基于细管流紫外反应系统探讨紫外和真空紫外/紫外辐照下水中微量磺胺甲噻二唑的光降解效果

水环境中存在的微量有机污染物可在较低浓度下对人类造成较大的危害.基于细管流紫外反应系统(MFPS)研究了典型微量有机污染物磺胺甲噻二唑(SML)在紫外(UV)和真空紫外/紫外(VUV/UV)辐照下的光降解过程,发现SML在VUV/UV辐照下的降解速率明显快于UV辐照.采用MFPS测定了各光化学动力学参数:UV和VUV/UV辐照下光子剂量基反应速率常数分别为0.88×10~3和4.64×10~3m~2·einstein-1;量子产率分别为0.227和0.379;羟基自由基(HO·)和SML的二级反应速率常数测定为6.59×10~9L·mol~(-1)·s~(-1).探讨了pH值和初始SML浓度对降解效果的影响,结果表明,VUV/UV辐照下pH 7.0时的SML降解速率达到最大,而UV辐照下SML的降解速率随pH增加而逐渐增大;初始SML浓度的增大会降低UV和VUV/UV辐照下的降解速率.此外,本研究表明MFPS作为实验室光反应系统可快速、准确地测量各光反应动力学参数,VUV/UV在去除水中微量有机污染物方面的效果优于UV,可较好的处理水中微量有机污染物.     

沼气产生的两步一级反应耦合模型

根据有机物厌氧产生沼气的生化机理,假设沼气通过两步相互衔接的一级反应生成,即复杂有机物的水解酸化反应和简单有机酸的产气反应.根据假设,建立了基于两步一级反应耦合的沼气产气率与产气量随时间变化的数学模型.该模型用统一的数学公式对沼气产气率随时间变化的倒“U”形曲线进行了解释,指出这一过程是两步相互衔接的一级反应相互作用的结果.已知有机物质量,通过拟合或根据经验得出K值后,利用该模型可解出任一时刻有机物的产气率、产气量、最大产气率及其发生的时间.拟合表明,两步反应的反应常数趋于相等.利用该模型可导出已有的Scholl Canyon模型,并可对Palos Verdes模型和Sheldon Arleta模型的经验假设进行解释.      

粉煤灰浆中碳酸钙沉淀反应动力学

利用设计的试验装置研究了燃煤电厂粉煤灰浆中碳酸钙沉淀反应动力学 .该试验装置可以有效地完成灰与水的瞬间混合 ,并通过设计的特殊真空取样装置完成灰浆的快速取样 .取样完成后 ,迅速通过离心、快速密闭过滤措施 ,实现灰与水的分离 ,从而终止体系中所发生的沉淀反应 ,制取清水样品供测试 .采用此法 ,首次以粉煤灰浆水相中的总无机碳含量为检测因子 ,直接测得了该体系中碳酸钙沉淀反应的动力学数据 .根据动力学数据特征 ,提出了能够表征该反应动力学规律的数学表达式 ,并经数学推导、计算机拟合求得了针对具体动力学数据的表达式参数 .     

厌氧(水解)—好氧处理工艺的理论与实践

对厌氧、好氧工艺在污水处理领域的作用和新的应用领域进行了探讨。厌氧和好氧处理工艺各有优点和缺点,而厌氧 好氧联合处理工艺可以发挥单独工艺的优点,厌氧 好氧联合处理工艺在难降解污水的处理上有其独特的优点。对水解工艺理论分析结果和进一步的实验研究表明,工艺本身还有巨大的潜力,用作高固体含量废水厌氧处理的预处理单元。可以解决高悬浮物和含脂类物质给厌氧工艺带来的抑制和破坏等问题,为解决这类工业废水的厌氧处理开拓了一条可行的技术路线。对于厌氧、好氧和兼性微生物,特别是兼性微生物作用的深入研究,有助于进一步开发高效率、低能耗的污水处理新工艺。     

辣根过氧化物酶处理酚和氯酚的催化特性研究

为了研究辣根过氧化物酶处理酚和氯酚的动力学过程,采用人工配不试验,测定了ｐＨ对酶催化反应的影响,Ｈ２Ｏ２抑制酶催化反应的动力学参数和不同度物的酶催化反应动力学参数,结果表明,在试验的ｐＨ范围内,ｐＨ为９时过氧化物酶对苯酚和对氯苯酚的去除效率最高,分别达到９９．５％和９５％。     

One-step ball milling-prepared nano Fe2O3 and nitrogen-doped graphene with high oxygen reduction activity and its application in microbial fuel cells

• Nano Fe₂O₃ and N-doped graphene was prepared via a one-step ball milling method. • The maximum power density of Fe-N-G in MFC was 390% of that of pristine graphite. • Active sites like nano Fe₂O₃, pyridinic N and Fe-N groups were formed in Fe-N-G. • The improvement of Fe-N-G was due to full exposure of active sites on graphene. Developing high activity, low-cost and long durability catalysts for oxygen reduction reaction is of great significance for the practical application of microbial fuel cells. The full exposure of active sites in catalysts can enhance catalytic activity dramatically. Here, novel Fe-N-doped graphene is successfully synthesized via a one-step in situ ball milling method. Pristine graphite, ball milling graphene, N-doped graphene and Fe-N-doped graphene are applied in air cathodes, and enhanced performance is observed in microbial fuel cells with graphene-based catalysts. Particularly, Fe-N-doped graphene achieves the highest oxygen reduction reaction activity, with a maximum power density of 1380±20 mW/m² in microbial fuel cells and a current density of 23.8 A/m² at –0.16 V in electrochemical tests, which are comparable to commercial Pt and 390% and 640% of those of pristine graphite. An investigation of the material characteristics reveals that the superior performance of Fe-N-doped graphene results from the full exposure of Fe₂O₃ nanoparticles, pyrrolic N, pyridinic N and excellent Fe-N-G active sites on the graphene matrix. This work not only suggests the strategy of maximally exposing active sites to optimize the potential of catalysts but also provides promising catalysts for the use of microbial fuel cells in sustainable energy generation.     

Redox reactions of iron and manganese oxides in complex systems

• Mechanisms of redox reactions of Fe- and Mn-oxides were discussed. • Oxidative reactions of Mn- and Fe-oxides in complex systems were reviewed. • Reductive reaction of Fe(II)/iron oxides in complex systems was examined. • Future research on examining the redox reactivity in complex systems was suggested. Conspectus Redox reactions of Fe- and Mn-oxides play important roles in the fate and transformation of many contaminants in natural environments. Due to experimental and analytical challenges associated with complex environments, there has been a limited understanding of the reaction kinetics and mechanisms in actual environmental systems, and most of the studies so far have only focused on simple model systems. To bridge the gap between simple model systems and complex environmental systems, it is necessary to increase the complexity of model systems and examine both the involved interaction mechanisms and how the interactions affected contaminant transformation. In this Account, we primarily focused on (1) the oxidative reactivity of Mn- and Fe-oxides and (2) the reductive reactivity of Fe(II)/iron oxides in complex model systems toward contaminant degradation. The effects of common metal ions such as Mn²⁺ , Ca²⁺, Ni²⁺, Cr³⁺ and Cu²⁺, ligands such as small anionic ligands and natural organic matter (NOM), and second metal oxides such as Al, Si and Ti oxides on the redox reactivity of the systems are briefly summarized.     

ORS-ICP-MS测定工业污泥中的重金属元素

建立了八极杆碰撞/反应池电感耦合等离子体质谱(ORS-ICP-MS)法测定工业污泥中Cr、Ni、As、Cd、Sb、Sn、Hg和Pb等8种重金属元素的分析方法。应用ORS技术消除了多原子离子对待测元素产生的质谱干扰,通过研究He碰撞气流速的变化对Cr、Ni、As和Sb预估检测限(EDL)的影响情况确定了最佳碰撞气流速,采用Rh为内标元素校正了质谱分析中基体效应并补偿了信号漂移。方法对工业污泥样品的检出限为13.5~34.3 ng/L,加标回收率在93.0%~107.6%之间,相对标准偏差(RSD)为1.5%~2.8%。     

MnOx／Al-SBA-15催化剂低温NH3选择性催化还原NO的原位红外研究

用原位红外分别进行了MnOx／Al-SBA-15催化剂上NH3和NO＋O2的吸附态和瞬态实验以及NH3＋NO＋02反应的稳态实验。结果表明,催化剂上存在着L酸位和B酸位,NH3吸附在催化剂上形成配位态的NH3和NH4＋,配位态的NH3能脱氢形成-NH2活性中间态。NO＋O2在催化剂上吸附形成硝酸盐类、硝基类和亚硝酸盐类。将NO＋O2通入预吸附NH3的催化剂中时,表面的配位态的NH3、NH4＋和-NH2都会减少直至消失,SCR反应显著。而将NH3通人预吸附NO＋O2的催化剂中时,只有硝基类和亚硝酸盐类减少,硝酸盐类基本不发生变化,SCR反应微弱。NH3＋NO＋O2稳态反应中,催化剂表面稳定存在着NH4＋和硝酸盐类,SCR反应显著。     

利用高炉瓦斯泥-H_2O_2处理硝基苯废水

以高炉瓦斯泥为铁源,通过其在酸性条件下与H2O2形成Fenton/类Fenton反应体系来处理硝基苯废水,考察了p H、H2O2用量、高炉瓦斯泥用量及反应时间对硝基苯降解率的影响,并对降解机理进行了分析表征。实验结果表明,在p H为3、高炉瓦斯泥用量为0.5 g/L、H2O2用量为10 m L/L、反应时间为60 min的条件下,100 mg/L的硝基苯溶液中硝基苯的降解率达87.88%;硝基苯先被氧化生成硝基苯酚、硝基苯二酚、对苯醌等中间产物,然后再进一步氧化生成二氧化碳和水达到降解的目的。