Reaction pathways of dimethyl phthalate degradation in TiO2-UV-O2 and TiO2-UV-Fe(VI) systems

The photocatalytic degradation of dimethyl phthalate (DMP) in aqueous TiO₂ suspension under UV illumination has been investigated using oxygen (O₂) and ferrate (Fe(VI)) as electron acceptors. The experiments demonstrated that Fe(VI) was a more effective electron acceptor than O₂ for scavenging the conduction band electrons from the surface of the catalyst. Some major intermediate products from DMP degradation were identified by HPLC and GC/MS analyses. The analytical results identified dimethyl 3-hydroxyphthalate and dimethyl 2-hydroxyphthalate as the two main intermediate products from the DMP degradation in the TiO₂–UV–O₂ system, while in contrast phthalic acid was found to be the main intermediate product in the TiO₂–UV–Fe(VI) system. These findings indicate that DMP degradation in the TiO₂–UV–O₂ and TiO₂–UV–Fe(VI) systems followed different reaction pathways. An electron spin resonance analysis confirmed that hydroxyl radicals existed in the TiO₂–UV–O₂ reaction system and an unknown radical species (most likely an iron–oxo species) is suspected to exist in the TiO₂–UV–Fe(VI) reaction system. Two pathway schemes of DMP degradation in the TiO₂–UV–O₂ and TiO₂–UV–Fe(VI) reaction systems are proposed. It is believed that the radicals formed in the TiO₂–UV–O₂ reaction system preferably attack the aromatic ring of the DMP, while in contrast the radicals formed in the TiO₂–UV–Fe(VI) reaction systems attack the alkyl chain of DMP.     

长江中下游海相三叠系膏盐层与铜(金)、铁矿床

长江中下游海相三叠系膏盖层中含有很大比例的大、中型铜（金）、铁、多金属矿床。膏盐层不仅是铜（金）、铁矿床的主要赋矿层位之一，而且是部分成矿金属的矿源层；膏盐层还为燕山期岩浆提供部分钠质、钾质及挥发组分，影响岩浆演化的方向，改变了含矿流体的性质；另外，从岩体和矿床中金属硫化物中流同位素重硫成分的增高，说明在成者、成矿过程中，膏盐层是硫的供应者之一。因此膏盐层与铜（金）、铁、多金属矿床之间存在着特殊的成因联系。     

铁氮掺杂碳纳米管/纤维复合物制备及其催化氧还原的效果

阴极催化剂是影响微生物燃料电池(microbial fuel cell,MFC)性能的关键因素.通过研究制备成本低廉、氧还原反应(ORR)催化活性高的阴极催化剂来替代Pt/C对于实现MFC规模化应用具有重大意义.研究采用化学气相沉淀法,以三聚氰胺作为碳氮前驱物、以黑珍珠2000或乙炔炭黑作为碳源,外加醋酸亚铁作为铁前驱物,合成了两种铁氮掺杂碳纳米管/纤维复合物(FeNCB和FeNCC),作为MFC的阴极催化剂.通过循环伏安法和旋转圆盘-环电极分析FeNCB、FeNCC和Pt/C的ORR催化活性的差异,并用MFC验证其差异.结果表明,FeNCB性能与Pt/C相当,优于FeNCC,其催化路径是通过4电子途径催化氧还原反应;MFC-FeNCB性能略优于MFC-Pt/C,显著优于MFC-FeNCB有助于MFC的扩大化,其最大功率密度为1 212.8mW·m~(-2),开路电压为0.875 V,电池稳定电压为(0.500±0.025)V.用X射线衍射、X射线光电子光谱、拉曼光谱等进一步分析显示,复合物中碳纳米管管径的大小、铁氮掺杂的类型和含量以及氧含量是引起制备的复合物催化氧还原性能差异的原因所在.     

Fe0-C微电解去除地下水中2,4-DNT的影响因素

采用批实验研究初始pH值、溶解氧（DO）和地下水中常见的阴、阳离子等因素对Fe0-C微电解对地下水中2,4-二硝基甲苯（2,4-DNT）去除率的影响,并分析Fe0-C降解2,4-DNT的产物。结果表明,在pH=7,DO=0.23 mg·L-1的条件下,Fe0-C去除溶液中2,4-DNT有明显的效果,反应200 min时,去除率达到83.09%,比Fe0和C的去除率提高了74.56%和9.89%;酸性条件下有利于2,4-DNT去除,初始pH=5的条件下,溶液中2,4-DNT的去除率为82%,而初始pH=10时,2,4-DNT的去除率分别为64%;反应体系中含有较高浓度的溶解氧有利于2,4-DNT的去除,在DO=9.26 mg·L-1条件下,2,4-DNT的去除率比 DO=0.23 mg·L-1时提高了9.5%;地下水中一定浓度的阴（Cl-、SO2-4）、阳离子（Ca2+、Mg2+、Na+、K+）可以提高2,4-DNT的去除率,提高率小于10%。反应过程中2,4-DNT降解的产物包括2-氨基-4-硝基甲苯（2A4 NT）、4-氨基-2-硝基甲苯（4A2 NT）和2,4-二氨基甲苯（2,4-DAT）。     

Quantitation of Hydroxyl Radicals from Photolysis of Fe(III)-Citrate Complexes in Aerobic Water (5 pp)

Background For their high photoreactivity, Fe(III)-carboxylate complexes are important sources of H2O2 for some atmospheric and surface waters. Citrate is one kind of carboxylate, which can form complexes with Fe(III). In our previous study, we have applied Fe(III)-citrate complexes to degrade and decolorize dyes in aqueous solutions both under UV light and sunlight. Results have shown that carboxylic acids can promote the photodegradation efficiency. It is indicated that the photolysis of Fe(III)-citrate complexes may cause the formation of some reactive species (e. g. H2O2 and ·OH). This work is attempted to quantify hydroxyl radicals generated in the aqueous solution containing Fe(III)-citrate complexes and to interpret the photoreactivity of Fe(III)-citrate complexes for degrading organic compounds. Methods By using benzene as the scavenger to produce phenol, the photogeneration of ·OH in the aqueous solution containing Fe (III)-citrate complexes was determined by HPLC. Results and Discussion In the aqueous solution containing 60.0/30.0 mM Fe(III)/citrate and 7.0 mM benzene at pH 3.0, 96.66 mM ·OH was produced after irradiation by a 250W metal halide light (l ≥ 313 nm) for 160 minutes. Effects of initial pH value and concentrations of Fe(III) and citrate on ·OH radical generation were all examined. The results show that the greatest photoproduction of ·OH in the aqueous solution (pH ranged from 3.0 to 7.0) was at pH 3.0. The photoproduction of ·OH increased with increasing Fe(III) or citrate concentrations. Conclusion In the aqueous solutions containing Fe(III)-citrate complexes, ·OH radicals were produced after irradiation by a 250W metal halide light. It can be concluded that Fe(III)-citrate complexes are important sources of ·OH radicals for some atmospheric and surface waters. Recommendations and Outlook It is believed that the photolysis of Fe(III)-citrate complexes in the presence of oxygen play an important role in producing ·OH both in atmospheric waters and surface water where high concentrations of ferric ions and citrate ions exist. The photoproduction of ·OH has a high oxidizing potential for the degradation of a wide variety of natural and anthropogenic organic and inorganic substances. We can use this method for toxic organic pollutants such as organic dyes and pesticides.     

Fe和Fe2+对混合细菌产氢发酵的影响

在研究Fe粉剂量和Fe²⁺浓度对混合细菌产氢发酵的影响基础上,确定Fe和Fe²⁺促进混合细菌产氢能力的最佳阈值,并对乙醇型发酵菌群在不同Fe粉和Fe²⁺浓度下的产氢量和最大比产氢速率进行考察和对比.结果表明,Fe粉和Fe²⁺对乙醇型发酵菌群的产氢能力均有明显的促进作用.以葡萄糖为底物,投加Fe²⁺试验中,Fe²⁺浓度200mg/L获得最大产氢量143.7mL/g,较对照组提高32%;Fe²⁺浓度50mg/L获得单位VSS最大比产氢速率21.2 mL/(h·g),较对照组提高33%.投加单质Fe试验中,Fe粉剂量1000mg/L获得最大产氢量156.1mL/g,较对照组提高44%;Fe粉剂量500mg/L获得单位VSS最大比产氢速率23.5mL/(h·g),较对照组分别提高47%.单质Fe浓度高于50mg/L时,对发酵菌群产氢的促进作用要优于同浓度下的Fe²⁺.同时对混合细菌中铁的全量和形态分布进行了考察.     

制备条件对Fe/AC脱硫活性的影响

考察了Fe/AC脱硫剂的煅烧温度和载铁量对脱硫活性的影响，并对脱硫剂进行了X－射线衍射（XRD）和EXAFS表征，结果表明：经250℃煅烧的Fe/AC脱硫剂具有最高的脱硫活性，200℃煅烧，前驱体未完全分解，高于250℃煅烧，会使活性组分聚集，二者均导致脱硫活性降低。Fe/AC脱硫剂适宜的载铁量为3．5－14％，大于14％担载量使脱硫剂微孔堵塞严重，致使其脱硫活性下降。     

17O-NMR研究Al(Ⅲ),Fe(Ⅲ)盐对水缔合的影响

测试了AlCl3,Al2(SO4)3,FeCl3,Fe2(SO4)3等对水的^17O-NMR化学位移和半峰宽的影响。并利用水^17O-NMR化学位移和半峰宽的变化与氢键的关系，分析了AlCl3,Al2(SO4)3。FeCl3,Fe2(SO4)3等对水缔合的影响，研究表明，AlCl3,Al2(SO4)3。FeCl3,Fe2(SO4)3等对水缔合有促进作用。且Fe^3 对水缔合的作用大于Al^3 。     

膨润土负载纳米铁/镍还原阿莫西林的环境影响因素研究

采用液相还原法制备膨润土负载纳米铁/镍(Bent-Fe/Ni)用于还原阿莫西林,研究了不同浓度的阴离子(SO2-4、HCO-3)和阳离子(Ca2+、Cu2+)对Bent-Fe/Ni还原阿莫西林的影响.结果表明,SO2-4、HCO-3浓度对Bent-Fe/Ni还原阿莫西林的影响较大,当其浓度分别为0和500mg·L-1时,阿莫西林的去除率分别为93.7%和21.5%(SO2-4),以及93.7%和5.8%(HCO-3);Ca2+对Bent-Fe/Ni还原阿莫西林起到抑制作用,当其浓度为0和500 mg·L-1时,阿莫西林的去除率分别为93.7%和77.8%;低浓度的Cu2+对Bent-Fe/Ni还原阿莫西林起到促进作用,而高浓度的Cu2+对Bent-Fe/Ni还原阿莫西林起到抑制作用,当其浓度为0、10和100 mg·L-1时,阿莫西林的去除率分别为93.7%、94.8%和86.7%.     

Fe对污水和污泥处理过程中微生物和工艺性能的影响

铁元素作为微生物体内生化所必须的微量元素,影响微生物的生长及污水处理效果。分析了污水和污泥处理过程中,不同浓度和不同价态Fe促进微生物酶的合成和酶促反应的机理,概括了可能导致的微生物群落结构改变的因素;总结了Fe对EPS的分泌、絮体结构的影响,以及Fe加速生物膜的形成和污泥颗粒化的原理。从工艺角度总结了铁元素对UASB、MBR、污泥厌氧消化和生物制氢等工艺的作用,旨在为未来Fe及其他金属元素促进污水处理中微生物活性技术的研究提供思路及借鉴。