自组装纳米Au电极及其对H2O2催化氧化的研究

 研究了纳米粒子-金溶胶在铂金电极表面的单分子层自组装,并探讨了K₃Fe(CN)₆在金溶胶表面的电化学吸附性质;同时,以金溶胶修饰电极为工作电极,铂金电极为对电极,Ag/AgCl电极为参比电极组成的三电极系统对H₂O₂有良好的催化氧化作用,在1.0×10^-6～1.0×10^-3mol/L的浓度范围内与氧化峰峰电流呈良好的线性关系,为纳米自组装修饰电极在电化学及生物催化反应等方面的应用开辟了新的途径.     

TiO2/SiO2/GQDs双层增透膜的制备及其在太阳能板中的应用

采用溶胶-凝胶法制备了SiO₂ 和TiO₂ 纳米溶胶,采用水热法制备了石墨烯量子点（graphene quantum dots,GQDs）。为进一步提高光伏太阳能板的透光率,设计了一种TiO₂/SiO₂/GQDs双层增透膜结构。探究了薄膜的结构、自清洁性能和增透性能,并进一步讨论了GQDs在增透性中的作用。结果表明,SiO₂-TiO₂/TiO₂-GQDs结构的双层薄膜厚度为120 nm时,太阳能板上的光透过率由未涂敷的85%增加至95%。接触角实验和室外耐环境性能实验测试表明,复合膜层接触角为10°,并具有良好的亲水性和耐环境性能。此外,户外实验结果表明,涂覆该薄膜的太阳能电板发电效率提高6%。由此说明双层增透膜可有效地提高太阳能电池板的光能利用率和使用寿命,可高效地利用太阳能。     

锰氧化物-海藻酸钠凝胶微球材料的制备及其在偶氮染料废水处理中的应用

采用水热法制备锰氧化物（MnO_x）,并与海藻酸钠（SA）相结合,成功制备了锰氧化物-海藻酸钠凝胶微球（MnO_x@MABs）材料.通过场发射扫描电镜（FE-SEM）、X射线衍射（XRD）、红外光谱（FT-IR）等一系列的表征手段,对所制备的凝胶微球的形貌结构、组成成分等进行分析.然后,根据过硫酸盐高级氧化的原理,利用凝胶微球活化过硫酸盐来降解偶氮染料废水的代表污染物日落黄.研究了MnO_x@MABs材料的投加量、废水的pH值、废水温度、过一硫酸盐（PMS）的投加量和不同日落黄初始浓度对日落黄降解效果的影响.结果表明：MnO_x@MABs/PMS体系能在广泛的pH值范围内降解日落黄,当日落黄初始质量浓度为200 mg·L^-1时,在0.5 mmol·L^-1的PMS、30 g·L^-1的MnO_x@MABs以及体系反应温度为40℃条件下,60 min内对日落黄的降解率可达到100%.     

纳米Al2O3颗粒对Cu-Al2O3性能的影响

采用溶胶-凝胶法制备纳米Al₂O₃颗粒,通过粉末冶金法制备氧化铝铜（Cu-Al₂O₃）。采用X射线光电子能谱仪、扫描电子显微镜、洛氏硬度仪和涡流计分别测试了Cu-Al₂O₃的结合能、微观组织、硬度和导电率。结果表明：随Al₂O₃颗粒含量的增加,Cu-Al₂O₃的硬度先升高后降低,当Al₂O₃颗粒的质量分数达到0.084%时,Cu-Al₂O₃的硬度达到最大值75.73（HRB）。Cu-Al₂O₃的导电率随着Al₂O₃颗粒含量的增加逐渐下降。Al₂O₃颗粒的质量分数为0.084%时为最佳值,Cu-Al₂O₃的硬度达到最大值,导电率达到69.1% IACS。     

薄膜厚度对玻璃纤维表面SnO2薄膜透光导电性能的影响

 以SnCl₄·5H₂O为原料,乙醇为溶剂,配制SnO₂溶胶,并采用溶胶-凝胶法在玻璃纤维表面生成一层均匀的涂膜,通过控制反应物初始浓度和玻璃纤维提拉次数在玻璃纤维表面制备具有不同厚度的SnO₂薄膜.研究了薄膜厚度对薄膜的物相结构、透光率和电阻率的影响及原因.结果表明:随着薄膜厚度的增加,薄膜的晶化程度提高,晶粒尺寸增大,导电性能提高,而透光率呈现逐渐减小的趋势.当薄膜厚度为557 nm时,薄膜的电阻率最小,为0.16 Ω·m.薄膜厚度在56~340 nm之间时,薄膜的透光率在76%以上,而当薄膜厚度继续增加时,透光率下降到低于62%.     

纳米Al2O3分离富集环境样品中的铊

 研究了纳米Al₂O₃对铊的吸附性能,考察了吸附热力学,最佳酸度和吸附容量.实验结果表明:在最佳pH条件下,铊定量、快速地被吸附在纳米Al₂O₃材料上;其2,20,40 ℃时最大吸附容量分别为4.44, 5.78, 6.28 mg·g^-1;等温吸附线呈现可逆的Langmuir吸附形式.吸附反应的焓变ΔH⁰和熵ΔS⁰均为正值,ΔG⁰为负值,说明该过程是自发的吸热反应.被吸附在纳米Al₂O₃上的金属离子能采用1.00 mL 0.25 mol·L^-1 HCl溶液定量洗脱, 其回收率达到98%.该法对铊的检出限为0.84 μg·L^-1,相对标准偏差(RSD)为2.4%, 已成功地应用于实际水样和多金属结核样品GBW07296的测定,分析结果令人满意.     

基于Pt-Au-MoS2-ITO传感器对于H2O2的还原检测

实验探究了二硫化钼（MoS₂）作为一种新型材料与贵金属纳米粒子金（Au）、铂（Pt）的复合基底对于过氧化氢（H₂O₂）的还原性检测,采用氧化铟锡导电玻璃（ITO）作为电极,制备出了基于Pt-Au-MoS₂-ITO的生物传感器,为H₂O₂还原性检测的便携性操作打下了基础.实验采用电化学沉积的方法制备材料,同时使用循环伏安（CV）法、计时电流法等传统电化学手段表征了传感器电化学性能,采用场发射扫描电子显微镜（FE-SEM）来表征传感器表面形貌.建立了用于H₂O₂还原检测的、具有高检测限、高灵敏度和宽检测范围的传感器.     

热处理温度对TiO2薄膜光催化活性影响的研究

 采用溶胶-凝胶法及浸渍提拉法,在普通玻璃载玻片上制得了TiO₂薄膜,通过差热分析仪及X射线衍射仪分析了热处理温度对TiO₂的晶型、晶粒大小、孔隙率及薄膜的光催化活性的影响,结果表明存在一个最佳的热处理温度范围,在这一温度范围内薄膜的光催化活性最好.     

TiO2/CB-NiCo2O4修饰玻碳电极的制备及其对葡萄糖的电化学测定

利用低温下的水化学生长法合成了镍钴氧化物（NiCo₂O₄）纳米针,因其自组装而表现出立方晶相,再用二氧化钛/炭黑（TiO₂/CB）对NiCo₂O₄表面进行了改性,合成了TiO₂/CB-NiCo₂O₄复合纳米材料.用X射线光电子能谱仪（XPS）、扫描电子显微镜（SEM）、能量色散X射线光谱仪（EDX）图谱对材料的形貌进行了表征,运用循环伏安法（CV）、时间-电流（i-t）曲线法考察了TiO₂/CB-NiCo₂O₄修饰玻碳电极的电化学行为.实验发现：TiO₂/CB-NiCo₂O₄修饰电极对葡萄糖的氧化有良好的电催化性能,其线性范围为0.001~1.780 mmol·L^-1,检测限为0.53 μmol·L^-1（信噪比S/N=3）.将该法用于实际样品中葡萄糖的测定,结果令人满意.     

杭州市2014年城区大气污染物浓度变化特征观测分析

为了研究杭州市城区大气污染物的浓度变化特征,本文选取了2014年杭州市环境监测中心站空气质量自动监测站的大气污染物浓度数据,并结合地面气象要素资料进行分析,结果表明,在观测期间,杭州市城区大气中的PM_2.5污染状况最严重,日平均浓度的超标率达30.7%;各污染物全年分布呈现明显的季节变化：O₃浓度呈现与该季节气温和太阳辐射强度在全年中的排列相一致的夏、秋、春和冬季依次递减的分布,NO₂则呈现冬高夏低,春秋介于两者之间的分布,SO₂浓度从高到低依次为冬季>春季>秋季>夏季,CO、PM_2.5和PM₁₀浓度都呈现出冬高夏季、春秋季变化平缓的季节变化特征;各污染物浓度日变化呈现不同变化规律：O₃和O_x浓度四季的日变化都呈单峰型分布,浓度峰值都出现在13:00～15:00,SO₂也呈现单峰型分布,在09:00～10:00左右达到峰值,于次日04:00左右达到谷值,NO₂、CO、PM_2.5和PM₁₀浓度的日变化特征类似,呈现双峰型变化,且峰值都与早晚高峰时间基本重合,冬季相对于其他季节首峰值时间推迟一小时左右;利用成对样本T检验进行比较,结果表明：NO₂浓度在17:00～次日09:00工作日均明显高于周末,而在09:00～14:00工作日略低于周末,14:00～17:00浓度基本相等,O₃浓度则在工作日的各时刻均高于周末;气象要素是大气污染物分布的重要影响因子,O₃与气温和风速呈极显著正相关关系,与湿度呈极显著负相关关系,NO₂与之相反,SO₂、CO、PM_2.5和PM₁₀与风速呈现一致的显著负相关关系外,与其他气象要素在不同季节差异性较大,SO₂和PM₁₀与相对湿度呈现极显著负相关关系,CO和PM_2.5与气温和湿度的相关性在不尽相同。     

色谱法分离卵磷脂

对以硅胶为吸附剂的1. 5 cm×40 cm色谱柱分离卵磷脂的操作条件进行了研究.利用薄层层析法确定了洗脱剂的组成为甲醇/ 氯仿混合液( pH 值3~ 4) .通过洗脱方式及梯度差实验,得出梯度差为V( CH₃OH)∶V( CHCl₃) = ( 1∶2) ~ ( 2∶1)的凹形梯度洗脱为最佳洗脱方式的结论,其洗脱剂用量仅为柱体积的5~ 6倍,洗脱时间为6 h 左右.     

Modification and investigation of silica particles as a foam stabilizer

As a solid foam stabilizer, spherical silica particles with diameters ranging from 150 to 190 nm were prepared via an improved Stöber method and were subsequently modified using three different silane coupling agents to attain the optimum surface hydrophobicity of the particles. Fourier transform infrared (FTIR) spectra and the measured contact angles were used to characterize the surface properties of the prepared particles. The foam stability was investigated by the foam drainage half-life and the expansion viscoelastic modulus of the liquid film. The results demonstrate that all of the modified silica nanoparticles effectively improve the foam stability. The surface hydrophobicity of the modified particles is found to be a key factor influencing the foam stability. The optimum contact angle of the particles lies in the approximate range from 50° to 55°. The modifier molecular structure used can also influence the stabilizing foam property of the solid particles. The foam system stabilized by (CH₃)₂SiCl₂-modified silica particles exhibits the highest stability; its drainage half-life at maximum increases by 27% compared to that of the blank foam system and is substantially greater than those of the foam systems stabilized by KH570- and KH550-modified particles.     

Synthesis of new bis-diphenyl-22-and diphenyl-11-membered ring N-pivot lariat crown ethers

Bis-diphenyl 22 and 11-Membered Ring N-pivot lariat Crown Ethers^[1,2] were prepared by one step reaction of 2,2′-dihydroxy-diphenyl with N-tosyl-diethanolamine ditoskylate in DMF at refluxing temperature under N₂, Using anhydrous potassium carbonate as condensing agent, respectirely. The tosyl group of (1,2) were removed by treatment with 40% HBr in AcoH in the presence gf a large amount of phenol to give correspondence crown ether compounds (3,4). New N-pirot lariat crown thers (5,6) were prepared by one step reaction of (3) with RBr (R=?CH₂CH=CH₂, ?CH₂(CH₂)₁₄CH₃) in CH₃CN at, refluxing temperature under N₂, Using anhydrous K₂CO₃ as condensing, agent. New N-pivot lariat croon ether(7) were prepared by one step reaction (4) withn-bromohexadecane in CH₃CN at refluxing temperature under N₂, Using anhydrous potassium carbonate as condensing agent. New compounds (1,3,5,6,7) were characterized by IR,¹H NMR, Ms and elemental analysis.     

Effect of elevated CO2 on CH4 emission

Global CH₄ emission may increase under CO₂ enrichment condition, which is projected for the future. CO₂ enrichment could affect CH₄ emission in two ways: (i) Photosynthesis of plants that also include plants in rice paddies and natural wetlands will be stimulated under CO₂ enrichment condition. CH₄ emission rate may be increased due to the accumulation of more plant biomass, root exudes and soil organic matters. (ii) Combined with other global warming forces, CO₂ enrichment may bring a change of atmospheric temperature and precipitation around the world. CH₄ emission will also be changed with the variation of the area and distribution of rice paddies and natural wetlands.     

Methane emissions from wetlands on the Qinghai-Tibet Plateau

The areal extent of cold freshwater wetlands on the Qinghai-Tibet Plateau (QTP) is estimated at 0.133 × 10⁶ km², suggesting a significant methane potential. Methane fluxes from wet alpine meadows, peatlands,Hippuris vulgaris mires and secondary marshes were 43.18, 12.96, −0.28 and 45.90 mg · m⁻² · d⁻¹, respectively based on the transect flux studies at the Huashixia Permafrost Station (HPS) from July to August 1996. Average CH₄ fluxes in the thaw season were extrapolated at 5.68 g · m⁻² according to the areal percentage of wetland areas in the Huashixia region. The CH₄ fluxes at four fixed sites, representative of similar ecosystems, ranged from −19.384–347.15 mg · m⁻² · d⁻¹, and the average CH₄ fluxes varied from 6.54 to 71.97 mg · m⁻² · d⁻¹ at each site during the observation period from April to September 1997. The CH₄ emissions at each site during the entire thaw season was estimated from 1.21 to 10.65 g · m⁻², displaying strong spatial variations. Seasonal variations of CH₄ fluxes also were observed at four sites: CH₄ outbursts occurred upon the spring thaw in May and June, CH₄ fluxes increased afterwards with rising soil temperatures. Episodic fluxes were observed in summer, which influenced the average CH₄ fluxes considerably. Annual CH₄ emissions from cold wetlands on the QTP were estimated at about 0.7–0.9 Tg based on the distribution of wetlands, representative CH₄ fluxes, and number of thaw days. The centers of CH₄ releasing were located in the sources of the Yangtze and Yellow rivers, and Zoigê Peatlands.     

多针负电晕放电的甲醛净化试验

为实现高效的甲醛净化效率，采用多针电极进行负极性直流电晕放电，研究其对甲醛的净化特性. 结果表明，增加电极针数能够提高总的电晕电流、加强放电能量、提高甲醛的净化效率. 同时，提高输入电压和减小间距也能够提高甲醛的净化效率. 此外，甲醛易溶于水，电极湿度会影响甲醛的去除效果，湿式状态下甲醛分解速率减缓，净化效率有所降低.     

Theoretical characterization of single-electron iodine-bond weak interactions in CH3…I-Y（Y=BH2,H,CH3,C2H3,C2H,CN,NC）systems

Iodine-involved single-electron halogen bonds (SEXBs) weak interactions in the systems of CH3···I-Y(Y = BH2, H, CH3, CH==CH2, C≡CH, CN, NC) were investigated for the first time using B3LYP/6-311++G(d,p) and MP2/aug-cc-pVTZ computational levels (the relativistic effective core potential basis set of Lanl2dz was used on iodine atom). The interaction energies between two moieties with basis set super-position error corrections for the seven complexes are -0.57, -1.36, -3.80, -2.17, -4.49,-6.33 and -8.64 kJ mol-1 (MP2/aug-cc-pVTZ ), respectively, which shows that SEXBs interactions are all weak. Natural bond orbital theory analysis revealed that charges flow from CH3 to the I-Y moiety. The total amount of natural bond orbital charge transfer (ΔNC) from the CH3 radical to I-Y increases in the order CH3…IBH2 < CH3…IH ≈ CH3…ICH3 ≈ CH3···IC2H3 < CH3…ICCH< CH3…ICN< CH3…INC. Atoms-in-molecules theory was used to investigate the topological properties of the bond critical points in the seven SEXB structures.     

The fluid inclusions in jadeitite from Pharkant area, Myanmar

A lot of liquid-gas and liquid-gas-solid inclusions were found in Pharkant jadeitites, northwestern Myanmar and their characteristics, geological setting and porphyroclastic jadeites with inclusions in them were described in detail. The results analyzed by Raman spectrometer showed that the component of liquid-gas phase and solid phase (daughter minerals) in fluid inclusions is H₂O + CH₄ and jadeite separately. The results indicated that Pharkant jadeitites were crystallized from H₂O + CH₄ bearing jadeitic melt which may originate from mantle. The P-T conditions in which the jadeitites were crystallized were speculated to be T ＞650℃, P ＞1.5 GPa.     

EPR and UV—vis studies of biomimetic complexes of molybdoenzyme and tungstoenzyme

The biomimetic synthesis and the study of the ca-talysis mechanism of molybdenum and tungsten oxotransfer enzyme have been attracted considerable at-tention for a long time, because the oxotransfer enzymes play an important part in the nitrogen, sulfur and carbon cycles in the biological system[1—4]. With the development of the X-ray crystallography, it is possible to determine the structure of molybdenum and tungsten enzymes. However, due to the complexity and dedicated nature of the protein…     

CO_2/CH_4在干酪根中竞争吸附规律的分子模拟

选取有机质作为研究对象,构建干酪根模型,采用巨正则系综蒙特卡罗(GCMC)方法和分子动力学方法(MD)研究不同摩尔分数、不同压力下CH_4和CO_2的气体的竞争吸附行为以及吸附引起的干酪根本体形变。结果表明:CH_4和CO_2单组分吸附时吸附量随着压力的增大而增大,CO_2吸附会在较小的压力时达到饱和,两种气体吸附符合Langmuir吸附规律,可以使用Langmuir方程进行拟合;在相同的压力和温度下,CO_2/CH_4吸附选择性会随着CO_2摩尔分数的增大而减小,CO_2更易被干酪根吸附;干酪根与CO_2有较强的相互作用,干酪根中不同的原子对吸附起着不同的作用;低压阶段吸附是引起体积应变的主要原因,高压阶段压力对体积应变发挥明显作用。