Synthesis of nanoscale zero-valent iron supported on exfoliated graphite for removal of nitrate

Nano ZVI particles supported on micro-scale exfoliated graphite were prepared by using KBH4 as reducing agent in the H2O/ethanol system. The supported ZVI materials generally have higher activity and greater flexibility for environmental remediation applications. The exfoliated graphite as the support was treated beforehand to hydrophilic material. Nano iron particles are deposited onto the rough graphite surface while those were formed by borohydride reduction. The possible nitrate reduction pathways were proposed. The TEM image shows that iron particles are highly dispersed on the surface of graphite and several of iron particles are imbedded in the pit of support surface. In this synthesis, iron particles have a nearly spherical shape with a grain size of 50?100 nm. The surface areas of materials with different iron loadings of 3.5%, 7.0%, 10.0%, 15.0% and 20.0%(mass fraction) are 2.89, 9.55, 8.45, 23.8 and 6.18 m2·g?1 by BET surface analyzer. The chemical reduction of nitrate by supported nano ZVI in aqueous solution were tested in series batch experiments. Experiment results suggest that NO3? can be more rapidly reduced to NH4+ at neutral pH and anaerobic conditions by supported nano ZVI than unsupported nano ZVI or ZVI scraps. The 15% nano Fe/graphite shows the best reduction efficiency contrasted with other Fe loading particles.

LDPE/m-nZVI复合膜的制备及性能

为克服脱氧剂小袋包装与食品混装带来的安全问题,采用硼氢化钾(KBH4)液相还原法制备了油酸钠(NaOl)改性纳米零价铁(m-nZVI),将其与低密度聚乙烯(LDPE)熔融共混后热压成膜,制备了包装用LDPE/m-nZVI阻氧复合膜。利用傅里叶变换红外光谱仪、热重分析仪、差示扫描量热仪、万能拉伸试验机和气体渗透仪对复合膜的结构与性能进行表征和测定。结果表明:m-nZVI和LDPE的复合是物理共混;加入m-nZVI后,LDPE的热稳定性基本不变;随着m-nZVI含量的增加,复合膜的抗拉强度和断后伸长率先增大后减小,m-nZVI质量分数为2%时,抗拉强度和断后伸长率达到最大,较LDPE膜分别提高了41.4%和23.4%;复合膜的氧气透过系数也呈现出先减小后增大,当m-nZVI质量分数为3%时,复合膜的氧气透过系数最小,较LDPE膜降低了40.9%。复合膜结晶过程中,m-nZVI起异相成核的作用,改善了复合膜的结晶行为,使复合膜的结构和性能得到改善,力学性能和阻隔性能都得到提高。

Synthesis of clay-supported nanoscale zero-valent iron using green tea extract for the removal of phosphorus from aqueous solutions

This study addresses the synthesis of nanoscale zero-valent iron(n ZVI) in the presence of natural bentonite(B-n ZVI) using green tea extract. The natural bentonite and B-n ZVI were then applied for the removal of phosphorus from aqueous solutions at various concentrations, p H levels and contact time. The desorption of phosphorus(P) from adsorbents was done immediately after sorption at the maximum initial concentration using the successive dilution method. The characterization of FTIR, SEM, and XRD indicated that n ZVI was successfully loaded to the surface of natural bentonite. The sorption of phosphorus on B-n ZVI was observed to be p H-dependent, with maximum phosphorus removal occurring at the p H range of 2 to 5. The results demonstrate that the maximum sorption capacities of natural bentonite and B-n ZVI were 4.61 and 27.63 mg·g^(-1), respectively.Langmuir, Freundlich, and Redlich–Peterson models properly described the sorption isotherm data. For either adsorbent, desorption isotherms did not coincide with their corresponding sorption isotherms, suggesting the occurrence of irreversibility and hysteresis. The average percentages of retained phosphorus released from natural bentonite and B-n ZVI were 80% and 9%, respectively. The results indicated that sorption kinetics was best described by the pseudo-second-order model. The present study suggests that B-n ZVI could be used as a suitable adsorbent for the removal of phosphorus from aqueous solutions.

Fe/Co双金属材料活化过一硫酸盐氧化降解水中2,4-D

为了处理有机氯除草剂2,4-二氯苯氧乙酸(2,4-D)造成的环境污染,本研究采用液相还原法制备了铁钴双金属纳米颗粒(n-Fe/Co),并通过Fe、Co的合成比例优化了活化过一硫酸盐(PMS)体系对2,4-D的降解性能。结果表明:在pH为4.5的条件下,使用0.03 g·L^(-1)的n-Fe/Co和0.5 mmol·L^(-1)的PMS,2,4-D(10 mg·L^(-1))在30 min内完全去除,与单纯的纳米零价铁(nZVI)相比,2,4-D的去除率提升了60.9个百分点。n-Fe/Co可以在很宽的pH范围(2~9)和复杂的阴离子条件下有效去除2,4-D。自由基抑制实验表明羟基自由基是参与反应的主要活性物种(贡献率达到62.2%)。在中间产物分析的基础上,提出了2,4-D在n-Fe/Co-PMS体系中的降解机理和降解途径。研究表明,n-Fe/Co复合材料活化PMS系统在处理水中的2,4-D除草剂污染方面有很大的应用前景。

Fischer-Tropsch synthesis by nano-structured iron catalyst

Effects of nanoscale iron oxide particles on textural structure,reduction,carburization and catalytic behavior of precipitated iron catalyst in Fischer-Tropsch synthesis（FTS） are investigated.Nanostructured iron catalysts were prepared by microemulsion method in two series.Firstly,Fe2O3 ,CuO and La2O3 nanoparticles were prepared separately and were mixed to attain Fe/Cu/La nanostructured catalyst（sep-nano catalyst）;Secondly nanostructured catalyst was prepared by co-precipitation in a water-in-oil microemulsion method（mix-nano catalyst）.Also,conventional iron catalyst was prepared with common co-precipitation method.Structural characterizations of the catalysts were performed by TEM,XRD,H2 and CO-TPR tests.Particle size of iron oxides for sep-nano and mix-nano catalysts,which were determined by XRD pattern（Scherrer equation） and TEM images was about 20 and 21.6 nm,respectively.Catalyst evaluation was conducted in a fixed-bed stainless steel reactor and compared with conventional iron catalyst.The results revealed that FTS reaction increased while WGS reaction and olefin/paraffin ratio decreased in nanostructured iron catalysts.

Eco friendly adsorbents for removal of phenol from aqueous solution employing nanoparticle zero-valent iron synthesized from modified green tea bio-waste and supported on silty clay

The present research investigated a novel route for the synthesis of nanoparticle zero-valent iron(NZVI)utilizing an aqueous extract of green tea waste as a reductant with ferric chloride.Also,the supported nanoparticle zerovalent iron was synthesized using natural silty clay as a support material(SC-NZVI).The NZVI and SC-NZVI were characterized by infrared spectroscopy(FTIR),scanning electron microscope(SEM),X-ray diffraction(XRD),Brunauer–Emmett–Teller(BET),and zeta potential(ζ).The interpretation of the results demonstrated that the polyphenol and other antioxidants in green tea waste can be used as reduction and capping agents in NZVI synthesis,with silty clay an adequate support.Additionally,the experiments were carried out to explore phenol adsorption by NZVI and SC-NZVI.To determine the optimum conditions,the impact of diverse experimental factors(i.e.,initial pH,adsorbent dose,temperature,and concentration of phenol)was studied.Langmuir,Freundlich,and Tempkin isotherms were used as representatives of adsorption equilibrium.The obtained results indicated that the adsorption processes for both NZVI and SC-NZVI well fitted by the Freundlich isotherm model.The appropriateness of pseudofirstorder and pseudosecondorder kinetics was investigated.The experimental kinetics data were good explained by the second-order model.The thermodynamic parameters(ΔH0,ΔS0,andΔG0)for NZVI and SC-NZVI were determined.The maximum removal rates of phenol at optimum conditions,when adsorbed onto NZVI and SC-NZVI,were found to be 94.8%and 90.1%,respectively.

Deactivation studies of nano-structured iron catalyst in Fischer-Tropsch synthesis

A nano-structured iron catalyst for syngas conversion to hydrocarbons in Fischer-Tropsch synthesis（FTS） was prepared by micro-emulsion method.Compositions of bulk iron phase and phase transformations of carbonaceous species during catalyst deactivation in FTS reaction were characterized by temperature-programmed surface reaction with hydrogen（TPSR-H 2 ）,and XRD techniques.Many carbonaceous species on surface and bulk of the nano-structured iron catalysts were completely identified by combined TPSR-H 2 and XRD spectra and which were compared with those recorded on conventional co-precipitated iron catalyst.The results reveal that the catalyst deactivation results from the formation of inactive carbide phases and surface carbonaceous species like graphite,and it will be increased when the particle size of iron oxides was reduced in FTS iron catalyst.

Study of diclofenac removal by the application of combined zero-valent iron and calcium peroxide nanoparticles in groundwater

Diclofenac(DCF)is one of the most frequently detected pharmaceuticals in groundwater,posing a great threat to the environment and human health due to its toxicity.To mitigate the DCF contamination,experiments on DCF degradation by the combined process of zero-valent iron nanoparticles(nZVI)and nano calcium peroxide(nCaO_(2))were performed.A batch experiment was conducted to examine the influence of the adding dosages of both nZVI and nCaO_(2)nanoparticles and pH value on the DCF removal.In the meantime,the continuous-flow experiment was done to explore the sustainability of the DCF degradation by jointly adding nZVI/nCaO_(2)nanoparticles in the reaction system.The results show that the nZVI/nCaO_(2)can effectively remove the DCF in the batch test with only 0.05 g/L nZVI and 0.2 g/L nCaO_(2)added,resulting in a removal rate of greater than 90%in a 2-hour reaction with an initial pH of 5.The degradation rate of DCF was positively correlated with the dosage of nCaO_(2),and negatively correlated with both nZVI dosage and the initial pH value.The order of significance of the three factors is identified as pH value>nZVI dosage>nCaO_(2)dosage.In the continuous-flow reaction system,the DCF removal rates remained above 75%within 150 minutes at the pH of 5,with the applied dosages of 0.5 g/L for nZVI and 1.0 g/L for nCaO_(2).These results provide a theoretical basis for the nZVI/nCaO_(2)application to remove DCF in groundwater.

Nano-Phytotechnological Remediation of Endosulfan Using Zero Valent Iron Nanoparticles

Endosulfan, an organochlorine pesticide, is known for its toxicity and ability to accumulate in the environment. In India endosulfan was banned only in 2011 and hence toxic residues are still persistent in the environment. The abilities of three plant species Chittaratha (Alpinia calcarata), Tulsi (Ocimum sanctum), and Lemongrass (Cymbopogon citratus) to remove endosulfan from soil in the absence and presence of zerovalent iron nanoparticles (nZVIs) (1000 mg/Kg of soil), i.e., by phytoremediation and nano-phytoremediation, were determined. Extracted soil samples from the experimental plot were analyzed using Gas Chromatograph with Electron Capture Detector (GC-ECD) and final dehalogenated product was confirmed by Mass Spectrometer (MS). A. calcarata had the best efficiency compared to the other two plant species and the efficiency decreased in the order A. calcarata > O. sanctum> C. citrates. The initial endosulfan removal rate was high (82% was removed within 7 days) when nano phytoremediation experiments were conducted with A. calcarata but then gradually decreased, probably because the activity of nZVI decreased over time. The nZVI endosulfan degradation mechanism appears to involve hydrogenolysis and sequential dehalogenation which was confirmed by GC-MS analysis. Only small amounts of endosulfan were accumulated in the plants because the added nZVIs might have promoted the reductive dechlorination of endosulfan.

纳米偏高岭土对铁尾矿砂-再生混凝土抗压性能影响及微观结构分析

为综合利用固体废弃物,以再生粗骨料部分取代天然骨料、以铁尾矿砂部分取代天然砂分别作为粗、细骨料,同时以纳米偏高岭土(NMK)部分取代水泥作为胶凝材料制成铁尾矿砂-再生混凝土(IRC),进行立方体抗压强度试验,探究NMK对IRC抗压强度的影响。利用扫描电镜(SEM)及氮吸附法(BJH)研究再生混凝土微观结构的变化规律。研究结果表明:铁尾矿砂取代率的增加会提高再生混凝土强度变化率,且取代率越大,抗压强度变化率越高;适量掺入NMK可以提高再生混凝土的抗压强度,当NMK取代率为5%时,抗压强度最大;掺入适量的NMK可以通过促进二次水化反应生成大量的C-S-H凝胶,提高砂浆内部及砂浆与骨料之间的密实度,提升界面过渡区强度,优化内部孔隙结构,进而提升IRC的抗压强度。

Factors Affecting the Reductive Properties of the Core-Shell SiO2-Coated Iron Nanoparticles

In this study, novel core-shell SiO2-coated iron nanoparticles (SiO2-nZVI) were synthesized using a one-step Stoeber method. The Malachite green degradation abilities of the nanoparticles were investigated. The effects of ethanol/distilled water volume ratio, presence and absence of PEG, tetraethyl orthosilicate (TEOS) dosage, and hydrolysis time used in the nanoparticles preparation process were investigated. The results indicated that the SiO2-coated iron nanoparticles had the highest reduction activity when the particles synthesized with ethanol/H2O ratio of 2:1, PEG of 0.15 ml, TEOS of 0.5 ml and the reaction time was 4 h. The SiO2-nZVI nanoparticles were characterized using Transmission Electron Microscopy (TEM), Energy Dispersive Spectrometry (EDS) and powder X-Ray Diffraction (XRD). The results showed that the average particles diameter of the SiO2-nZVI was 20 - 30 nm. The thickness of the outside SiO2 film is consistent and approximately 10 nm. The results indicated that the nanoparticles coated completely with a transparent SiO2-film. Such nanoparticles could have wide applications in dye decolorization.

Pulsed Electrochemical Deposited Nano-Iron for Water Treatment

The application of nanotechnology in drinking water treatment and pollution cleanup is promising, as demonstrated by a number of field-based (pilot and full scale) and bench scale studies. In recent years, the use of zero-valent iron (ZVI) for the treatment of toxic contaminants in groundwater and wastewater has received wide attention and encouraging treatment efficiencies have been documented. In this review, nanoscale iron was prepared by pulse electrodeposition of nano iron by chemical reduction of iron chloride and iron sulfate. Our research focuses on iron nanoparticles preparation and its use for aqueous Cr(VI) reduction. The Cr(VI) reduction by the nFe0 prepared by electrochemical and blasting method at neutral pH were carried. The results show that blasting-nFe0 show lower reaction than the electrochemical-nFe0. It is because the blasting-nFe0 surface contains more Fe2O3 than the other one.

STPP-nZVI修复铀污染地下水的性能及机理研究

铀是一种重要的战略资源,同时也是一种具有化学毒性和放射性毒性的重金属元素。目前,对铀矿山地下水中铀的高效修复仍是环境保护和生态安全面临的巨大挑战。采用三聚磷酸钠对纳米零价铁改性,成功制备了三聚磷酸钠改性纳米零价铁(STPP-nZVI),研究了溶液pH、STPP-nZVI用量、温度、时间、U(Ⅵ)浓度和干扰离子对STPP-nZVI修复地下水中U(Ⅵ)的影响,并采用FTIR、SEM-Mapping和XPS探讨了STPP-nZVI修复铀污染地下水的机理。结果表明,STPP-nZVI适合处理弱酸性和碱性铀污染地下水,在pH=5.0时,STPP-nZVI对U(Ⅵ)的最大吸附量达102.72 mg/g,对U(Ⅵ)的吸附为自发的吸热过程,STPP-nZVI对铀的去除主要归功于吸附和还原作用。STPP-nZVI材料对于处理弱酸性和碱性铀污染地下水具有一定的应用前景。

Removing Iron Ions Contaminants from Groundwater Using Modified Nano-Hydroxyapatite by Nano Manganese Oxide

In this article, we study modified nano-hydroxyapatite (HAp) by nano manganese oxide (Mn3O4) as adsorbent material to remove iron ions from groundwater. Different parameters were studied to option optimum conditions of removing such as contact time, pH, initial concentration, a dosage of adsorbent, agitation speed and temperature. Kinetics studies included first order (R2 = 0.915), pseudo-first order (R2 = 0.936), second order (R2 = 0.948), pseudo-second order (R2 = 0.995), Elovich equation model (R2 = 0.977), intraparticle diffusion (R2 = 0.946), Natarajan and Khalaf (R2 = 0.915) were carried out, the obtained results revealed that the pseudo-second order is the best to describe the adsorption process because the correlation coefficient is approaching one (R2 = 0.995). Adsorption isotherm was calculated by using Freundlich, Langmuir and Temkin constants, adsorption capacity from Langmuir model was 0.606 mg/g. Thermodynamic parameters (ΔG, ΔH = ?51 KJ/mol, and ΔS = ?142 (KJ/mol)) for the adsorption process were also calculated and discussed.

Remediation of Malathion Contaminated Soil Using Zero Valent Iron Nano-Particles

In this study, iron nano-particles were used to remediate malathion contaminated soil in the concentration range of 1 - 10 μg?g–1. The zero valent iron nano-particles were prepared by reducing ferric chloride solution with sodium boro- hydride for remediation of the soil. The optimized quantity of iron nano particles was found to be 0.1 g?kg–1 of soil con- taminated with 10 μg?g–1 of malathion. Malathion was determined in the soil after leaching to water at pH 8.2 and fol- lowed by its oxidation with slight excess of N-bromosuccinimide (NBS). The unconsumed NBS was estimated by measuring the decrease in the color intensity of rhodamine B. Degradation product formed during the oxidation of ma-lathion by zero valent iron was monitored by the Attenuated Total Reflectance Fourier Transform Infrared Spectros- copy (ATR-FTIR). The results clearly showed that quantitative oxidation of malathion was achieved within eight min- utes after the addition of zero valent iron nano particles.

Carbon dioxide catalytic conversion to nano carbon material on the iron–nickel catalysts using CVD-IP method

The over-consumption of fossil fuels resulted in the large quantity emission of carbon dioxide （CO2）, which was the main reason for the climate change and more extreme weathers. Hence, it is extremely pressing to ex- plore efficient and sustainable approaches for the carbon-neutral pathway of CO2 utilization and recycling. In our recent works with this context, we developed successfully a novel ＂chemical vapor deposition integrated process （CVD-IP）＂ technology to converting robustly CO2 into the value-added solid-form carbon materials, The monometallic FeNi0-Al2O3 （FNi0） and bimetallic FeNix-Al2O3 （FNi2, FNi4, FNi8 and FNi20） samples were synthesized and effective for this new approach. The catalyst labeled FNi8 gave the better performance, exhibited the single pass solid carbon yield of 30%. These results illustrated alternative promising cases for the CO2 capture utilization storage （CCUS）, by means of the CO2 catalytic conversion into the solid-form nano carbon materials.

Sin-QuEChERS Nano净化柱结合气相色谱-串联质谱法快速筛查石斛中84种农药残留

利用Sin-QuEChERS Nano净化柱结合气相色谱-串联质谱(GC-MS/MS)分析,建立了石斛基质中84种不同极性农药残留的快速筛查方法。比较了采用不同的提取溶剂(1%乙酸乙腈、丙酮)和不同的提取方式(加水浸泡和不加水浸泡)下目标物的提取效率。利用金钗石斛样品系统比较了Sin-QuEChERS Nano法与经典的基质固相分散法(dSPE)、固相萃取法(SPE)、QuEChERS法的净化效果及提取回收率,以及净化效果较好的Sin-QuEChERS Nano法与dSPE法基质效应的差异。目标物经DB-1701MS石英毛细管色谱柱(30 m×0.25 mm×0.25μm)程序升温分离,GC-MS/MS多反应监测(MRM)模式检测,基质匹配溶液外标法定量。通过GC-MS/MS检测方法对金钗石斛和铁皮石斛中的84种代表性农药进行了方法学验证。结果表明:各目标物在不同范围内呈良好的线性相关,相关系数(r^(2))均>0.990,方法的检出限(LOD,S/N=3)为1.5~5.8μg/kg,方法的定量限(LOQ,S/N=10)为5.0~15.0μg/kg。在两个水平下,目标农药的加标回收率为68.7%~116.2%,相对标准偏差(RSD,n=6)均低于15%。与其他经典的前处理方法相比,Sin-QuEChERS Nano法在净化效果方面表现更好,该法不仅可以有效去除色素、有机酸、碱性干扰物等物质,还可以节省样品制备时间,避免溶剂转移造成的损失,无需进一步涡旋或离心,是一种简单而有效的提取物纯化程序。该方法灵敏、快速、简便、可靠,有效地提高了石斛中农药快速筛查时的检测效率,具有较强的实际应用价值。此外,所开发的方法可以进一步扩展目标农药的类型,并可以用于检测其他更多食品及中药材中的农药残留。

Simple-QuEChERS Nano结合GC-MS/MS同时检测全血中的97种农药

建立了Simple-QuEChERS Nano结合气相色谱-串联质谱(GC-MS/MS)同时检测血液中97种农药的方法,并对基质条件、提取溶剂以及净化材料进行了优化。0.5 mL血液样品经3倍水稀释混匀,使用2.0 mL乙酸乙酯提取后振荡、离心,过Simple-QuEChERS Nano净化柱及0.22μm有机微孔滤膜后,采用多反应监测模式(MRM)进行分析。结果显示,97种农药在一定质量浓度范围内线性关系良好(r2≥0.9873),除丙烯菊酯(检出限和定量下限分别为11.03、36.76 ng/mL)外,其余农药的检出限为0.06~4.27 ng/mL,定量下限为0.18~14.24 ng/mL。采用空白全血进行加标回收实验,97种农药在100、200、400 ng/mL 3个加标水平下的回收率为32.2%~120%,日内精密度为1.9%~11%,日间精密度为3.6%~13%。该方法由传统QuEChERS方法改进,绿色环保、操作简单、快速高效,可用于血液中多种农药的同时检测,用于实际案件血液样品中农药的筛查与定性定量检验,获得了良好的结果。

羧甲基纤维素改性纳米钯铁双金属去除水中2,4-二氯苯酚的影响因素及机理

利用液相还原法制备了纳米零价铁(nZVI)、纳米钯铁双金属(Pd/Fe)、羧甲基纤维素(CMC)改性nZVI(CMC-Fe)和CMC改性钯铁双金属(CMC-Pd/Fe)4种铁基纳米材料,并用扫描电子显微镜(SEM)和X射线衍射仪(XRD)对其进行了表征。研究了这4种材料对水中2,4-二氯苯酚(2,4-DCP)的表观去除率,考察了铁基纳米材料投加量、Pd负载量、溶液初始pH及污染物浓度等因素对CMC-Pd/Fe去除2,4-DCP的影响,并探讨了可能的作用机理。结果表明,在4种材料中,CMC修饰的CMC-Pd/Fe的分散性最好,粒径明显小于未用CMC修饰的nZVI和Pd/Fe。4种材料对2,4-DCP的表观去除率为CMC-Pd/Fe>CMC-Fe>Pd/Fe>nZVI。随着CMC-Pd/Fe投加量和Pd负载量的增加,CMC-Pd/Fe对2,4-DCP的表观去除率增大,而随着2,4-DCP浓度的升高,CMC-Pd/Fe对2,4-DCP的表观去除率下降。当溶液初始pH=3、5和7时,CMC-Pd/Fe对2,4-DCP的表观去除率分别为94.34%、99.50%和96.62%;但当溶液初始pH=11时,其表观去除率仅为51.28%,这主要是由于在碱性条件下,带负电的2,4-DCP与CMC的静电排斥作用远大于π-π共轭吸附作用,阻碍了CMC-Pd/Fe的电子向污染物传递,导致2,4-DCP表观去除率下降。

NANO碳净化-超高效液相色谱-串联质谱法测定东北黑土壤中多农残含量

本文使用NANO碳净化柱对土壤中的31种农药进行净化,并且通过超高效液相色谱-串联质谱法(UPLC-MS/MS)进行测定。土壤样品经过NANO碳净化柱,净化效果良好。31种农药的检出限为0.001~0.01mg/kg,定量限为0.003~0.033mg/kg,添加回收率在70%~120%之间,相对标准偏差(RSD)在0%~10%之间。结果表明,该方法简单、快捷、灵敏度高,线性范围、回收率和精密度均适合土壤中的31种农药残留检测,在土壤农药残留筛查中具有较好的应用前景。