气体电极反应动力学的薄膜旋转圆盘电极方法研究

薄膜旋转圆盘电极方法是一种常用的评价气体物质在纳米电催化剂上的反应活性的方法,但是在数据分析过程中经常忽视了气体反应物在催化剂层中到活性位点的传质可能对估算的反应动力学参数的影响.本文以氧电极反应为例,使用薄膜旋转圆盘电极研究了不同担载量Pt/C电极的氧还原活性.实验结果表明,根据Koutecky-Levich方程求算相同电位下的"表观动力学电流密度"(对Pt活性面积归一化的mA/cm2Pt)或比质量电流(mA/μg Pt)随Pt担载量的减小而增大,说明在估算动力学电流时不能忽略O2在催化剂层中的扩散传质,而气体在催化剂层中的传质与催化剂层的结构、厚度、纳米催化剂的分散度等密切相关.建议在使用薄膜旋转圆盘电极方法来研究纳米催化剂气体电极反应活性时,首先系统考察担载量、分散度与催化剂层厚的影响,然后根据不同担载量催化剂归一化后的动力学电流密度(或比质量电流)-电势曲线是否重合来验证得到的是否是真实的动力学电流,从而得到更为准确的评价结果.     

浊度干扰下硝酸盐浓度紫外导数光谱检测方法研究

硝酸盐是水中“三氮”（硝酸盐氮、氨氮、总氮）之一,是反映水体受污染程度的一项重要指标。传统 “现场采样-离线分析” 的硝酸盐化学检测方法操作繁琐、耗时长,难以满足现代水环境实时在线检测需求。由于硝酸根在紫外区具有很强的紫外吸收特性,并且紫外吸收光谱法具有简便快速、可实现实时在线监测等特点,近年来被广泛用于硝酸盐浓度的测量。但使用紫外吸收光谱法检测水体硝酸盐含量时,容易受到水体浊度影响,造成谱线非线性抬升,导致测量误差。目前对浊度补偿算法的研究大都用于水中COD含量的检测,对硝酸盐检测中浊度干扰去除研究较少。为此提出一种基于一阶导数紫外吸收光谱的硝酸盐浓度测量方法,该方法可以减小浊度干扰,从而提高紫外光谱快速检测硝酸盐含量的准确度。通过测量福尔马肼与硝酸钠标准溶液和它们混合溶液在190~300 nm波段的紫外吸收光谱并做一阶导数光谱处理,处理后的光谱采用Savitzky-Golay滤波进行去噪平滑处理,比较浊度与硝酸盐紫外吸收一阶导数光谱特征,分波段研究浊度对硝酸盐紫外一阶导数光谱影响,结果表明硝酸盐导数光谱在220~230 nm波段受浊度影响小;选取220~230 nm波段作为光谱分析区间,以30种不同浓度混合的福尔马肼与硝酸钠溶液作为训练样本,利用偏最小二乘算法建立硝酸盐定量分析模型,使用该建模模型预测剩下的6种不同浓度福尔马肼与硝酸钠混合溶液中硝酸盐的浓度,结果表明福尔马肼干扰下硝酸盐测量结果的预测决定系数（correlation coefficient,R2）为0.994 3,预测均方根误差（root mean square error of prediction,RMSEP）为0.346 9 mg·L-1。为进一步验证该方法的准确性与稳定性,使用该建模模型预测高岭土与硝酸钾配制的混合水样中硝酸盐的浓度,结果表明该方法对高岭土干扰下硝酸盐测量结果的预测决定系数r2为0.991 5,预测均方根误差RMSEP为0.362 8 mg·L-1。综上所述,提出的硝酸盐浓度紫外导数光谱检测方法,采用220~230 nm波段的紫外导数光谱数据,结合PLS建模,可以快速准确测量在浊度干扰下水体硝酸盐的浓度,为发展实际水体硝酸盐在线监测技术与设备提供方法基础。     

一种基于三维激光点云数据的单木树冠投影面积和树冠体积自动提取算法

树冠投影面积和树冠体积是研究单木生物量估测、三维绿量测算等的重要测量因子。针对树冠结构复杂、形态各异,树冠因子难以精确测量等问题,为实现单木树冠投影面积和树冠体积的自动提取和精准测量,以三维激光扫描获取的树木点云数据为数据源,运用平面散乱点集凸包算法——Graham扫描算法和不规则体切片分割累加算法,以VC++6.0和Matlab 7.0混合编程,实现树冠投影面积和树冠体积的自动提取。以实验区选取具有代表性的22株不同树种的样木为研究对象,并与传统人工测量方法进行了对比分析。试验结果表明,树冠投影面积人工测量(A₄)结果与点云数据的自动计算(A_V)结果相关性较好,r=0.964(p<0.01),A₄高于A_V的平均值为25.5%。近似规则几何体方法树冠体积测量(V_C)结果与基于点云数据的自动计算(V_VC)结果之间呈现较强的相关性,r=0.960(p<0.001),V_C低于V_VC的平均值为8.03%。该方法基于高精度单木点云数据,实现了树冠结构的高精度快速重构、单木树冠投影面积和树冠体积的无损自动提取,可以为单木树冠结构的研究提供参考,在精准林业领域具有推广应用价值。     

二氧化钛分子电致发光激发特性研究

采用密度泛函B3P86方法优化得到了沿分子平面不同外电场作用下TiO₂分子的基态稳定构型, 在优化构型下利用杂化CIS (CI-Singles)-B3P86方法在6-311＋G*基组水平上, 研究了不同外电场下TiO₂分子前六个激发态的激发能和跃迁波长等激发特性. 研究结果表明, TiO₂分子多个激发态满足偶极跃迁定则, 跃迁光谱对应多个峰值, 在分子水平上, 可以增大利用太阳光的比例. 在外电场作用下, 能隙随电场的增大而减小, 电子易从最高占据轨道跃迁到最低空轨道形成空穴, 各个激发态跃迁波长均有随电场增大发生红移的趋势, 最长589 nm, 因而利用外电场可以控制材料的发光光谱范围在可见光区域扩展.     

线偏振周期量级脉冲中H-强场光解离的不对称性

Photodetachment of H^- irradiated by linearly polarized few-cycle laser field is investigated by time-dependent Schr?dinger equation numerically. The photo-electron left-right asym-metry parameter as a function of carrier-envelop (CE) phase of few-cycle pulses is attained. We confirm the asymmetry of photoelectron distribution in H^- photodetachment and find that the maximal asymmetry parameter of H^- is equal to that of H atom under the same conditions but the corresponding CE phases are quite different. Thus a CE phase shift ap-pears. Compared to that of H atom and field free electron, the zero asymmetry CE phase shift is sensitively affected by Coulomb field. The Coulomb effect on the asymmetry of H^- photodetachment mainly behaves in the CE phase shift of H^- instead of the amplitude of asymmetry parameter curve.     

Theoretical and experimental study of Chen chaotic system with notch filter feedback control

Since the past two decades, the time delay feedback control method has attracted more and more attention in chaos control studies because of its simplicity and efficiency compared with other chaos control schemes. Recently, it has been proposed to suppress low-dimensional chaos with the notch filter feedback control method, which can be implemented in a laser system. In this work, we have analytically determined the controllable conditions for notch filter feedback controlling of Chen chaotic system in terms of the Hopf bifurcation theory. The conditions for notch filter feedback controlled Chen chaoitc system having a stable limit cycle solution are given. Meanwhile, we also analysed the Hopf bifurcation direction, which is very important for parameter settings in notch filter feedback control applications. Finally, we apply the notch filter feedback control methods to the electronic circuit experiments and numerical simulations based on the theoretical analysis. The controlling results of notch filter feedback control method well prove the feasibility and reliability of the theoretical analysis.     

Weak Noether symmetry for a nonholonomic controllable mechanical system

This paper discusses the weak Noether symmetry for a nonholonomic controllable mechanical system of Chetaev type, and presents expressions of three kinds of conserved quantities obtained by using weak Noether symmetry. Finally, the application of these new results is illustrated by an example.     

紫外光和可见光对Fe3O4掺杂的TiO2催化降解有机物的影响

基于TiO2光催化剂的催化机理尚不明确, 因此发展一种具有不同波段的光催化材料对光催化机理的研究至关重要. 本文采用溶胶-凝胶方法合成了一个Fe3O4掺杂的金红石型TiO2复合物, 通过红外、粉末衍射以及扫描电镜对其结构进行了表征. 紫外-可见吸收光谱表明, 无论在可见光或者是紫外光的照射下, 它都表现出良好的光催化性能, 说明Fe3O4掺杂对改善TiO2的催化性能有一定影响.     

Parallel generation of 31 tripartite entangled states based on optical frequency combs

Quantum entangled states, especially those having particular properties, are key resources for quantum information and quantum computation. In this paper, we put forward a new scheme to produce 31 continuous–variable(CV) tripartite entanglement fields based on three optical frequency combs via cascade nonlinear processes in an optical parametric cavity,and investigate the spectral characteristics of three frequency combs. The center wavelengths of the three combs are designed as 852 nm, 780 nm(atomic transition lines), and 1550 nm(fiber communication wavelength). The positivity under partial transposition(PPT) criterion, which is sufficient and necessary, is used to evaluate the entanglement in each group of comb lines. This scheme is experimentally feasible and valuable for constructing quantum information networks in future.