钛修饰电极的制备及电化学性能比较

通过电沉积法在钛网(Ti)上负载钯、钯镍双金属及聚吡咯(PPy)双金属,对比研究不同修饰对电极电化学催化活性的影响。循环伏安测试(CV)表明,在最佳制备条件下,Pd/Ti电极在-500 mV(以Hg/Hg₂SO₄为参比电极)左右获得氢吸附峰值为-59.47 mA;引入Ni制备双金属修饰电极(PdNi/Ti电极)获得氢吸附峰值为-64.40 mA,双金属修饰电极表现出较好的电催化性能;吡咯修饰后制得的Pd-Ni/PPy/Ti电极获得的氢吸附峰值最大,峰值为-80.14 mA,电催化性能更优。扫描电镜(SEM)分析了Ni和PPy的引入对电极表面形态的改变。利用原子发射光谱(AES)分析了电极表面Pd、Ni金属的负载量。实验表明,Ni与PPy的引入使Pd-Ni/PPy/Ti电极在大大减少钯负载量的情况下,仍具有很好的电催化性能,电化学脱氯潜能也很大。     

Impacts of natural weathering on the transformation/neoformation processes in landfilled MSWI bottom ash: a geoenvironmental perspective

Natural weathering processes are significant mechanisms that noticeably affect the fundamental nature of incineration ash residues. To provide a greater understanding of these processes, a MSWI (mono)landfill site in the north east of the US was selected as the target for systematic investigation of the natural weathering of bottom ash residues. Samples of various ages were collected from locations A (1 yr), B (10 yrs), C (13-14 yrs) and D (20 yrs) of the landfill in 2009. We investigated the phase transformation of the collected bottom ash particles, neoformation processes as well as the behavior and distribution of certain heavy metals (Cu, Pb, Zn, Ni, and Cr) in the neoformed phases using optical microscopy, SEM-EDX, and bulk examinations. Key findings: at the preliminary stage, the waste metallic particles (Al, Fe, and Cu) and unstable minerals such as lime, portlandite, ettringite and hydrocalumite convert to oxide and hydroxide (hydrate) phases, calcite, alumina gel and gypsum. At the intermediate stage, the decomposition of melt products including magnetite spinels and metallic inclusions is triggered due to the partial dissolution of the melt glass. At the longer time horizon it is possible to track the breakdown of the glass phase, the extensive formation of calcite and anhydrite, Al-hydrates and more stable Fe-hydrates all through the older ash deposits. Among the dominant secondary phases, we propose the following order based on their direct metal uptake capacity: Fe-hydrates>Al-hydrates>calcite. Calcite was found to be the least effective phase for the direct sorption of heavy metals. Based on overall findings, a model is proposed that demonstrates the general trend of ash weathering in the landfill.     

Reactive chemical hazards of diazonium salts

Many diazonium salts are thermally unstable and sensitive to friction and shock. Most diazonium salts are known for their violent decomposition hazard in the solid state. There are many industrial and laboratory incidents caused by this group of chemicals. For safety purposes, the hazards related to the preparation and the handling of diazonium salts are discussed. Twelve cardinal rules are provided:1. Use only a stoichiometric amount of sodium nitrite when generating diazonium salts, avoiding excess sodium nitrite.2. Check for the excess of nitrous acid by starch–potassium iodide papers and neutralize it.3. Minimize the presence of nitrous acid by combining amine and acid first, then subsequently adding the sodium nitrite.4. Keep the temperature below 5 °C.5. Always vent the gases generated.6. Determine the thermal stability of diazonium compounds in your system.7. Understand the explosive properties of diazonium salts. If unknown, always assume they are explosive.8. Never allow the undesired precipitation of diazonium salts out of solution.9. Analyze the residual diazo compounds in the final product, especially for new process conditions.10. Quench the remaining diazonium salts before any further treatments.11. Isolate no more than 0.75 mmol of explosive diazonium salts at one time; also consider the addition of an inert material to stabilize the diazonium salts.12. Use a plastic spatula when handling the solid. The dried powder should not be “scratched” with a metal spatula or ground finely.An example of a testing strategy and data interpretation is provided for a process which has multiple steps and two diazonium compounds. Differential Scanning Calorimetry (DSC) and Heat of Mixing calorimetry (HOM) successfully serve as efficient tests to screen thermal stability and gas generation, identifying the candidates for advanced tests.     

堆肥制作中微生物侵染秸秆的环境扫描电镜(ESEM)观察

为了探索堆肥制作中木质纤维素类物质的生物降解过程,在堆肥进程中取不同分解阶段的秸秆样品,利用环境扫描电镜(ESEM)观察微生物的分布情况,并从机械作用的角度探讨了微生物在秸秆分解过程中的作用。结果表明,堆肥制作前新鲜秸秆表面未发现微生物分布,堆肥制作前期微生物开始附着在秸秆表面,随着堆肥进程,秸秆表面微生物密度有所增加,秸秆分解时产生的裂缝中发现也有微生物分布。堆肥制作中,参与秸秆分解的微生物以群落形式分布,从个体形态来看,这些微生物主要由球菌和丝状菌组成,但不同形态微生物个体大小差异较大。分析认为大型丝状菌通过秸秆分解产生的裂缝侵入秸秆内部时所产生的机械作用可促进秸秆的崩解。     

Mapping eucalypt forest susceptible to dieback associated with bell miners (Manorina melanophys) using laser scanning, SPOT 5 and ancillary topographical data

Mapping the location and extent of forest at risk from damaging agents or processes assists forest managers in prioritizing their planning and operational mitigation activities. In Australia, Bell Miner Associated Dieback (BMAD) refers to a form of canopy decline observed in eucalypt crowns occupied by colonies of bell miners (Manorina melanophrys). High densities of bell miners are associated with decreased avian abundance and diversity and an increase in psyllid abundance on crown foliage. BMAD has recently been nominated as a key threatening process in New South Wales (NSW). Consequently, a modelling system for predicting bell miner distribution in coastal eucalypt forests of NSW has been developed. The presence or absence of bell miners was recorded in 130 plots located within a 12,800 ha catchment study area containing a range of eucalypt forest types. The modelling system was produced by integrating a machine learning software suite (WEKA), and the statistical software R within the geographic resources analysis support system (GRASS) geographical information system (GIS). The variable modelled was the binary variable: presence or absence of bell minors. Six modelling techniques (Logistic regression; generalised additive models; two tree-based ensemble classification algorithms, random forest and Adaboost and Neural Networks) were integrated with airborne laser scanning; SPOT 5 and topographic derived variables. Model evaluation and parameter selection were measured by three threshold dependent measures (sensitivity, specificity and kappa) and the threshold independent Receiver Operator Curve (ROC) analysis. The final presence and absence maps were obtained through maximisation of the kappa statistic and applied at a resolution of 10 m across the entire catchment study area. For this data set, the most accurate algorithm for predicting the distribution of bell miner colonies was random forest (kappa = 0.84; ROC area under curve = 0.97). Variables most commonly selected in the six models were the laser scanning metrics; coefficient of variation, skewness, and the 10th and 90th percentiles derived from the shape of the height frequency distribution which, in turn, is directly influenced by vertical structure of the forest. An image textural statistic based on the shortwave infrared (SWIR) band of SPOT 5 was also commonly selected by the models. The SWIR band is sensitive to vegetation and soil moisture content. These models predicted that forest stands with a sparse eucalypt canopy over a moist, dense understorey were susceptible to being colonised by bell miners and hence BMAD.     

碳质大气颗粒物的扫描质子微探针分析

碳质颗粒物是大气颗粒物的重要组成部分,对全球气候变化、环境质量、人类健康等有重要影响.本研究使用扫描质子微探针对上海两个典型环境监测点的大气颗粒物及7类污染排放源的单颗粒进行了分析.利用微束非卢瑟福弹性背散射谱micro-EBS(non-Rutherford elastic backscattering,EBS)分析了单颗粒中的C含量,发现燃煤烟尘、燃油烟尘、汽车尾气、柴油公交车尾气等污染源中碳质颗粒物占优,而水泥尘、钢铁工业尘、土壤尘中无机颗粒物占优;中心城区的碳质颗粒物占优,而工业区的无机颗粒物占优,单颗粒物的元素分布可以反映颗粒物发生大气化学反应的重要信息,利用微束质子激发X射线荧谱micro-PIXE(particle induced X-ray emission,PIXE)分析得到了大气颗粒物的S、Ca、Fe等元素分布,发现含Ca的碳质颗粒在大气中发生了硫化反应.     

基于热爆炸理论的煤燃点确定及动力学分析

为准确判断煤燃点,提高煤自燃灾害防治能力,依据热爆炸理论,结合煤自燃过程放热曲线,将煤自燃升温过程中微分热流曲线上第1处极小值点作为煤的燃点,计算煤着火前后放热过程动力学参数变化.结果表明:随升温速率增加,煤自燃反应放热过程逐渐向高温区域移动,煤燃点逐渐增大,反应的活化能逐渐减小;同一升温速率下燃点之后煤的活化能增大;...     

δ-MnO_2降低无机三价砷毒性的研究

文章利用自制的δ-MnO2对剧毒性无机A(sⅢ)进行了氧化吸附过程的实验室研究,考察了反应进程中各形态砷的变化,同时进一步对与高浓度A(sⅢ)反应前后δ-MnO2的结构和形貌进行了X射线衍射(XRD)、扫描电子显微镜(SEM)和拉曼光谱(Raman)鉴定。实验结果表明,δ-MnO2通过氧化和吸附作用对A(sⅢ)的毒性去除效果显著,60 min内溶液中A(sⅢ)消失了72.3%。形态学研究表明,反应前后δ-MnO2的XRD图没有明显变化;而SEM图显示,反应后δ-MnO2的蜂窝状结构其固体孔隙比反应之前明显变小;EDX的数据显示δ-MnO2固体中出现了一定含量的As元素;δ-MnO2反应前后Raman光谱的吸收强峰由649 cm-1处变化到865 cm-1处,也表明出现了一部分可以永久固定在δ-MnO2固体内的A(sV)。该研究认为,δ-MnO2具有较强氧化和吸附活性,可以大大降低三价无机砷的毒性。     

陶瓷涂层性能影响因素及工艺优化研究

为了提高Al2O3陶瓷涂层的综合性能,对陶瓷涂层性能影响因素进行了正交试验设计。以磨损量、结合强度和耐腐蚀性为评价指标,得出了在Al2O3陶瓷颗粒粒径为160目,颗粒填入量为125%,涂层厚度为1 mm时,综合性能最好。同时利用差示扫描量热（DSC）技术推算出胶粘剂体系的最佳固化工艺为50℃（1h）→100℃（2 h）→225℃（1h）;采用磷酸阳极化（PAA）方法对铝合金基体表面进行处理,使其与涂层之间获得最好的结合强度。