表面改性纳米二氧化钛-芳香聚酰胺复合反渗透膜的制备与表征

采用TMC对亲水纳米TiO2进行表面改性,然后添加在复合反渗透膜的聚酰胺层中,制备了改性纳米TiO2-聚酰胺复合反渗透膜。改性纳米TiO2使用红外光谱法(FTIR)和粒径分析仪进行表征;采用渗透试验,扫描电镜(SEM)、静态接触角仪、原子力显微镜等对复合膜的性能和结构分别测试和表征。结果表明,改性TiO2的表面接枝上酰氯基团,在有机溶剂中的分散性得到提高;SEM和AFM照片证实,TiO2在膜表面分布均匀,膜表面粗糙度增加;杂化复合膜亲水性也有一定程度的提高;膜性能测试结果证实了添加TiO2的复合膜水通量均高于纯聚酰胺膜,同时脱盐率变化很小。当改性TiO2的添加量为0.05%(m/v)时,水通量由11.21 L/(m2.h)提升到32.61 L/(m2.h),对NaCl截留率达到98.9%。试验结果表明,改性TiO2很好地分散在聚酰胺层,提高了水通量,还保持了高脱盐率,膜性能得到提高。     

羟基化PPESK复合膜的制备及性能研究

采用NaBH₄对杂萘联苯聚芳醚砜酮(PPESK)支撑膜进行羟基化亲水改性，通过间苯二胺和均苯三甲酰氯的界面聚合反应制备复合膜。利用傅里叶变换红外光谱仪(FT-IR)、水接触角仪、扫描电子显微镜(SEM)和X射线光电子能谱仪(XPS)研究羟基化改性对膜表面的形貌结构、原子组成的影响，并测定复合膜对2 000 mg·L^-1 Na₂SO₄水溶液的分离性能。结果表明：羟基化改性的PPESK-OH支撑膜的亲水性增强；PPESK-OH复合膜的聚酰胺层的交联度较高；PPESK-OH复合膜和PPESK复合膜的脱盐率接近，PPESK-OH复合膜的水通量较PPESK复合膜增大了约38%。     

有机纳米颗粒改性聚酰胺反渗透膜的制备与研究

采用间苯二胺(MPD)和均苯三甲酰氯(TMC)分别为水油相,通过界面聚合反应,加入纳米聚苯胺(PANI),得到改性的反渗透复合膜。复合膜结构的表征采用扫描电子显微镜(SEM)和原子力显微镜(AFM)。同时对复合膜的耐-氯性能进行评估。结果表明,改性后复合膜的通量提高,同时脱盐率也有一定提升,在PANI含量为0.1 g/L时,截留性能最佳。在保持良好的分离性能的同时随着PANI含量的提升,复合膜的耐氯性也得到很大的改善。     

二氧化钛调控基膜结构对氧化石墨烯复合膜性能的影响

以聚醚砜(PES)超滤膜为基膜，通过聚多巴胺(PDA)表面改性后压力沉积不同量的二氧化钛(TiO₂)纳米粒子作为基底，再沉积氧化石墨烯(GO)片层制得TiO₂/GO复合分离膜，重点考察基膜表面形貌对GO膜分离性能的影响。通过扫描电子显微镜、接触角测试仪、固体表面Zeta电位分析仪、X射线衍射分析仪等对有无TiO₂沉积层的GO复合膜进行表征，并考察TiO₂沉积量对GO复合膜分离性能的影响。结果表明，TiO₂纳米粒子以团簇状态均匀分布在改性的超滤膜表面，随TiO₂沉积量的增加，团簇密度增大，GO沉积后表层的峰谷结构更为明显，但表层的层间距并无明显改变。TiO₂/GO复合膜的水通量随TiO₂沉积量的增加而明显增大，TiO₂的沉积对GO沉积量低的复合膜通量的影响更明显，当 GO沉积量为4.11 μg/cm²，TiO₂沉积量为20.55 μg/cm²时，复合膜的水通量较无TiO₂的复合膜提高了108.38%。复合膜对无机盐溶液的截留性能主要基于膜表面所带负电的道南排斥作用，TiO₂/GO复合膜对刚果红的截留率在99%以上，对甲基橙的截留率可达82%，TiO₂层的加入并未降低复合膜的截留效果。     

PVDF-TiO2复合中空纤维膜的制备与表征

将纳米二氧化钛(TiO₂)粒子与4类制膜添加剂复配处理,采用相转化法制备聚偏氟乙烯(PVDF)-TiO₂复合中空纤维膜,讨论了纳米TiO₂粒子对复合膜结构和性能的影响。通过扫描电子显微镜、X射线衍射、能谱分析、热重分析、拉伸试验、接触角测定和超滤实验分别表征了复合膜的微观孔结构、晶相结构和复合均匀性、热稳定性、机械性能、亲水性、超滤性能以及抗污染性能。结果表明：通过添加TiO₂粒子复配添加剂,复合膜的性能得到有效改善。复配添加剂中w(TiO₂)为2%(占PVDF固含量的质量分数)时,纯水通量由348 L/(m²·h)提高至377 L/(m²·h),牛血清蛋白截留率由68%提高至90%,断裂强度和抗污染性能提高,复合膜综合性能优异。     

Ag3PO4改性PVDF超滤膜的结构与性能

将不同量Ag₃PO₄均匀地分散在聚偏氟乙烯(PVDF)铸膜液中, 利用相转化法制备了改性PVDF膜, 通过扫描电镜(SEM)、接触角测定、过滤实验和污染性测试等研究了其微结构、分离性和耐污染性等, 并考察了膜污染后的清洗效果。结果表明, 添加Ag₃PO₄ 的PVDF膜具有不同的微结构与性能, 当添加1% 的Ag₃PO₄时, 膜皮层变薄、微孔数增多, 并呈现出最优化的水通量、亲水性、力学性、抗污染能力和截留率等。采用太阳光-水清洗能使改性膜的通量恢复率达到85%以上。     

PVDF-PFTS/SiO2膜制备及抗混合污染性能

采用表面接枝技术制备了PVDF-PFTS/SiO₂超疏水复合膜,通过扫描电子显微镜（SEM）和红外光谱（FTIR）分析了膜污染前后的表面结构和组成,考察了直接接触式膜蒸馏（DCMD）装置出水电导率和膜通量的变化,利用XDLVO理论分析了PVDF-PFTS/SiO₂超疏水复合膜的抗混合污染性能和机理。结果表明：在1H, 1H, 2H, 2H-全氟辛基三氯硅烷（PFTS）和SiO₂共同作用下,PVDF-PFTS/SiO₂超疏水复合膜表面形成微纳米复合乳突结构,水接触角（WCA）由99°增至155°。与PVDF基膜相比,PVDF-PFTS/SiO₂超疏水复合膜对混合污染物具有较好的抗污染性能;连续运行10h,膜通量和截留率分别保持在10.06kg/(m²·h)和99.80%。XDLVO理论分析表明,PVDF-PFTS/SiO₂超疏水复合膜表面与污染物之间的作用力由引力转变为斥力是其抗混合污染性能增强的主要原因之一。     

APTES-TiO2-B4C/PVDF膜的制备及其光降解有机染料的性能研究

采用3-氨丙基三乙氧基硅烷（APTES）对纳米碳化硼（B₄C）和二氧化钛（TiO₂）的混合颗粒进行改性,制备出功能化APTES-B₄C/TiO₂复合颗粒。利用相转化技术将APTES-B₄C-TiO₂复合颗粒引入聚偏氟乙烯（PVDF）膜基质中,得到具有光催化性能的APTES-B₄C-TiO₂/PVDF复合膜。通过XRD、SEM、EDS和水接触角测试对制备的复合膜进行表征。以50 mg/L的罗丹明B（RhB）水溶液模拟废水考察APTES-B₄C-TiO₂/PVDF复合膜的光催化性能。结果表明,当复合粒子的质量分数为0.5%时,复合膜具有最高的孔隙率（68.3%）、最大的膜比表面积（8.25 m²/g）和最低的水接触角（69°）。光催化实验结果表明,APTES-B₄C-TiO₂复合粒子的质量分数为0.5%时,A...     

聚苯胺中间层改性Ti/PbO2电极的制备及其降解性能

引入导电聚合物聚苯胺膜（PANI，polyaniline）对Ti/PbO₂电极进行改性，采用两步电沉积法成功制备出Ti/PANI/PbO₂电极。通过扫描电镜（SEM）、X射线衍射(XRD)、线性伏安扫描(LSV)和交流阻抗(EIS)对制备的电极进行表征，以甲基橙为目标污染物，探讨了PANI的沉积时间对电极性能的影响，并研究了Ti/PANI/PbO₂电极对罗丹明B和4-硝基苯酚的降解性能。结果表明，PANI的引入未影响活性层PbO₂的晶相结构和形貌特征，但显著提高了电极的析氧电位，Ti/PANI/PbO₂的析氧电位可达3.43V。当PANI聚合时间为30min时，电极Ti/PANI-30/PbO₂的电化学性能和电催化降解效果最佳。在电流密度为30mA/cm²、污染物初始浓度为50mg/L、Na₂SO₄浓度为0.1mol/L的实验条件下，反应120min后，Ti/PANI-30/PbO₂对甲基橙、罗丹明B和4-硝基苯酚的去除率分别为99.8%、99.9%和94.0%。     

亲水性添加剂多巴胺对聚酰胺反渗透膜性能的影响

多巴胺作为界面反应中亲水性添加剂来制备高通量的聚酰胺反渗透膜。研究了不同水相缓冲体系下,多巴胺浓度对反渗透膜亲水性、脱盐性能以及表面形貌结构的影响。反渗透膜的脱盐性能评价采用2 000 mg/LNaCl的进水溶液,测试压力为1.0 MPa,温度为25℃;膜表面形貌结构分别采用扫描电子显微镜(SEM)和原子力显微镜(AFM)进行表征。结果显示,三乙胺樟脑磺酸盐体系下制备的RO膜较三乙胺盐酸盐体系具有更高的水通量;多巴胺的加入可有效提高膜的水通量,采用三乙胺樟脑磺酸盐体系,当多巴胺添加量质量分数为1%时,RO膜的截留率和水通量分别为99.5%和41 L/(m2·h),水通量提高了32%;SEM和AFM结果显示,添加多巴胺的RO膜表面结构更为平整、均一,平均粗糙度更小。     

氨基化氧化石墨烯界面聚合制备超薄复合纳滤膜

采用氨基化氧化石墨烯（NGO）为界面聚合水相单体,制备了超薄复合纳滤膜。研究采用傅里叶变换红外光谱（FTIR）、X射线光电子能谱（XPS）、透射电子显微镜（TEM）、扫描电子显微镜（SEM）、原子力显微镜（AFM）表征了NGO以及复合纳滤膜的化学组成和形貌。系统考察了水相单体浓度、有机相单体浓度对于制备的超薄复合纳滤膜性能的影响。该超薄复合膜在低压（0.2 MPa）下纯水通量可达27.8 L·m^-2·h^-1,对小分子染料有较高的截留率（甲基橙截留率74.8%,橙黄钠截留率96.0%,刚果红截留率98.5%,甲基蓝截留率99%）,对于无机盐的截留率较低（Na₂SO₄截留率21.4%,MgSO₄截留率10.7%,NaCl截留率5.3%,MgCl₂截留率1.5%）,展现出优异的染料/盐分离性能。同时制备的复合纳滤膜展现了较好的长周期稳定性以及抗污染特性。     

Fabrication of anti-fouling polyamide nanofiltration membrane by incorporating streptomycin as a novel co-monomer

Polyamide (PA) thin-film composite (TFC) nanofiltration (NF) membrane has extremely broad application prospects in separation of monovalent/divalent inorganic salts mixed solution. However, membrane fouling is the main obstacle to the application of PA, TFC and NF membrane. Streptomycin (SM) is a hydrophilic antibiotic containing a large number of hydroxyl and amino groups. In this work, the NF membrane was prepared via interfacial polymerization (IP) between trimesoyl chloride (TMC) in the organicphaseand SM/piperazine (PIP) mixture in theaqueousphase. The NF membrane structure and performance were characterized in detail. The results showed that SM successfully participated in the IP. The negative charge and hydrophilicity of membrane surface were improved. The prepared membrane exhibited good anti-adhesion and anti-bacterial performance. Additionally, when the SM concentration was 2%, the prepared membrane exhibited the optimal permselectivity. The water permeance was 89.4 L·m^-2·h^-1·MPa^-1. The rejection of NaCl and Na₂SO₄ were 17.17% and 97.84%, respectively. The NaCl/Na₂SO₄ separation factor of the SM2-PIP/TMC membrane in 1000 mg·L^-1 NaCl and 1000 mg·L^-1 Na₂SO₄ mixed solution was 40, which was 3.3 times that of PIP/TMC membrane. It indicated that SM2-PIP/TMC demonstrated excellent monovalent/divalent salts separation performance. This work provided an easy and effective approach to preparing anti-fouling NF membrane while possessing superior monovalent/divalent salts separation performance.     

MOF-199@GO改性PVDF荷电纳滤膜的制备及其性能

采用原位生长法制备了MOF-199@氧化石墨烯（GO）纳米复合材料，并对聚偏氟乙烯（PVDF）支撑膜进行表面改性，以克服PVDF膜表面疏水性。通过界面聚合反应，制备了基于MOF-199@GO改性PVDF的聚酰胺复合荷电纳滤膜。采用XRD、SEM、TEM、AFM和zeta电位等手段表征了MOF-199@GO复合材料及MOF-199@GO改性PVDF聚酰胺复合纳滤膜的结构及微观形貌，并测试了MOF-199@GO改性PVDF聚酰胺复合纳滤膜的脱盐性能。结果表明：通过MOF-199@GO复合材料对PVDF支撑膜的表面改性，有效克服了PVDF支撑膜的疏水性，实现了表面聚酰胺薄层的均匀连续生长，荷电纳滤膜表面荷负电性能显著增强，其中经MOF-199@GO充分改性的复合荷电纳滤膜表现出优异的脱盐性能，对MgSO₄、Na₂SO₄、NaCl和MgCl₂四种盐的截留率分别达到了93.56%、93.04%、87.48%和87.11%。     

Preparation and properties of MOF-199@GO modified PVDF charged composite nanofiltration membrane

As novel functional materials, metal-organic framework (MOF) and graphene oxide (GO) have received great attentions in recent years. In this work, MOF@GO nanocomposite (MOF-199@GO) is prepared by an in-situ growth method. A novel and highly efficient nanofiltration (NF) membrane can be facilely fabricated via surface decoration of MOF-199@GO onto poly(vinylidene fluoride) (PVDF) substrate before interfacial polymerization of m-phenylenediamine (MPD) and trimesoyl chloride (TMC) in order to overcome the hydrophobicity of PVDF membrane. The structure and morphology of MOF-199@GO and MOF-199@GO modified PVDF polyamide composite membrane are characterized by XRD, SEM, TEM, AFM and zeta potential. MOF-199@GO modified PVDF composite NF membrane which possesses dense and uniform polyamide thin-layer exhibits higher negative surface potential (up to ~37 mV) at pH 9.5. The performance of MOF-199@GO modified PVDF polyamide composite NF membrane has been investigated by determination of pure water flux and salt rejection. The prepared NF membrane MG3 exhibited highly efficient rejection of MgSO₄, Na₂SO₄, NaCl and MgCl₂, which are 93.56%, 93.04%, 87.48% and 87.11%, respectively. This work provides a worthy reference for designing highly efficient NF membranes modified by MOF and relevant materials.     

二苯并-18-冠醚-6/聚醚嵌段酰胺膜富集水中苯酚性能研究

为提高聚醚嵌段酰胺 （PEBA）膜对水中苯酚的选择分离性能,采用二苯并-18-冠醚-6 (CE) 对PEBA膜进行改性制备了PEBA/CE渗透蒸发膜。通过FT-IR、SEM表征证实了CE与PEBA紧密结合且CE均匀分布在膜表面;AFM表征表明CE的修饰有效地提高了膜表面与苯酚的接触面积;水接触角测试表明CE的修饰极大地提高了PEBA/CE膜的疏水性。同时系统地研究了膜中CE含量、原料液苯酚浓度、进料温度对膜渗透汽化性能的影响,结果表明CE能显著提高PEBA膜对苯酚的选择性,在料液苯酚为0.8%（质量）及70℃操作温度条件下,当CE 的添加量为PEBA的6%（质量）时,PEBA/CE-6膜的分离因子和渗透通量分别为23.34和494.40 g/(m²·h),远超PEBA膜性能[分离因子8.46,总渗透通量547.48 g/(m²·h)]。长期性能稳定性测试表明所制备PEBA/CE-6膜具有良好稳定性,具有较好的工业运用潜力。     

Ceramic Supported PDMS and PEGDA Composite Membranes for CO2 Separation

Composite membranes have attracted increasing attentions owing to their potential applications for CO2 separation. In this work, ceramic supported polydimethylsiloxane （PDMS） and poly （ethylene glycol） diacrylate （PEGDA） composite membranes were prepared. The microstructure and physicochemical properties of the compos- ite membranes were characterized. Preparation conditions were systematically optimized. The gas separation performance of the as-prepared membranes was studied by pure gas and binary gas permeation measurement of CO〉 N2 and H〉 Experiments showed that PDMS, as silicone rubber, exhibited larger permeance and lower separation factors. Conversely, PEGDA composite membrane presented smaller gas permeance but higher ideal selectivity for CO2/N2. Compared to the performance of those membranes using polymeric supports or freestanding membranes, the two kinds of ceramic supported composite membranes exhibited higher gas permeance and acceptable selectivity. Therefore, the ceramic supported composite membrane can be expected as a candidate for CO2 separation from light gases.     

自支撑石墨烯炭膜的制备及气体分离性能

通过溶剂蒸发法得到聚酰胺酸（PAA）与氧化石墨烯（GO）的复合石墨烯膜,并经600℃炭化制备了具有良好柔韧性的仿贝壳珍珠层结构的自支撑石墨烯炭膜。通过X射线衍射和场发射扫描电镜对薄膜微观结构进行表征,并测试不同PAA固含量制备的石墨烯炭膜对CO₂和CH₄的分离性能。结果表明,炭化后,GO被还原成石墨烯,呈层状堆叠,堆叠的层间填充了空穴和残炭;石墨烯炭膜的CO₂渗透通量和CO₂/CH₄分离理想选择性随PAA加入量增加,CO₂通量最高可达824 barrer,此时CO₂/CH₄理想选择性达38.9。石墨烯层骨架和碳分子筛构成石墨烯炭膜的气体传输通道,本研究成果为柔性自支撑气体分离炭膜的制备开辟了新思路。     

Preparation and properties of hollow fibre nanofiltration membrane with continuous coffee-ring structure

Polyamide(PA)hollow fibre composite nanofiltration(NF)membranes with a coffee-ring structure and beneficial properties were prepared by adding graphene oxide(GO)into the interfacial polymerization process.The presentation of the coffee-ring structure was attributed to the heterogeneous,finely dispersed multiphase reaction system and the“coffee-stain”effect of the GO solution.When the piperazine concentration was 0.4 wt-%,the trimesoyl chloride concentration was 0.3 wt-%,and the GO concentration was 0.025 wt-%,the prepared NF membranes showed the best separation properties.The permeate flux was 76 L·m^?2·h^?1,and the rejection rate for MgSO4 was 98.6%at 0.4 MPa.Scanning electron microscopy,atomic force microscopy,and attenuated total reflectance-Fourier transform infrared spectroscopy were used to characterize the chemical structure and morphology of the PA/GO NF membrane.The results showed that GO was successfully entrapped into the PA functional layer.Under neutral operating conditions,the PA/GO membrane showed typical negatively charged NF membrane separation characteristics,and the rejection rate decreased in the order of Na2SO₄>MgSO₄>MgCl₂>NaCl.The PA/GO NF membrane showed better antifouling performance than the PA membrane.     

疏水SiO2/PTFPMS杂化复合膜的制备及其气体分离性能

为了提高气体分离膜的耐溶胀特性,以多孔聚醚酰亚胺（PEI）为支撑层,采用溶液共混法制备了疏水SiO₂/PTFPMS杂化复合膜,研究了疏水SiO₂质量共混比对膜形态、耐溶胀性以及不同操作压差下的纯气渗透分离性能的影响。光学显微照片显示,当共混比不超过0.018时,杂化膜的透明度较高,表明疏水SiO₂与PTFPMS具有较好的相容性;当SiO₂与PTFPMS的共混比超过0.018时,SiO₂团聚明显。SEM表征结果显示,杂化膜表面光洁,断面杂化涂层紧密贴合支撑层。疏水SiO₂/PTFPMS杂化膜在异辛烷中的溶胀度为0,在乙酸乙酯中的溶胀度比PTFPMS均质膜的下降了11.9%,显示了其优异的耐溶胀性能。在操作压力为1.0 MPa,操作温度为25℃下,SiO₂共混比为0.012时,疏水SiO₂/PTFPMS杂化复合膜的CO₂渗透通量达到最高156.1GPU,CO₂/N₂选择性为15.86。     

Langmuir-Blodgett法制备高H2选择性取向ZSM-5分子筛分离膜

利用Langmuir-Blodgett（LB）技术首先在多孔氧化铝载体表面有序组装了单层b-轴取向Silicalite-1分子筛晶种层,再采用二次生长法,以溴化六丙双铵（dimer-TPABr）为结构导向剂配制二次生长合成液,在175℃反应48h制备了高度b-轴取向ZSM-5（Si/Al=120）分子筛膜。扫描电镜（SEM）表征显示ZSM-5分子筛膜致密连续且厚度约为2.6μm。X射线衍射（XRD）表征结果显示,膜的b-轴晶体优先取向值高达0.858。气体分离性能测试结果显示,制备的ZSM-5分子筛膜在高温焙烧脱除有机模板剂过程中会产生缺陷。经硅烷试剂四甲氧基硅烷（TMOS）对缺陷修复后,ZSM-5分子筛膜表现出高的H₂选择性分离性能,H₂/CO₂分离因子高达68 （T=25℃,p=0.1MPa）,对应的H₂渗透速率为1.36×10^-8mol/(m²·s·Pa)。