Characterizing the optimal operation of photocatalytic degradation of BDE-209 by nano-sized TiO2

Brominated flame retardants have been widely used in industry. There is a rapid growing public concern for their availabilities in the environment. Advanced oxidation process (AOP) is a promising and efficient technology which may be used to remove emerging chemicals such as brominated flame retardants. This project aims at investigating optimal operational conditions for the removal of BDE-209 using nano-scaled titanium(IV) oxide. The residual PBDE congeners after photocatalytical degradation of BDE-209 by TiO₂ were analysed by gas chromatography-mass spectrometry (GC-MS). It was found that the degradability of BDE-209 by TiO₂ was attributed to its photocatalytic activity but not the small size of the particles. The half-life of removing BDE-209 by TiO₂ was 3.05 days under visible light. Tetra- and penta-BDEs were the major degraded products of BDE-209. Optimum conditions for photocatalytical degradation of BDE-209 was found to be at pH 12 (93% ± 1%), 5, 10, 20 mg/L (93.0% ± 1.70%, 91.6% ± 3.21%, 91.9% ± 0.952%, respectively), respectively of humic acid and in the form of anatase/rutile TiO₂ (82% ± 3%). Hence, the efficiency of removing BDE-209 can be maximized while being cost effective at the said operating conditions.     

Soil warming effect on net ecosystem exchange of carbon dioxide during the transition from winter carbon source to spring carbon sink in a temperate urban lawn

The significant warming in urban environment caused by the combined effects of global warming and heat island has stimulated widely development of urban vegetations. However, it is less known of the climate feedback of urban lawn in warmed environment. Soil warming effect on net ecosystem exchange (NEE) of carbon dioxide during the transition period from winter to spring was investigated in a temperate urban lawn in Beijing, China. The NEE (negative for uptake) under soil warming treatment (temperature was about 5℃ higher than the ambient treatment as a control) was -0.71 μmol/(m².sec), the ecosytem was a CO₂ sink under soil warming treatment, the lawn ecosystem under the control was a CO₂ source (0.13 μmol/(m².sec)), indicating that the lawn ecosystem would provide a negative feedback to global warming. There was no significant effect of soil warming on nocturnal NEE (i.e., ecosystem respiration), although the soil temperature sensitivity (Q₁₀) of ecosystem respiration under soil warming treatment was 3.86, much lower than that in the control (7.03). The CO₂ uptake was significantly increased by soil warming treatment that was attributed to about 100% increase of α (apparent quantum yield) and A_max (maximum rate of photosynthesis). Our results indicated that the response of photosynthesis in urban lawn is much more sensitive to global warming than respiration in the transition period.     

Preparation, characterization and application of CuCrO2/ZnO photocatalysts for the reduction of Cr(VI)

The delafossite CuCrO₂ elaborated by sol-gel from 40 nm diameter colloid is optically active in the visible region. It is characterized physically and photoelectrochemically. The microstructure is fairly homogenous with a mean crystallite size of ca. 2 μm. The optical gap (1.30 eV), determined from the diffuse reflectance, is well suited to the sunlight spectrum. The Mott Schottky plot is characteristic of P-type conductivity with a flat band potential of -0.26 V_SCE. As application, the photoreduction of chromate is successfully achieved in air-equilibrated suspension CuCrO₂/ZnO (1/1). CuCrO₂ is photoactivated by visible light and the electrons in the conduction band (-1.34 V_SCE) are injected to ZnO. In the presence of salicylic acid, a conversion of Cr(VI) to Cr(III) of 57% is obtained under optimal conditions (pH 3 at 25℃, 5×10^-4 mol/L) because of the HCrO₄^- dark adsorption onto ZnO (4HCrO₄^- + 3C₇H₆O₃ + 18O₂ + 16H⁺ → 4Cr³⁺ + 21CO₂ + 19H₂O, ΔG⁰ = -557 kcal/mol). Prolonged illumination is accompanied by a deceleration in the photoactivity owing to the competitive water reduction, an issue of energetic concern. The hetero-system exhibits self sensitization for hydrogen production with an evolution rate of 149 μmol/(hr·g).     

耐汞好氧反硝化菌的鉴定及适应汞离子的特性研究

从实验室保存的高效好氧反硝化菌种中筛选得到一株抗汞细菌并命名为X1,经生理生化特性和16SrRNA基因序列分析,初步鉴定该菌为恶臭假单胞菌(Pseudomonasputida).对菌株X1进行Hg2适应特性研究,结果表明,对于Hg2浓度为2、67++4、、mg·L-1的实验组,菌体分别需要被延滞12、284018、、h后进入对数期,而8mg·L-1实验组则不能进入对数期;在好氧反硝化过程中,Hg2浓度在7mg·L+-1范围内各实验组的好氧反硝化过程中NO3-N浓度变化速率、NO2-N累积峰值、pH特征点出现时刻随着Hg2浓度的增大而增大(延迟),而Hg2浓度呈现出同硝氮一致的下降趋势,并且在对数期内除汞率能达到100%.研究表明,菌株X1对Hg2最大适宜耐受浓度为7mg·L+-1,相应适应时间约为40h.在最大耐受浓度范围内,菌株X1的生长和好氧反硝化过程呈现出"被抑制-适应-受刺激"的变化规律,其中,被抑制的时间和受刺激的程度都随着Hg2浓度的增大而增大,主要表现为延滞期的延长和对数期的缩短.此外,在对数期,菌株X1的生长速率、达到稳定期的浓度和好+氧反硝化速率也都随着Hg2浓度的增大而增大,且大于无Hg2菌组.++     

不同煅烧温度制备的Mn、N掺杂TiO2光催化性能研究

以MnSO4·H2O为锰源,尿素为氮源,采用溶胶-凝胶法制备不同锻烧温度的纯TiO2、Mn-TiO2及Mn-N-TiO2光催化剂,利用X射线衍射、紫外-可见光漫反射光谱及电子自旋共振等技术对样品形貌和结构进行表征,并以罗丹明B的光催化降解为模型反应,考察不同锻烧温度对其光催化活性的影响.结果表明,Mn、N成功掺入TiO2后,有利于提高光催化剂的热稳定性,抑制锐钛矿相向金红石相转化,且光吸收拓展到可见光区域.Mn、N共掺杂样品比单Mn掺杂样品具有更高的光催化活性,400℃下锻烧的Mn-N-TiO2在可见光下对罗丹明B的降解具有最高的光催化活性,光照2h降解率达到100%.高温锻烧Mn-N-TiO2和Mn-TiO2样品在紫外光照射30min后对罗丹明B的降解率在90%以上.     

有机粘土疏水性吸附过程的分子模拟:烷基碳原子数和有机物logK_(ow)的影响

基于从分子尺度上解析改性剂烷基碳原子数和有机物疏水性对有机粘土吸附能力的影响机制,以从头算的量子化学计算方法(MP2/6-31g(d))模拟了有机粘土在水溶液中的吸附过程.通过计算吸附前后几何构型、能量、化学键和电荷分布等参数的变化,分析了影响有机粘土疏水性吸附的关键因素,并对疏水性吸附作用力的化学本质进行了初步探讨.计算结果表明,烷基碳原子数增加对提高有机物吸附能的作用并不显著,长链烷基提高有机粘土吸附容量的真正原因在于其可提供更多的有机物吸附位.有机物的疏水性(以正辛醇-水分配系数logKow表征)是影响疏水性吸附过程的关键因子,水分子的引力作用对疏水性吸附具有决定性影响,理论上解释了普遍存在的有机物吸附量与logKow呈正相关的实验现象.疏水性吸附力的作用前提是有机物为疏水性,即当水分子的引力作用较弱时疏水性作用力才可以表现出来;而对于亲水性有机物,疏水性吸附力会被水分子的引力所抵消,吸附强度减弱.模拟红外光谱和电荷分布结果表明,吸附前后无化学键断裂和电子得失的发生,只有原子电荷密度的微小变化,据此推测疏水性吸附力以分子间弱相互作用力——London色散力为主.     

道南膜技术测定Ca(NO3)2溶液体系中汞的化学形态

虽然道南膜技术(DMT)已经成功用于土壤/溶液中多种重金属自由态离子浓度的测定,但DMT技术测定Hg的形态尚未解决.采用DMT测定Ca(NO3)2溶液体系中Hg化学形态.实验结果表明,Hg在阳离子交换膜内的吸附除静电吸附外还存在结合力更强的化学吸附,Hg在阳离子交换膜内扩散成为Hg跨膜传输受阻的主要因素,限制道南膜技术用于Hg形态测定.Hg2+和Hg(OH)2都表现出在阳离子交换膜上的强烈吸附,供端(Donor)Hg损失达50%以上.缩短试验时间至8h以内,可在一定程度上降低Hg吸附.计算结果表明,由于大量的Hg滞留在阳离子交换膜内,在计算受端(Acceptor)Hg浓度时引入滞留系数补偿供端Hg的损失,较好地预测了Ca(NO3)2溶液体系中Hg的化学形态.     

活性焦负载MnO2对气态Hg0的吸附脱除研究

研究了活性焦(AC)及负载MnO2的活性焦(MnO2/AC)对气态Hg0的吸附脱除,发现负载MnO2到AC明显提高了其对Hg0的吸附脱除能力.考察了MnO2负载量、温度、Hg0浓度和烟气成分等对MnO2/AC吸附脱除Hg0的影响.结果表明,MnO2/AC对Hg0的吸附脱除能力随MnO2负载量的增加而增强;在120～200℃的温度范围内,随着温度升高,MnO2/AC对Hg0的吸附脱除能力增强;O2和HCl对MnO2/AC吸附脱除Hg0具有促进作用,而SO2和H2O具有抑制作用.SEM-EDX和逐级化学提取结果证实,MnO2将Hg0催化氧化为HgO并吸附在AC上,这是MnO2/AC具有较高的吸附脱除Hg0能力的原因.     

Adsorption characteristics and mechanism of Cr （Ⅵ） on chitoan-yttrium porous microsphere

以壳聚糖和Y2（OH）5NO3为原料通过乳液交联法制备了壳聚糖-钇（Ch—Y）复合微球,通过扫描电镜、透射电镜、X射线衍射、红外光谱等方法对其表面形貌、结构进行了表征.探讨了溶液的pH值、反应时间、投加量、离子初始浓度对其吸附性能的影响.研究结果表明,壳聚糖-钇（Ch—Y）复合微球在pH值为3的酸性环境中对Cr（Ⅵ）保持了较高的吸附能力,吸附容量为52.39mg·g-1,其吸附行为符合Langmuir吸附等温模型;通过吸附机理的研究,发现壳聚糖-钇（Ch—Y）对Cr（Ⅵ）吸附是化学吸附静电吸附协同氧化Cr（Ⅵ）离子作用来实现的.     

Catalytic performance of copper and cerium oxides-based γ-Al_2O_3 on combustion of toluene

以γ-Al2O3为载体,以复合氧化物CuxCe1-xO2为活性组分,其中,x=0.1,0.2,0.4,0.6,0.8,通过浸渍法制备了一系列CuxCe1-xO2/γ-Al2O3催化剂.在固定床反应器中评价了催化剂对甲苯的催化活性,通过XRD、SEM对催化剂进行表征,并运用ICP-MS分析并计算Cu、Ce的摩尔比以及活性组分的负载量.结果表明,在CuxCe1-xO2/γ-Al2O3催化剂中Cu、Ce摩尔比的实际值与理论值相近,活性组分的负载量在19%以上,而且对甲苯都有较好的低温催化活性,其中当x=0.2时,即Cu0.2Ce0.8O2/γ-Al2O3催化剂对甲苯的催化活性最高,其中T10=160℃,T90=265℃;当甲苯的进口浓度在700～3000mg·m-3时,进口浓度对Cu0.2Ce0.8O2/γ-Al2O3催化剂的催化活性影响较小,且经过连续80h的稳定性操作后转化率仍然保持在90%以上.