UiO-66的制备、功能化及膜分离研究进展

UiO-66是一种具有优异物理化学稳定性的金属有机骨架（MOFs）材料,近年来引起了研究者们的强烈关注。本文详细介绍了UiO-66的结构,重点探讨了溶剂热法过程中的一系列影响因素,包括使用不同的金属前体,改变合成温度、溶剂、各组分配比以及模板剂等,制备各种性能的UiO-66。针对溶剂热法合成效率较低的问题,介绍了微波合成法、微流控、连续流和无溶剂法等其它UiO-66的制备方法。为了扩大UiO-66的应用范围,对其有机配体进行功能化改性或与其他材料复合改性,具体介绍了改性后UiO-66在气体吸附、水处理、催化、电化学和化学传感等方面的应用。最后综述了利用UiO-66具有多孔特性构建分离膜方面的研究进展,具体阐述了纯UiO-66膜和UiO-66复合膜在气体分离和水处理方面的应用。     

PVA/UiO-66复合薄膜的制备及性能表征

采用溶剂热法合成出了金属有机骨架材料UiO-66,并通过流延法制备出了一系列PVA/UiO-66复合膜.通过红外光谱仪(FTIR)、X射线衍射仪(XRD)、扫描电子显微镜(SEM)、接触角、溶胀度、拉伸强度和透光性等表征方法,详细研究了UiO-66含量对复合膜各种物性的影响.结果表明,PVA在经富马酸交联后,耐水溶胀性...     

UiO-66膜的制备及其对正/异丁烷体系的分离

用擦涂法在α-Al_2O_3支撑体上引入ZrO_2层,利用晶种二次生长法,在α-Al_2O_3支撑体的ZrO_2层上引入UiO-66晶种,成功制备了UiO-66膜。通过XRD和SEM对UiO-66晶种及膜的结构和形貌进行了表征,考察了调节剂乙酸含量和ZrO_2过渡层对UiO-66膜结构和形貌的影响。在温度25℃、压力0.08MPa下,测试了气体分子的渗透性能,检测了UiO-66膜的完整性。考察了跨膜压差和温度对i-C_4H_(10)和n-C_4H_(10)两种气体在UiO-66膜上渗透速率的影响,探究了UiO-66膜对i-C_4H_(10)和n-C_4H_(10)两种气体的渗透选择性能。结果表明,采用多次擦涂法引入ZrO_2层后,获得了覆盖度高且膜层厚度均匀的UiO-66膜,膜厚度为5μm。UiO-66膜对i-C_4H_(10)和n-C_4H_(10)两种气体具有反向渗透性能,在跨膜压差为0.08MPa、温度为25℃时,UiO-66膜对i-C_4H_(10)/n-C_4H_(10)两种气体的理想渗透选择性达3.6,渗透速率分别为4.39×10-7和1.22×10-7 mol/(m2·s·Pa)。     

PANI/N-K_2Ti_4O_9/UiO-66复合材料的制备及光催化性能研究

用自组装法将金属有机框架UiO-66负载到低带隙半导体N-K2Ti4O9的表面,然后采用原位氧化复合法制备导电聚合物聚苯胺粘结的PANI/N-K2Ti4O9/UiO-66复合光催化剂(复合材料A),制备了N-K2Ti4O9和UiO-66不同比例物理混合后再粘结聚苯胺的复合材料B。采用红外(IR)、场发射透射电镜(FETEM)、荧光光谱(PL)对复合材料的结构、形貌进行表征。结果表明,UiO-66负载到棒状N-K2Ti4O9的表面呈现核壳结构,聚苯胺(PANI)粘结在核壳结构N-K2Ti4O9/UiO-66的表面形成复合材料,PANI粘结可以有效降低电子-空穴复合率,复合材料A具有最好的光催化性能。     

UiO-66(Zr)型改性膜在水处理中的研究进展

从制备方法、分离效果和分离机理等方面,简述了UiO-66(Zr)型改性膜在油水分离、染料去除、重金属离子去除和脱盐等领域中的应用,对UiO-66(Zr)型改性膜在水处理中的应用提出了展望。     

负载UiO-66-NH_2棉织物的制备及化学战剂降解性能表征

提供了一种UiO-66-NH_2高效负载棉织物的制备方法,得到的功能棉织物具有良好的化学战剂催化降解效果。首先利用γ-缩水甘油醚氧丙基三甲氧基硅烷(GPTMS)对棉织物进行预处理,然后利用溶剂热合成法在预处理棉织物上原位生长UiO-66-NH_2晶体,由此制备的负载UiO-66-NH_2棉织物经10次皂洗后,其UiO-66-NH_2负载量无明显变化,表明该织物具有良好的耐皂洗牢度。此外该负载UiO-66-NH_2棉织物对有机磷酸酯类化学战剂模拟物甲基对氧磷(DMNP)的催化降解转化率在210 min时高达70.73%,半衰期约为30 min。     

钛修饰的锆基-金属有机框架材料催化苯甲硫醚制备苯甲砜

本文以UiO-66型Zr-MOFs为基础,通过后合成修饰的方法合成了UiO-66(Zr,Ti).以水为绿色溶剂,在相对温和的条件下,UiO-66(Zr,Ti)高效绿色催化双氧水分解,进而促使苯甲硫醚选择性氧化制备苯甲砜.研究发现,当原料苯甲硫醚用量为1mmol,最佳反应温度为60℃,反应时间为12h,UiO-66(Zr...     

功能化Zr-MOF强化混合基质膜CO2分离

混合基质膜（MMMs）在气体分离领域具有良好的应用前景,金属有机框架（MOFs）由于具有高孔隙率和有机连接基团,常被用作填料制备MMMs。但由于MOFs与聚合物的界面相容性问题,MMMs的气体分离性能提升受到限制。本文合成了功能化的Zr-MOF（UiO-66-AC）,并利用其与聚醚共聚酰胺（Pebax）共同制备了混合基质膜。填料中引入的羰基和羧基等基团提供了MOFs与聚合物基质之间较强的界面相互作用。与纯Pebax膜相比,UiO-66-AC/Pebax MMMs的气体渗透性能得到了显著提高。当填料质量分数为6%时,膜的CO₂渗透系数为102.4 Barrer,CO₂/N₂和CO₂/CH₄选择性分别为90.6和26.0,CO₂/N₂分离性能突破了Robeson上限(2008),表明该混合基质膜在CO₂的分离应用上具有潜力。     

UiO-66/GO纳米复合材料的制备及吸附性能

以四氯化锆(ZrCl_4)、对苯二甲酸(H_2BDC)和氧化石墨烯(GO)为原料,采用溶剂热法合成了一种纳米复合材料UiO-66/氧化石墨烯(UiO-66/GO)。采用SEM、TEM、XRD、FTIR和N_2吸附-解吸对UiO-66/GO进行了测试和表征。结果显示:UiO-66均匀生长在GO片上形成一种2D负载结构;GO的添加不影响UiO-66的晶型;当GO的质量分数为2%时,UiO-66/GO-2复合材料具有最高的比表面积(738 m~2/g)。UiO-66/GO-2的协同效应使其对刚果红(CR)的去除率远高于UiO-66和GO,其Langmuir模型的理论最大吸附量为561.79 mg/g,分别是相同条件下UiO-66和GO对CR吸附量的2.8倍和7.1倍。     

PANI/N-K2Ti4O9/UiO-66复合材料的制备及光催化性能研究

用自组装法将金属有机框架UiO-66负载到低带隙半导体N-K2Ti4O9的表面,然后采用原位氧化复合法制备导电聚合物聚苯胺粘结的PANI/N-K2Ti4O9/UiO-66复合光催化剂（复合材料A）,制备了N-K2Ti4O9和UiO-66不同比例物理混合后再粘结聚苯胺的复合材料B.采用红外（IR）、场发射透射电镜（FETEM）、荧光光谱（PL）对复合材料的结构、形貌进行表征.结果表明,UiO-66负载到棒状N-K2Ti4O9的表面呈现核壳结构,聚苯胺（PANI）粘结在核壳结构N-K2Ti4O9/UiO-66的表面形成复合材料,PANI粘结可以有效降低电子-空穴复合率,复合材料A具有最好的光催化性能.     

具有PDA-UiO-66中间层耐溶剂复合纳滤膜的制备及性能

将多巴胺和Ui O-66纳米颗粒共沉积在经1,6-己二胺交联的聚醚酰亚胺（PEI）基膜上构建了纳米复合中间层（PDA-UiO-66），并在中间层上进行界面聚合反应制备了耐溶剂复合纳滤膜（TFN-U）。通过FTIR、XRD、SEM、AFM、水接触角测量仪对膜结构进行了表征和测试，探究了Ui O-66质量浓度对TFN-U膜耐溶剂性、耐污染性以及运行稳定性的影响。结果表明，PDA-Ui O-66纳米复合中间层的引入能提高TFN-U膜的渗透通量，当Ui O-66纳米颗粒质量浓度为0.2 g/L时，TFN-U2膜水通量为63.83 L/(m2·h)，甲醇通量为28.50L/(m2·h)，对刚果红水溶液和刚果红甲醇溶液的截留率为98.2%和93.2%，经无水乙醇、丙酮、乙酸乙酯、正己烷及N,N-二甲基甲酰胺（DMF）浸泡48h后，其对刚果红的截留率均>94%，通量恢复率达到78.1%，在连续24 h过滤刚果红甲醇溶液后，该膜的甲醇通量为14.13L/(m2·h)，截留率为98.3%，表明TFN-U2膜具有良好的耐溶剂性、耐污染性以及一定的运行稳定性。     

Investigation on the enhancement of solvent-resistant nanofiltration membrane performance utilizing PDA-UiO-66@CNT as an interlayer

With the growing complexity of separation systems, the application of thin film composite nanofiltration (TFN) membranes in organic solvent separation faces numerous challenges. To augment its solvent stability, an in-situ constructed dopamine hydrogel doped with UiO-66@CNT was developed as an intermediate layer on a polyetherimide (PEI) ultrafiltration membrane. Subsequent interfacial polymerization on this interlayer led to the formation of a solvent-resistant nanofiltration membrane with a vast covalent bond structure, large specific surface area, and enhanced hydrophilicity. Our findings revealed that when the CNT loading in the UiO-66@CNT composite nanoparticles was 2 wt%, the TFN-U₂C₂ membrane exhibited a maximum pure water flux of 126.32 L/(m²·h) and a methanol flux of 45.45 L/(m²·h). The rejection rates for Congo red aqueous and methanol solutions were 96.88% and 92.14%, respectively. The membrane also demonstrated commendable anti-fouling properties. Remarkably, even after 48 h of immersion in various organic solvents, the membrane retained its morphology and separation efficiency. Compared to the TFN-U₂ membrane without CNT addition, the enhancement in separation performance was considerably significant. Hence, this membrane has significant potential for application in treatment of wastewater containing organic solvents and is promising in related fields.     

Using a simple method to prepare UiO-66-NH2/chitosan composite membranes for oil–water separation

Chitosan (CS) was used as a cross-linking agent to modify UiO-66-NH₂, and the modified UiO-66-NH₂ was fixed on the mixed cellulose membrane (MCE) through vacuum filtration technology to prepare a new type of membrane. The membrane exhibited excellent hydrophilicity in the air and excellent super-oleophobic performance underwater, and effectively separated various oil–water emulsions. When separating petroleum ether-water emulsion, the filtration flux of the modified membrane was 2000 L m⁻² h⁻¹ higher than that of MCE, and the separation efficiency can reach more than 95%. After 10 cycles, the flux of the modified membrane was about four times of that MCE, which was 500 L m⁻² h⁻¹. Most importantly, the membrane still maintained underwater superoleophobicity in the environment of strong acid, strong base, and salt solution.     

Preparation and properties of PPSU/GO mixed matrix membrane

Polyphenylene sulfone/graphene oxide (PPSU/GO)mixed matrix membraneswith different GOcontents are prepared by phase inversion technique using, PEG-1000 as porogen, and N,N-dimethylacetamide (DMAC) as solvent. The hydrophilicity and pure water flux of the membrane are investigated. The morphology, hydrophilicity, thermodynamic stability and compatibility of the membranes are characterized by various techniques such as SEM, TGA, FTIR and so on. The permeation properties of the membrane are measured in terms of pure water flux and bovine serum albumin (BSA) retention. The results indicate that when the GO content is 1.5 wt%, an evenly distributed finger structure has been formed in the mixed matrix membranes. Owing to the presence of GO, the hydrophilicity and the thermal stability of the membranes are improved, and the fouling resistance is also enhanced.     

Development of a novel graphene oxide-blended polysulfone mixed matrix membrane with improved hydrophilicity and evaluation of nitrate removal from aqueous solutions

In this study, four types of mixed matrix membranes were fabricated using polysulfone (as the base polymer) and different contents of graphene oxide (GO) nanosheets (as modifier) through wet phase inversion method. Based on the amounts of GO (0, 0.5, 1, and 2?wt%), the synthesized membranes named as M1, M2, M3, and M4, respectively. The membranes characteristics were evaluated using FE-SEM, FT-IR, and water contact angle measurements. In addition, the performance of the prepared membranes was investigated in terms of basic parameters: filtrate water flux, nitrate removal efficiency, and antifouling properties. Results showed significant improvements of the characteristics of modified membranes with GO. Accordingly, the permeability and hydrophilicity were enhanced and water flux was considerably improved. At operating pressure of 4?bar and nitrate concentration of 110?mg/L, the removal efficiency for unmodified membrane (M1) was 15.5% and for modified M2, M3, and M4 membranes were 22.78%, 39.12%, and 41.37%, respectively. In addition, the results of flux recovery ratio (FRR) showed that the anti-fouling properties of the GO modified membranes were improved due to the increase in membrane surface hydrophilicity.     

氧化石墨烯掺杂反渗透混合基质膜制备及性能

由于芳香族聚酰胺反渗透膜在抗污染性以及耐氯性方面存在不足,限制了其在海水淡化等方面的应用。采用往油相中添加氧化石墨烯（GO）的二次界面聚合法改性了商业反渗透膜,评价了GO掺杂反渗透混合基质膜的分离性能和耐氯性能,并用接触角仪、Zeta电位仪、扫描电镜和原子力显微镜等仪器表征了膜的亲水性能、荷电性能以及膜表面形貌。结果表明,GO的添加提高了膜的分离性能、耐氯性能和亲水性能;当GO添加量为30 mg·L^-1时,膜的通量为（77.7±0.9） L·m^-2·h^-1,膜的截留率为97.6%±0.5%,相比商业膜分别提高了38.4%和4.5%。当氯化强度低于4800 mg·L^-1·h时,膜的水通量和盐截留率变化不明显。     

Fabrication of in-situ polymerized UiO-66/PVDF supramolecular membranes with high anti-fouling performance

The composite membrane with the advantages of high separation efficiency and wide application, has been widely concerned in the field of water purification and molecular separation. However, the common composite membrane cannot achieve continuity, or the grafting process is complex, which significantly hinders its further development. In this work, the in-situ polymerization of UiO-66/PVDF supramolecular flat membranes as the continuous and high-performance composite membrane can be easily synthesized using the supramolecular force, (such as, hydrogen bond, etc.). These supramolecular membranes exhibit good hydrophilic (61°) and anti-fouling performance for bovine serum albumin (BSA) solution with rejection rate 97.79% than the original membrane. Moreover, this membrane can achieve more MOF doping based on maintaining the membrane performance, which undoubtedly greatly improves its hydrophilicity and mechanical properties. In addition, we also characterized the porous microstructure of the UiO-66/PVDF supramolecular membrane to analyze the influence of different doping amounts on the membrane structure. This supramolecular membrane has the advantages of simple synthesis, good hydrophilicity and water separation performance, which provides a more convenient and effective way for the preparation of MOFs/polymer flat membrane, and also provides a new method and new idea for expanding the application of MOFs/polymer ultrafiltration membrane in water treatment.     

Design and synthesis of Al-MOF/PPSU mixed matrix membrane with pollution resistance

To enhance the performance of the polyphenylene sulfone(PPSU) membrane,a novel mixed matrix membrane with hydrophilicity and antifouling properties was prepared.Using PPSU as the ba sic membrane material,polyvinyl pyrrolidone(PVP) as the porogen,N-Methyl pyrrolidone(NMP) as the solvent,and MOF-CAU-1(Al_4(OH)_2(OCH_3)_4(H_2 N-BDC)_3·xH_2 O) as the filler,PPSU/CAU-1 mixed matrix membrane(MMM) was prepared by an immersion precipitation and phase transformation technique.By changing the amount of MOF-CAU-1,the properties and performance of the MMM membrane were investigated in terms of hydrophilicity,pore morphology,surface roughness,and dye removal.The results show that the highest pure water flux of the mixed reached 47.9 L·m~(-2)·h~(-1), when the CAU-1 addition amount was 1.0 wt%, which was 23% higher than that of the pure PPSU membrane.Both the rejection rate and the antifouling performance of the MMM membrane also noticeably improved.