Most importantly, He/N2 permeation measurements show that the effective pore size of the membrane can be tuned from 20 to 5 nm based on the number of dip-coating cycles used. The observed He/N2 permselectivity of 2.7 +/- 0.11 is nearly identical to the theoretical value obtained (2.65) assuming Knudsen diffusion dominates. The selectivity of these membranes is higher than that of most commercial "5 nm" membranes (2.29), which is ascribed to the lack of pinhole defects in the materials reported here. The hybrid membranes as well as the silica obtained after dissolution of the Anopore substrate have been characterized using scanning and transmission electron microscopy and X-ray diffraction. Those results indicate that the silica deposited in the Anopore membrane possesses uniform pores approximately 5 nm in size, consistent with the permeation studies. The current work presents an alternative approach to materials that possess many of the properties of mesoporous silica thin films (i.e., pores of controlled size and topology) without the difficulty of growing mesoporous silica thin films on porous supports.     

钴掺杂二氧化硅膜的制备、表征及氢气分离性能

采用正硅酸乙酯(TEOS)和Co(NO3)2.6H2O为前驱体通过溶胶-凝胶法制备掺钴微孔二氧化硅膜,研究钴在二氧化硅膜材料中的存在状态、膜材料孔结构以及膜材料的气体渗透和分离性能。结果表明钴元素以Si-O-Co的形式存在于SiO2骨架之中,掺杂Co 10%的微孔SiO2膜具有典型的微孔结构,其孔体积为0.119 cm3·g-1,平均孔径在0.52 nm左右且孔径主要分布在0.4～0.55 nm之间。氢气在膜材料中的输运低温下遵循Knudsen扩散机理,高于100℃时遵循活化扩散机理,300℃时膜材料的H2渗透率达到6.41×10-7 mol.m-2.s-1.Pa-1,H2/CO2分离系数达到6.61,高于Knudsen扩散的理想分离系数。     

溶胶-凝胶法制备硅系有机-无机杂化分离膜

以α-Al₂O₃多孔陶瓷片为载体,用溶胶-凝胶法制备有机-无机杂化分离膜.通过考察前驱物的组成及杂化溶胶的合成条件对制膜工艺过程的影响,得到了制备有机-无机杂化分离膜的各种适宜性参数.红外光谱(FTIR)分析结果表明,杂化溶胶的性能不仅决定分离膜的性能,而且对膜热处理过程中的龟裂有很大影响.膜层的厚度为1～2μm;在膜两侧压差为0.10MPa、n(PTMOS)/n(TEOS)=1.16时,膜对O₂/N₂,CO₂/N₂和CO₂/O₂的分离因子分别为2.30,4.31和1.17,渗透系数为75.81×10^-17,75.28×10^-17和72.78×10^-17m₃(STP)·m/(m₂·s·Pa).     

Highly hydrothermally stable microporous silica membranes for hydrogen separation

Fluorocarbon-modified silica membranes were deposited on gamma-Al2O3/alpha-Al2O3 supports by the sol-gel technique for hydrogen separation. The hydrophobic property, pore structure, gas transport and separation performance, and hydrothermal stability of the modified membranes were investigated. It is observed that the water contact angle increases from 27.2+/-1.5 degrees for the pure silica membranes to 115.0+/-1.2 degrees for the modified ones with a (trifluoropropyl)triethoxysilane (TFPTES)/tetraethyl orthosilicate (TEOS) molar ratio of 0.6. The modified membranes preserve a microporous structure with a micropore volume of 0.14 cm3/g and a pore size of approximately 0.5 nm. A single gas permeation of H2 and CO2 through the modified membranes presents small positive apparent thermal activation energies, indicating a dominant microporous membrane transport. At 200 degrees C, a single H2 permeance of 3.1x10(-6) mol m(-2) s(-1) Pa(-1) and a H2/CO2 permselectivity of 15.2 were obtained after proper correction for the support resistance and the contribution from the defects. In the gas mixture measurement, the H2 permeance and the H2/CO2 separation factor almost remain constant at 200 degrees C with a water vapor pressure of 1.2x10(4) Pa for at least 220 h, indicating that the modified membranes are hydrothermally stable, benefiting from the integrity of the microporous structure due to the fluorocarbon modification.     

Magnesium aminoethyl phosphonate (Mg(AEP)(H2O)): an inorganic-organic hybrid nanomaterial with high CO2:N2 sorption selectivity

The inorganic-organic hybrid magnesium aminoethyl phosphonate (Mg(AEP)(H(2)O), particle diameter: 20 nm; specific surface area: 322(10) m(2) g(-1); pore volume: 0.9(1) cm(3) g(-1)) shows reversible CO(2) sorption (152(5) mg g(-1)) at high pressure (≤110 bar). In contrast, N(2) uptake remains below 1.0(1) mg g(-1). Based on this selectivity (～100%) Mg(AEP)(H(2)O) expands the range of materials available for CO(2) capture.     

十七氟癸基修饰的有机-无机杂化二氧化硅膜材料的制备及气体分离性能

以十七氟癸基三乙氧基硅烷(PFDTES)和1,2-双(三乙氧基硅基)乙烷(BTESE)为前驱体, 通过溶胶-凝胶法制备了十七氟癸基修饰的SiO₂溶胶, 采用浸渍提拉法在γ-Al₂O₃/α-Al₂O₃多孔陶瓷支撑体上涂膜, 然后在N₂气氛保护下烧结成完整无缺陷的有机-无机杂化SiO₂膜. 利用扫描电子显微镜对膜材料的形貌进行观察, 通过动态光散射技术对溶胶粒径及分布进行测试, 利用视频光学接触角测量仪、 红外光谱仪和热分析仪表征了十七氟癸基修饰对有机-无机杂化SiO₂膜疏水性的影响. 结果表明, 十七氟癸基已经成功修饰到SiO₂膜材料中, 且随着PFDTES加入量的增大, 溶胶粒径和膜材料对水的接触角不断增大. 当n(PFDTES): n(BTESE)=0.25: 1时, 溶胶粒径分布较窄, 平均粒径为3.69 nm, 膜材料对水的接触角为(112.0±0.4)º. 在修饰后的有机-无机杂化SiO₂膜中H₂的输运遵循微孔扩散机理, 在300℃时, H₂的渗透率达到5.99×10^-7 mol·m^-2·Pa^-1·s^-1, H₂/CO和H₂/CO₂的理想分离系数分别达到9.54和5.20, 均高于Knudsen扩散的理想分离因子, 表明膜材料具有良好的分子筛分效应.