Efficient reduction of hexavalent chromium with microscale Fe/Cu bimetals: Efficiency and the role of Cu

Microscale zero valent iron (mFe⁰) is one of the most potential water pollution remediation materials, but the effective utilization ability of electrons released by mFe⁰ in the reduction of hexavalent chromium (Cr(VI)) is not satisfactory. Here, we find the microscale iron-copper (mFe/Cu) bimetals coated with copper on the surface of mFe⁰ can significantly improve the effective utilization of electrons released by mFe⁰. Electrochemical analysis displays that copper plating on the surface of mFe/Cu can promote the release the electrons from mFe⁰ and reduce the impedance of mFe⁰. Spin-polarized density functional theory (DFT) calculation reveals that Cu on the surface of mFe/Cu bimetals promotes the release of electrons from mFe⁰ and reduces the adsorption energy of Fe to Cr. As the electron transporter, moreover, Cu can always attract Cr to the hollow position near itself of the Fe surface, which could promote the effective utilization of electrons released by Fe. Effective utilization ability of electrons in mFe/Cu system is 12.5 times higher than that in mFe⁰ system. Our findings provide another basis for the efficient reduction of Cr(VI) by mFe/Cu bimetals, which could promote the application and popularization of mFe/Cu bimetals.     

Synthesis of Calcium Silicate Hydrate from Coal Gangue for Cr(VI) and Cu(II) Removal from Aqueous Solution

Both the accumulation of coal gangue and potentially toxic elements in aqueous solution have caused biological damage to the surrounding ecosystem of the Huainan coal mining field. In this study, coal gangue was used to synthesize calcium silicate hydrate (C-S-H) to remove Cr(VI) and Cu(II)from aqueous solutions and aqueous solution. The optimum parameters for C-S-H synthesis were 700 °C for 1 h and a Ca/Si molar ratio of 1.0. Quantitative sorption analysis was done at variable temperature, C-S-H dosages, solution pH, initial concentrations of metals, and reaction time. The solution pH was precisely controlled by a pH meter. The adsorption temperature was controlled by a thermostatic gas bath oscillator. The error of solution temperature was controlled at ± 0.3, compared with the adsorption temperature. For Cr(VI) and Cu(II), the optimum initial concentration, temperature, and reaction time were 200 mg/L, 40 °C and 90 min, pH 2 and 0.1 g C-S-H for Cr(VI), pH 6 and 0.07 g C-S-H for Cu(II), respectively. The maximum adsorption capacities of Cr(VI) and Cu(II) were 68.03 and 70.42 mg·g⁻¹, respectively. Furthermore, the concentrations of Cu(II) and Cr(VI) in aqueous solution could meet the surface water quality standards in China. The adsorption mechanism of Cu(II) and Cr(VI) onto C-S-H were reduction, electrostatic interaction, chelation interaction, and surface complexation. It was found that C-S-H is an environmentally friendly adsorbent for effective removal of metals from aqueous solution through different mechanisms.     

乙醇/水体系负载型纳米Cu/Fe二元合金的合成、改性及其还原三氯乙烯的性能

在乙醇/水体系中采用KBH4液相还原法, 以石墨微粉为载体, Cu为复合金属, 通过两步法合成了具有球状团簇结构的负载型纳米Cu/Fe二元合金. 与单纯负载型纳米Fe0相比, 该复合材料对三氯乙烯(TCE)具有更高的还原脱氯性能, 纳米Fe0的质量浓度为10 g/L时, 5 h内能将10 mg/L的TCE完全去除. 将十六烷基三甲基溴化铵(CTAB)用于负载型纳米二元合金的表面改性, 改性后的材料对TCE的还原脱氯性能提高. 改性材料连续降解TCE 36 d, 10.2 mg/L TCE在7 h内即完全去除, 材料改性后不易氧化失活, 还原性能保持长期稳定.     

Enhanced Removal of Cu(II) Ions from Aqueous Solution by Poorly Crystalline Hydroxyapatite Nanoparticles

Poorly crystalline and well-dispersed hydroxyapatite (HAP) nanoparticles were synthesized and used as novel adsorbents for the removal of Cu(II) from aqueous solution. Various factors affecting the adsorption such as adsorbent crystallinity, pH, adsorbent dosage, contact time, temperature, competing cations, and the presence of humic acid were investigated in detail. Results showed that the HAP calcined at lower temperature was poorly crystalline and had better adsorption capacity for Cu(II) than those calcined at higher temperature. Cu(II) removal was increased with increases of pH, adsorbent dosage, temperature, and the presence of humic acid, but decreased as the existence of competing divalent cations. Kinetic studies showed that pseudo-second-order kinetic model better described the adsorption process. Equilibrium data were best described by Langmuir model, and the estimated maximum adsorption capacity of poorly crystalline HAP was 41.80 mg/g at 313 K, displaying higher efficiency for Cu(II) removal than many previously reported adsorbents. Thermodynamics studied revealed that the adsorption of Cu(II) by poorly crystalline HAP was spontaneous, endothermic, and entropy-increasing in nature. This study showed that poorly crystalline HAP could be used as an efficient adsorbent material for the removal of Cu(II) from aqueous solution.     

表面印迹纳米磁性壳聚糖的制备及对Cu(Ⅱ)的吸附研究

将壳聚糖与自制的纳米四氧化三铁反应,加入一定量的铜盐使其与壳聚糖络合,再用环氧氯丙烷交联,用酸洗脱铜离子,得到表面印迹的纳米磁性壳聚糖.考察了阴离子、交联剂浓度对铜印迹效果的影响.用振动磁力仪及透射电镜对样品的性质进行表征.研究了表面印迹的纳米磁性壳聚糖对Cu2 的吸附性能.研究结果显示,用硝酸铜印迹制备的表面印迹纳米磁性壳聚糖吸附剂平均粒径为25nm,饱和磁化强度为98.56emu/g,壳聚糖含量为18.7%.吸附剂吸附容量大,吸附速度快.在Cu2 初始浓度为3.91mmol/L,pH为5时,15min即达到吸附平衡,以壳聚糖计Cu2 的饱和吸附量为4.07mmol/g,比纯壳聚糖粉高2倍.在含Zn2 或Cd2 、Pb2 的二元体系溶液中,离子印迹吸附剂对Cu2 具有明显的选择吸附性,而未印迹的纯壳聚糖粉几乎没有选择性.吸附剂易回收,重复使用性好,重复使用4次后,吸附量约保留最初饱和吸附量的98%.     

亚微米级Cu0/Fe3O4复合物多相催化过一硫酸盐降解有机污染物

过一硫酸盐催化活化技术因其可产生强氧化性活性氧化物种,可快速氧化降解并矿化有机污染物的优异性能而备受关注.本文成功制备了亚微米级Cu0/Fe3O4复合物,发现其能多相催化过一硫酸盐产生单线态氧降解有机污染物.首先,以CuCl2·2H2O,FeCl2·4H2O和FeCl3·6H2O为铜源和铁源,水合肼为还原剂,采用水热法在180oC反应24 h制备了亚微米级磁性Cu0/Fe3O4复合物.表征结果显示,所制材料为Cu0和Fe3O4的复合物,颗粒大小约为220 nm;单一相Cu0和Fe3O4晶体粒径分别为33.8和106.2 nm,而Cu0/Fe3O4复合物中Cu0和Fe3O4晶体粒径分别减为20.8和31.9 nm.这表明Cu0和Fe3O4复合降低了Cu0和Fe3O4晶体粒径,有利于Cu0和Fe3O4的分散.BET测试结果表明,Cu0/Fe3O4复合物比表面积为4.6 m2/g,与Cu0颗粒的(4.2 m2/g)相当,但远小于Fe3O4的(15.6 m2/g).制备的Cu0/Fe3O4复合物可有效催化过一硫酸盐产生单线态氧降解罗丹明B、亚甲基蓝、金橙II、苯酚和对氯酚.当Cu0/Fe3O4复合物的用量为0.1 g/L,过一硫酸盐浓度为0.5 mmol/L和初始pH为7时,Cu0/Fe3O4复合物可在30 min内完全降解20μmol/L的罗丹明B、亚甲基蓝、金橙II以及0.1 mmol/L的苯酚和对氯酚.对比试验显示,在相同条件下,Cu0和Fe3O4颗粒分别可以降解28%和20%的罗丹明B.这表明Cu0/Fe3O4复合物中的Cu0和Fe3O4晶体在催化过一硫酸盐降解污染物的反应中具有协同作用,这主要来源于Cu0/Fe3O4复合物中Cu0和Fe3O4的晶体粒径变小和更好的分散.采用分光光度法测定了降解反应液中铜和铁离子的溶出量.当Cu0/Fe3O4复合物的用量为0.1 g/L,过一硫酸盐浓度为0.5 mmol/L和初始pH为7时,反应60 min后,降解液中铜和铁离子的浓度分别为0.22和0.1 mg/L,仅占复合物中总铜和总铁量的1.1%和0.2%,表明Cu0/Fe3O4复合物具有较强的化学稳定性.所制Cu0/Fe3O4复合物具有超顺磁性,借助磁场实现快速分离回收,可循环利用五次,表明其优越的催化稳定性.通过加入乙醇和叠氮化钠,考察了Cu0/Fe3O4复合物催化活化过一硫酸盐体系中的活性氧化物种.发现100 mmol/L乙醇的加入对污染物的降解无明显影响,而加入同等量的叠氮化钠可完全抑制污染物的降解,表明Cu0/Fe3O4复合物催化活化过一硫酸盐产生的主要活性氧物种为单线态氧.采用电子顺磁共振谱进一步证实了单线态氧的生成.基于以上研究,Cu0/Fe3O4复合物催化活化过一硫酸盐的机理为Cu0/Fe3O4作为一个电子媒介加速过一硫酸盐和污染物之间的电子转移,从而导致污染物被快速降解.该反应机理不同于常见的金属催化过一硫酸盐产生硫酸根和羟自由基的反应机理.我们推测,电导性优良的Cu0在此催化反应中起着关键性作用.本催化方法可作为一种绿色的氧化技术用于环境污染物的氧化降解处理.     

Solvent-free synthesis of propargylamines via A3 coupling reaction and organic pollutant degradation in aqueous condition using Cu/C catalyst

The present report focuses on the efficient and operationally simple synthesis of biomass-derived carbon as support to immobilize copper particles as a catalyst for the one-pot synthesis of propargylamines from furfural via the A³ coupling reaction. This new catalyst showed remarkable catalytic performance leading to a 97% yield within 5 h at 80 °C using 5 mg (0.0022 mmol Cu) of Cu/C catalyst under solvent-free condition. Moreover, nitro-substituted compounds such as 4-nitrophenol (4-NP) are highly toxic and not easily degradable. Hence, a quick and effective method is required to neutralize these toxic compounds. The synthesized active support Cu/C catalyst having various electron-donating groups containing small amounts of Cu plays an essential role in the catalytic reduction of 4-NP (0.1 g). Using only 3 mg (0.0013 mmol Cu) of Cu/C catalyst and NaBH₄ (10 mmol), a 99% yield (100% selectivity) in the aqueous condition at 25 °C was achieved. The catalytic reduction follows the pseudo-first-order kinetics with reaction rate constant of 0.028 s⁻¹. Moreover, results demonstrate that the Cu/C catalyst has superior catalytic activity due to the presence of electron-donating molecules such as O, S, and N atoms, which enable synergistic effect in enhancing the overall catalytic performance. Notably, the recoverability and recyclability of the synthesized catalyst were evaluated for up to four cycles, which confirmed its stability in these cycles.     

乙二胺硅胶材料对铜和锌离子的动态吸附

合成了胺基含量为1.35 mmol/g的乙二胺硅胶材料(EDA/SiO2),研究了EDA/SiO2对Cu2+和Zn2+的动态吸附及动态竞争吸附。结果表明,铜溶液流量和初始浓度对材料动态吸附性能有显著影响,随着溶液初始浓度的增大、流速的加快,穿透时间明显缩短。动态吸附实验结果符合Thomas模型,计算结果显示,铜溶液初始浓度由1.99 mmol/L增大至10.00 mmol/L时,模型平衡吸附容量q0从0.272 mmol/g增大至0.476 mmol/g,影响显著;流量对q0影响不显著。溶液流量和初始浓度对吸附速率常数kTh均有影响,随溶液流量增大、初始浓度的降低,速率常数值增大。在单一体系中,EDA/SiO2对Cu2+和Zn2+的工作吸附量分别为0.340和0.127 mmol/g,混合体系的吸附量均小于单一体系中的吸附量,并且对Zn2+的吸附量下降显著,表明EDA/SiO2对Cu2+的吸附能力强于Zn2+。6次循环实验表明,盐酸和氨水可对EDA/SiO2材料实现再生,再生后材料对铜的吸附容量和穿透时间的下降幅度不大,可重复使用。     

Radiation-induced catalytic degradation of p-nitrophenol (PNP) in the presence of TiO2 nanoparticles

The gamma radiation induced catalytic degradation of p-nitrophenol (PNP) in the presence of titanium dioxide (TiO₂) nanoparticles in aqueous solution was investigated. The initial concentration of PNP solution was 50 mg/L, and the additional TiO₂ doses were 0, 0.5, 1.0, and 2.0 g/L. The experimental results indicated that the PNP decomposition kinetics conformed to the modified pseudo-first order reaction equation under all applied conditions. When the TiO₂ dose was in the range of 0–2.0 g/L, the effect of additional TiO₂ on PNP decomposition rate was not obvious because PNP could be removed quite well by irradiation even in the absence of TiO₂ nanoparticles; however, the removal of total organic carbon (TOC) and total nitrogen (TN) was significantly accelerated in the presence of TiO₂ nanoparticles, the TOC removal efficiency increased from about 16% to 42%, and therefore the mineralization of PNP could be enhanced by TiO₂ nanoparticles. The inorganic nitrogen products were quantitatively measured to estimate the decomposition degree of PNP. The major aromatic intermediates, as well as carboxylic acids were identified by LCMS and IC. Possible reactions involved in radiation induced catalytic decomposition of PNP in aqueous solutions were proposed.     

Treatment of industrial contaminants with zero-valent iron- and zero-valent aluminium-activated persulfate: a case study with 3,5-dichlorophenol and 2,4-dichloroaniline

Zero-valent iron (ZVI)- and zero-valent aluminium (ZVA)-activated persulfate (PS) oxidation procedure was applied to remove the industrial pollutants 3,5-dichlorophenol (3,5-DCP; 12.27 µM) and 2,4-dichloroaniline (2,4-DCA; 12.34 µM) from aqueous solutions. The effects of PS concentration and pH were investigated to optimize heterogeneous treatment systems. Negligible removals were obtained for both pollutants by individual applications of nanoparticles (1 g/L) and PS (1.00 mM). PS activation with ZVI resulted in 59% (1.00 mM PS; 1 g/L ZVI; pH 5.0; 120 min) and 100% (0.75 mM PS; 1 g/L ZVI; pH 5.0; 80 min) 3,5-DCP and 2,4-DCA removals, respectively. The ZVA/PS treatment system gave rise to only 31% 3,5-DCP (1.00 mM PS; 1 g/L ZVA; pH 3.0; 120 min) and 47% 2,4-DCA (0.25 mM PS; 1 g/L ZVA; pH 3.0; 120 min) removals. The pH decreases from 5.0 to 3.0 and from 3.0 to 1.5 enhanced contaminant removals for ZVI/PS and ZVA/PS treatments, respectively. Pollutant removal rates were in correlation with the consumption rates of the oxidants. Metal ion (Al, Fe) release increased in the presence of PS and with decreasing pH.     

Removal of p-Nitrophenol Using Persulfate Activated by Biochars Prepared from Different Biomass Materials

Three biochars from wheat straw(WSC), chicken manure(CMC) and rice husk(RHC) were prepared as persulfate(PS) activators for p-nitropheol(PNP) removal. RHC exhibitted the best adsorption performance, followed by WSC and CMC, which was consistant with the surface area value. PS addition further promoted the PNP removal, indicating that a synergistic effect existed in the biochar/PS combined system. The composition and textual properties of biochar had a significant effect on the reactivity of activator and the function groups containing oxgygen or nitrogen might play important roles in the reaction. WSC could perform efficiently over a pH range from 4.4 to 10.4. The decrease in activation performance in cycle experiments was possiblely related to the loss of oxgygen-containing groups.     

Tetracycline Removal by Activating Persulfate with Diatomite Loading of Fe and Ce

Persulfate (PS)-based oxidation technology is efficient in removing refractory organics from water. A novel diatomite (DIA) support Fe and Ce composite (Fe-Ce/DIA) was prepared for activating persulfate to degrade tetracycline in water. The Fe and Ce were uniformly loaded on DIA, and the total pore size of Fe-Ce/DIA was 6.99 × 10⁻² cm³/g, and the average pore size was 12.06 nm. Fe-Ce/DIA presented a good catalytic activity and 80% tetracycline was removed under the persulfate system. The Fe-Ce/DIA also had photocatalytic activity, and the corresponding tetracycline removal efficiency was 86% under UV irradiation. Fe-Ce/DIA exhibited less iron dissolution rate compared with Fe-DIA. The tetracycline degradation rate was enhanced when the temperature increased. The optimal tetracycline removal efficiency was obtained when the conditions were of persulfate 10 mM, Fe-Ce/DIA dosage 0.02 g/L, and tetracycline concentration 50 mg/L. In addition, Fe-Ce/DIA showed a wide pH application and good reusability and stability.     

部分还原氧化石墨烯-Fe_3O_4对水中Mn(Ⅱ)的快速去除

采用改进的Hummers法制备了氧化石墨烯(GO),继而用一步共沉淀法制备了部分还原氧化石墨烯-四氧化三铁复合物(PRGO-Fe_3O_4).采用X射线衍射(XRD)、场发射扫描电子显微镜(FESEM)、X射线能量色散光谱(EDX)、高分辨透射电子显微镜(HRTEM)、选区电子衍射(SAED)及傅里叶变换红外光谱(FTIR)等技术对其进行了分析表征;考察了p H值、接触时间、吸附材料用量、共存物质、GO的还原、循环使用次数等因素对Mn(Ⅱ)吸附行为的影响.结果表明,PRGO-Fe_3O_4中Fe_3O_4颗粒分布均匀,大小为15~20 nm,剩磁和矫顽力均很小.因Fe_3O_4颗粒的锚定作用,石墨烯片层很薄,使PRGO-Fe_3O_4对Mn(Ⅱ)表现出高效的吸附性能和良好的循环使用性能:当p H=7、PRGO-Fe_3O_4用量为500 mg/g时,对201.3211 mg/L的Mn(Ⅱ)溶液仅3 min即达吸附平衡,吸附率和吸附量分别为99.35%和404.49 mg/g,磁分离仅需10 s,经5次循环吸附后,容量保持率为首次的78%.机理与热力学研究结果表明,吸附为吸热、自发的单层化学吸附.     

ZnO/Cu2O异质结中深能级表面光伏特性

采用恒电压沉积法在导电玻璃(FTO)上制备了具有三棱柱金字塔状的ZnO/Cu2O异质结薄膜. 利用场发射扫描电镜(FESEM)与X射线衍射仪(XRD)对薄膜的微观形貌和晶体结构进行了表征. 利用表面光电压谱(SPS)、场诱导表面光电压谱(FISPS)和相位谱(PS)研究了单一Cu2O与ZnO/Cu2O异质结薄膜的表面光伏性质. 结果表明, 与单一Cu2O薄膜相比, ZnO/Cu2O异质结薄膜的光伏响应范围拓展到了600~800 nm. 根据SPS, FISPS和PS的作用原理, 拓展部分的光伏响应归因于ZnO/Cu2O异质结中Cu2O层的深能级跃迁, 该跃迁在ZnO-Cu2O界面电场(方向由ZnO指向Cu2O)的作用下得到加强, 同时深能级跃迁产生的电子-空穴对在ZnO-Cu2O界面电场的作用下得到了有效分离和传输.     

MIL-53(Fe)@聚多巴胺@Fe_3O_4磁性复合材料的制备及其用于环境水样中磺酰脲类除草剂的磁固相萃取

制备了MIL-53(Fe)和聚多巴胺(PDA)修饰的磁性Fe_3O_4复合材料MIL-53(Fe)@PDA@Fe_3O_4,并将其作为吸附剂用于磁固相萃取-高效液相色谱法(MSPE-HPLC)检测环境水样中4种磺酰脲类除草剂(甲嘧磺隆、苄嘧磺隆、吡嘧磺隆和氯嘧磺隆)。实验优化了高效液相色谱条件(乙腈和含0.01%(体积分数)三氟乙酸的水溶液为流动相进行梯度洗脱,检测波长为233 nm)及磁固相萃取条件(洗脱剂为5 mL丙酮,萃取时间为4.5 min,吸附剂用量为60 mg,NaCl加入量为0.5 g,溶液pH值为3),在最佳条件下进行方法学考察,4种磺酰脲类除草剂均得到良好的线性关系,相关系数(r)≥0.998 0。方法的检出限(LOD,S/N=3)为0.28~0.77μg/L。将建立的方法用于3种环境水样中4种磺酰脲类除草剂的检测,其加标回收率为78.8%~109.7%。结果表明,制备的功能化复合材料结合了MIL-53(Fe)和Fe_3O_4的优点,可以简便快速地萃取分离环境水样中磺酰脲类除草剂。     

复合催化剂α-(Fe，Cu)OOH/RGO的制备、表征及其协同H2O2在可见光下去除环丙沙星性能

采用一步回流法制备了α-(Fe,Cu)OOH/RGO复合催化剂,通过粉末X射线衍射、扫描电子显微镜和X射线光电子能谱等对催化剂进行了表征,并以30 mg·L^-1的环丙沙星(CIP)为目标污染物,研究了不同制备条件下所得催化剂在可见光照射下协同H2O2对CIP的去除效果。结果表明,成功实现了α-(Fe,Cu)OOH纳米棒在石墨烯二维薄片上原位生长,α-(Fe,Cu)OOH/RGO复合材料的可见光吸收边发生红移,禁带宽度从2.02 eV变为1.76 eV。石墨烯复合不但增强了对污染物的吸附能力,而且加快了光生电子的分离、迁移速率,还提高了反应体系中电子的传导效率。当石墨烯复合比例(质量分数)为1%时,复合催化剂的催化性能最佳。当催化剂投加量为0.40 g·L^-1,H2O2浓度为0.10 mol·L^-1时,反应120 min,CIP被全部去除。α-(Fe,Cu)OOH/RGO循环使用5次,对CIP的去除率均在90%以上,表明催化剂具有较强的催化活性和较好的稳定性。     

Optimization of polyacrylonitrile-cysteine resin synthesis and its selective removal of Cu(Ⅱ) in aqueous solutions

Polyacrylonitrile beads(PAN) cysteine(CS) was synthesized from polyacrylonitrile beads(PAN) and cysteine(CS).The content of the functional group and the percentage conversion of the functional group of PAN-CS prepared under the optimum condition using response surface methodology(RSM) for the first attempt were 3.22 mmol/g and 35.78%.The structure was characterized by ET-IR and elemental analysis.The adsorption properties of the resin for Cu(Ⅱ) were investigated by batch and column experiments.Batch adsorption results suggested that PAN-CS had higher adsorption capability for Cu(Ⅱ)than other metal ions and maximum saturated adsorption capacity was 184.7 mg/g.The resin and its metal complexes were studied by FT-IR.Furthermore,the resin can be eluted easily using 1 mol/L HC1.PAN-CS can provide a potential application for selective removal of copper from waste solution.     

固相萃取-超高效液相色谱-串联质谱法测定人尿中苯氧乙酸除草剂和有机磷、拟除虫菊酯农药代谢物北大核心CSCD

基于96孔固相萃取-超高效液相色谱-串联质谱法,建立了人尿中2种苯氧乙酸除草剂、2种有机磷农药代谢物和4种拟除虫菊酯农药代谢物的测定方法。通过对液相色谱条件、质谱条件和样品前处理过程的系统优化,实现了在16 min内对8种目标分析物的分析测定。具体方法:1 mL尿液经β-葡萄糖醛酸酶酶解过夜,Oasis HLB 96孔固相萃取进行目标分析物的提取净化,甲醇洗脱;以0.1%(体积分数)乙酸乙腈和0.1%(体积分数)乙酸水作为流动相,Acquity BEH C_(18)作为分析柱进行色谱分离;负离子电喷雾(ESI-)多反应监测(MRM)模式下检测目标化合物,同位素内标法定量。2,4-二氯苯氧乙酸(2,4-D)、2,4,5-三氯苯氧乙酸(2,4,5-T)2种苯氧乙酸除草剂和3-苯氧基苯甲酸(3-PBA)、4-氟-3-苯氧基苯甲酸(4F-3PBA)、反式二氯乙烯基二甲基环丙烷羧酸(trans-DCCA)3种拟除虫菊酯农药代谢物在0.1~100μg/L内、对硝基苯酚(PNP)、3,5,6-三氯-2-吡啶酚(TCPY)2种有机磷农药代谢物、顺式二氯乙烯基二甲基环丙烷羧酸(cis-DCCA)1种拟除虫菊酯代谢物在0.2~100μg/L内线性关系良好,相关系数均大于0.9993;方法检出限为0.02~0.07μg/L,方法定量限为0.08~0.2μg/L;低、中、高3个水平下的加标回收率为91.1%~110.5%,日内精密度为2.9%~7.8%,日间精密度为6.2%~10%。应用该方法测定了214份尿液样本。结果显示除2,4,5-T外,其余7种目标分析物均有检出。TCPY、PNP、3-PBA、4F-3PBA、trans-DCCA、cis-DCCA、2,4-D的检出率为2.8%~99.1%。检出浓度(中位值)由高到低分别是2.0μg/L(TCPY)、1.8μg/L(PNP)、0.99μg/L(trans-DCCA)、0.81μg/L(3-PBA)、0.44μg/L(cis-DCCA)、0.35μg/L(2,4-D)和未检出(4F-3PBA)。该方法操作简便,定量准确,灵敏度高,每批次可完成96个样品测定,适用于人尿中多种农药及农药代谢物的批量分析测定。     

Fe(0)/Cu双金属还原与Fenton氧化集成工艺处理印染生化尾水树脂脱附液的研究

通过比较Fe(0)和Fe(0)/Cu还原工艺处理印染生化尾水树脂脱附液的效果,发现Fe(0)/Cu双金属还原对脱附液TOC和UV254去除率均优于Fe(0)。若将Fe(0)/Cu双金属还原与Fenton氧化工艺集成可以进一步提高处理效果。该组合工艺处理后,TOC去除率高达66%,UV254去除率高于90%,脱附液的BOD5/CODcr从低于0.1升高至0.38左右。由此可见,该组合工艺对复合功能树脂碱脱附液具有良好的处理效果,处理后废水的毒性降低,可生化性显著提高,为其返回生物系统进一步生化降解提供了较好的保证。     

A pathway of free radical generation via copper corrosion and its application to oxygen and ozone activation for the oxidative destruction of organic pollutants

This study investigated the commercially available zero-valent copper powder and copper foil to activate molecular oxygen (O₂) and ozone for the degradation of organic pollutants. Under aerobic atmospheric conditions, copper powder effectively removed 50 mg/L of acetaminophen (ACT) within 2 h, though the degradation rate using the foil was less than 20% of the powder. However, copper foil activated ozone to effectively degrade ACT. The total organic carbon (TOC) removal reached a high of 58.3% at a catalyst concentration of 40 g/L, but only 26.8% with ozone alone. The initial solution pH and dosage of copper foil were key operational parameters affecting the ozone activation process. H₂O₂ and Cu(I) were important intermediates in the process as hydroxyl radicals (^·OH) were identified via EPR (electron paramagnetic resonance) experiments and free radical scavengers. The generation of ^·OH was attributed to a Fenton-like reaction between Cu(I) and H₂O₂; this free-radical generation mechanism differs from typical transition metal oxide catalysts. This study outlines a promising approach to significantly increase the generation of ^·OH and effectively remove refractory organic compounds. Furthermore, these copper products are applied in structural components of practical water treatment. Thus, the study of corrosion resistance to oxygen and ozone in aqueous solution have both a practical and theoretical significance. It was determined that copper products were resistant to oxygen corrosion in aqueous solution, but not resistant to ozone corrosion.