SILAR法制备TiO2/CdS/Co-Pi水氧化光阳极及其性能

采用连续离子层吸附法（SILAR）沉积CdS制备type-Ⅱ异质结TiO₂/CdS光阳极,用光电化学沉积法在TiO₂/CdS表面沉积催化剂（Co-Pi）得到TiO₂/CdS/Co-Pi水氧化光阳极。通过X射线衍射（XRD）仪、扫描电子显微镜（SEM）、X射线光电子能谱（XPS）仪等对样品结构及组成进行分析,证明CdS与Co-Pi已成功负载在TiO₂表面。用已制备的光阳极在中性溶液中模拟水氧化测试,在较低外偏压（0 V（vs Ag/AgCl））和无电子牺牲剂的情况下,即使在可见光照射下,依然得到较高的初始光电流和稳定光电流,分别为1.3和0.5 mA·cm^-2,表明制备的光阳极可以在可见光照下有效地驱动水氧化反应。光电化学池的工作原理为,CdS吸收光子产生光生电子-空穴,TiO₂和Co-Pi分别传输电子和空穴,空穴进行水氧化,电子转移到阴极完成质子还原。     

可见/近红外光谱的油茶籽油三元体系掺假检测模型优化

采用可见/近红外光谱技术结合化学计量学方法对油茶籽油三元体系掺假进行定量检测研究。将菜籽油和花生油按不同比例掺入纯油茶籽油中,获得掺假样本。采集纯油茶籽油及掺假样本在350~1 800 nm范围内的可见/近红外光谱数据,随机分为校正集和预测集,并从不同建模波段、预处理方法及建模方法角度对掺假预测模型进行优化。研究结果表明,菜籽油、花生油和总掺伪量的最优建模波段及预处理方法分别为750~1 770,900~1 770 ,870~1 770 nm和多元散射校正(MSC)、标准归一化处理(SNV)和二阶微分,而最优的建模方法均为最小二乘支持向量机(LSSVM)。对于最优掺假模型,菜籽油、花生油和总掺伪量的预测集相关系数(R_p)和预测均方根误差(RMSEP)分别为0.963,0.982,0.993和2.1%,1.5%,1.8%。由此可见,可见/近红外光谱技术结合化学计量学方法可以用于油茶籽油的三元体系掺假定量检测。     

可见光-近红外光谱的矽卡岩型铁矿反演模型

铁矿资源是我国国民经济基础产业中的重要组成要素,在我国经济发展中有举足轻重的地位。铁矿品位的检定效率对铁矿石开采效率有重大影响。目前,铁矿石品位的化学分析检定法,不仅存在成本较高,化验周期长的问题,更主要的是其无法实现铁矿品位原位测定,相对配矿流程存在滞后效应,无法有效降低矿石开采的损失贫化率;基于可见光-近红外光谱分析的铁矿品位原位测定技术是解决这一问题的有效途径。以225个红岭矽卡岩型铁矿测试样本的可见光-近红外光谱数据及化学分析数据为数据源,首先对原始数据进行了平滑处理,并分析了矽卡岩型铁矿可见光-近红外光谱特征,然后利用倒数对数、多元散射校正（MSC）两种预处理方法对平滑后的光谱数据进行处理,再分别以主成分分析法（PCA）、遗传算法（GA）两种降维算法对预处理前后的光谱数据进行了处理,获取了六种不同预处理组合算法处理后的数据源。其中以PCA降维算法所降维数分别为3维、3维、7维;以GA降维算法所降维数分别为477维、489维、509维。最后基于随机森林（RF）和极限学习机（ELM）建立了矽卡岩型矿石金属铁品位的定量反演模型,以决定系数（R2）、均方根误差（RMSE）和平均相对误差（MRE）三个指标分别对模型的稳定性、精确度、可信度进行评价。结果表明,经MSC处理及PCA降维后的数据基于ELM算法建立的定量反演模型效果最优,其R2可达0.99、RMSE为0.005 7、MRE为2.0%,该方法所建模型对红岭矽卡岩型铁矿品位反演精度有明显的提升。对矽卡岩铁矿品位的实时、快速分析提供了一种有效的方法,对实现矽卡岩型铁矿的高效开采具有重要的现实意义。     

转基因水稻及其亲本叶片的可见/近红外光谱分析

应用可见/近红外光谱技术实现了转基因水稻叶片的快速识别和叶绿素含量(SPAD)的快速检测。建立偏最小二乘-支持向量机(LS-SVM)鉴别模型,校正集的正确率为100%,同时应用连续投影算法(SPA)提取有效波长,建立SPA-LS-SVM鉴别模型,只用了全变量的0.3%进行建模,其预测集的正确率达到87.27%。在定量分析中,各模型的最优结果均来自经过正交信号校正(OSC)的光谱数据,经过SPA处理后的模型均优于最优的全波段PLS模型,说明SPA是一种有效的波长选择方法。最优SPAD值预测模型为SPA-LS-SVM,其相关系数(r)和预测均方根误差(RMSEP)分别为0.902 2和1.312 1,获得了满意的结果。这说明提出的SPA-LS-SVM方法能快速识别转基因水稻叶片并对SPAD值进行准确预测,为实现大田活体鉴别与连续监测提供了新方法。     

Preparation of Cu-doped Cd0.1Zn0.9S solid solution by hydrothermal method and its enhanced activity for hydrogen production under visible light irradiation

A series of Cu-doped Cd_0.1Zn_0.9S solid solution with various amounts of Cu dopant was successfully prepared by hydrothermal method. The properties and the photocatalytic activity of the prepared samples for hydrogen production under visible light irradiation were compared to those prepared by co-precipitation method. The Cu-doped Cd_0.1Zn_0.9S samples prepared by hydrothermal method showed both improved crystallinity and photoabsorption ability as compared to the undoped sample. On the other hand, even though Cu-doped Cd_0.1Zn_0.9S prepared by co-precipitation method also showed improved photoabsorption ability in the visible light region, the samples showed poor crystallinity compared to the undoped one. With the same amount of Cu dopant, all samples prepared by hydrothermal method were found to exhibit higher photocatalytic activity for hydrogen production than the samples prepared by co-precipitation method. It was revealed that the amount of Cu dopant, crystallinity and narrow band gap energy are important factors to obtain highly active and stable photocatalysts.     

基于可见-近红外光谱技术的水稻穗颈瘟染病程度分级方法研究

采用Vis-NIR技术对水稻穗颈瘟染病程度分级方法进行了研究。分别基于原始光谱,变量标准化(SNV)预处理后和多元散射校正(MSC)预处理后的光谱,应用无信息变量消除法(UVE)结合连续投影算法(SPA)对Vis-NIR光谱区进行有效波长的选择。选择后的波长作为输入变量建立最小二乘-支持向量机(LS-SVM)模型。结果表明SNV-UVE-SPA建立的LS-SVM模型预测效果最好。通过SNV-UVE-SPA从全波段600个波长中选择了6个最能够反应光谱信息的波长(459, 546, 569, 590, 775和981 nm)。SNV-UVE-SPA-LS-SVM组合模型对预测集样本预测得到的确定系数(R2_p),预测集的预测标准差(RMSEP)和剩余预测偏差(RPD)分别达到了0.979,0.507和6.580。结果表明,采用Vis-NIR光谱技术对水稻穗颈瘟染病程度进行分级是可行的。通过UVE-SPA得到的有效波长能够很好地代替全波长。     

颗粒系的可见消光光谱分析及最佳波长的选择

在光全散射法颗粒粒径测量中,被测颗粒系的消光光谱包含有颗粒粒径、折射率等信息。对常用的单峰及双峰R-R分布的可见消光光谱进行模拟,分析了可见消光光谱随粒径和相对折射率变化的规律。选取二阶微分可见消光光谱不连续点对应的波长作为测量波长,并将可见光边界波长同时作为测量波长,在非独立模式下,采用遗传优化算法反演粒径分布。仿真计算与实验验证结果表明,通过消光光谱分析,可以预先确定被测颗粒系的分布状况,缩小优化算法中反演参数的搜索范围。结合最佳波长选择方法,使测量的精度和可靠性明显提高。对测量光谱加入1%随机噪声时,单峰及多峰分布粒径反演均能得到满意的结果。     

Singlet-triplet excitation ratios in Ne III, Ar III and N II under ion impact

Peculiar properties of ion-atom collision systems, in particular deviations from statistical populations of singlet and triplet levels, can be studied by optical spectroscopy. We have extended earlier studies by VUV spectroscopy of a number of collision systems at various collision energies in the 0.01-MeV/nucleon to 1-MeV/nucleon range, involving H₂ ⁺, H⁺, He⁺, He²⁺, Ne⁺, Ar⁺, and N₂ ⁺ as projectiles and Ne, Ar, and N₂ as target gases. Statistically significant deviations of the relative intensities of singlet and triplet lines from simple ratios are observed in the displaced terms of the valence shell of Ne III, corroborating and extending earlier work. For Ar III, the energy dependences of singlet-to-triplet excitation ratios are very different for different projectiles. For N II, in contrast, all observed line ratios are practically independent of the projectile energy. Received 17 November 2000 and Received in final form 31 January 2001     

Positronium formation at low temperatures: the role of trapped electrons

Measurements have been carried out of electron spin densities (by electron spin resonance technique) and positronium (Ps) formation probability as functions of Co-60 γ-irradiation dose in poly(methyl methacrylate) and linear poly(ethylene) at 77 K. We observe a linear relationship between the enhancement of the Ps formation and the density of trapped electrons in both polymers. This clear correlation strongly supports the previous suggestion by the authors that the increase in Ps formation with time (that has been observed at low temperatures for a number of polymers) can be explained as a reaction of free positrons with trapped electrons produced by the previously injected positrons.