在烷基聚葡糖苷W/O微乳液中Novozym 435脂肪酶催化酯合成反应动力学的研究

研究了Novozym435脂肪酶在烷基聚葡糖苷形成的W／O微乳液体系中,催化正丁醇与正己酸合成酯的反应动力学．反应初始速率V0与正丁醇（ROH）和正己酸（HA）摩尔浓度的比值（CROH^0／CHA^0）有关,在CROH^0／CHA^0=0．2-17范围内,随CROH^0／CHA^0比值减小,初始速率V0增大,尤其是当CROH^0／CHA^0〈3时,V0迅速增大．其原因可能是醇浓度较高时,醇与酶结合形成的死端复合物在较高浓度酸的作用下分解,重新析出游离态酶所致．脂肪酶加入量、水相介质组成和醇的种类等对反应速率有重要影响．     

微乳液中2,4—二硝基氯苯水解反应的研究

研究了２,４－硝基氯苯在十二烷基磺酸钠／油／醇／水组成的Ｏ／Ｗ型微乳液中的水解反应。考察了烃,醇与表面活性剂的种类及用量,ＯＨ＾－浓度和温度等对Ｏ／Ｗ型微乳液中２,４－二硝基氯苯水解反应的影响。     

NiFe2O4直接分解二氧化碳成碳循环反应过程结构演变研究

用XRD Rietveld分析法,对共沉淀法制备的NiFe2O4在H2／CO2循环反应中的结构演变进行研究,发现随着循环反应次数的增加,NiFe2O4物相的含量逐渐降低,Fe2Ni1-x物相的含量及其(200)衍射的平均晶粒逐渐增大,并出现Fe3C物相,其含量增长较快．纯NiEe2O4经15次循环反应后,体系中NiFe2O4物相的含量只剩下5％左右,样品基本失去分解CO2的活性．NiFe2O4掺杂4％铬后,明显提高了NiFe2O4骨架结构的稳定性,虽经50次H2／CO2循环反应,体系中NiFe2O4物相含量仍然有20％,分解CO2的活性仍达到初始活性的40％．     

O3/UV降解喹啉过程中的毒性变化

利用发光细菌新鲜菌悬液进行毒性测试，研究了O3／UV降解喹啉过程中的毒性变化．研究表明，在选取的浓度范围内，无论是HgCl2还是喹啉，发光细菌发光抑制率(或相对发光量)与物质浓度的对数均呈线性关系．采用处于对数生长期初期的发光细菌进行毒性测试时的灵敏度和最低检测限都很理想，适合于毒性测试．O3／UV降解喹啉时，体系毒性出现先迅速上升并保持一段时间随后缓慢下降然后又缓慢上升的现象．O3／UV降解喹啉过程中产生了毒性更强的中间产物，这些产物是导致体系毒性上升的主要因素。     

液膜法处理硫普罗宁废水的研究

采用W／O型乳状液膜法提取水溶液中的硫普罗宁，考察了载体、温度、硫普罗宁浓度以及油内比、试剂比、乳水比对提取率的影响，并得出了液膜法提取硫普罗宁的最佳乳液配方：油内比＝1：1，乳水比＝1：2，试剂比＝6－8，载体浓度＝5％，温度20℃，转速＝240－250r.min^-1，其提取率高达90％。     

交联淀粉微球微波辅助反相乳液法合成及性能研究

以甲基紫吸附去除效率作为考核指标,研究了淀粉(ST)、交联剂N,N’-亚甲基双丙烯酰胺(MBAA)、引发剂(K2S2O8/NaHSO3)用量、聚合温度以及聚合反应时间等因素对微波辅助反相乳液法制备交联淀粉微球(CSM)的影响,利用傅里叶红外光谱仪(FT-IR)、电镜扫描仪(SEM)、比表面积分析仪等对CSM进行了表征,对比了优化条件下水浴和微波两种不同加热方式合成CSM的吸附效率.结果表明,MBAA成功与淀粉交联成类球状聚合物,聚合微球平均粒径约为9.253μm,聚合微球明显增加了微孔面积,微波加热合成的CSM对甲基紫的吸附率高于水浴加热合成的CSM.     

纳米Fe3O4的制备及其辅助吸附重金属离子的特性

采用自制半透膜水解法,以自制生物聚合铁为原料,以NaOH为沉淀剂,制备Fe3O4纳米粒子,并用XRD和TEM等方法对产物进行了表征,研究它对Pb^2 ,Cu^2 及Cr(Ⅵ)的辅助吸附及分离特性,结果表明：Fe2O4纯度较高,平均粒度在15nm左右;利用Fe2O4的大比表面和表面原子配位不足及顺磁性的特点,将其与浮游球衣菌复合,提高了对重金属离子的吸附效果,该复合吸附剂经再生可重复使用;纳米Fe2O4粒子可成为浮游球衣菌的絮凝核心而有助于体系的澄清。     

农田N2O排放研究进展

农田土壤是大气中N2O的重要来源，与1990年相比，2000年我国氮肥用量升高了40％，因此，迫切需要对我国农田土壤N2O的排放通量作出新的估算。土壤理化性状的空间变异和不同生态条件下进行长期的、多点的农田N2O原位监测数据的匮乏成为提高N2O排放测定精度的制约因素。目前，航空采样法-驰豫涡动技术(微气象学方法)能够成功克服空间变异，且已经被成功应用在农业生态系统N2O排放的定量化观测上；另外Century-NGAS和DNDC模型是目前应用较广泛的机理模型，但应用不同模型所获得的N2O排放量相差较大。因此，今后农业土壤N2O排放的工作重点应集中在如何提高N2O原位观测精度，寻找合适的机理模型和提出相应的减排措施。     

过渡金属对Pt Rh Pd/Al2O3催化剂性能的影响

研究了过渡金属(重点考察了铜)对Pt Rh Pd／Al2O3催化剂尾气净化效能的影响,并应用XRD,TPD,TPR等手段对过渡金属在Pt Rh Pd／Al2O3催化剂中的作用机制进行了探讨．结果表明,过渡金属对Pt Rh Pd／Al2O3催化剂具有较大的改性作用,过渡金属与混合贵金属产生的协同效应有利于催化剂活性的提高．     

以工业级TiO2为载体负载不同助催化剂V2O5基脱氮催化剂的性能

在工业级TiO2载体上,通过浸渍法负载V2O5,WO3和MoO3等活性物质,制备不同V2O5基的烟气脱氮催化剂．在固定床反应器中测试DeNOx活性,研究不同的助催化剂(WO3和MoO3)对该类型催化剂DeNOx活性的影响,结果表明,在三元催化剂中,V2O5是主活性物质,MoO3和WO3是助催化剂,此外,V2O5-MoO3／TiO2的脱氮效率高于V2O5-WO3／TiO2,但N2O的生成量较大。     

Synthesis of nanoiron by microemulsion with Span/Tween as mixed surfactants for reduction of nitrate in water

Denitrification of nitrate in groundwater using iron nanoparticles has received increasing interest in recent years. In order to fabricate iron nanoparticles with homogeneously spherical shape and narrow size distribution, a simple and “green” method was developed to synthesize iron nanoparticles. The conventional microemulsion methods were modified by applying Span 80 and Tween 60 as mixed surfactants. The maximum content of water in the Water-in-oil (W/O) microemulsion and its appropriate forming conditions were found, and then the microemulsion system consisting of saturated Fe²⁺ solution was used to synthesize α-Fe ultrafine particles by redox reaction. The nanoparticles were characterized by using powder X-ray diffraction (XRD) and transmission electron microscopy (TEM). The results show that the average diameter of the particle is about 80–90 nm. The chemical activity of the obtained iron nanoparticles was studied by the denitrification experiment of nitrate. The results show that under the experimental conditions, iron removed most of the 80 mg/L nitrate within 30 min. The mass balance of nitrate reduction with nanoscale Fe indicates that endproducts are mainly ammonia. Two possible reaction pathways for nitrate reduction by nanoscale iron particles have been proposed in this work.     

Preparation of a permanent magnetic hypercrosslinked resin and assessment of its ability to remove organic micropollutants from drinking water

A rapid and effective method based on a novel permanent magnetic hypercrosslinked resin W150 was proposed for the removal of organic micropollutants in drinking water. W150 was prepared by suspension and post-crosslinking reaction and found to possess a high specific surface area of 1149.7 m²·g^-1, a small particle size of 50 μm to 100 μm, and a saturation magnetization as high as 8 emu·g^-1. W150 was used to eliminate nitrofurazone (NFZ) and oxytetracycline (OTC) from drinking water compared with commercial adsorbents XAD-4 and F400D. The adsorption kinetics of NFZ and OTC onto the three adsorbents well fitted the pseudo-second-order equation (r>0.972), and the adsorption isotherms were all well described by the Freundlich equation (r>0.851). Results showed that the reduction in adsorbent size and the enlargement in sorbent pores both accelerated adsorption. Moreover, the effect of particle size on adsorption was more significant than that of pore width. Given that the smallest particle size and the highest specific surface area were possessed by W150, it had the fastest adsorption kinetics and largest adsorption capacity for NFZ (180 mg·g^-1) and OTC (200 mg·g^-1). For the adsorbents with dominant micropores, the sorption of large-sized adsorbates decreased because of the inaccessible micropores. The solution pH and ionic strength also influenced adsorption.     

V2O5/AC催化剂对氨还原NO的研究

考察了V2O5/AC催化剂对NH3选择催化还原NO的影响，结果表明，以浓硝酸预氧化处理的活性焦为载体对催化剂活性有很大提高，这是由于浓硝酸预氧化后，活性焦表面产生了较多的含氧官能团可能吸附更多的NH3,并且提高了活性组分V2O5的含量，反应气氛中加入SO2后，二都活性都增加，但差异消失，这是由于SO2存在时，反应生成的SO4^2-离子的酸性强于浓硝酸预氧化产生的含氧官能团的酸性，催化剂在使用前经过煅烧和氧化对催化剂活性有很大改善。SO2存在时，V2O5含量为1wt%的催化剂活性提高。     

芬顿试剂法制备磁性碳纳米管及其对亚甲基蓝的吸附性能

采用芬顿试剂法在碳纳米管纯化样品表面负载纳米磁性氧化铁颗粒,制备磁性碳纳米管杂化材料(MWCNTs/Fe2O3),该杂化材料具有较高的纳米氧化铁负载率(>50%)和优异的磁性能,制备过程中无需额外添加阳离子,不会对环境造成不利影响.将磁性碳纳米管杂化材料应用于染料废水处理中,结果发现MWCNTs/Fe2O3对亚甲基蓝染料吸附性能较好,吸附后用磁铁易于达到固液分离的效果.吸附性能研究表明,磁性碳纳米管对水溶液中亚甲基蓝的吸附在40 min内吸附容量迅速上升,其值达到最大平衡吸附容量的88%以上,60 min基本达到平衡,吸附过程符合准二级动力学模型(R2>0.999).磁性碳纳米管吸附亚甲基蓝的平衡吸附量qe与亚甲基蓝溶液的平衡浓度Ce的关系满足Langmuir(R2>0.999)、Freundlich(R2>0.97)以及Dubinin-Radushkevich(D-R)(R2>0.96)等温吸附模型.通过Langmuir模型计算可知磁性碳纳米管对亚甲基蓝的最大吸附容量为69.98 mg.g-1,吸附过程为有利吸附,由D-R模型计算结果可以推断MWCNTs/Fe2O3对水溶液中亚甲基蓝的吸附机制以化学吸附为主.     

全Pd三效催化剂研究涂层材料的研究

制备了作为Pd三效催化剂涂层材料组成的活性Al2O3/金属氧化物添加剂试样，用BET法、XRD法及H2－TPR法对这些涂层原材料体系进行表征。结果表明：金属氧化物添加剂提高了活性Al2O3的热稳定性；添加ZrO2改善了CeO2的热稳定性；与含Ca的试样不同，含La试样没有贮氧能力。用含有Al2O3-CeO2/ZrO2和Al2O3-La2O3/BaO的涂层材料制备的Pd催化剂有好的CO，HC和NOx同时净化的三效性能和低的起燃活性。加入0．003％（V／V）SO2降低了催化剂活性，含La2O3/BaO涂层材料的Pd催化剂上NOx反应易被SO2中毒。     

中性条件下超声波/零价铁协同降解活性艳红X-3B

考察了中性条件下超声波降解、零价铁还原及超声波-零价铁联用对活性艳红X-3B模拟废水的降解效果,通过对比降解过程中UV-Vis光谱的变化,探讨了超声波-零价铁协同处理活性艳红X-3B的可行性.结果表明,在中性条件下超声波对活性艳红X-3B降解缓慢,经过25min辐射后,活性艳红X-3B的分解率不足7.5%;零价铁直接还原速率较慢,反应25min后,活性艳红X-3B的分解率仅为48.82%;"超声波/零价铁"对降解活性艳红X-3B有明显的协同效应,25min后分解率达99.42%(600W),反应符合准一级动力学过程.与零价铁直接还原相比,在200W,400W和600W超声波的协同作用下,X-3B降解的表观反应速率常数分别提高了2.12,2.76和4.00倍,半衰期相应缩短.另外,添加H2O2会抑制协同效应.     

H2O超声过程中H2O2生成动力学

采用50kHz超声清洗槽式声化学反应器,以纯水为空化液体,研究了超声过程中H2O2生成动力学．分别探讨了空化气体种类(Ar,O2)及组成与流量、空化液体体积与反应器形状对H2O2生成速率及产率的影响．结果表明,超声过程中H2O2的生成可采用零级反应动力学方程来进行描述．在此频率下和考察范围内,采用Ar作为空化气体比O2更有利于H2O2的生成．当混合气体组成为Ar:O2=70：30(V/V)时,H2O2的生成速率最快．随着空化气体流量的增加,H2O2产率增加,随后降低．增加空化液体的体积,H2O2的生成速率降低．与锥形瓶相比,圆底烧瓶中H2O2的产率明显降低．     

An antifouling catechol/chitosan-modified polyvinylidene fluoride membrane for sustainable oil-in-water emulsions separation

• Underwater superoleophobic membrane was fabricated by deposition of catechol/chitosan. • The membrane had ultrahigh pure water flux and was stable under harsh pH conditions. • The membrane exhibited remarkable antifouling property in O/W emulsion separation. • The hydration layer on the membrane surface prevented oil droplets adhesion. Low-pressure membrane filtrations are considered as effective technologies for sustainable oil/water separation. However, conventional membranes usually suffer from severe pore clogging and surface fouling, and thus, novel membranes with superior wettability and antifouling features are urgently required. Herein, we report a facile green approach for the development of an underwater superoleophobic microfiltration membrane via one-step oxidant-induced ultrafast co-deposition of naturally available catechol/chitosan on a porous polyvinylidene fluoride (PVDF) substrate. Membrane morphology and surface chemistry were studied using a series of characterization techniques. The as-prepared membrane retained the original pore structure due to the ultrathin and uniform catechol/chitosan coating. It exhibited ultrahigh pure water permeability and robust chemical stability under harsh pH conditions. Moreover, the catechol/chitosan hydrophilic coating on the membrane surface acting as an energetic barrier for oil droplets could minimize oil adhesion on the surface, which endowed the membrane with remarkable antifouling property and reusability in a cyclic oil-in-water (O/W) emulsion separation. The modified membrane exhibited a competitive flux of ~428 L/(m²·h·bar) after three filtration cycles, which was 70% higher than that of the pristine PVDF membrane. These results suggest that the novel underwater superoleophobic membrane can potentially be used for sustainable O/W emulsions separation, and the proposed green facile modification approach can also be applied to other water-remediation materials considering its low cost and simplicity.     

磁性介孔硅胶萃取剂的制备及萃取性能研究

合成了C18基团修饰的磁性介孔硅胶材料,并利用该材料建立了磁性固相萃取-色谱分析方法,测定了几种环境水样中酞酸酯类(PAEs)污染物的含量.结果表明,该材料具有较大的比表面积(273 m.2g-1)和饱和磁通量(29 emu.g-1),对水样中痕量的PAEs有较强的萃取能力,而且萃取剂的磁分离特性使得萃取操作更为方便、快捷.在优化条件下,30 mg萃取剂在40 min内即可从500 mL水样中萃取痕量PAEs,回收率可达80%以上.此外,该萃取剂在处理复杂环境样品时仍能保持较强的萃取能力,环境水样中4种PAEs的检测限可达15.6—32.5 ng.L-1,加标回收率为62%—109%,相对标准偏差为2%—8%.     

均匀沉淀法制备纳米TiO2及其在环保方面的应用

本文以偏钛酸为原料,采用均匀沉淀法制备纳米ＴｉＯ２,所制得的纳米微晶平均粒径约为８．５ｎｍ,并能在７００℃保持锐钛矿型晶体结构,当它应用于染料溶液的光催化分解,与ＭＴ－１５０Ｗ光催化相比,具有较好的催化活性。同时,我们用Ａｌ２Ｏ３陶瓷膜回怍纳米ＴｉＯ２循环再利用,这为纳米ＴｉＯ２在环保方面的大规模应用创造了条件。