Pt及其修饰电极上甲醇吸附和氧化的CV和EQCM研究

运用电化学循环伏安和石英晶体微天平 (EQCM )研究了 0 .1mol·L- 1H2 SO4 溶液中甲醇在Pt电极和以Sb ,S不可逆吸附原子修饰的Pt(Pt/Sbad和Pt/Sad)电极上的吸附和氧化过程 .结果表明甲醇的氧化与电极表面氧物种有着极其密切的关系 .Pt电极表面Sb吸附原子能在较低的电位下吸附氧 ,可显著提高甲醇电催化氧化活性 .与Pt电极相比较 ,Sb吸附原子修饰的Pt电极使甲醇氧化的峰电位负移了 0 .13V .相反 ,Pt电极表面S吸附原子的氧化会消耗表面氧物种 ,抑制了甲醇的电氧化 .本文从表面质量变化提供了吸附原子电催化作用的新数据     

电化学粗糙银电极表面上共吸附体系的SERS研究

自1974年发现表面增强喇曼散射(SERS)光谱以来,人们不但对其进行实验和理论上的探讨,还开展了应用方面的研究,如用于痕量分析、催化和腐蚀等,并已开始用于研究物质的吸附状态以及多物种共存体系。本文通过对吡啶、苯甲酸共存体系的SERS谱及其随外加电位变化的实验研究,运用镜像场等理论探讨了在电化学粗糙银电极表面上吡啶和苯甲酸共存体系中的吸附状态。     

铂纳米粒子电极上NO吸附和还原的CV及原位FTIR研究

运用电化学循环伏安法(CV)和原位傅里叶变换红外反射光谱(in situ FTIRS)研究了酸性介质中铂纳米粒子电极(nm-Pt/GC)上NO吸附及其电催化还原过程.结果表明,NO分子的吸附是电催化还原的重要步骤.在铂纳米粒子电极上饱和吸附的NO存在两种不同键合强度的吸附态,其中弱吸附的NO(NOW)在0.60 V至-0.05 V电位区间还原生成N2O和NH4+;而强吸附的NO(NOS)则在-0.05 V至-0.15 V区间还原,其产物为NH+.     

吸附态和溶液相CO在Pt(110)电极上氧化过程的CV和in situ FTIRS研究

应用电化学原位傅里叶变换红外反射光谱(in situ FTIRS)研究了酸性介质中Pt(110)单晶电极上吸附态CO(COad)和溶液相CO(COsol)的氧化过程.循环伏安测试表明,COsol氧化的峰电位比COad氧化的正移了168mV,其峰电流密度为后者的6.7倍.电化学原位红外光谱检测到CO主要生成线型的吸附态物种(COL),均匀分布在Pt(110)表面上.当溶液中不存在CO时,COL仅在电位高于0.15V才发生氧化.而且,该谱峰在其稳定吸附的电位区间内随电位增加蓝移,Stark系数为30cm-1·V-1;在COL发生氧化的电位区间,其谱峰强度随电位增加减小、峰位红移,线性变化率为-56cm-1·V-1.溶液中饱和CO时,原位红外光谱在-0.05V即可检测到CO2的存在,显示COL起始氧化的电位提前了200mV;电位高于-0.05V,该谱峰即发生红移,对应的线性变化率为-26.5cm-1·V-1.     

Pt和Sb、S吸附原子修饰的Pt电极上正丙醇氧化的CV和EQCM研究

运用电化学循环伏安法和石英晶体微天平研究了正丙醇在Pt电极和以Sb、S吸附原子修饰的Pt（Pt/Sbad和Pt/Sad）电极上的吸附和氧化过程.从电极表面质量变化角度指出正丙醇的氧化与电极表面氧物种有着极其密切的关系.Pt电极表面Sb吸附原子能在较低的电位下吸附氧，可显著提高正丙醇电催化氧化活性，与在Pt电极上相比较,正丙醇氧化的峰电位负移了0.29 V,峰电流增加了近2倍.相反,Pt电极表面S吸附原子的氧化会消耗表面氧物种，饱和吸附S原子的Pt电极上正丙醇的电氧化受到抑制.本文从表面质量变化提供了吸附原子电催化作用的新数据.     

表面增强拉曼光谱研究硫脲及其衍生物在银电极上的共吸附行为

用表面增强拉曼光谱技术研究了ＨＣｌＯ４介质中硫脲，一甲基硫脲和烯丙基硫脲在银电极表面的共吸附行为。首次报道了它们的混合物在银电极表面上竞争共吸附随电极电位变化的行以及在所研究的共吸附体系中作为支持电解的弱吸附ＣｌＯ＾－４离子被诱导物理共吸附的现象。     

中性介质中L-丝氨酸在Pt电极上解离吸附和氧化的原位FTIR研究

运用电化学循环伏安(CV)和原位红外反射光谱(in situ FTIRS)研究了中性介质中L-丝氨酸在Pt电极上的解离吸附和氧化过程. 结果表明, 在中性溶液中, 以两性离子形式存在的丝氨酸可以在很低的电位下(-0.6 V, vs. SCE)在Pt电极表面发生解离吸附, 生成强吸物种一氧化碳(COL)、(COB)和氰负离子(CN-). 研究结果还表明, 当电位低于0.7 V(vs. SCE)时, CN-能稳定存在于电极表面, 抑制丝氨酸的进一步反应. 在更高电位时则主要为丝氨酸分子的氧化过程.     

Pt及其修饰电极上乙醇吸附和氧化的CV和EQCM研究

运用电化学循环伏安和石英晶体微天平研究了乙醇在Pt电极和以Sb,S吸附原子修饰的Pt(Pt/Sbad和Pt/Sad)电极上的吸附和氧化过程。结果表明乙醇的氧化与电极表面氧物种有着极其密切的关系。Pt电极表面Sb吸附原子能在较低的电位下吸附氧,可显著提高乙醇电催化氧化活性。相反,Pt电极表面S吸附原子的氧化会消耗表面氧物种,抑制了乙醇的电氧化。本文从表面质量变化提供了吸附原子电催化作用的新数据。     

硫酸溶液中Pt电极表面过程的EQCM研究

应用电化学循环伏安和石英晶体微天平(EQCM)方法研究了0.1mol·L-1硫酸溶液中Pt电极表面的吸附和氧化过程.从电极表面质量变化的结果分析,可认为正向电位扫描时氢区表面质量的增加是由于水分子取代Had引起的,而双电层区的质量增加则是由于水的吸附模式逐渐由氢端吸附转向氧端吸附所致.根据频率变化和电量数据,进一步推算出水在双电层区是以低放电吸附形式出现的,1molPt原子和水分子只发生0.054mol的电荷转移.本文结果可为认识Pt电极表面过程提供定量的新数据.     

Pt-Sn/Pt电极对乙二醇的电催化氧化

Pt-Sn/Pt电极;乙二醇;自发解离;电氧化     

Electrocatalytic oxidation of carbon monoxide and methanol at Pt nanoparticles confined in SBA-15: voltammetric and in situ infrared spectroscopic studies

Electrocatalytic oxidation of carbon monoxide and methanol at Pt nanoparticles confined in mesoporous molecular sieve SBA-15 was studied by using cyclic voltammetry and in situ FTIR spectroscopy. Cyclic voltammetric studies revealed that the Pt nanoparticles confined in SBA-15 exhibit a high activity in the presence of hydrated phase consisting of SiO₂ in the SBA-15. In situ FTIR spectroscopy results discovered that IR absorption of CO adsorbed on Pt nanoparticles confined in SBA-15 has been enhanced 11-fold, and the full-width at half-maximum of the CO band is significantly increased, in comparison with IR feature of CO adsorbed on a bulk Pt electrode. The linearly adsorbed CO species is the only intermediate derived from dissociative adsorption of methanol, which is more readily oxidized to form CO₂ in the aid of the active oxide in SBA-15.This paper is dedicated to Professor G. Horanyi on the occasion of his 70th birthday and in recognition of his outstanding contribution to electrochemistry     

Cyclic voltammetric studies of the redox behavior of iron(III)-vitamin B6 complex at carbon paste electrode

Electrochemical redox behavior of Fe-vit B₆ complex is investigated in HEPES buffer in the pH range 5.1–13.1 using cyclic voltammetry. Well-defined anodic and cathodic peaks are observed in the voltammograms at pH 13.1. At pH 8.0, only one cathodic peak and at pH 5.1, only one anodic peak are found. At all the pH values, the peak potential separation is much higher than that of a reversible electrochemical reaction. The peak current ratio (i _pa/i _pc) is less than unity and decreases with the scan rate. Published in Russian in Elektrokhimiya, 2006, Vol. 42, No. 6, pp. 691–697. The text was submitted by the authors in English.     

In situ scanning FTIR microscopy and IR imaging of Pt electrode surface towards CO adsorption

In situ scanning FTIR microscopy was built up for the first time in the present work, which consists of an FTIR apparatus, an IR microscope, an X-Y mapping stage, and the specially designed electrochemical IR cell and computer software. It has been demonstrated that this new space-resolvd in situ IR technique can be used to study vibration properties of micro-area, and to perform IR imaging of electrode surface. The chemical image obtained using this technique fur CO adsorption on Pt electrode illustrated, at a space-resolution of 10~(-2) cm, the inhomogeneity and the distribution of reactivity of micro-area of electrode surface.     

In situ scanning FTIR microscopy and IR imaging of Pt electrode surface towards CO adsorption

In situ scanning FTIR microscopy was built up for the first time in the present work, which consists of an FTIR apparatus, an IR microscope, an X-Y mapping stage, and the specially designed electrochemical IR cell and computer software. It has been demonstrated that this new space-resolvdin situ IR technique can be used to study vibration properties of micro-area, and to perform IR imaging of electrode surface. The chemical image obtained using this technique for CO adsorption on Pt electrode illustrated, at a space-resolution of 10^-2 cm, the inhomogeneity and the distribu-tion of reactivity of micro-area of electrode surface. Project supported by the National Natural Science Foundation of China (Grant No. 29525307).     

Copper oxide nanopowder modified carbon paste electrode for the voltammetric assay of vonoprazan

Vonoprazan (VPZ) is a novel promising member of gastric acid-suppressive medicinal administrated in Japan in 2015. Only a few HPLC analysis protocols were reported for VPZ assaying, therefore, the present work describes for the first time a novel copper oxide nanoparticles-based sensor as a promising analytical tool for differential pulse voltammetric determination of vonoprazan with enhanced sensitivity compared with the bare electrode. An irreversible oxidation process with the two-electron transfer was elucidated with scan rate measurements. At the optimized conditions, peak heights showed against VPZ in the concentration range from 0.99 to 20.00 µg mL^?1, and detection limit of 0.24 µg mL^?1. The proposed sensor showed prolonged stability with a 95% recovery of the original peak height within the first 30 days. Good reproducibility and repeatability of the fabrication protocol was reported with RSD 1.3%. Noticeable resolution between the VPZ, ascorbic acid, and uric voltammetric peaks allows accurate assaying of VPZ in biological fluids with average recoveries agreeable with the conventional HPLC techniques.     

Behavior of a nickel electrode in the presence of carbon monoxide

The electrochemical behavior of a nickel electrode with limited volume (LVE) electrodeposited as a thin layer on gold has been studied. The influence of the gold matrix on the electrochemical Ni electrode behavior has been considered. The electrosorption and oxidation of carbon monoxide on the Ni surface and its influence on hydrogen sorption has also been demonstrated. Received: 21 May 1997 / Accepted: 9 June 1997     

Electrochemistry and voltammetric determination of tannic acid on a single-wall carbon nanotube-coated glassy carbon electrode

The voltammetric behavior of tannic acid (TA) on a single-wall carbon nanotubes (SWNTs) modified glassy carbon electrode has been investigated by cyclic voltammetry. TA can generate a well-defined anodic peak on the modified electrode at around 0.42 V (vs. SCE) in 0.10 M phosphate buffer solutions (pH = 4.0). The electrochemical reaction involves 1e transfer, accompanied by one proton. The electrode process is controlled by adsorption. The parameters affecting the response of TA, such as solution pH, accumulation time and accumulation potential are optimized for the determination of TA. Under the optimum conditions, the peak current changes linearly with the TA concentration in the range of 5.0 × 10⁻⁸–1.0 × 10⁻⁶ M. The lowest detectable concentration of TA is 8.0 × 10⁻⁹ M after 180 s accumulation. This method has been successfully applied to the determination of TA in tea and beer samples. In addition, the influence of potential interferents is examined. In the presence of bovine serum albumin, the peak current of TA decreases linearly due to the formation of a super-molecular complex.     

The influence of hydrogen peroxide on carbon monoxide electrooxidation at Pt/C and Pt:Ru/C electrodes

Polymer electrolyte fuel cells constitute one of the most important efficiency energy converters for non-centralised uses. However, the use of fuels arising from reformate processes significantly lowers the current efficiency because of anodic catalytic poison coming from adsorbed carbon monoxide (CO_ad). In this work, the influence of the addition of hydrogen peroxide in the flow current is studied, considering the adsorption and electrochemical oxidation of carbon monoxide on carbon-supported Pt (20% Pt/Vulcan) and Pt:Ru (1:1, 20% Pt:Ru/Vulcan) catalysts in 2 M sulphuric acid. The investigation was conducted applying cyclic voltammetry and on-line differential electrochemical mass spectrometry. A series of experiments has been performed to investigate the influence of the temperature as well as the time of contact and the concentration of hydrogen peroxide. Oxidation of CO_ad to carbon dioxide occurs at lower potentials in the presence of hydrogen peroxide. Moreover, it is possible to remove ca. 70% of CO_ad on Pt/C electrodes. On the other hand, for PtRu/C electrodes, similar charge values to those of Pt/C electrodes were obtained for the CO stripping, but the process occurs at more negative potentials. In this case, the effect of partial desorption for CO_ad by interaction with hydrogen peroxide is added to the bifunctional mechanism usually considered for this alloy. This paper is dedicated to Prof. Francisco Nart, in memoriam.     

Cyclic voltammetric and nanogravimetric studies of NADP+ redox transformations on a yeast-modified platinum electrode

The dominant voltammetric response of a yeast suspension in neutral or slightly alkaline media can be assigned to the redox transformations of nicotinamide adenine dinucleotide (NAD⁺/NADH) and nicotinamide adenine dinucleotide phosphate (NADP⁺/NADPH). By immobilization of yeast on platinum, a stable electrode can be prepared which shows an electrocatalytic activity towards the reduction of NADP⁺ and the reoxidation of the product formed. Reversible cyclic voltammetric responses were obtained. The peak currents depend practically linearly on the NADP-Na₂ concentration and on the square root of the scan rate. The surface mass changes accompanying the redox transformations were monitored by an electrochemical quartz crystal nanobalance.