A metal-OH group modification strategy to prepare highly-hydrophobic MIL-53-Al for efficient acetone capture under humid conditions

A series of highly-hydrophobic MIL-53-Al (MIL = Materials of Institut Lavoisier) frameworks synthesized via decoration of the Al-OH groups by alkyl phosphonic acid were developed as adsorbents for removing acetone from humid gas streams. The newly prepared materials were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscope (SEM), N₂ adsorption-desorption and thermogravimetric analysis (TGA). Their adsorption behaviors toward acetone vapor under dry and wet conditions were studied subsequently. Results showed that alkyl phosphonic acid was successfully grafted into MIL-53-Al skeleton through coordinating interaction with Al³⁺ generating [email protected]_x (x = 12, 14, 18). The [email protected]_x exhibited similar crystal structure and thermal stability to parent MIL-53-Al. Furthermore, the modified materials showed significantly enhanced hydrophobicity. The water vapor uptake of [email protected]₁₄ decreased by 72.55% at 75% relative humidity (RH). Dynamic adsorption experiments demonstrated that water vapor had almost no effect on the acetone adsorption performance of [email protected]₁₄. Under the condition of 90% RH, the acetone adsorption capacity of [email protected]₁₄ was 102.98% higher than that of MIL-53-Al. Notably, [email protected]₁₄ presented excellent adsorption reversibility and regeneration performance in 10 adsorption-desorption cycles. Taken together, the strategy of metal-OH group modification is an attractive way to improve the acetone adsorption performance over metal-organic frameworks (MOFs) under humid conditions. Besides, [email protected]₁₄ would be deemed as a promising candidate for capturing acetone in high moisture environment.     

Simplified creation of polyester fabric supported Fe-based MOFs by an industrialized dyeing process: Conditions optimization, photocatalytics activity and polyvinyl alcohol removal

MIL-53(Fe) was successfully prepared and deposited on the surface carboxylated polyester (PET) fiber by an optimized conventional solvothermal or industrialized high temperature pressure exhaustion (HTPE) process to develop a PET fiber supported MIL-53(Fe) photocatalyst ([email protected]) for the degradation of polyvinyl alcohol (PVA) in water under light emitting diode (LED) visible irradiation. On the basis of several characterizations, [email protected] was tested for the photocalytic ability and degradation mechanism. It was found that temperature elevation significantly enhanced the formation and deposition of MIL-53(Fe) with better photocatalytic activity. However, higher temperature than 130°C was not in favor of its photocatalytic activity. Increasing the number of surface carboxyl groups of the modified PET fiber could cause a liner improvement in MIL-53(Fe) loading content and photocatalytic ability. High visible irradiation intensity also dramatically increased photocatalytic ability and PVA degradation efficiency of [email protected] Na₂S₂O₈ was used to replace H₂O₂ as electron acceptor for further promoting PVA degradation in this system. [email protected] prepared by HTPE process showed higher MIL-53(Fe) loading content and slightly lower PVA degradation efficiency than that prepared by solvothermal process at the same conditions. These findings provided a practical strategy for the large-scale production of the supported MIL-53(Fe) as a photocatalyst in the future.     

Monodisperse amino-modified nanosized zero-valent iron for selective and recyclable removal of TNT: Synthesis, characterization, and removal mechanism

Nitroaromatic explosives are major pollutants produced during wars that cause serious environmental and health problems. The removal of a typical nitroaromatic explosive, 2,4,6-trinitrotoluene (TNT), from aqueous solution, was conducted using a new recyclable magnetic nano-adsorbent ([email protected]₂NH₂). This adsorbent was prepared by grafting amino groups onto [email protected]₂ particles with a well-defined core-shell structure and demonstrated monodispersity in solution. The removal performance of the nano-adsorbent towards TNT was found to be 2.57 and 4.92 times higher than that towards two analogous explosives, 2,4-dinitrotoluene (2,4-DNT) and 2-nitrotoluene (2-NT), respectively, under neutral conditions. The difference in the removal performance among the three compounds was further compared in terms of the effects of different conditions (pH value, ionic strength, humic acid concentration, adsorbent modification degree and dosage, etc.) and the electrostatic potential distributions of the three compounds. The most significant elevation is owing to modification of amino on [email protected]₂ which made a 20.7% increase in adsorption efficiency of TNT. The experimental data were well fit by the pseudo-second-order kinetic model and the Freundlich adsorption isotherm model, indicating multilayer adsorption on a heterogeneous surface. The experimental results and theoretical considerations show that the interactions between [email protected]₂NH₂ NPs and TNT correspond to dipole-dipole and hydrophobic interactions. These interactions should be considered in the design of an adsorbent. Furthermore, the adaptability to aqueous environment and excellent regeneration capacity of [email protected]₂NH₂ NPs makes these remediation materials promising for applications.     

Nickel phosphide on Ni foam as anode and peroxymonosulfate as the chemical oxidizer for effective direct urea fuel cell

The direct urea fuel cell (DUFC) is a low cost and competitive approach for contemporaneous urine or urea-contaminated wastewater treatment and electricity generation. However, the lack of efficient urea oxidation reaction (UOR) electrocatalysts and suitable electron acceptors remains a challenge for practical applications. Here, we developed a DUFC system using Ni₂[email protected] foam as the anode and peroxymonosulfate (PMS) as the chemical oxidizers. The Ni₂[email protected] foam anode showed a high oxidation activity for UOR with an onset potential of 0.30 V vs. Ag/AgCl and Tafel slope of 34.4 mV/dec. PMS with high theoretical potential improved the cell voltage to 1.43 V. A power density of DUFC up to 4.91 mW/cm² was achieved using PMS at room temperature, which was approximately twice as high as using H₂O₂ (2.38 mW/cm²). Ni^II/Ni^III was the redox active species on the Ni₂P anode in the DUFC process, and Ni^II was electrochemically oxidized to Ni^III, which reverted to Ni^II by urea reduction. When real human urine was used as the fuel, a power density of 4.46 mW/cm² can be achieved at room temperature. This DUFC with high cell performance showed potential application in urea wastewater treatment.     

Reuse of Fenton sludge as an iron source for NiFe2O4 synthesis and its application in the Fenton-based process

The potentially hazardous iron-containing sludge from the Fenton process requires proper treatment and disposal, which often results in high treatment cost. In this study, a novel method for the reuse of Fenton sludge as an iron source for the synthesis of nickel ferrite particles(NiFe_2O_4) is proposed. Through a co-precipitation method followed by sintering at 800°C, magnetic NiFe_2O_4 particles were successfully synthesized, which was confirmed by powder X-ray diffraction(XRD), scanning electronic microscopy(SEM), energy dispersive spectroscopy(EDS), Fourier transform infrared spectroscopy(FT-IR) and Raman spectroscopy. The synthesized NiFe_2O_4 could be used as an efficient catalyst in the heterogeneous Fenton process. In phenol degradation with H_2O_2 or NiFe_2O_4 alone, the phenol removal efficiencies within the reaction time of 330 min were as low as 5.9% ± 0.1% and 13.5% ±0.4%, respectively. However, in the presence of both NiFe_2O_4 and H_2O_2, phenol removal efficiency as high as 95% ± 3.4% could be achieved, indicating the excellent catalytic performance of NiFe_2O_4 in the heterogeneous Fenton process. Notably, a rapid electron exchange between_Ni II and_Fe III ions in the NiFe_2O_4 structure could be beneficial for the Fenton reaction. In addition, the magnetic catalyst was relatively stable, highly active and recoverable, and has potential applications in the Fenton process for organic pollutant removal.     

化学预氧化对苏氨酸生成三氯乙醛的影响

以具有最大比三氯乙醛生成潜能(SCHFP)的苏氨酸为研究对象,分析了次氯酸钠(NaClO)、二氧化氯(ClO_2)、高锰酸钾(KMnO_4)、过氧化氢(H_2O_2)、臭氧(O_3)和臭氧过氧化氢(O_3/H_2O_2)等预氧化剂对三氯乙醛(CH)生成的影响,以确定合适的预氧化剂及其适宜投加量,为CH的控制提供指导.结果表明,能够有效去除一天CH生成量(CH1d)的预氧化方式依次为H_2O_2、ClO_2、KMnO_4和NaClO,适宜投加量分别为3、0.5、0.6和0.5mg·L-1,对CH1d相应的去除率分别为61.54%、47.63%、29.77%和10.94%;能够有效去除CH生成潜能(CHFP)的预氧化方式依次为KMnO_4、NaClO、H_2O_2和ClO_2,适宜投加量分别为0.6、0.5、3和0.5mg·L~(-1),对CHFP相应的去除率分别为41.01%、33.38%、8.36%和2.40%;O_3和O_3/H_2O_2预氧化能够使CH1d和CHFP增加,不适用于对CH的控制.     

Recycling plant wax constituents for chemical defense: hemi-biosynthesis of triterpene saponins from β-amyrin in a leaf beetle

Several species of Doryphorina leaf beetles from Central- and South America produce oleanane triterpene glycosides in their defensive glands. The presence of pentacyclic triterpenes in insects is intriguing since they lack the key enzymes necessary to synthesize these compounds. Since -amyrin is a common constituent of leaf waxes, we hypothesized that these leaf beetles use this compound as a precursor to their oleanane glycosides. To test this hypothesis we first confirmed the presence of -amyrin in Ipomoea batatas, the food plant of Platyphora kollari. Next, adults of P. kollari were fed for 10 days with I. batatas leaf disks painted with a solution of [2,2,3-²H₃]-amyrin ([2,2,3-²H₃]-1). The secretion from their defensive glands was collected and analyzed by HPLC-ESIMS. The results demonstrated that the secretion of beetles fed with an amount of [2,2,3-²H₃]-amyrin corresponding to the quantity of unlabeled (natural) -amyrin present in the leaf disks contained on average 5.1% of [2,2,3-²H₃]-3-O--d-glucopyranosyl-(1-->4)--d-glucuronopyranosyl-hederagenin ([2,2,3-²H₃]-2), whereas the secretions of beetles fed with 10 times this amount of [2,2,3-²H₃]-amyrin contained on average 23.9% of [2,2,3-²H₃]-2. In both series of experiments, the percentage of labeled versus unlabeled triterpene glycoside in the secretion was positively correlated with the amount of deuterated -amyrin ingested. These results demonstrate for the first time that some leaf beetles are able to metabolize a widespread triterpenic constituent of leaf wax into more complex glycosides that are stored in their defensive glands.     

Assessing the effects of surface-bound humic acid on the phototoxicity of anatase and rutile TiO2 nanoparticles in vitro

In this study,the cytotoxicity of two different crystal phases of TiO₂ nanoparticles,with surface modification by humic acid（HA）,to Escherichia coli,was assessed.The physicochemical properties of TiO₂ nanoparticles were thoroughly characterized.Three different initial concentrations,namely 50,100,and 200 ppm,of HA were used for synthesis of HA coated TiO₂ nanoparticles（denoted as A/RHA50,A/RHA100,and A/RHA200,respectively）.Results indicate that rutile（LC50（concentration that causes 50%mortality compared the control group）=6.5）was more toxic than anatase（LC₅0=278.8）under simulated sunlight（SSL）irradiation,possibly due to an extremely narrow band gap.It is noted that HA coating increased the toxicity of anatase,but decreased that of rutile.Additionally,AHA50 and RHA50had the biggest differences compared to uncoated anatase and rutile with LC₅0of 201.9 and21.6,respectively.We then investigated the formation of reactive oxygen species（ROS）by TiO₂ nanoparticles in terms of hydroxyl radicals（OH）and superoxide anions（O₂^-）.Data suggested that O₂^- was the main ROS that accounted for the higher toxicity of rutile upon SSL irradiation.We also observed that HA coating decreased the generation of OH and O₂^- on rutile,but increased O₂^- formation on anatase.Results from TEM analysis also indicated that HA coated rutile tended to be attached to the surface of E.coli more than anatase.     

Catalytic performance of Fe3O4-CoO/Al2O3 catalyst in ozonation of 2-(2,4-dichlorophenoxy)propionic acid, nitrobenzene and oxalic acid in water

Fe3O4-CoO/Al2O3 catalyst was prepared by incipient wetness impregnation using Fe(NO3) 3·9H2O and Co(NO3) 2·6H2O as the precursors,and its catalytic performance was investigated in ozonation of 2-(2,4-dichlorophenoxy) propionic acid(2,4-DP) ,nitrobenzene and oxalic acid.The experimental results indicated that Fe3O4-CoO/Al2O3 catalyst enabled an interesting improvement of ozonation eciency during the degradation of each organic pollutant,and the Fe3O4-CoO/Al2O3 catalytic ozonation system followed a radical-type mechanism.The kinetics of ozonation alone and Fe3O4-CoO/Al2O3 catalytic ozonation of three organic pollutants in aqueous solution were discussed under the mere consideration of direct ozone reaction and OH radical reaction to well investigate its performance.In the catalytic ozonation of 2,4-DP,the apparent reaction rate constants(k) were determined to be 1.456×10-2 min-1 for ozonation alone and 4.740×10-2 min-1 for O3/Fe3O4-CoO/Al2O3.And O3/Fe3O4-CoO/Al2O3 had a larger Rct(6.614×10-9) calculated by the relative method than O3 did(1.800×10-9) ,showing O3/Fe3O4-CoO/Al2O3 generated more hydroxyl radical.Similar results were also obtained in the catalytic ozonation of nitrobenzene and oxalic acid.The above results demonstrated that the catalytic performance of Fe3O4-CoO/Al2O3 in ozonation of studied organic substance was universal to a certain degree.     

Egyptian blue — Cuprorivaite a window to ancient Egyptian technology

Egyptian Blue, a multicomponent synthetic blue pigment has been recorded in ancient Egypt since the Fourth Dynasty of the Old Kingdom (2600–2480 B.C.). The pigment consisting of cuprorivaite (CaCuSi₄O₁₀) with variable amounts of wollastonite (CaSiO₃), Cu-rich glass and cuprite (Cu₃O) or tenorite (CuO) was prepared by melting the copper-rich ingredient with lime and desert sand. Low melting temperatures (below 742 °C) were achieved by addition of flux-like plant ashes. The high quality of the pigments collected from monuments of the Fifth Dynasty (2480–2320 B.C.) may indicate that the first manufacture was in early dynastic or perhaps predynastic eras. During the reign of Thutmosis III (18th Dynasty, 1490–1436 B.C.) probably bronze filings were first applied as starting material, thus indicating a technological innovation. This new method was employed till the Roman times.     

Multiple transformation pathways of p-arsanilic acid to inorganic arsenic species in water during UV disinfection

p-Arsanilic acid(p-ASA) is widely used in China as livestock and poultry feed additive for promoting animal growth.The use of organoarsenics poses a potential threat to the environment because it is mostly excreted by animals in its original form and can be transformed by UV–Vis light excitation.This work examined the initial rate and efficiency of p-ASA phototransformation under UV-C disinfection lamp.Several factors influencing p-ASA phototransformation,namely,p H,initial concentration,temperature,as well as the presence of Na Cl,NH4+,and humic acid,were investigated.Quenching experiments and LC–MS were performed to investigate the mechanism of p-ASA phototransformation.Results show that p-ASA was decomposed to inorganic arsenic(including As(Ⅲ) and As(V))and aromatic products by UV-C light through direct photolysis and indirect oxidation.The oxidation efficency of p-ASA by direct photosis was about 32%,and those by HOU and1O2 were 19% and 49%,respectively.Cleavage of the arsenic–benzene bond through direct photolysis,HOU oxidation or1O2 oxidation results in simultaneous formation of inorganic As(Ⅲ),As(IV),and As(V).Inorganic As(Ⅲ) is oxidized to As(IV) and then to As(V) by1O2 or HOU.As(IV) can undergo dismutation or simply react with oxygen to produce As(V) as well.Reactions of the organic moieties of p-ASA produce aniline,aminophenol and azobenzene derivatives as main products.The photoconvertible property of p-ASA implies that UV disinfection of wastewaters from poultry and swine farms containing p-ASA poses a potential threat to the ecosystem,especially agricultural environments.     

Interfacial mechanisms of heterogeneous Fenton reactions catalyzed by iron-based materials: A review

The heterogeneous Fenton reaction can generate highly reactive hydroxyl radicals(·OH)from reactions between recyclable solid catalysts and H_2O_2 at acidic or even circumneutral pH.Hence,it can effectively oxidize refractory organics in water or soils and has become a promising environmentally friendly treatment technology.Due to the complex reaction system,the mechanism behind heterogeneous Fenton reactions remains unresolved but fascinating,and is crucial for understanding Fenton chemistry and the development and application of efficient heterogeneous Fenton technologies.Iron-based materials usually possess high catalytic activity,low cost,negligible toxicity and easy recovery,and are a superior type of heterogeneous Fenton catalysts.Therefore,this article reviews the fundamental but important interfacial mechanisms of heterogeneous Fenton reactions catalyzed by iron-based materials..OH,hydroperoxyl radicals/superoxide anions(HO_2./O_2~-.)and high-valent iron are the three main types of reactive oxygen species(ROS),with different oxidation reactivity and selectivity.Based on the mechanisms of ROS generation,the interfacial mechanisms of heterogeneous Fenton systems can be classified as the homogeneous Fenton mechanism induced by surface-leached iron,the heterogeneous catalysis mechanism,and the heterogeneous reaction-induced homogeneous mechanism.Different heterogeneous Fenton systems catalyzed by characteristic iron-based materials are comprehensively reviewed.Finally,related future research directions are also suggested.     

UVC Inactivation of dsDNA and ssRNA Viruses in Water: UV Fluences and a qPCR-Based Approach to Evaluate Decay on Viral Infectivity

Disinfection by low-pressure monochromatic ultraviolet (UVC) radiation (253.7 nm) became an important technique to sanitize drinking water and also wastewater in tertiary treatments. In order to prevent the transmission of waterborne viral diseases, the analysis of the disinfection kinetics and the quantification of infectious viral pathogens and indicators are highly relevant and need to be addressed. The families Adenoviridae and Polyomaviridae comprise human and animal pathogenic viruses that have been also proposed as indicators of fecal contamination in water and as Microbial Source Tracking tools. While it has been previously suggested that dsDNA viruses may be highly resistant to UVC radiation compared to other viruses or bacteria, no information is available on the stability of polyomavirus toward UV irradiation. Here, the inactivation of dsDNA (HAdV2 and JCPyV) and ssRNA (MS2 bacteriophage) viruses was analyzed at increasing UVC fluences. A minor decay of 2-logs was achieved for both infectious JC polyomaviruses (JCPyV) and human adenoviruses 2 (HAdV2) exposed to a UVC fluence of 1,400 J/m², while a decay of 4-log was observed for MS2 bacteriophages (ssRNA). The present study reveals the high UVC resistance of dsDNA viruses, and the UV fluences needed to efficiently inactivate JCPyV and HAdV2 are predicted. Furthermore, we show that in conjunction with appropriate mathematical models, qPCR data may be used to accurately estimate virus infectivity.     

水合氧化铝负载的磁性核/壳结构Fe3O4@SiO2纳米颗粒对水中磷的去除及再利用

在磁铁矿纳米颗粒表面包被硅壳后再包被水合氧化铝,制备了具备核壳结构的磁性纳米颗粒除磷吸附剂(磁性氧化铝),通过XRD、TEM、VSM、BET比表面积测定进行了表征.XRD和TEM结果显示了核壳结构的存在,其饱和磁化强度达56.00 emu·g~(-1),比表面积达47.27 m~2·g~(-1).Langmuir模型计算的磷最大吸附量为12.90 mg·g~(-1),且在25℃和50℃下均保持稳定,反应快速,40min磷去除率达96%以上.磁性纳米吸附剂对磷的吸附与pH关系密切,在p H为5~9时磷去除率达90%以上.采用实际污水实验,最佳投量为1.25 kg·t~(-1).吸附-脱附-再生实验结果表明,磷吸附率随循环次数增加稍有下降,吸附的磷可以通过1 mol·L~(-1)的NaOH脱附,脱附率为90%左右,且吸附剂可以进行再生,具有反复利用和回收磷资源的潜力.     

铜在壳核结构磁性颗粒上的吸附:效能与表面性质的关系

为了揭示吸附剂的吸附效能与其组成、结构及表面性质之间的关系,本研究对两种壳核结构磁性颗粒Fe_3O_4/Mn O2与Fe-Mn/Mn O2的形貌特征、表面性质进行了系统表征,并对铜在磁性颗粒表面的吸附行为与机制进行了详细研究.表征结果表明磁核Fe_3O_4与Fe-Mn具有相似的尖晶石类晶体结构,包覆Mn O2后,晶体结构均未发生明显变化.但Mn的引入,增强了磁核与外壳间的结合作用,Fe-Mn比Fe_3O_4包覆MnO_2的量更多、更均匀,进而使Fe-Mn/Mn O2具有更高的比表面积与更低的等电点.吸附实验结果表明,Fe-Mn的最大铜吸附容量33.7 mg·g-1(pH 5.5)高于Fe_3O_4的17.5 mg·g-1(pH 5.5);包覆MnO_2以后,铜吸附性能显著增强,Fe-Mn/MnO_2最大铜吸附容量升高至58.2 mg·g-1(p H 5.5),为Fe_3O_4/MnO_2的2.6倍,且优于多数文献报道的磁性吸附剂.机制研究表明铜在Fe_3O_4/Mn O2与Fe-Mn/MnO_2的表面发生了特性吸附,形成了内层表面络合物.综上所述,磁性颗粒的吸附效能与其组成成分、形貌结构及表面性质之间具有显著的相关性.     

Oxygen isotope fractionation between bird bone phosphate and drinking water

Oxygen isotope compositions of bone phosphate (δ¹⁸O_p) were measured in broiler chickens reared in 21 farms worldwide characterized by contrasted latitudes and local climates. These sedentary birds were raised during an approximately 3 to 4-month period, and local precipitation was the ultimate source of their drinking water. This sampling strategy allowed the relationship to be determined between the bone phosphate δ¹⁸O_p values (from 9.8 to 22.5‰ V-SMOW) and the local rainfall δ¹⁸O_w values estimated from nearby IAEA/WMO stations (from ?16.0 to ?1.0‰ V-SMOW). Linear least square fitting of data provided the following isotopic fractionation equation: δ¹⁸O_w = 1.119 (±0.040) δ¹⁸O_p ? 24.222 (±0.644); R ² = 0.98. The δ¹⁸O_p–δ¹⁸O_w couples of five extant mallard ducks, a common buzzard, a European herring gull, a common ostrich, and a greater rhea fall within the predicted range of the equation, indicating that the relationship established for extant chickens can also be applied to birds of various ecologies and body masses. Applied to published oxygen isotope compositions of Miocene and Pliocene penguins from Peru, this new equation computes estimates of local seawater similar to those previously calculated. Applied to the basal bird Confuciusornis from the Early Cretaceous of Northeastern China, our equation gives a slightly higher δ¹⁸O_w value compared to the previously estimated one, possibly as a result of lower body temperature. These data indicate that caution should be exercised when the relationship estimated for modern birds is applied to their basal counterparts that likely had a metabolism intermediate between that of their theropod dinosaur ancestors and that of advanced ornithurines.     

四氧化三铁/聚乙烯亚胺纳米颗粒的制备及除磷性能的研究

采用化学共沉淀法,以聚乙烯亚胺(PEI)为改性剂,制备了聚乙烯亚胺改性的纳米四氧化三铁复合材料(Fe3O4/PEI).Zeta电位、透射电镜和FTIR表征结果显示,PEI修饰提高了纳米Fe3O4在水中的分散性和稳定性,同时也增强了其表面正电荷,从而提高了Fe3O4对水中磷酸根的去除能力.在磷酸根初始浓度为50 mg·L~(-1),Fe3O4/PEI投加量为200 mg,p H=3,温度为25℃的条件下,Fe3O4/PEI对100 m L磷酸根的吸附去除率达到91%.吸附过程在3 h内达到平衡.吸附等温数据表明,该吸附过程符合Langmuir吸附等温方程,可决系数R2达到0.99,最大吸附量为29.88 mg·L~(-1).Fe3O4/PEI复合材料重复利用性好,在第5次吸附-解析后还能保持对磷酸根75%以上的吸附去除率.磷的解析效率随着p H增加而增加,在p H=13时,解析效率达到65%.