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1.
谢续明 《高分子科学》2016,34(10):1261-1269
Poly(acrylamide-co-acrylic acid) nanocomposite physical (P(AAm-co-AAc)NCP) hydrogels have been prepared through the in situ free radical solution polymerization based on a “single network, dual cross-linkings” strategy. The P(AAm-co-AAc) NCP hydrogels are composed of nanobrushes of P(AAm-co-AAc) chains grafted on the surface of vinylhybrid silica nanoparticles (VSNPs). In the hydrogel system, the VSNPs act as the “analogous chemical cross-linking points” once the hydrogen bonds formed between the P(AAm-co-AAc) chains of the nanobrushes, thus leading to the fabrication of high-strength P(AAm-co-AAc) NCP hydrogels. Compared with conventional thermosensitive P(AAm-co-AAc) hydrogels, the P(AAm-co-AAc) NCP hydrogels have a broader range of phase transition temperature, which can be adjusted by altering the monomer ratio, the VSNPs concentration, the addition of urea and N,N-dimethylacrylamide (DMAAm). At the same time, the mechanical properties of the P(AAm-co-AAc) NCP hydrogels have been improved significantly by the introduction of VSNPs. Furthermore, both the phase transition and the tensile strength of the P(AAm-co-AAc) NCP hydrogels are largely influenced when Fe3+ ions are introduced as the ionic crosslinkers into the hydrogel networks.  相似文献   

2.
Fluorescent hydrogels have promising applications in biomedical and engineering fields. However, they are usually mechanically weak. Here, we report a fluorescent composite hydrogel with high toughness, which is facilely prepared by solution casting ethanol solution of poly(hydroxyurethane) (PHU) and poly(stearyl acrylate-co-acrylic acid) (P[SA-co-AAc]) followed by swelling the casted film in water. The composite hydrogels with water content of 62–78 wt% possess remarkable mechanical performances, with tensile breaking stress of 0.3–1.1 MPa, breaking strain of 280%–400%, Young's modulus of 0.2–0.7 MPa, and tearing fracture energy of 1250–2630 J/m2. The high toughness is attributed to the effective energy dissipation of the network with hydrophobic association of SA units and hydrogen bonds between PHU and P(SA-co-AAc) as the physical crosslinks. The intense aggregation of carbamates and the formation of carbamate clusters through intra- and intermolecular hydrogen bonds endow the composite hydrogel with strong fluorescence. These hydrogels with high toughness and strong fluorescence should find applications in flexible electronics, information display, and biomedical devices.  相似文献   

3.
This paper presents the degradation trends of selected polyhydroxyalkanoate (PHA) films in a tropical mangrove environment. The biodegradability of homopolymer poly(3-hydroxybutyrate) [P(3HB)] and its co-polymers, poly(3-hydroxybutyrate-co-5 mol% 3-hydroxyvalerate) [P(3HB-co-5 mol% 3HV)] and poly(3-hydroxybutyrate-co-5 mol% 3-hydroxyhexanoate) [P(3HB-co-5 mol% 3HHx)], was investigated along with P(3HB) films containing 38 wt% titanium dioxide (TiO2) [P(3HB)-38 wt% TiO2]. The degradation of these formulations was monitored for 8 weeks at three different zones in an intermediate mangrove compartment along Sungai Pinang, adjacent to a famous fishing village on south of Penang Island. The degradation rate was observed both on the surface and in the sediment and was expressed in percentage of weight loss. The microbial enumeration done using sediment from the different zones indicated similar colony-forming unit (CFU) counts even though differences were noticed in the degradation profile of the various films in the respective zones. The results obtained revealed that co-polymers disintegrated at similar or higher rate than the homopolymer, P(3HB). However, the incorporation of TiO2 into PHB films caused the degradation rate of P(3HB)-38 wt% TiO2 composite film to be far slower than all the other PHA films. The overall rate of degradation of all PHA films placed on the sediment surface was slower than those buried in the sediment. Microscopic analyses showed that the surface morphology of P(3HB-co-5 mol% 3HHx) was more porous compared to P(3HB) and P(3HB-co-5 mol% 3HV) films, which may be an important factor for its rapid degradation.  相似文献   

4.
非共价修饰碳纳米管/二氧化钛复合材料的合成及性能   总被引:2,自引:0,他引:2  
采用溶胶-凝胶法在聚乙烯吡咯烷酮(PVP)非共价修饰的碳纳米管表面均匀沉积二氧化钛粒子制得纳米复合材料。用TEM、XRD、FTIR、N2吸脱附等对复合材料进行了表征。结果表明:纳米二氧化钛纳米粒子均匀沉积在被修饰碳纳米管表面,且二氧化钛为纯锐钛矿晶体结构,没有金红石和板钛矿相。非共价修饰碳纳米管/二氧化钛复合材料具有良好的介孔结构,其孔径分布主要集中在6~10 nm,且比表面积与纯的二氧化钛相比明显增大,在紫外光照射下降解亚甲基蓝,相比纯的二氧化钛和碳纳米管/二氧化钛,具有较高的催化活性。  相似文献   

5.
The photolytic and photocatalytic degradation of the copolymers poly(methyl methacrylate-co-butyl methacrylate) (MMA-BMA), poly(methyl methacrylate-co-ethyl acrylate) (MMA-EA) and poly(methyl methacrylate-co-methacrylic acid) (MMA-MAA) have been carried out in solution in the presence of solution combustion synthesized TiO2 (CS TiO2) and commercial Degussa P-25 TiO2 (DP 25). The degradation rates of the copolymers were compared with the respective homopolymers. The copolymers and the homopolymers degraded randomly along the chain. The degradation rate was determined using continuous distribution kinetics. For all the polymers, CS TiO2 exhibited superior photo-activity compared to the uncatalysed and DP 25 systems, owing to its high surface hydroxyl content and high specific surface area. The time evolution of the hydroxyl and hydroperoxide stretching vibration in the Fourier transform-infrared (FT-IR) spectra of the copolymers indicated that the degradation rate follows the order MMA-MAA > MMA-EA > MMA-BMA. The same order is observed for the rate coefficients of photocatalytic degradation. The photodegradation rate coefficients were compared with the activation energy of pyrolytic degradation. In degradation by pyrolysis, it was observed that MMA-BMA was the least stable followed by MMA-EA and MMA-MAA. The observed contrast in the order of thermal stability compared to the photo-stability of these copolymers was attributed to the two different mechanisms governing the scission of the polymer and the evolution of the products.  相似文献   

6.
Highly swelling P(2-acrylamido-2-methyl-1-propanesulfonic acid- co-acrylic acid) (P(AMPS-co-AAc)) superabsorbent hydrogel was synthesized in aqueous solution by a simple one-step using glow-discharge electrolysis plasma technique, in which N,N’-methylenebisacrylamide was used as a crosslinking agent. The structure, thermal stability and morphology of P(AMPS-co-AAc) superabsorbent hydrogel were characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, and scanning electron microscopy. A mechanism for synthesis of P(AMPS-co-AAc) superabsorbent hydrogel was proposed. The reaction parameters affecting the equilibrium swelling (i.e., discharge voltage, discharge time, macroscopic temperature of the liquid phase, mass ratio of AMPS to AAc, and content of crosslinker) were systematically optimized to achieve a superabsorbent hydrogel with a maximum swelling capacity. The hydrogel formed which absorbed about 1,685 g H2O/g dry hydrogel of the optimized product was used to study the influence of various pH values and salts solutions (NaCl, KCl, MgCl2, and CaCl2) on the equilibrium swelling. In addition, swelling kinetics in distilled water and on–off switching behavior were preliminarily investigated. The results showed that superabsorbent hydrogel was responsive to the pH and salts.  相似文献   

7.
Based on the unique absorbent characters and three-dimensional network structure of polyacrylamide (PAM) superabsorbent polymer, a photocatalytic degradable TiO2/PAM composite was synthesized by an aqueous solution polymerization method with N,N′-methylene bisacrylamide as crosslinker, potassium peroxydisulfate as initiator, acrylamide as monomer, and TiO2 (P-25) as functional filler. The photocatalytic degradability of the composite was evaluated using methyl orange as photodegradation target, and the recovery and reproducibility of the composite was investigated. It was found that TiO2/PAM composite had a good photocatalytic degradability, the composite also possessed a good reproducibility of photocatalytic degradability, which is possible to be used in practical process.  相似文献   

8.
The search for alternative materials with high dye adsorption capacity, such as methylene blue (MB), remains the focus of current studies. This computational study focuses on oxides ZnTiO3 and TiO2 (anatase phase) and on their adsorptive properties. Computational calculations based on DFT methods were performed using the Viena Ab initio Simulation Package (VASP) code to study the electronic properties of these oxides. The bandgap energy values calculated by the Hubbard U (GGA + U) method for ZnTiO3 and TiO2 were 3.17 and 3.21 eV, respectively, which are consistent with the experimental data. The most favorable orientation of the MB adsorbed on the surface (101) of both oxides is semi-perpendicular. Stronger adsorption was observed on the ZnTiO3 surface (−282.05 kJ/mol) than on TiO2 (–10.95 kJ/mol). Anchoring of the MB molecule on both surfaces was carried out by means of two protons in a bidentate chelating (BC) adsorption model. The high adsorption energy of the MB dye on the ZnTiO3 surface shows the potential value of using this mixed oxide as a dye adsorbent for several technological and environmental applications.  相似文献   

9.
A novel composite Chitosan graft poly (acrylic acid-co-N-isopropylacrylamide)/graphite oxide (CTS-g-P(AA-co-NIPAM/GO) is synthesized and used to remove methylene blue (MB) and fuchsin basic (FB) from aqueous solutions by adsorption. Small amount of GO brings about great improvement of the thermostability together with the adsorption amount. Adsorption capacities of MB and FB increase from 842.1 and 633.7 mg/g, respectively, to 1496.3 and 1000.8 mg/g, respectively, with 0.02 g intercalation amount of GO. The interactions between GO and main body of CTS-g-P(AA-co-NIPAM) graft copolymer are hydrogen and amide bonds, whereas that between dye molecules and CTS-g-P(AA-co-NIPAM)/GO composite is hydrogen bond as well as electrostatic interaction. Effect of various conditions on the adsorption capacities is discussed. Adsorption isotherms and thermodynamics are studied. The adsorption of both MB and FB are spontaneous and satisfy the Redlich-Peterson equation. Kinetic study shows that the adsorption of both dyes is in accordance with the Pseudo first-order kinetic model.  相似文献   

10.
利用溶胶-凝胶法原位制备了二氧化钛/石墨烯(TiO2-GE)复合光催化剂,研究了纯TiO2以及不同方法制备的TiO2-GE复合光催化剂对亚甲基蓝及罗丹明B光催化降解性能。结果表明:石墨烯的引入提高了TiO2的光催活性,这主要是得益于石墨烯优异的电子传输性能及较好吸附特性。不同方法制备TiO2-GE复合催化剂的光催化活性也存在较大差别。原位制备的TiO2-GE复合光催化剂表现出最佳的光催化活性。  相似文献   

11.
Stimuli-sensitive polymers were synthesized by copolymerizing varying ratios of N-isopropyl acrylamide(NIPAAm) and acrylic acid(AAc). The influence of polyelectrolytes on the lower critical solution temperatures(LCSTs) of these temperature/pH sensitive polymers was investigated in the pH range of 2-12. Polyelectrolyte complexes were prepared by mixing poly(NIPAAm-co-AAc) as anionic polyelectrolyte with poly(allyl amine)(PAA) or poly(L-lysine)(PLL) as cationic polyelectrolytes, respectively. Back titration was performed to determine the pKa values of PAAc in poly(NIPAAm-co-AAc) and to study the effect of comonomer ionization on the cloud point temperature. The effect of polyelectrolyte complex formation on the conformation of PLL was studied as a function of temperature by means of circular dichroism(CD). The swelling ratio of poly(NIPAAm-co-AAc) hydrogels as a function of pH at various temperature was obtained by measuring the weight of the hydrogels in buffer solutions. The LCSTs of the poly(NIPAAm-co-AAc) were strongly affected by pH, polyelectrolyte solutes, AAc content, and charge density. The influence of more hydrophobic PLL as a polyelectrolyte on the cloud point of PNIPAAm/water in the copolymer was stronger than that of poly(allyl amine)(PAA). Indomethacin was loaded into these hydrogels, and controlled release of this molecule from the hydrogel was determined under various temperature and pH conditions using UV/Vis spectrophotometry.  相似文献   

12.
以钛酸丁酯为前驱体, 碘溶胶为碘源, 在室温下采用水解沉淀法制备了单质碘和纳米TiO2复合的双介孔结构光催化剂(M-I2-TiO2). 采用X射线衍射(XRD)、透射电子显微镜(TEM)、比表面分析(BET)、紫外-可见(UV-Vis)漫反射光谱和傅里叶变换-红外光谱(FT-IR)对M-I2-TiO2进行了表征. 以次甲基蓝(MB)溶液为模拟废水, 对M-I2-TiO2的光催化性能进行了评价, 研究了不同热处理温度对光催化活性的影响. 结果表明, M-I2-TiO2在可见光区有显著的吸收, 300 ℃热处理得到的样品比表面积高达227.6 m2/g, 600 ℃热处理所得样品的比表面积仍高达111.8 m2/g, 而400 ℃热处理所得样品具有最好的光催化降解性能. 双介孔结构纳米TiO2/I2复合材料的光催化降解性能显著高于相同方法制备的纯TiO2和Degussa P-25商业产品. 催化剂经6次重复使用其光催化活性基本保持不变.  相似文献   

13.
《先进技术聚合物》2018,29(1):254-262
Membrane technology has been successfully applied for the removal of dyes from wastewater in the textile industry. A novel poly(vinylidene fluoride) (PVDF) membrane was prepared via blending with different dosages of Ag‐TiO2‐APTES composite for dyeing waste water treatment in our study. And the effect of Ag‐TiO2‐APTES blended into the PVDF membrane was discussed, including the rejection rate of methylene blue (MB) dye, membrane morphology, surface hydrophilicity, antibacterial activity, and a certain photocatalytic self‐cleaning performance. X‐ray diffraction and Fourier transform infrared characterization confirmed that Ag‐TiO2 was functionalized by amount of hydroxyl group (−OH) and amino group (NH−), which provided by APTES. Contact angle measurement certified that the hydrophilicity of the membrane surface increased, with the contact angle decrease to 61.4° compared with 81.8° of original PVDF membrane. MB rejection rate was also increased to 90.1% after addition of Ag‐TiO2‐APTES, and the rejection of original membrane was only 74.3%. The morphologies of membranes were observed by scanning electron microscope, which indicated that Ag‐TiO2‐APTES had a good dispersion in membrane matrix and also improved the microstructure of membranes. Besides, UV irradiation experiments were performed on the composite films contaminated by MB, and the result showed that Ag‐TiO2‐APTES nanoparticle provided PVDF membrane with a certain photodegradation capacity under UV irradiation. Moreover, antibacterial activity of the composite membrane was also demonstrated through antibacterial experiment, Escherichia coli as the representative bacteria. Perhaps, this research may provide a new way for PVDF blending modification.  相似文献   

14.
A series of dye-modified TiO2 photocatalysts were synthesized using dye Chrysoidine G (CG), tolylene-2,4-diisocyanate (TDI), and commercial TiO2 (Degussa P25) as starting materials. TDI was used as a bridging molecule whose two -NCO groups reacted with Ti-OH of TiO2 and -NH2 groups of CG, respectively. As a result, special organic complexes were formed on the TiO2 surface via stable π-conjugated chemical bonds between TiO2 and dye molecules, confirmed by FT-IR, XPS, and UV-vis spectra. Due to the existence of π-conjugated surface organic complexes, the as-synthesized photocatalysts showed a great improvement in visible absorption (400-550 nm). Methylene blue, as a photodegradation target, was used to evaluate the photocatalytic performance, and the dye-modified TiO2 exhibited much better activity under the visible light irradiation than bare TiO2.  相似文献   

15.
Textile and dye effluents have strong color, unstable pH and COD, a lot of inorganic salt, and high biotoxicity. It is difficult and inefficient to remove dyes from high-saline wastewater by traditional methods. In this study, a simple synthetic CuO/CeO2 photocatalyst is used to achieve high efficiency photodegradation of methylene blue in high salt wastewater. The p-type CuO/n-type CeO2 heterojunction photocatalyst is synthesized by a modified hydrothermal-calcination method. The XRD and XPS reveal the successful synthesis of CuO/CeO2 composite. The SEM and TEM images show that the sample consists of large amounts of well-dispersed CuO nanosphere loading on the CeO2 layers. DRS exhibits the absorption band (about 510 nm) and the band gap energy (2.43 eV) of the CuO/CeO2 composite. Compared with pure CuO, CeO2, and TiO2 (P25), the prepared CuO/CeO2 can increase the mineralization rate of MB by 18.19%~33.74%. More than 80% of MB can be effectively removed in the wastewater containing 5~80 g/L NaCl with a wide pH value range of 2.11~9.02, and the degradation processes follow the pseudofirst-order reaction kinetics. Active species trapping experiments confirm that the degradation of methylene blue is mainly attributed to hydroxyl radical; besides, O2▪− and hole (h+) also play important roles. Chlorine ions have dual effects in photocatalytic reactions. This work could provide a new approach to construct new heterojunction photocatalysts and a deeper insight for the treatment of hypersaline dye wastewater.  相似文献   

16.
Sb2S3/Bi2S3 doped TiO2 were prepared with the coordination compounds [M(S2CNEt)3] (M=Sb, Bi; S2CNEt=pyrrolidinedithiocarbamate) as precursors via gel-hydrothermal techniques. The doped TiO2 were characterized by XRD, SEM, XPS and UV-vis diffuse reflectance means. The photocatalyst based on doped TiO2 for photodecolorization of 4-nitrophenol (4-NP) was examined. The optimal Bi2S3/Sb2S3 content, pH and different doped techniques have been investigated. Photocatalytic tests reveal that M2S3 doped TiO2 via the gel-hydrothermal route performs better photocatalytic activity for photodegradation reaction of 4-nitrophenol (4-NP).  相似文献   

17.
A series of polyaniline-anatase TiO2 (PANI-TiO2) nanocomposite powders with different PANI:TiO2 ratios were prepared by ‘in-situ’ deposition oxidative polymerization of aniline hydrochloride using ammonium persulfate (APS) as oxidant in the presence of ultrafine grade powder of anatase TiO2 cooled in an ice bath. And the solid-phase photocatalytic degradation of PANI-TiO2 nanocomposites was investigated under the ambient air in order to assess the feasibility of developing photodegradable polymers. The photodegradation of the composite powders was compared with that of pure PANI powders by performing weight loss monitoring, elemental analysis, FT-IR and UV-vis spectroscopy and X-ray photoelectron spectroscopy (XPS). The PANI-TiO2 nanocomposite powders showed highly enhanced photodegradation and the photodegradation increased with decreasing ratios of PANI:TiO2. A weight loss of about 6.8% was found for the PANI-TiO2 (1:3) nanocomposite; however, the weight loss of the PANI-HCl powder was only 0.3% after being irradiated for 60 h under air. The photocatalytic degradation of the nanocomposite powders accompanied the peak intensity decrease in the FT-IR spectra at 1235 cm−1, attributed to C-N stretching mode for benzenoid unit, and the depigmentation of the powders due to the visible light scattering from growing cavities. The elemental analysis and XPS analysis of the composite showed that the bulk and surface concentrations of N decreased with irradiation. A possible mechanism for the photocatalytical oxidative degradation was also mentioned.  相似文献   

18.
Bromine (Br) and nitrogen (N) co-doped TiO2 ((Br–N–TiO2) photocatalysts were prepared by a sol–gel method. The catalysts were characterized by X-ray Diffraction (XRD), N2 adsorption and desorption isotherms, X-ray Photoelectron Spectra (XPS), UV-Vis Diffraction Spectra and Electron Spin Response (ESR) Spectra. Experiments on photodegradation of Methylene Blue (MB) and Sulfosalicylic Acid (SSA) under visible light were carried out to evaluate the photocatalytic activities of the catalysts. Chemical Oxygen Demand (COD) analysis was also conducted to evaluate the mineralization degrees of the catalysts in MB photodegradation. Enhanced photocatalytic activities were observed for the Br–N–TiO2 catalysts in the experiments of MB and SSA photodegradation. A possible mechanism was proposed to explain the improved photocatalytic activities of the Br–N–TiO2 catalysts.  相似文献   

19.
Red mud wastes have been converted into mesoporous zeolite socony mobile-5 (ZSM-5) followed by deposited titanium dioxide (TiO2) nanoparticles to generate synergy adsorption-photodegradation for removal of dye removal in waste water. The amount of TiO2 loading was varied to achieve optimum photocatalytic activity while maintaining the mesoporosity and high surface area of ZSM-5. Sol-gel method facilitated the formation of anatase TiO2 on the ZSM-5. The fourier transform infrared spectra clarified the formation of Si–O–Ti at 957 cm?1 by the exchanging the hydrogen ion with titanium ion, which proved by decreasing the absorption band of Si–OH and Si–O interaction at 964 and 944 cm?1, respectively. Sol-gel method also preserved the mesopore diameter of ZSM-5 at 3.5 nm which allow the diffusion of methylene blue (MB) molecules into the pores. However, the surface area and the pore volume were slightly reduced with increasing the TiO2 loading. The adsorption performance of samples showed that the increasing in the TiO2 loading led to the decreasing in the adsorption capacity. All samples showed the suitability towards the pseudo second order kinetic. The Langmuir isotherm was suitable to describe the adsorption mechanism by monolayer adsorption. Mesoporosity of ZSM-5 accelerated the adsorption of dye via the increase of mass transfer in the pore channel which confirmed by the low intercept of intraparticle diffusion model at the first stage. The photocatalytic test showed that 10% TiO2 loading on the ZSM-5 exhibited the highest methylene blue removal followed by 5% and 20% TiO2 loading. Optimization on the amount of photocatalyst and the pH of solution indicated the reaction favoured 1 g L?1 of catalysts and at alkaline pH. 10% TiO2/ZSM-5 also exhibited high stability and reusability up to four reaction cycles. Photocatalytic performance of 10% TiO2/ZSM-5 was further investigated on photodegradation of malachite green and rhodamine B organic dyes, which showed the photocatalytic efficiency of 73 and 88%, respectively. Superoxide radical, hydroxyl radical, and photogenerated electron were identified as the main active species for MB photodegradation based on the reduction of degradation rate following the addition scavenger molecules.  相似文献   

20.
TiO2/PVA composite nanofiber mat was prepared via an electrospinning technology. SH‐TiO2‐SiO2 hybrid particles and PVA solution were injected through a coaxial syringe, yielding a composite nanofiber mat. The as‐prepared SH‐TiO2‐SiO2/PVA composite nanofiber mat was immersed in Cd2+ cation solution and S2? anion solution in turn. Thus, yellow TiO2@CdS/PVA composite nanofiber mats were prepared. By adjusting the number of times a mat was immersed in the Cd2+ and S2? solutions, different amounts of CdS particles attaching to the mats were obtained. Both SH‐TiO2‐SiO2/PVA and TiO2@CdS/PVA composite nanofiber mats were employed to catalyze the photodegradation of a model dye, methylene blue. The photodegradation performance could be greatly enhanced by the introduction of CdS particles anchoring onto TiO2 particles. The photodegradation efficiency reached 99.2% within 180 min. Also, the nanofiber mat could be recycled and reused at least 10 times. The photodegradation efficiency of TiO2@CdS/PVA composite nanofiber mats remained 68.8% for 10 cycles.  相似文献   

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