H2O2 treatment boosts activity of NiFe layered double hydroxide for electro-catalytic oxidation of urea

Urea oxidation reaction (UOR) provides a method for hydrogen production besides wastewater treatment, but the current limited catalytic activity has prevented the application. Herein, we develop a novel H₂O₂ treatment strategy for tailoring the surface oxygen ligand of NiFe-layered double hydroxides (NiFe-LDH). The sample after H₂O₂ treatment (NiFeO-LDH) shows significant enhancement on UOR efficiency, with the potential of 1.37 V (RHE) to reach a current density of 10 mA/cm². The boost is attributed to the richness adsorption O ligand on NiFeO-LDH as revealed by XPS and Raman analysis. DFT calculation indicates formation of two possible types of oxygen ligands: adsorbed oxygen on the surface and exposed from hydroxyl group, lowered the desorption energy of CO₂ product, which lead to the lowered onset potential. This strategy is further extended to NiFe-LDH nano sheet on Ni foam to reach a higher current density of 440 mA/cm² of UOR at 1.8 V (RHE). The facile surface O ligand manipulation is also expected to give chance to many other electro-catalytic oxidations.     

An approach to preimplantation diagnosis of β-thalassaemia

Using the polymerase chain reaction (PCR), it was possible to amplify a single copy fragment of the β-globin gene from 2–32 human embryonic cells obtained from arrested preimplantation embryos. For the detection of β-thalassaemia mutations, allele specific priming of the PCR using nested primers was employed using approximately 10 pg of DN A from individuals known to carry these mutations. This approach was successful in detecting the presence or absence of five Asian Indian β-thalassaemia mutations that were selected for this study. In spite of meticulous precautions against contamination, false-positive amplification was observed, a problem that will have to be overcome before this approach can be used in clinical practice.     

Size distributions and sources of elements in particulate matter at curbside, urban and rural sites in Beijing

Size distributions of 29 elements in aerosols collected at urban, rural and curbside sites in Beijing were studied. High levels of Mn, Ni, As, Cd and Pb indicate the pollution of toxic heavy metals cannot be neglected in Beijing. Principal component analysis (PCA) indicates 4 sources of combustion emission, crust related sources, traffic related sources and volatile species from coal combustion. The elements can be roughly divided into 3 groups by size distribution and enrichment factors method (EFs). Group 1 elements are crust related and mainly found within coarse mode including Al, Mg, Ca, Sc, Ti, Fe, Sr, Zr and Ba; Group 2 elements are fossil fuel related and mostly concentrated in accumulation mode including S, As, Se, Ag, Cd, Tl and Pb; Group 3 elements are multi-source related and show multi-mode distribution including Be, Na, K, Cr, Mn, Co, Ni, Cu, Zn, Ga, Mo, Sn and Sb. The EFs of Be, S, Cr, Co, Ni, Cu, Ga, Se, Mo, Ag, Cd, Sb, Tl and Pb show higher values in winter than in summer indicating sources of coal combustion for heating in winter. The abundance of Cu and Sb in coarse mode is about 2-6 times higher at curbside site than at urban site indicating their traffic sources. Coal burning may be the major source of Pb in Beijing since the phase out of leaded gasoline, as the EFs of Pb are comparable at both urban and curbside sites, and about two times higher in winter than that in summer.     

广州市不同功能区大气二噁英含量和分布特征研究

应用气相色谱-高分辨率质谱仪(GC-HRMS)对广州市秋冬季6个区域环境空气样品中的17种2,3,7,8-氯代二英含量进行了检测.结果表明,广州市各观测区域大气中二英毒性当量浓度范围为0.151～2.230pg.m-3,均值为0.418pg.m-3.各观测区域空气中二英毒性当量浓度分布存在一定的差异,本研究的背景区、居民住宅区和商业区二英毒性当量浓度较低且水平相近,分别为(0.294±0.099)、(0.305±0.115)、(0.308±0.102)pg.m-3.交通枢纽区、郊区和工业区二英毒性当量浓度相对较高,分别为(0.342±0.049)、(0.423±0.113)和(0.838±0.704)pg·m-3.广州市不同功能区二英毒性当量浓度呈现背景区<住宅区<商业区<交通枢纽区<郊区<工业区的分布特点.与2004年相比,广州市城区二英毒性当量浓度有所下降,郊区毒性当量浓度有所上升.     

几种网格数据处理方法的应用与评述

对于利用网格布点所测得数据的处理,可采用积分法、趋势面法、多项式法和平均值法,各种处理方法各有其特点。平均值法计算简单,各个网格权重相同,意义明了,但精度不高;积分法和趋势面法考虑到了位于中心的网格对整个区域的贡献率大,组成的三角形多,统计时利用次数就多,边缘的网格数据利用次数少,物理意义明确。积分法还可计算总量,趋势面法可以在图上表示区域分布及变化趋势;多项式法除了计算其平均值外,还可模拟测定值,可计算测得数值序列趋势值和偏差值,分析污染物分布及变化情况。使用时要根据分析对象的物理意义及研究目的不同,选择不同的数学模型和计算公式。     

铁氮掺杂碳纳米管/纤维复合物制备及其催化氧还原的效果

阴极催化剂是影响微生物燃料电池(microbial fuel cell,MFC)性能的关键因素.通过研究制备成本低廉、氧还原反应(ORR)催化活性高的阴极催化剂来替代Pt/C对于实现MFC规模化应用具有重大意义.研究采用化学气相沉淀法,以三聚氰胺作为碳氮前驱物、以黑珍珠2000或乙炔炭黑作为碳源,外加醋酸亚铁作为铁前驱物,合成了两种铁氮掺杂碳纳米管/纤维复合物(FeNCB和FeNCC),作为MFC的阴极催化剂.通过循环伏安法和旋转圆盘-环电极分析FeNCB、FeNCC和Pt/C的ORR催化活性的差异,并用MFC验证其差异.结果表明,FeNCB性能与Pt/C相当,优于FeNCC,其催化路径是通过4电子途径催化氧还原反应;MFC-FeNCB性能略优于MFC-Pt/C,显著优于MFC-FeNCB有助于MFC的扩大化,其最大功率密度为1 212.8mW·m~(-2),开路电压为0.875 V,电池稳定电压为(0.500±0.025)V.用X射线衍射、X射线光电子光谱、拉曼光谱等进一步分析显示,复合物中碳纳米管管径的大小、铁氮掺杂的类型和含量以及氧含量是引起制备的复合物催化氧还原性能差异的原因所在.     

光助芬顿反应催化降解气体中甲苯

以甲苯作为挥发性有机污染物(VOCs)的代表,利用连续进气动态实验装置,研究光助芬顿反应降解气体中甲苯的作用.考察了芬顿试剂溶液初始p H、H2O2浓度、Fe2+浓度以及甲苯初始浓度对降解甲苯的影响,并利用在线质谱和色谱对产物进行了定性、定量分析.结果表明,紫外光照加快了羟基自由基的生成,显著提高了气体中甲苯的去除率;p H=3.0、H2O2浓度为20 mmol·L-1、Fe2+浓度为0.3 mmol·L-1的条件下,甲苯去除率最高;当甲苯初始浓度为260 mg·m-3时,去除率能够达到98%;光助芬顿反应催化降解气体中甲苯实验未检测到CO2之外的中间产物,CO2产率分析表明去除的甲苯全部转化为CO2.     

微波催化燃烧气态甲苯特性及床层温度分布

采用浸渍法制备Cu-Mn-Ce/堇青石蜂窝催化剂,于微波催化燃烧装置中考察其对甲苯废气的催化活性与稳定性,并对固定床温度进行了测试分析.研究表明,微波加热下床层温度分布均匀,甲苯的最佳反应温度在230~270℃之间.当停留时间大于9.7s且床层温度高于270℃时,甲苯的降解率大于90%.铜锰铈单金属氧化物及其复合氧化物尖晶石是主要的活性组分,甲苯在其表面上进行准一级反应而被催化氧化.高温对催化剂结构有影响,但重复性试验证实了催化剂的高活性和良好的稳定性.本文为微波催化燃烧技术治理VOCs废气的中试研究及下一步的实际应用提供了理论支持.     

辽东湾大气中多环芳烃的含量组成及气粒分配

2016年5月和8月对辽东湾大气环境中气相和颗粒相样品进行了走航和定点采集,并对24种PAHs在气相和颗粒相中的含量和组成进行探讨,对15种PAHs的气粒分配过程进行了分析.结果表明：5月和8月辽东湾大气气相和颗粒相中∑₂₄PAHs总平均含量分别为28.8 ng·m^-3和24.0 ng·m^-3,气相中∑₂₄PAHs含量5月小于8月,颗粒态∑₂₄PAHs含量5月大于8月,低分子量PAHs主要分布在气相中,高分子量PAHs组分主要分布在颗粒相,中等分子量PAHs的气粒分配更容易受到气温等环境条件影响;气粒分配系数K_p随着PAHs分子量增加而增加;lgK_p-lgP_L模型和lgK_p-lgK_OA模型的斜率m分别为-0.35和0.37,偏离平衡态m为-1或+1,辽东湾气粒分配未达到平衡;假设达到平衡态时的lgK_p-lgK_OA模型、lgK_p-lgP_L模型和碳黑-空气模型均表明,5环PAHs的模型预测结果与实际测定结果之间的吻合程度较好,15种PAHs的碳黑-空气模型能够更好地接近野外实际测定值,低分子量和中等分子量PAHs的气粒分配受到碳黑影响较大.     

热处理温度对热障涂层微观形貌及元素互扩散的影响

目的提高热障涂层抗氧化性能,并减小二次反应区的形成。方法采用真空电弧离子镀技术在二代单晶高温合金DD32表面制备NiCoCrAlYHf(HY5)金属粘结层,分别在870℃及1000℃下进行真空扩散处理,利用电子束物理气相沉积(EB-PVD)技术制备氧化钇部分稳定氧化锆(YSZ)陶瓷层。采用扫描电子显微镜(SEM)、电子探针(EPMA)以及能谱(EDS)等测试方法,研究高温循环氧化过程中热障涂层的微观形貌、成分及扩散机制,同时计算了1、125 h氧化时间下Al元素互扩散系数。结果经过1000℃热循环、1000℃热处理的涂层氧化质量增量的绝对值较小,氧化速率常数为7.21×10-4,抗循环氧化性能较好。1100℃热处理试样,从涂层表面到基体方向Ni、Al、Cr等元素分布都比较均匀,在涂层与基体界面处,元素含量变化较为平滑。870℃热处理试样,Ni等元素质量分数分布不均,在涂层与基体界面处元素含量陡然变化,元素均质化程度低。Al元素扩散系数随着浓度的增加而增大,随着氧化时间的延长,粘结层与高温合金之间的元素扩散程度加剧,Al元素扩散系数减小。经过125h循环氧化,粘结层/基体界面出现互扩散区,互扩散区局部区域富Cr,Al含量低。循环氧化250 h后,热障涂层试样扩散区下方有拓扑密堆相TCP析出,形成二次反应区SRZ。真空扩散温度为870℃的试样,二次反应区更加明显。结论金属粘结层在1000℃下进行真空热处理可以有效提高涂层的抗氧化性能。涂层内部元素均质化程度高,Al元素扩散速率慢。同时,扩散区宽度较小,二次反应区不明显。