金属有机框架MIL-101(Fe)对水中微囊藻毒素-LR的吸附

通过溶剂热法制备了性质稳定的金属有机框架材料MIL-101(Fe),并用于吸附去除水中的微囊藻毒素-LR。采用电子显微镜、傅立叶变换红外光谱(FT-IR)、Zeta电位和N_2吸附-脱附等方法对制备的纳米材料进行了表征。MIL-101(Fe)具有多孔结构和较高的比表面积(375.2 m~2/g),尺寸约为500 nm。考察了pH值、离子强度、温度、吸附时间、浓度等参数对吸附剂吸附能力的影响。结果表明,静电作用和配位作用是主要的作用机理。MIL-101(Fe)对微囊藻毒素-LR的吸附速度很快(20 min内达到吸附平衡),吸附过程符合准二级动力学模型;MIL-101(Fe)对微囊藻毒素-LR表现出良好的吸附性能,其最大吸附量为256.4 mg/g。溶液中存在的腐植酸对MIL-101(Fe)的吸附性能产生一定的影响。受腐殖酸、盐类的影响,相同条件下MIL-101(Fe)对江水中微囊藻毒素-LR的吸附性能有所下降,但仍可达到68.1 mg/g。因此,该方法简便、高效,适用于快速除去污染水体中的微囊藻毒素-LR。     

Highly stable water splitting on oxynitride TaON photoanode system under visible light irradiation

Highly stable photoelectrochemical water splitting is demonstrated for the first time on a tantalum oxynitride (TaON) photoanode under visible light irradiation. Highly dispersed CoO(x) nanoparticles on the TaON photoanode efficiently scavenge photogenerated holes and effectively suppress self-oxidative deactivation of the TaON surface, resulting in a stable photocurrent. The use of highly dispersed CoO(x) cocatalyst on TaON together with phosphate solutions significantly increased the photocurrent due to the formation of a cobalt/phosphate phase. This enabled us to stably split water into H(2) and O(2) under visible light irradiation at a relatively low applied bias (0.6 V vs Pt counter electrode).     

Cobalt-catalyzed aminocarbonylation of (hetero)aryl halides promoted by visible light

The catalytic aminocarbonylation of (hetero)aryl halides is widely applied in the synthesis of amides but relies heavily on the use of precious metal catalysis. Herein, we report an aminocarbonylation of (hetero)aryl halides using a simple cobalt catalyst under visible light irradiation. The reaction extends to the use of (hetero)aryl chlorides and is successful with a broad range of amine nucleophiles. Mechanistic investigations are consistent with a reaction proceeding via intermolecular charge transfer involving a donor–acceptor complex of the substrate and cobaltate catalyst.

An aminocarbonylation of (hetero)aryl halides using a simple cobalt catalyst under visible light irradiation is presented.     

Evaluation of the reaction mechanism for photocatalytic degradation of organic pollutants with MIL-88A/BiOI structure under visible light irradiation

Research on Chemical Intermediates - In this study, we synthesized novel visible light photocatalyst MIL-88A/BiOI using depositing BiOI particles on the surface of a metal–organic framework...     

可见光照射下取代型杂多酸盐对染料的催化降解

将杂多酸(GaWmFen)负载到阴离子交换树脂(Resin)上,得到GaWmFen/Resin(GaWmFenR)固相光催化剂,在可见光的照射下,以罗丹明B(RhB)为模型化合物,含镓的GaWmFen/Resin(GaWmFenR)催化剂可以有效地活化H2O2降解染料RhB,随着铁原子的取代数目的增多,RhB浓度比降低的趋势加快,GaW9Fe3最快,C/C0降低0.937.在光照300 min 以后,体系的总有机碳(TOC)的变化趋于平缓,减少了0.15 mg.L-1.催化剂的8次重复试验结果表明GaWmFenR固相光催化剂易于分离,并且具有良好的稳定性,可以重复利用.     

MIL-101 (Fe) @Ag Rapid Synergistic Antimicrobial and Biosafety Evaluation of Nanomaterials

Metal-organic frameworks (MOFs), which have become popular in recent years as excellent carriers of drugs and biomimetic materials, have provided new research ideas for fighting pathogenic bacterial infections. Although various antimicrobial metal ions can be added to MOFs with physical methods, such as impregnation, to inhibit bacterial multiplication, this is inefficient and has many problems, such as an uneven distribution of antimicrobial ions in the MOF and the need for the simultaneous addition of large doses of metal ions. Here, we report on the use of MIL-101(Fe)@Ag with efficient metal-ion release and strong antimicrobial efficiency for co-sterilization. Fe-based MIL-101(Fe) was synthesized, and then Ag⁺ was uniformly introduced into the MOF by the substitution of Ag⁺ for Fe³⁺. Scanning electron microscopy, powder X-ray diffraction (PXRD) Fourier transform infrared spectroscopy, and thermogravimetric analysis were used to investigate the synthesized MIL-101(Fe)@Ag. The characteristic peaks of MIL-101(Fe) and silver ions could be clearly seen in the PXRD pattern. Comparing the diffraction peaks of the simulated PXRD patterns clearly showed that MIL-101(Fe) was successfully constructed and silver ions were successfully loaded into MIL-101(Fe) to synthesize an MOF with a bimetallic structure, that is, the target product MIL-101(Fe)@Ag. The antibacterial mechanism of the MOF material was also investigated. MIL-101(Fe)@Ag exhibited low cytotoxicity, so it has potential applications in the biological field. Overall, MIL-101(Fe)@Ag is an easily fabricated structurally engineered nanocomposite with broad-spectrum bactericidal activity.     

Photocatalytic oxidation of 4-chlorophenol using thermosensitive zinc phthalocyanine copolymer under visible light irradiation

A novel thermosensitive photocatalyst,P(NIPA-co-ZnMPc),has been prepared using zinc tetra(N-carbonylacrylic)aminophthalocya-nine(ZnMPc) to copolymerize with N-isopropylacrylamide(NIPA).The lower critical solution temperature(LCST) of P(NIPA-co-ZnMPc) measured by differential scanning calorimetry(DSC) was 33.5 °C.P(NIPA-co-ZnMPc) effectively catalyzes the oxidation of 4-chlorophenols(4-CP) using oxygen as oxidant under the visible light irradiation,and it has higher photocatalytic activity than ZnMPc under t...     

Anti-Influenza Virus Study of Composite Material with MIL-101(Fe)-Adsorbed Favipiravir

Nanomaterial technology has attracted much attention because of its antibacterial and drug delivery properties, among other applications. Metal-organic frameworks (MOFs) have advantages, such as their pore structure, large specific surface area, open metal sites, and chemical stability, over other nanomaterials, enabling better drug encapsulation and adsorption. In two examples, we used the common pathogenic bacterium Staphylococcus aureus and highly infectious influenza A virus. A novel complex MIL-101(Fe)-T705 was formed by synthesizing MOF material MIL-101(Fe) with the drug favipiravir (T-705), and a hot solvent synthesis method was applied to investigate the in vitro antibacterial and antiviral activities. The results showed that MIL-101(Fe)-T705 combined the advantages of nanomaterials and drugs and could inhibit the growth of Staphylococcus aureus at a concentration of 0.0032 g/mL. Regarding the inhibition of influenza A virus, MIL-101(Fe)-T705 showed good biosafety at 12, 24, 48, and 72 h in addition to a good antiviral effect at concentrations of 0.1, 0.2, 0.4, 0.8, 1.6, and 3 μg/mL, which were higher than MIL-101(Fe) and T-705.     

可见光照射下温敏锌酞菁共聚物光催化氧化对氯苯酚

将含有不饱和双键的四马来酰胺基锌酞菁（ZnMPc）与N-异丙基丙烯酰胺（NIPA）共聚,制备得到一种新型温敏锌酞菁共聚物光催化剂：P（NIPA—co—ZnMPc）,采用差示扫描量热法测得其低临界溶解温度（LCST）为33．5℃．在可见光照射下利用氧气作为氧化剂,P（NIPA—co-ZnMPc）~g有效地催化氧化对氯苯酚（4-CP）,与小分子ZnMPc相比,P（NIPA-co-ZnMPc）具有更高的光催化活性．两者在水溶液中的紫外．可见光谱图显示,共聚后大分子链的阻隔作用能有效地抑制酞菁分子的二聚,从而大大提高了其催化活性．温度对其光催化活性的实验结果显示,P（NIPA-co-ZnMPc）在其LCST附近具有最高的催化效率,说明催化剂的聚集态结构对其光催化活性产生直接影响,通过测定其在不同温度下的流体力学半径,可推测在其LCST附近发生了分子间的疏水聚集,会对4-CP起富集作用,从而加快了光催化反应速率．该光催化剂可通过均相催化异相分离实现循环利用,实验表明该催化剂具有较高的稳定性．     

Crystal facet dependence of water oxidation on BiVO4 sheets under visible light irradiation

Monoclinic BiVO(4) crystals with preferentially exposed (040) facets were hydrothermally synthesized by using a trace amount of TiCl(3) as the directing agent; this function was confirmed by X-ray diffraction patterns (XRD) and high-resolution transmission electron microscopy (HRTEM). The effects of the directing agent TiCl(3) and the pH values applied during synthesis have been studied, and the optimized BiVO(4) sample with highly exposed (040) facet could be obtained by using 1.2 at.% of TiCl(3) as the directing agent at a pH value of 2. Some complementary techniques were also applied to exclude the effects of the structural and physical property changes, such as surface area and hydrophilicity. The photocatalytic activity of oxygen evolution on BiVO(4) is found to be proportionally correlated with the exposed surfaces of the (040) facet. It is assumed that the active sites with a BiV(4) structure on the exposed (040) facet is assigned to be responsible for the high activity of O(2) evolution.     

Water reduction and oxidation on Pt-Ru/Y2Ta2O5N2 catalyst under visible light irradiation

Y(2)Ta(2)O(5)N(2) is presented as a novel photocatalyst with high activity for water splitting under visible-light irradiation in the presence of appropriate sacrificial reagents; the activity for reduction to H(2) is increased by the incorporation of Pt or Ru as a co-catalyst, with a significant increase in production efficiency when both Pt and Ru are present.     

Photodegradation of toluene over TiO(2-x)N(x) under visible light irradiation

We report the photooxidation of toluene over nitrogen doped TiO(2) (TiO(2-x)N(x)) under visible light irradiation. The photocatalytic oxidation of toluene in air over TiO(2-x)N(x) powders was studied using diffuse reflectance Fourier transform infrared spectroscopy (DRIFTS), gas chromatography (GC), ion chromatography (IC), and gas chromatography mass spectrometry (GC-MS), focusing on the photocatalytic decomposition processes of toluene. Results obtained indicate that toluene, weakly adsorbed on the catalyst surface, is initially photooxidized to benzaldehyde which adsorbs onto the TiO(2-x)N(x) surface more strongly, leading to the formation of ring-opening products such as carboxylic acids and aldehydes. No gaseous intermediates were detected during the photooxidation. Major intermediates adsorbed at the catalyst surface were oxalic acid, (COOH)(2), acetic acid, CH(3)COOH, formic acid, HCOOH, and pyruvic acid, CH(3)COCOOH, whereas more complicated carboxylic species, including propionic acid, CH(3)CH(2)COOH, isovaleric acid, (CH(3))(2)CHCH(2)COOH, and succinic acid, (CH(2)COOH)(2), were also found in the early stage of the photooxidation. These intermediate products were gradually photodegraded to CO(2) and H(2)O under visible light irradiation.     

The oxidation of alkanols with air oxygen in the catalytic system copper(ii) acetate—hydroquinone promoted by visible light

2-Propanol or 1-propanol in acetonitrile, when exposed to air and irradiated with a tungsten lamp in the presence of catalytic amounts of copper(ii) acetate and hydroquinone, are oxidized to give acetone or propanal, respectively.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1147–1149, June, 1994.We express our gratitude to the administration of the University of Neuchfitel (Switzerland) for having provided the possibility and means to complete this work. We also thank Dr. S. Claude, Mr. A. Béguin, and Mr. G. Meister of the same University for their assistance in the experiments.The financial support of the Russian Foundation for Basic Research (Grant No. 93-03-5226) and the International Science Foundation (Grant MMS 000) is gratefully acknowledged.     

Amino-functionalized MIL-101(Fe) metal-organic framework as a viable fluorescent probe for nitroaromatic compounds

Microchimica Acta - A highly luminescent iron(III)-based amino-functionalized metal-organic framework (MOF) of type NH2-MIL-101(Fe) was synthesized by a solvothermal method. Its structure and...     

Photodegradation of organic pollutants catalyzed by iron species under visible light irradiation

The green oxidation technology is the most economically attractive and environmentally friendly oxidation technique in the treatment of organic pollutants. Photocatalytic degradation of organic pollutants by iron species is a desired green oxidation technique due to using hydrogen peroxide or ideally molecular oxygen as oxidant and water as solvent. However, the system has some disadvantages. The reaction has to be performed in acidic conditions in order to avoid Fe ion precipitation and iron sludge will be accumulated in the reaction. Moreover, the utilization of H(2)O(2) means a high cost and risks in the storage and transportation and organic pollutants can not be completely mineralized. In this perspective, we report a systematic investigation of the improvement in the Fenton system for treatment of organic pollutants in water. Several strategies have been studied on the Fenton system for overcoming the above mentioned shortcomings and enhance the efficiency. For example, in order to extend the application of the Fenton system and perform it at neutral pH, iron complexes were used to replace the Fe(2+)/Fe(3+). Moreover, iron complexes have a strong absorption in the visible region, which leads to decomposition of colorless organic pollutants under visible light irradiation. Iron complexes with special structures can activate molecular O(2) instead of H(2)O(2) under mild conditions and the supported iron species maintains a high catalytic activity after repeated use and can be reused simply by filtration. Finally, prospects for further work required to be performed for its practical application is discussed.     

Photo-electrochemical water splitting system with three-layer n-type organic semiconductor film as photoanode under visible irradiation

A three-layer structure of n-type organic semiconductors(PTCDA/PTCDA:PCBM/PCBM) is successfully identified as photoanode for photoelectrochemical water oxidation during the overall splitting of water into hydrogen/oxygen in a nearly stoichiometric ratio(H2:O2=2:1) under visible irradiation(λ > 420 nm).A possible charge separation mechanism under visible light illumination was also proposed.     

Inhibition of immediate type hypersensitivity reaction by combined irradiation with ultraviolet and visible light

Recently we found that ultraviolet B (UVB) irradiation in erythematous doses significantly inhibited the immediate type hypersensibility reaction in the skin. In the present study we investigated the effects of different wavelengths on the skin prick test reaction (SPT). The forearm of ragweed allergic patients was irradiated with increasing doses of ultraviolet A (UVA), visible light (VIS) or combined UVB, UVA and VIS light, referred to as mUV/VIS. SPTs were performed 24 h after irradiation both on irradiated and non-irradiated control skin areas using ragweed extract. UVA and VIS irradiation led to a slight, not significant inhibition of allergen-induced wheal formation. Mixed irradiation with mUV/VIS light resulted in a dose-dependent inhibition of the allergen-induced wheal formation. The inhibition was significant already at suberythematous doses. As there is a good correlation between SPT and the nasal symptoms in patients with hay fever these data suggest that phototherapy with mUV/VIS light might be an effective and safe treatment modality for immediate type hypersensibility reactions in the skin and nasal mucosa.     

PdAg/MIL-101(Fe)催化NaBH4水解制氢

将PdAg纳米颗粒负载到MIL-101(Fe)上作为硼氢化钠水解制氢的催化剂。采用XRD、TEM、HRTEM、XPS、SEM和EDS等方法对催化剂PdAg/MIL-101(Fe)的结构进行了表征。PdAg/MIL-101(Fe)在硼氢化钠水解制氢中表现出较高的催化活性,在温和的条件下水解制氢最大速率为2.60 L·min^–1·g_cat.^–1。详细研究了反应温度、催化剂用量、氢氧化钠和硼氢化钠浓度对该催化反应的影响规律。结果发现,制氢速率很大程度上依赖于反应温度,随着反应温度的升高,制氢速率明显增加,制氢的表观活化能为54.89 kJ·mol^–1。该催化剂重用性能好,5次循环后仍能保持活性。     

Photocatalytic degradation of methylene blue on Fe3+-doped TiO2 nanoparticles under visible light irradiation

Fe³⁺-doped TiO₂ composite nanoparticles with different doping amounts were successfully synthesized using sol-gel method and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and ultravioletvisible spectroscopy (UV-Vis) diffuse reflectance spectra (DRS). The photocatalytic degradation of methylene blue was used as a model reaction to evaluate the photocatalytic activity of Fe³⁺/TiO₂ nanoparticles under visible light irradiation. The influence of doping amount of Fe³⁺ (ω: 0.00%–3.00%) on photocatalytic activities of TiO₂ was investigated. Results show that the size of Fe³⁺/TiO₂ particles decreases with the increase of the amount of Fe³⁺ and their absorption spectra are broaden and absorption intensities are also increased. Doping Fe³⁺ can control the conversion of TiO₂ from anatase to rutile. The doping amount of Fe³⁺ remarkably affects the activity of the catalyst, and the optimum efficiency occurs at about the doping amount of 0.3%. The appropriate doping of Fe³⁺ can markedly increase the catalytic activity of TiO₂ under visible light irradiation. __________ Translated from Journal of Northwest Normal University (Natural Science), 2006, 42(6): 55–56 [译自: 西北师范大学学报(自然科学版)]