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1.
现场拉曼光谱研究非水体系中铂电极上甲醇的解离吸附   总被引:1,自引:0,他引:1  
本文在共焦显微拉曼系统上 ,利用表面增强拉曼散射效应 ( SERS)初步研究了非水体系中甲醇在粗糙铂电极上的解离吸附过程。结果表明 :甲醇在粗糙铂电极上解离吸附后产生了毒性中间物 CO,在较负的电位区间内 ,H与 CO共吸附于电极表面并影响 CO的吸附行为 ,随电位的正移 ,υPt- C和 υC- O的变化可以用电化学 Stark效应来进行解释。  相似文献   

2.
非水乙腈体系中CO在铂电极表面吸附的SERS研究   总被引:2,自引:0,他引:2  
在非水乙腈体系中,借助LabRam Ⅰ型共焦显微拉曼系统,尝试用表面增强拉曼光谱(SERS)对作为燃料电池中毒化中间体的CO在过渡金属铂电极表面的催化氧化进行了研究,并考察了在电极电位的变化过程中CO的催化氧化与周围环境分子的相互作用。不仅观察到CO在铂金属表面的吸附和氧化,还得到溶剂乙腈分子发生解离的表面增强拉曼光谱,并对CO和CH3CN分子在铂电极上的竞争吸附进行了分析。  相似文献   

3.
现场拉曼光谱研究乙腈在金电极上的解离吸附行为   总被引:2,自引:1,他引:1  
利用共焦显微拉曼系统、结合合适的电极表面粗糙方法研究了非水体系 0 1mol/LLiClO4 /CH3CN溶液中 ,乙腈分子在金表面的吸附和解离行为。结果表明非水体系中乙腈可在金表面发生还原反应 ,产物CN- 离子与电极表面作用形成的表面配合物可在较宽的电位区间吸附于电极表面。溶液中的微量水、激光照射以及电极电位均对该反应有较大的影响。通过拉曼谱图的比较得出乙腈分子解离出的CN- 在金电极表面比在银电极表面有更强的吸附作用。  相似文献   

4.
吸附在铂电极上茄尼醇分子的SERS研究   总被引:2,自引:1,他引:1  
本文首次报道了茄尼醇分子的常规拉曼光谱 (RRS)及该分子在铂电极上的表面增强拉曼散射(SERS)谱 ,并对它的谱带进行了初步指认。从其常规拉曼光谱和SERS谱的对比和分析推断 ,茄尼醇分子是通过CC等键吸附在铂电极表面的。这种分子RRS和SERS谱的明显差异表明 ,该分子与铂电极表面发生了强的相互作用。这种相互作用对吸附在铂电极上的茄尼醇分子结构发生了很大的扰动。  相似文献   

5.
硫脲在铂电极表面吸附行为的表面增强拉曼光谱研究   总被引:2,自引:0,他引:2  
本文通过电化学方法有效抑制了硫脲在铂电极表面的解离,从而实现了用SERS技术研究粗糙铂电极表面硫脲的吸附行为。结果表明,硫脲分子是以硫端斜躺吸附在电极表面,随着电位变负渐渐转为直立。  相似文献   

6.
利用分子动力学模拟研究油水分子在方解石和白云石表面的吸附,分析体系的平衡构型、相对浓度、径向分布函数和吸附能,研究方解石和白云石的亲水性并对比二者差异.根据油水分子吸附规律分析方解石/白云石-油水体系作用机理.研究表明:白云石-油水体系更易达到热力学稳定状态并且体系更加稳定;方解石和白云石表面均能够优先吸附水分子并在表面形成双层结构的水膜.其中,白云石表面对水分子吸附强度大于方解石;稳定吸附过程分为两步:范德华力、静电力和O(CaCO3,CaMg(CO32)-H(H2O)氢键共同影响下水分子向晶体表面移动并吸附形成紧密吸附层;O(H2O)-H(H2O)氢键作用下游离的H2O向晶体表面靠近形成扩散层.从分子尺度解释方解石/白云石亲水特性,为碳酸盐岩储层润湿性研究奠定理论基础.  相似文献   

7.
利用循环伏安法研究了酸性介质中甲醛在粗糙铂电极上电氧化行为 ,考察了支持电解质浓度 ,电极表面结构等因素对甲醛氧化行为的影响 ,发现了甲醛在粗糙铂电极上的自发解离现象。采用共焦显微拉曼技术研究了甲醛在粗糙铂电极上解离吸附行为 ,获得了甲醛在该电极表面解离吸附的分子水平信息 ,并且从分子水平验证了甲醛在粗糙铂电极上的自发解离现象。  相似文献   

8.
甲酸在铂钌电极上电催化氧化的原位SERS研究   总被引:2,自引:2,他引:0  
采用循环伏安法和电化学原位表面增强拉曼光谱(in-situ SERS)技术研究了甲酸在铂钌电极上解离吸附与氧化行为。发现甲酸在铂钌电极上也能自发解离吸附。铂钌电极上CO的氧化峰电位与粗糙铂电极相比负移了180mV,把CO氧化完毕的电极电位亦负移了300 mV,从分子水平证实铂钌电极对甲酸电催化氧化的活性比纯铂电极更高。该研究结果表明,SERS技术可望拓展为研究电催化体系的有效工具。  相似文献   

9.
运用广义梯度密度泛函理论(GGA)的PW91方法结合周期平板模型研究了H2O在CuCl (111)表面上的吸附及分解. 通过构型优化参数的计算和比较发现:对于O和OH,三重穴位吸附较为稳定,吸附能分别为309.5和416.5 kJ/mol;水分子与预吸附氧的表面作用时分解成为OH,并放热180.1 kJ/mol. 同时对于吸附前后的吸附O与表面Cu的伸缩振动频率、态密度以及吸附质与底物的电荷转移情况进行了计算和分析,并给出了可能的分解反应机理.  相似文献   

10.
He Q  Li S  Yu DN  Zhou GM  Ji FY  Subklew G 《光谱学与光谱分析》2010,30(12):3249-3253
联合FTIR,FT-拉曼表征了乐果的振动光谱,获得了固态及不同酸碱条件下饱和液态乐果的振动特征信息;以金/银核-壳复合粒子为基底,获得了乐果在酸碱条件下一系列浓度的表面增强拉曼散射(SERS)光谱,考察了乐果分子在该基底表面的吸附状态及其酸碱影响,推测了乐果与金/银核-壳复合粒子作用机理;结果表明:νas(NH),νas(CH3),ν(O=C-N),τ(O=C-N),ν(P—O),ν(P S),ν(C—C),δ(P—O—C)为乐果分子特征振动;酸、碱条件下,在1.0×10-3mol.L-1为乐果与基底作用的最佳浓度;乐果主要以P—O—C,O=C-C,(S—CH2),P=S,CH3与金/银核-壳复合粒子基底相作用,探讨了酸碱条件下磷酸酯键不同离解历程对吸附的影响。为研究有机磷农药的形态变化提供有益参考。  相似文献   

11.
Total internal reflection fluorescence (TIRF) spectroscopy was used to investigate the adsorption behavior of meso-tetrakis(p-sulfonatophenyl)porphyrin (TPPS) at the glass/water interface in the presence of a cationic surfactant (cetyltrimethylammonium bromide, CTAB) far below the critical micelle concentration. The adsorption model of TPPS at the glass/water interface in the presence of low concentration of CTAB was proposed, which was different from the adsorption of TPPS in the presence of micelles of CTAB at the glass/water interface. TPPS and CTAB did not form stable complex at the interface in dilute system. The interfacial species of TPPS were analyzed by comparing the spectra of TPPS at the glass/water interface and in the aqueous phase. The influences of the TPPS concentration, the CTAB concentration, and the pH values on the interfacial fluorescence spectra and intensities were studied. It was demonstrated that electrostatic interaction and hydrophobicity performed an important role on the adsorption of TPPS in the presence of CTAB. The different effects of TPPS concentration on the adsorption behaviour of TPPS at different pH were observed for the first time. It was found that the adsorption isotherms of TPPS at glass/water interface could fit Freundlich equation at pH 7.1.  相似文献   

12.
继非水体系中CO在过渡金属表面吸附的表面增强拉曼光谱(SERS)研究之后,本文是又一篇关于非水体系中过渡金属表面SERS研究的文章。从拉曼谱峰的变化结果发现,吡啶在Pt电极表面是强烈的化学吸附,并且由于其吸附的量和吸附取向随电位在不断地变化,与水体系中吡啶(Py)在Pt电极表面的吸附相比较,SERS谱峰除了强度较低之外,在可研究的电位区间、谱峰位置以及其随电位变化等方面都存在着不同,这缘于结构较为复杂的有机溶剂分子在电极表面组成了更为复杂的界面结构,造成固/液界面的电迁移等电极动力学过程发生了变化,为了说明这一现象,文中还采用强吸附离子I^-进行研究,得到相似的结果。  相似文献   

13.
非水体系表面增强拉曼光谱研究   总被引:1,自引:1,他引:0  
自七十年代中期表面增强拉曼散射(SERS)现象发现以来,SERS技术由于其高的表面检测灵敏度等为人们在分子水平认识贵金属/溶液界面提供了丰富的信息。然而,已有的SERS光谱研究绝大多数均是在水体系中进行的,无疑限制了SERS的研究范围[1]。此外,由...  相似文献   

14.
表面增强拉曼光谱在非水体系中的研究进展   总被引:2,自引:0,他引:2  
本文论述了表面增强拉曼光谱(SERS)在非水体系中的研究历史、现状及应用前景,系统阐述了非水体系固/液界面结构、无机离子和有机分子的吸附以及非水电极过程方面SERS技术的研究进展。  相似文献   

15.
The adsorption of silica nanoparticles onto representative mineral surfaces and at the decane/water interface was studied. The effects of particle size (the mean diameters from 5 to 75?nm), concentration and surface type on the adsorption were studied in detail. Silica nanoparticles with four different surfaces [unmodified, surface modified with anionic (sulfonate), cationic (quaternary ammonium (quat)) or nonionic (polyethylene glycol (PEG)) surfactant] were used. The zeta potential of these silica nanoparticles ranges from ?79.8 to 15.3?mV. The shape of silica particles examined by a Hitachi-S5500 scanning transmission electron microscope (STEM) is quite spherical. The adsorption of all the nanoparticles (unmodified or surface modified) on quartz and calcite surfaces was found to be insignificant. We used interfacial tension (IFT) measurements to investigate the adsorption of silica nanoparticles at the decane/water interface. Unmodified nanoparticles or surface modified ones with sulfonate or quat do not significantly affect the IFT of the decane/water interface. It also does not appear that the particle size or concentration influences the IFT. However, the presence of PEG as a surface modifying material significantly reduces the IFT. The PEG surface modifier alone in an aqueous solution, without the nanoparticles, yields the same IFT reduction for an equivalent PEG concentration as that used for modifying the surface of nanoparticles. Contact angle measurements of a decane droplet on quartz or calcite plate immersed in water (or aqueous nanoparticle dispersion) showed a slight change in the contact angle in the presence of the studied nanoparticles. The results of contact angle measurements are in good agreement with experiments of adsorption of nanoparticles on mineral surfaces or decane/water interface. This study brings new insights into the understanding and modeling of the adsorption of surface-modified silica nanoparticles onto mineral surfaces and water/decane interface.  相似文献   

16.
The autoxidation of vitamin C has been studied in acetonitrile by electronic spectroscopy. Some interesting data on the role of acetonitrile in autoxidation have been obtained, perhaps for the first time. A parallelism between hydroxyl ions and CH2CN, the ions from the self-ionization of acetonitrile, has been established. The CH2CN anion is similar to hydroxyl anions in initiating and propagating the decomposition of ascorbic acid, at least in this system. The intermediates involved in the overall reaction in nonaqueous media have been identified by simple means.__________Published in Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 2, pp. 274–276, March–April, 2005.  相似文献   

17.
We have established a model for the water forming reaction on Pd in the temperature range 350–475 K. Importantly, the model takes into account the possibility that hydrogen may absorb and adsorb at interface sites on supported Pd catalysts. It is shown that already at modest conditions interface adsorption may significantly affect reaction rates. The model may also be used to quantify the response of a hydrogen sensitive Pd-MOS device during hydrogen sensing in oxygen. In the case of Pd supported on SiO2, the concentration of interface sites is so low that interface hydrogen adsorption will have only a minor influence on a catalytic reaction. The fact that a Pd-MOS device may be used as a very sensitive hydrogen detector at atmospheric oxygen conditions, despite a steric oxygen blocking of hydrogen dissociation sites, is predicted by the model.  相似文献   

18.
We present an experimental study of the adsorption of hydrophobic highly charged polyelectrolytes on a neutral and hydrophobic surface, the air/water interface. The polymer was a randomly sulphonated polystyrene with charge fractions between 0.3 and 0.9 and the adsorbed layers were characterised by Langmuir through measurements, ellipsometry and X-ray reflectivity. The adsorption rate is always very slow and the resulting layers are very thin (< 3 nm). A maximum of adsorption with the charge fraction is observed which we relate to the conformation of the chains in solution. We show that adsorption is partially irreversible, strongly hysteretic and that the state of an adsorbed layer depends on its history. Received 16 June 2000  相似文献   

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