宏观尺寸大孔-介孔TiO2-SiO2光催化剂的制备及其在染料降解中的应用宏观尺寸大孔-介孔TiO2-SiO2光催化剂的制备及其在染料降解中的应用

以柱撑式环氧树脂大孔聚合物为模板,制备宏观尺寸的大孔-介孔SiO₂;以其为载体,通过钛酸四丁酯原位水解和高温焙烧制得大孔-介孔TiO₂纳米晶-SiO₂复合材料。应用SEM、TEM、XRD、FTIR和N₂吸附-脱附法对材料进行表征。以偶氮荧光桃红为模拟污染物,用氙灯模拟日光光源,考察了不同条件下大孔-介孔TiO₂-SiO₂的光催化性能。结果表明,大孔-介孔SiO₂具有三维连续贯通的大孔孔道,孔壁为连续的纳米SiO₂薄膜;TiO₂纳米晶以纳米薄膜的形式均匀地原位生长在SiO₂纳米薄膜的两侧,得到的复合材料孔壁上存在丰富的介孔。当焙烧温度为600℃、TiO₂的负载量为15.7wt%、染料溶液浓度为10 mgL-1且pH为3时,大孔-介孔TiO₂-SiO₂光催化剂对污染物的光催化降解效率最高,而且具有良好的重复使用性。      

AB-8大孔吸附树脂固定化过氧化氢酶的研究

利用AB-8大孔吸附树脂作为载体、戊二醛为交联剂时过氧化氢酶进行了固定化,研究了其最优固定化条件及稳定性.结果表明,最佳固定化条件为:吸附温度35℃,pH值7.0,吸附时间6h,加酶量每克载体970U,戊二醛体积分数0.2%,交联时间2h.固定化过氧化氢酶的最高酶活收率达到45.2%.固定化酶的热稳定性、酸碱稳定性都较游离酶有了一定的提高,重复使用10次,酶活仍能稳定保持在初始酶活的60%以上,具有良好的操作稳定性.     

介孔SiO_2/膨胀石墨复合材料的直接合成及其对染料的吸附性能

采用简单的一步水热合成法,在含有模板剂、铝盐、膨胀石墨和硅源的水溶液中,利用铝盐水解后所产生的弱酸性环境,直接制备出介孔SiO_2/膨胀石墨复合材料,考察了铝盐的添加量对所得复合材料结构和性能的影响。采用XRD、N_2吸附和SEM对介孔SiO_2/膨胀石墨复合材料的结构和形貌进行了表征。以亚甲基蓝为目标污染物分子,系统评价了复合材料的吸附性能。结果表明,合成时铝盐的添加量在很大范围内变化(r_(Al/Si)=0.25~2.0,体系pH值为3.1~2.3)均可获得具有较大比表面积和孔体积的介孔SiO_2/膨胀石墨复合材料,且介孔SiO_2以多层膜的形式生长在膨胀石墨碳层上;当r_(Al/Si)=0.25、0.5、1.0时,复合材料孔道有序规整;当rAl/Si=1.0、2.0时,复合材料中介孔孔道规整性下降。介孔SiO_2/膨胀石墨复合材料吸附亚甲基蓝的饱和吸附量在52~55mg·g~(-1)左右,吸附行为主要符合Langmuir方程和伪二级动力学模型。     

氧化硅介孔泡沫材料固定木瓜蛋白酶的研究

以氧化硅介孔泡沫材料(Siliceous Mesocellular Foam, MCF)为载体对木瓜蛋白酶进行了固定, 并对固定化酶的性能和影响因素以及酶的稳定性作了系统的研究. 结果表明, 木瓜蛋白酶在MCF上能获得较大的负载量（334mg/g MCF）. 固定化木瓜蛋白酶的最适反应温度较游离酶提高了10℃, 最适pH向碱性方向偏移0.5个单位. 固定化木瓜蛋白酶的米氏常数（Km）为6.99×10^-3mol/L, 在八批次操作后酶活保留65.1%. 在4℃条件下放置60d后, 固定化酶的剩余活性仍保持75%以上, 而游离酶的活性只有初始活性的53.6%. 与游离酶相比, 固定化木瓜蛋白酶的pH稳定性、热稳定性、操作稳定性和储藏稳定性都有明显改善, 有利于酶的重复使用和储藏. 介孔泡沫材料是一种良好的木瓜蛋白酶固定载体.     

有机-无机杂化介孔材料包埋南极假丝酵母脂肪酶的研究

以四甲氧基硅烷(TMOS)和一定比例的甲基三甲氧基硅烷(MTMS)、二甲基二甲氧基硅烷(DMDMS)、三甲基甲氧基硅烷(TMMS)为硅源,采用酸催化的溶胶-凝胶法包埋南极假丝酵母脂肪酶。比较了有机-无机杂化介孔材料和纯硅基介孔材料固定化南极假丝酵母脂肪酶的酶活力和保留活力,同时还比较了有机-无机杂化介孔材料固定化南极假丝酵母脂肪酶和游离南极假丝酵母脂肪酶的pH、温度以及储存稳定性。结果表明,有机-无机杂化介孔材料固定化南极假丝酵母脂肪酶具有比纯硅基介孔材料固定化南极假丝酵母脂肪酶更高的酶活力和保留活力。其中三取代的有机-无机杂化介孔材料固定化南极假丝酵母脂肪酶的酶活力最高,其保留活力可达到84.9%。此外与游离的南极假丝酵母脂肪酶相比,有机-无机杂化介孔材料固定化南极假丝酵母脂肪酶具有更好的pH、温度和储存稳定性,以及更宽的pH值和温度的酶活力范围。     

介孔炭材料及介孔炭/氧化硅复合材料对大分子有机污染物的吸附

介孔炭材料与活性炭相比具有较大的孔体积和孔径,高的比表面积以及规则的孔道结构,而介孔炭/氧化硅复合材料兼顾了活性炭与介孔材料的优点,因此在吸附大分子有机污染物方面有很好的应用前景。笔者综述了近年来介孔炭,负载/修饰后的介孔炭,介孔炭/氧化硅复合材料的制备和最新研究进展。在制备方面,根据其制备机理的不同可分为硬模板法和软模板法,制备出有序的介孔炭与介孔炭/氧化硅复合材料。在应用方面,重点介绍了介孔炭材料和介孔炭/氧化硅复合材料对大分子有机污染物的吸附性能。进而对介孔炭/氧化硅复合材料在吸附方面的应用进行了展望。     

环氧基功能化块体SiO_2大孔材料对漆酶的固定化

采用后嫁接法在溶剂热条件下对新型块体SiO2大孔材料进行环氧基化改性,以环氧基功能化SiO2大孔材料作为载体,通过共价结合法固定化诺维信(Novozymes)工业级漆酶,对固定化条件进行了优化,研究了固定化酶与游离酶的酶学性质。结果表明,在固定化时间为4 h、pH值为4.5、初始酶液浓度为25 mg/mL时,固定化效果最好,固定化漆酶活力达到101.7 U/g;固定化漆酶的最适pH值为4.0,最适温度为50℃,其pH值稳定性和热稳定性都显著优于游离漆酶。固定化漆酶具有可重复操作的性质,与底物反应反复操作10批次后剩余活性为43.4%。     

一步法合成多级孔超高交联吸附树脂

以4,4’-二氯甲基联苯为单体在混合溶剂中通过Friedel-Crafts反应直接聚合制得超高交联吸附树脂。该吸附树脂具有多级孔结构,孔径可调,且具有超高的孔容(2.53 cm3/g)和比表面积(1 592 m2/g)。混合溶剂中的正己烷可作为介孔模板剂,通过调节混合溶剂的比例可有效地控制吸附树脂的孔道结构。     

大孔磁性聚合物载体的制备及其固定化硫酸盐还原菌的研究

化学共沉淀法制备了油酸修饰的Fe_3O_4颗粒,以苯乙烯为连续相,水为分散相,Fe_3O_4颗粒为稳定剂,采用高内相乳液模板法合成了磁性大孔聚合物小球(MPMS),并对MPMS的形貌、疏水性、结构、热稳定性、磁性等进行了表征。将硫酸盐还原菌(SRB)固定于MPMS,以模拟硫酸盐废水,比较了固定化SRB与游离SRB的脱硫性能。结果表明,大孔材料MPMS呈现多级孔道结构,具有丰富的泡孔和窗孔,MPMS的饱和磁化强度为2.043 A·m~2/kg,固定化SRB后的MPMS饱和磁化强度为0.188 A·m~2/kg,聚合物载体在负载后仍保留一定磁性;SRB在MPMS上固定化一周左右,可生成稳定的生物膜,对比固定化SRB和游离SRB的脱硫性能,可得出:固定化SRB生长状态优于游离SRB,当硫酸根浓度为2 000 mg/L时,脱硫速率达到2 597.76 mg/(L·d)。     

Al_2O_3/SiO_2/介孔SiO_2包覆型复合磨料的制备及表征研究

先以纳米Al_2O_3为核,Na_2SiO_3和柠檬酸为原料,采用非均匀成核法制备出Al_2O_3/SiO_2包覆型复合纳米粉体;再以十六烷基三甲基溴化铵(CTAB)为介孔模板剂,通过自组装法制得Al_2O_3/SiO_2/介孔SiO_2包覆型复合磨料;并借助X射线衍射、红外光谱、透射电镜、能谱和N_2吸附-脱附等手段对样品进行表征。结果表明:SiO_2和介孔SiO_2依次包覆在Al_2O_3表面形成了Al_2O_3/SiO_2/介孔SiO_2包覆型复合磨料,其具有MCM-48型介孔孔道结构,平均孔径为2.3nm,比表面积为454m~2/g,孔体积为0.43cm~3/g。     

Synthesis of retinyl palmitate catalyzed by Candida sp.99-125 lipase immobilized on fiber-like SBA-15 mesoporous material

Candida sp.99-125 lipase was suitable for transesterification of fats and oils to produce fatty acid methyl ester. The adsorption of Candida sp.99-125 lipase onto the fiber-like SBA-15 mesoporous material has been studied. The unaltered structural order of the fiber-like SBA-15 before and after the adsorption has been confirmed by FT-IR, SEM and N2 adsorption. The amount of adsorbed Candida sp.99-125 lipase depends both on the solution pH and reaction time. Good adsorption capacity of Candida sp.99-125 lipase on fiber-like SBA-15 may be due to solution pH from 5.0 to 9.0 especially at 7.0 (93.99 mg enzyme per gram silica is obtained and the activity recovery is 281.05%). A high lipase loading (135.9 mg enzyme per gram silica) was obtained, but it did not produce a proportionate level of catalytic activity. The immobilized Candida sp.99-125 lipase showed increased adaptability in the hydrolysis of p-nitrophenyl acetate compared to free Candida sp.99-125 lipase at pH 5.0-9.0. Meanwhile, the immobilized Candida sp.99-125 lipase showed higher thermal stability than that of free Candida sp.99-125 lipase. And the synthesis of retinyl palmitate in organic solvent with the immobilized Candida sp.99-125 lipase was investigated. The influence factors, such as: the solvent used, the molar ratio and concentrations of substrates, the reaction time and the amount of lipase were studied and optimized. In the conditions of transesterificating 0.164 g retinyl acetate and 0.32 g palmitic acid, 10 mL of solvent hexane, 1:4 of mass ratio of lipase to retinyl acetate, and 6 hours of reaction time, 74.6% of retinyl acetate was converted into retinyl plamitate.     

P(GMA-co-HEMA)/SiO_2大孔复合材料的制备及其在固定化脂肪酶中的应用

以块体SiO2大孔材料为基质,甲基丙烯酸缩水甘油酯(GMA)和甲基丙烯酸羟乙酯(HEMA)为功能单体,通过原位聚合和溶剂蒸发制备P(GMA-co-HEMA)/SiO2大孔复合材料,用SEM、EDS、BET、FTIR和TGDTA对样品进行表征,并将其用于固定褶皱假丝酵母脂肪酶(CRL)。结果表明:SiO2大孔材料很强的毛细管作用使共聚物均匀地涂敷在其孔壁上,形成P(GMA-co-HEMA)/SiO2复合纳米薄膜。共聚物的负载量和亲疏水性可分别通过改变单体浓度和体积比进行调控,当单体体积浓度为10%、GMA和HEMA的体积比为9∶1时大孔复合材料固定化脂肪酶比酶活达到最高,为3 886.9U/g,与底物反应重复操作8批次后剩余酶活率为68.7%。     

Tailoring mesoporous-silica nanoparticles for robust immobilization of lipase and biocatalysis

The rational design of nano-carriers is critical for modem enzyme immobilization for advanced biocatalysis.Herein,we report the synthesis of octadecylalkylmodified mesoporous-silica nanoparticles (C18-MSNs) with a high C18 content (～19 wt.％) and tunable pore sizes (1.6-13 nm).It is demonstrated that the increased hydrophobic content and a tailored pore size (slightly larger than the size of lipase) are responsible for the high performance of immobilized lipase.The optimized C18-MSNs exhibit a loading capacity of 711 mg/g and a specific activity 5.23 times higher than that of the free enzyme.Additionally,93％ of the initial activity is retained after reuse five times,which is better than the best performance reported to date.Our findings pave the way for the robust immobilization of lipase for biocatalytic applications.     

Characterizations of immobilized neutral lipase on chitosan nano-particles

Characterizations of chitosan nano-particles prepared by the ionization gelation method were discussed in this paper. The optimal pH of an immobilized enzyme was 7.5. The optimal temperature of the immobilized enzyme was 45 °C. The thermal, operational and storage stabilities of an enzyme were improved after they were immobilized on chitosan nano-particles. The chitosan nano-particles were applied to protect the activity of free neutral lipase. They could improve the enzyme activity by 13.17% than that of the free neutral lipase. The Michaelis constant K_m of the immobilized enzyme was disclosed as 0.37 × 10² g/l by the Line-weaver Burk plot at 40 °C.     

Polyacrolein/mesoporous silica nanocomposite: Synthesis,thermal stability and covalent lipase immobilization

In this work, new polyacrolein/MCM-41 nanocomposites with good phase mixing behavior were prepared through an emulsion polymerization technique. Mesoporous silica was synthesized by in situ assembly of tetraethyl orthosilicate (TEOS) and cetyl trimethyl ammonium bromide (CTAB). The structure and properties of polyacrolein containing nanosized MCM-41 particle (5 and 10 wt%), were investigated by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction, Dynamic light scattering (DLS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), N₂ adsorption techniques, and thermogravimetric (TGA) analyses. The SEM images from the final powder have revealed good dispersion of the MCM-41 nanoparticles throughout polymeric matrix with no distinct voids between two phases. The results indicated that the thermal properties of the nanocomposite were enhanced by addition of MCM-41. Thermomyces lanuginosa lipase (TLL) was used as a model biocatalyst and successfully immobilized with polyacrolein and the nanocomposite via covalent bonds with the aldehyde groups. The activity between free enzyme, polyacrolein, and MCM-41 nanocomposite (10 wt%)-immobilized TLL was compared. The immobilized lipase with the nanocomposite shows better operational stability such as pH tolerance, thermal and storage stability. In addition, the immobilized lipase with the nanocomposite can be easily recovered and retained at 74% of its initial activity after 15 time reuses.     

Design of single-site Ti embedded highly hydrophilic silica thin films with macro-mesoporous structures

Single-site Ti-containing macroporous silica thin films with mesoporous frameworks were successfully prepared on quartz substrate with high transparency by using poly(methyl methacrylate) (PMMA) microspheres and organic surfactant as template of porous structures. The presence of mesoporous structure and the differences of macroporous structure of film surface were investigated by XRD and FE-SEM measurements. The local structure of Ti moieties embedded within silica matrixes were also confirmed by UV-vis investigations. It was found that the macroporous structure and the embedded single-site Ti moieties within mesoporous frameworks were quite effective for improvement of surface hydrophilicity, i.e., the water droplet was entirely spread on the film surface even before and after irradiation of UV light.     

ZnO纳米线/大孔SiO2复合物的制备及吸附性能

采用Zn(Ac)₂/聚乙二醇600(PEG600)/H₂O三元混合溶液作为前驱物,通过100~200 ℃温度范围内的两阶段加热使Zn(Ac)₂水解,再经过高温煅烧使ZnO晶种在SiO₂孔壁上形成.以锌氨络合物为锌源,在90 ℃下热分解后生成的Zn(OH)₂沉积在孔道中,并在100 ℃下利用水热合成原位制备ZnO纳米线,通过改变三元前驱物组分用量以调节ZnO晶种的尺寸与分布,进而控制纳米线的形貌,最终获得了直径为15~20 nm的ZnO纳米线,其以无规线团形貌均匀填充于三维孔道中.XRD和拉曼光谱表明纳米线为六方纤锌矿型ZnO晶体.考察了ZnO纳米线/大孔SiO₂复合物对猪胰脂肪酶的吸附性能,实验测得复合物的吸附量是单纯大孔SiO₂材料的5~6倍,其最大固定量为286.8 mg·g^-1,最高酶活为425.5 U·g^-1,被固定的酶蛋白在缓冲溶液中经过48 h浸泡不易脱落,且活性保持稳定.     

Two-phase porous silica: Mesopores inside controlled pore glasses

The structural and textural properties of Two-Phase Porous Silica consisting of a mesoporous pore system formed by finely dispersed silica-gel inside the original pores of a macroporous glass framework have been carefully investigated. Nitrogen adsorption at 77 K, Mercury Intrusion, Small Angle X-ray Scattering (SAXS), Temperature-Programmed Desorption (TPD) of ammonia and ²⁷Al MAS NMR spectroscopy were used. Different mesoporous glasses investigated show BET surface areas up to 300 m²/g, a total pore volume of about 0.16 cm³/g and pore sizes of <2–10 nm, depending on the acid leaching conditions of the phase-separated sodium borosilicate initial glass. The texture of the macroporous frame glass was characterized after removing the mesoporous finely dispersed silica-gel phase with alkaline solution. Leaching of the phase-separated initial glass with Al(NO₃)₃ solution and followed by thermal treatment lead to the formation of Brönsted acid sites at the surface of the resulting mesoporous glasses by an incorporation of aluminium in tetrahedral coordination in the silica framework.     

On-chip encapsulation of lipase using mesoporous silica: A new route to enzyme microreactors

A polydimethylsiloxane/glass microfluidic reactor containing lipase-mesoporous silica (FSM-22) conjugates has been successfully constructed without chemical cross-linking between enzyme and support. A direct visualization of conjugates of lipase and FSM-22 immobilized in the microreactor by optical microscopy revealed that the enzymes were uniformly dispersed throughout the particles of the FSM-22, because of the successful immobilization of the enzyme. Moreover, the lipase-FSM-22 conjugates contained in the microreactor indicated higher enzymatic activity in hydrolysis of triglyceride, as compared with a batch experiment. These results demonstrate that the microreactor using mesoporous silica performs not only the reagent-less enzyme immobilization but also the high reactivity of the enzyme.     

Study on synthesis of poly(GMA)-grafted Fe3O4/SiOX magnetic nanoparticles using atom transfer radical polymerization and their application for lipase immobilization

Functionalized superparamagnetic particles were prepared by atom transfer radical polymerization of glycidyl methacrylate onto the surface of modified Fe₃O₄/SiO_X nanoparticles. The obtained particles were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR) and vibrating sample magnetometer (VSM). Candida rugosa lipase was covalently immobilized on the magnetic particles in mild condition via covalent binding with a higher activity recovery. The resulting immobilized lipase had better resistance to pH and temperature inactivation in comparison to free lipase, the adaptive pH and temperature ranges of lipase were widened, and it exhibited good thermal stability and reusability.