KCeO_2MnPcX对表面活性剂的催化氧化性能研究

研究了一种新型含稀土酞菁锰(KCeO2MnPcX)催化剂对水中表面活性剂直链烷基苯磺酸钠氧化降解的催化性能,讨论了影响催化氧化反应的各种因素,并确定了最佳反应条件。同时初步探讨了这种催化剂对表面活性剂的催化氧化机理,为处理表面活性剂废水提供了新的途径。     

Carbon‐neutral jet‐fuel re‐synthesised from sequestrated CO2

A chemical pathway combining reverse water gas shift, Fischer‐Tropsch synthesis and hydro‐cracking was considered to re‐synthesise jet fuel from CO₂ captured at high purity by oxy‐fuelling of a typical coal‐fired power station (Drax, UK). The oxygen for oxy‐fuelling and hydrogen for the fuel re‐synthesis process are sourced by electrolysis of water. According to material and energy balances , 3.1 MT/year of jet fuel and 1.6 MT/year each of gas oil and naphtha can be produced from the Drax annual emissions of 20 MT of CO₂, sufficient to supply 23% of the UK jet fuel requirements. The overall re‐synthesis requires 16.9 GW, to be sourced renewably from (offshore) wind power, and releases 4.4 GW of exothermic energy giving scope for improvements via process integration. The energy re‐synthesis penalty was 82% ideally and 95% on a practical basis. With the cost of offshore wind power predicted to reduce to 2.0 p/kWh by 2020, this ‘re‐syn’ jet fuel would be competitive with conventional jet fuel, especially if carbon taxes apply. The re‐use of CO₂ sequestrated from coal power stations to form jet‐fuel would halve the combined CO₂ emissions from the coal power and aviation sectors.     

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.     

Removing lignin model pollutants with BiFeO3–g-C3N4 compound as an efficient visible-light-heterogeneous Fenton-like catalyst

BiFeO_3–g-C_3N_4 nanoscaled composite was prepared with a hydrothermal method and evaluated as a highly efficient photo-Fenton like catalyst under visible light irradiation. The BiFeO_3–g-C_3N_4 composite exhibited much stronger adsorption ability to lignin model pollutant(guaiacol) than that of BiFeO_3, which may be due to the higher specific surface area(BiFeO_3–g-C_3N_4: 35.59 m~2/g BiFeO_3: 7.42 m~2/g) and the adsorption form of π–π stack between g-C_3N_4 and guaiacol. The composite exhibited excellent visible light-Fenton like catalysis activity, being influenced by the solution pH value and the proportions of BiFeO_3 and g-C_3N_4 nanosheets. Under optimal conditions with visible light irradiation, the BiFeO_3–g-C_3N_4 composite yielded fast degradation of guaiacol with an apparent rate constant of 0.0452 min~(-1), which were 5.21 and 6.80 folds of that achieved by using BiFeO_3 and the mixture of BiFeO_3 and g-C_3N_4 nanosheets, respectively. The significantly enhanced visible light-Fenton like catalytic properties of the BiFeO_3–g-C_3N_4 composite in comparison with that of BiFeO_3 was attributed to a large surface area, much increased adsorption capacity and the semiconductor coupling effect between BiFeO_3 and g-C_3N_4 in the composite.     

氨基乙醇席夫碱Cu2+配合物的合成及其催化染料降解

合成了3个氨基乙醇席夫碱Cu2+配合物并进行了表征.利用分光光度法考查了配合物催化降解酸性蓝9的性能和动力学曲线;利用Graph Pad Prism 5软件进行了米氏常数的测定;利用HPLC法测定了降解产物.发现配合物均为单核五配位配合物.发现配合物能催化废水中酸性蓝9降解,催化活性Cu Cl Lb·H2O最好,Cu Cl La·H2O其次,Cu Cl Lc·H2O最差,说明给电子基团有利于催化活性,位阻基团不利于催化活性.发现Cu Cl La·H2O、Cu Cl Lb·H2O催化酸性蓝9的V-S曲线与米氏方程吻合,米氏常数分别为1.35×10-2mmol·L-1和1.54×10-2mmol·L-1,说明催化过程具有酶促特性,Cu Cl La·H2O与底物的结合能力比Cu Cl Lb·H2O与底物结合能力弱.发现降解产物有顺式丁烯二酸.推测了配合物的催化机理和酸性蓝9的降解机制.得到了两个性能优良的酸性蓝9降解的仿酶催化剂,催化活性可以通过基团进行调控,为开发新的染料废水的有效治理技术提供了理论和实践支持.     

NH3-H2O2气雾对氰化氢气体的消毒

采用NH_3-H_2O_2气雾对1 m3密闭试验舱内氰化氢气体进行消毒,采用单因素试验研究H_2O_2和NH_3质量浓度对消毒率和消毒反应速率的影响规律。结果表明,NH_3-H_2O_2气雾对HCN的消毒符合一级反应动力学特征,NH_3质量浓度对消毒反应速率有一定影响,但当NH_3质量浓度增加至20 mg/m3以上时,对反应速率几乎没有影响; H_2O_2质量浓度对消毒反应速率有显著影响,反应速率随H_2O_2质量浓度的提高明显增大。NH_3-H_2O_2气雾消毒剂的最佳配方为H_2O_2的质量浓度为120 mg/m3、NH_3的质量浓度为20 mg/m3,在此条件下对HCN进行消毒,在28 min时HCN的残余质量浓度为0. 92 mg/m3,可以达到GBZ 2. 1—2007《工作场所有害因素职业接触限值第1部分:化学有害因素》中有关HCN最高容许质量浓度MAC值(1 mg/m3)的规定。分析消毒机理为H_2O_2首先将HCN氧化为氰酸(HCNO),氰酸不稳定,在NH_3和水的作用下可以水解成碳酸铵,也可以进一步被氧化形成CO2和N2。     

常见金属及金属氧化物催化超声降解间苯二酚

探索了以常见金属铜、锌、铝单质及其氧化物为催化剂,提高超声降解间苯二酚速率的可行性。在超声/零价金属以及超声/金属氧化物同时存在的条件下,以间苯二酚为目标污染物,对间苯二酚的去除效果、溶液pH的变化及金属离子的溶出等进行考察,并对超声波与金属以及金属氧化物协同催化降解有机物的作用机理进行了初步的探讨。实验结果表明,铜、锌、氧化铜均可以有效地催化间苯二酚的超声降解,其过程均符合假一级动力学反应。各类金属和金属氧化物的催化能力排序为铜、锌混合物>氧化铜、锌混合物>锌>铜≈氧化铜。当间苯二酚初始浓度为0.05 mmol/L,初始pH=5,超声频率25 kHz,功率为200 W,铜、锌比例为1:1,投量为1 g/L时,US/Cu-Zn去除间苯二酚的速率常数为1.53×10-2min-1,是单独超声作用时的9倍。     

固体催化改良Fenton法处理苯酚废水的研究

针对目前常规Fenton法存在的H2O2耗量大的问题,提出了以活性炭作为催化剂载体的改良Fenton法。采用常规Fenton法以及改良Fenton法对苯酚废水的处理效果进行了对比实验研究,从H2O2投加量、接触反应时间和pH值影响因子出发分析比较了常规及改良Fenton法的COD及苯酚去除率。通过比较,改良Fenton法达到了优于常规Fenton法的处理效果,H2O2投加量20 mL/L,接触反应时间100 min,pH值为3是最佳的反应条件。降低了处理成本,提高了回收利用。     

非均质含水土层中石油运移的电阻率监测

通过自制三维有机玻璃水槽建立非均质土层,设立浅层和内部两个泄漏点,模拟流动相原油在含水土层中的运移及水位波动条件下的重分布过程,并利用自制高密度电极排及电法仪揭示相应的电阻率响应特征.结果表明：原油在土壤中运移受泄漏源位置、泄漏量及土层结构的影响.同一土层内部泄漏点横向扩散较垂向明显,浅层泄漏点为四周扩散,泄漏量越大污染范围越宽,土层渗透性越高污染深度越深.原油泄漏后存在高阻和低阻异常2种情况,土层结构简单且含油率较高时高阻异常明显;土层组分较复杂尤其是盐分和粘土矿物含量较高,或含水率和含油率较低时,易出现低阻异常.水位升高后土层整体电阻率降低,原油向污染区中心集中;水位下降后电阻率升高,原油向四周分散,水位波动使原油进一步弥散.受内部泄漏点影响,垂向深度上离泄漏点越近（0.08m）污染越重,除此之外泄漏点下部（0.15m）原油含量高于上部（0.04m）,显示内部泄漏点原油下移较上移明显.     

锰钴水滑石/石墨烯电极的制备及催化性能

采用水热法制备了以氧化还原石墨烯（rGO）为载体的锰钴水滑石（LDH）,即MnCo-LDH/rGO复合材料并研究其氧还原性能.在Mn/Co物质的量比为1：3的条件下,MnCo-LDH和MnCo-LDH/rGO的形貌和催化性能最为突出.与MnCo-LDH相比,MnCo-LDH/rGO在Na₂SO₄溶液中的氧化还原峰更加明显（-0.425V）,且峰电流更大,达到0.749mA/cm².将MnCo-LDH/rGO作为阴极,在120min内持续提供30mA/cm²的电流可使浓度为20mg/L的罗丹明B染料（RhB）降解98.6%,具备良好的降解性能.旋转圆盘（RDE）及自由基淬灭实验结果显示,反应中转移电子数为2,且主要自由基为·OH.