离子液体[BDMIM]PF_6修饰碳糊电极的制备及其电化学性能

以离子液体1,2-二甲基-3-丁基咪唑六氟磷酸盐（[BDMIM]PF6）代替传统液态石蜡为粘合剂与石墨粉相混合,制备了一种新型的离子液体修饰碳糊电极（IL/CPE）。采用扫描电子显微镜分别对其表面形貌和石蜡碳糊电极（CPE）表面形貌进行了表征。以亚铁氰化钾为电化学探针对IL/CPE的电化学行为进行了研究,并与CPE进行了比较。结果表明,[BDMIM]PF6由于具有较高的导电性,使IL/CPE比CPE具有更高的导电效率,铁氰化钾在电极上的可逆性变好,ΔEP值变小,峰电流响应增加10倍,电极过程由CPE上的吸附控制变为扩散控制,根据计时库仑法求解出铁氰化钾的扩散系数为5.52×10^-6cm2/s（25℃）。电化学交流阻抗图亦表明与不导电的液态石蜡油相比,离子液体的存在加快了电子传递。     

Electrochemical response of nitrogen-doped multi-walled carbon nanotubes decorated with gold and iridium nanoparticles toward ferrocyanide/ferricyanide redox system

Novel composite films consisting of nitrogen-doped multi-walled carbon nanotubes (N-MWCNTs) were fabricated by means of chemical vapor deposition technique and decorated with gold (AuNP) and iridium (IrNP) nanoparticles possessing diameters of 12.5 and 2.7 nm, respectively. The electrochemical responses of fabricated composite films, further denoted as N-MWCNTs/MNPs (M: Au and Ir), toward ferrocyanide/ferricyanide, [Fe(CN)₆]^3−/4− redox couple was probed by means of cyclic voltammetry and electrochemical impedance spectroscopy techniques. The findings demonstrate that both N-MWCNT/MNP composite films exhibit greater electrochemical response and sensitivity toward [Fe(CN)₆]^3−/4− compared to unmodified N-MWCNTs. The results verify that the N-MWCNT/MNP composite films are extremely promising for application in electrochemical sensing.

     

环三磷腈的单链侧基衍生化及其性质

以制得的4种原儿茶醛舭氨基酸钠缩合产物与六氯环三磷腈为基本原料,同位单链侧基衍生化后,其他氯原子分别以对氨基苯酚封闭,合成4种环三磷腈α-氨基酸钠支化衍生物。利用IR、^1H NMR、^13C NMR分析方法对产物进行了结构表征,证实为目标化合物。通过紫外-可见光谱、电化学工作站等实验方法,考察了衍生物对金属Cu^2＋离子的识别性能及电化学性质。结果表明：环三磷腈α-氨基酸钠支化衍生物对Cu^2＋离子的选择性识别作用明显,且呈明显的剂-效关系。Fe（CN）6^3-/4-电对在支化衍生物修饰玻碳电极表面的电化学反应过程为扩散控制。并随着衍生物修饰剂量的增大和扫描速率的增加氧化还原峰电流逐渐增强,对Fe（CN）6^3-/44电对的电极反应表现出电催化作用（本刊编者注：本文中Fe（CN）6的右上角应为3-/4-）.     

Electrochemical properties of compacts of nano-and microdisperse diamond powders in aqueous electrolytes

The electrochemical behavior of compacts of micro-and nanodisperse diamond powders were studied by using model redox K₃[Fe(CN)₆]-K₄[Fe(CN)₆] and Ce(SO₄)₂-Ce₂(SO₄)₃ systems in aqueous electrolytes. The current-voltage curves for compacts of microdisperse diamonds and the kinetics of reactions on these compacts in a solution of the [Fe(CN)₆]^3-/4- system are similar to those obtained by using a metal electrode. For nanodisperse diamonds, the same reactions are essentially irreversible.     

流动注射抑制化学发光法测定异烟肼

以异烟肼与K3 Fe(CN) 6的氧化还原反应对Luminol K3 Fe(CN) 6的化学发光反应的抑制为基础 ,设计出一种简便、快速、灵敏度高的流动注射抑制化学发光测定异烟肼的新方法。测定线性范围为 1 4× 10 -3 ～5 5 μg·mL-1,检出限为 4 8× 10 -4 μg·mL-1(3σ) ,RSD小于 3 5 % (n =9) ,并对 45种物质进行了干扰试验。本法成功地应用于药剂中异烟肼含量测定 ,回收率为 98 2 %～ 10 1%。本法与DSC法进行了对照 ,结果满意。     

Study of the electrochemical properties in substituted Li2Ti3O7 ramsdellite

Substituting the ramsdellite compound Li₂Ti₃O₇ has been considered in order to improve the structure stability and performances for its use as electrode material for Li-ion accumulators. Two substitutions have been carried out, Ti/Fe and (Ti, Li)/(Fe,Ni). The presence of ⁵⁷Fe as a local Mössbauer probe is interesting for studying its local environment and the electrochemical mechanisms induced by lithium insertion.     

丁二酰化壳寡糖稀土配合物与鲱鱼精DNA相互作用的电化学及光谱学研究

采用紫外光谱和循环伏安法,研究了丁二酰化壳寡糖稀土配合物（BCS-La、BCS-Nd）与鲱鱼精DNA之间的作用方式。BCS-La、BCS-Nd的存在导致Fe（CN）₆^3-/4-探针分子峰电流下降,式量电位正移,表明BCS-La、BCS-Nd和探针分子与DNA之间存在竞争性作用;BCS-La和BCS-Nd分子都是通过插入方式与DNA相互作用。在一定的扫描速率范围内（0.01~0.2 V/s）,在BCS-La或BCS-Nd参与的条件下,Fe（CN）₆^3-/4-在Au/DNA电极上的反应受吸附控制。BCS-La和BCS-Nd分别使得鲱鱼精DNA的特征峰产生明显的减色效应,最大吸收峰峰位红移,进一步表明BCS-La和BCS-Nd分别以插入方式与鲱鱼精DNA发生相互作用,导 致DNA分子的构象变化。BCS-La与DNA的结合比为：n（BCS-La）：n（DNA）=2：1;n（BCS-Nd）：n（DNA）=6：1。     

Mössbauer studies of photochemical reaction products of Ru(bpy)3 2+ iron cyanide double complexes

The reductive and the oxidative electron-transfer photochemical reaction system of light-irradiated the mix solutions of Ru(bpy)₃ ²⁺ with [Fe(CN)₆]^4–, [Fe(CN)₆]^3–, [Fe(CN)₅NO]^2– and PB (Prussian Blue) have been studied. The double complexes which isolated from the precipitates of the photochemical reaction have been identified by means of Mössbauer spectroscopy. In order to clarify the chemical states of these isolated double complexes, we have (prepared and) studied Mössbauer spectra of the double complexes such as [Ru(bpy)₃]₃[Fe(CN)₆]₂.14H₂O, [Ru(bpy)₃]₂[Fe(CN)₆].10H₂O, [Ru(bpy)₃][Fe(CN)₅NO].4H₂O, and [Ru(bpy)₃][PB]₂.xH₂O.     

紫外-可见多功能光谱电化学池的研制

利用研制的紫外－可见多功能光谱电化学池,以ＵＶ－Ｖｉｓ长光程薄层和光透支光谱电化学法的分别测定了Ｆｅ（ＣＮ）６＾３－／Ｆｅ（ＣＮ）６＾４－电对的反应电数ｎ;燕以ＵＶ－Ｖｉｓ光透半无限扩散和平行人射式光谱电学法分别测定了Ｆｅ（ＣＮ）６＾３－的扩散系数Ｄ。实验的结果均与文献值相近,从而表明了这种ＵＶ－Ｖｉｓ多功能光谱电化学池的可靠性。     

On the electrochemical reactivity of the redox couple Fe(CN)63−/Fe(CN)64− at the single crystal zinc oxide electrode

The system zinc oxide/hexacyanoferrate was used to test the applicability of the theoretical model for electrochemical reactions at semiconductor electrodes based upon direct electron transfer between levels of equal energy. This model appears to be valid for electron transfer involving the conduction band. From the pH-dependence of the cathodic reactivity, a value of 0.75 eV is found for the rearrangement energy of Fe(CN)₆^3?/Fe(CN)₆^4?. This result, combined with capacity and potential data, allows the construction of a general energy scheme for the system under consideration. It is shown that direct electron transfer from filled redox levels to empty levels in the valence band is highly improbable, so that the observed hole capture by Fe(CN)₆^4? from the UV-illuminated ZnO anode presumably occurs by a more complicated mechanism, e.g. involving surface states.     

GaP台面腐蚀研究

高效GaP绿色发光二极管制造中,器件的隔离和台面制作具有十分重要意义。本文介绍了用于GaP发光器件的隔离和台面制作的碱性铁氰化钾化学腐蚀技术。观察了腐蚀温度,腐蚀时间对腐蚀深度和表面形貌间关系。结果表明:碱性铁氰化钾对GaP台面腐蚀是一种优良的腐蚀剂,具有较高的腐蚀速率(2微米/分),并可获得光滑无凹坑或少凹坑的腐蚀面。对出现的实验现象从机理上作了解释。     

Synthesis and characterization of conducting polypyrrole-containing iron complexes

Electrochemical or chemical oxidation of pyrrole-containing complex anions of iron cyanide or iron chloride results in the formation of films or powders of conducting polypyrroles. Freshly prepared films exhibit an additional IR band at ca 1630–1640 cm⁻¹, slowly disappearing in air and not observed in previously studies polypyrrole-based systems. It is possible that this new band is associated with the existence of a CN bond in dehydrogenated pyrrole rings which are transformed into regular pyrrole rings, probably due to the protonation reaction occurring in air and simultaneous bond rearrangement. The polypyrrole structure favours the presence of Fe(CN)₆⁴⁻ over Fe(CN)₆³⁻ since the former is the only iron species detected by Mössbauer spectroscopy in electrochemically prepared samples. It is also the dominant iron species in the samples oxidized chemically. The polypyrrole-containing Fe(CN)₆⁴⁻ is more ordered than those containing monovalent anions, as evidence by X-ray diffraction studies. High-spin eron complexes can be inserted into polypyrrole during electrochemical oxidation of pyrrole in non-aqueous solutions containing LiCl/FeCl₃. The inserted species exhibit Mössbauer parameters characteristic of slightly distorted FeCl₄⁻.     

A comparative study of local sensors of power ultrasound effects: electrochemical, thermoelectrical and chemical probes

In order to propose standard methods for the local measurement of the effects of power ultrasound inside a reactor, we compare three methods: a chemical dosimeter (Weissler reaction), a thermal sensor (embedded thermocouple) and an electrochemical probe (developed in our laboratory). The same emission device, i.e. the resonant tube (Sonitube-Sodeva), was used for all these methods. Similar trends were observed using various measurements: ultrasound effects vary significantly along the tube axis (due to standing waves in the resonant tubular emitter), but only slightly from the tube axis to the wall. More reliable and reproducible results were obtained with the thermal and electrochemical probes than with the chemical dosimeter.     

Investigation of the photoelectron decay of silver halide microcrystal

The microwave absorption dielectric spectrum can be used to study the decay process of free photoelectrons and shallow-trapped electrons in semiconductor crystals. The decay curve of free photoelectrons and shallow-trapped electrons of silver halide grains is measured using this technique. The influence of iodide and K_4Fe(CN)_6 shallow electron trap dopants on the photoelectron lifetime of silver halide grains is studied. For the unsensitized cubic AgCl crystals, when the free photoelectron lifetime (FLT) reaches a maximum, the photographic efficiency is optimal. From our analysis, we conclude that FLT is the longest for the cubic AgCl crystals doped with 0.5% iodide at 80% doping position and 1×10^{-6} mol K_4Fe(CN)_6/molAg, whereas, for the highly photosensitized cubic AgBrCl crystals doped with K_4Fe(CN)_6, the photographic efficiency is optimal when the FLT reaches its minimum. The free photoelectron lifetime reaches minimum and the sensitivity of AgBrCl emulsion reaches maximum when the doping position is 30%Ag at K_4Fe(CN)_6 content of 10^{-6}mol/molAg.     

Direct growth of single crystalline ReO3 nanorods on a tungsten (W) microwire for enhanced electron-transfer reaction kinetics

We report the direct growth of highly single crystalline rhenium trioxide (ReO₃) nanorods on a tungsten (W) microwire electrode via the physical vapor transport process without any catalyst. In our growth mode, ReO₃ nanocubes were initially formed on the surface of a tungsten (W) microwire electrode and further they were anisotropically grown along the [001] crystallographic direction. Furthermore, we performed the fundamental electrochemical experiments so that from cyclic voltammetric measurements, ReO₃ nanorods on a W microwire exhibit a good capacitance and Nernstian behavior for a Fe(CN)₆³⁻/Fe(CN)₆⁴⁻ redox couple in 1 M KNO₃ aqueous solution, indicating a promising electrode material for electrochemical applications.     

Pt纳米微粒自组装体系的电化学和原位FTIR反射光谱研究

用化学还原法制备了铂金属纳米微粒 ,透射电子显微镜 (TEM)表征纳米Pt微粒的平均直径为 2 5nm。通过二硫醇将Pt纳米微粒组装到多晶金电极表面。以Fe(CN) 4- 3-6 的氧化还原作为探针反应的电化学研究表明 ,Au表面组装二硫醇后抑制了电极 /溶液界面的电子传递过程 ,而在二硫醇上再组装铂纳米微粒后 ,电子传递又可进行。运用电化学FTIR反射光谱研究了Pt纳米微粒组装电极在酸性介质中CO的吸附 ,检测到CO的线型、桥式吸附态 ,分别在 2 0 30和 184 5cm- 1 附近给出红外吸收谱峰 ,并且有增强红外效应。此外 ,还观察到Pt纳米微粒上的CO孪生吸附态。红外吸收峰位于 2 10 0cm- 1 附近。     

Electrochemical Studies on Substituted Iron-Hexacyanoiron(III) Bi-Layered Thin Films at Glassy Carbon Electrode/Electrolyte Interface

Thin films (30–50 nm) of bilayered HCM (hexacyanometalates) were prepared using direct electrodeposition or electrochemically driven insertion-substitution of PB (Prussian Blue) or InHCF (Indium Hexacyanoferrate) or K..In _x [Fe{CN}₆] _y , as starting material. The redox behavior of the immobilized counter/central ions at GCE/electrolyte interface have been investigated in aqueous KCl (pH 1) electrolytes using dynamic voltammetric techniques. Studies show that when the counter Fe or In ion is replaced by expandable partially filled d orbits elements such as Ru³⁺ a redox wave of the inserted counter ion is observed. Furthermore, the substitution of Fe as a counter ion with other poly-valent cations was found to be reversible if PB was the starting material. Studies were extended to include the EC (electrochemical) behavior of related HCM compounds such as K...Al _x [Fe{CN}₆] _y K, Ni _x [Fe{CN}₆] _y Cu _x [Fe{CN}₆] _y , K..Zn _x [Fe{CN}₆] _y and, K..Ru[Fe{CN}₆]₃. Unlike studied 3d cations, GCE modified with thin films of copper-hexacyanoiron (III) KCu _x [Fe{CN}₆] _y or CHF showed two redox waves with E^o _f 0.6, 0.9 V vs Ag/AgCl. Studies showed that even immobilized Cu ions were capable of catalyzing the oxidation of hydrazine and sulfite. The mechanism for electro-oxidation is also included.     

多价抗衡离子诱导聚甲基丙烯酸N,N-二甲基氨基乙酯(PDMAEMA)刷构象转变的UCST行为

本文应用分子场理论,研究pH、[Fe(CN)_6]~(3-)诱导聚甲基丙烯酸N,N-二甲基氨基乙酯(PDMAEMA)刷的上临界溶解温度(UCST)构象转变与结构特性.理论模型考虑p H和[Fe(CN)_6]~(3-)对PDMAEMA刷体系的静电调控作用.研究发现,在不同[Fe(CN)_6]~(3-)浓度、不同p H条件下,PDMAEMA刷呈现了UCST构象转变行为.由于p H调节PDMAEMA单体质子化,[Fe(CN)_6]~(3-)通过与PDMAEMA带正电荷的单体结合,形成了在PDMAEMA链内以[Fe(CN)_6]~(3-)为中介的带电单体间的静电吸引结合.随着温度升高,[Fe(CN)_6]~(3-)与PDMAEMA带正电荷的单体结合被破坏,[Fe(CN)_6]~(3-)在链内凝聚导致的静电屏蔽效应减弱,PDMAEMA链内带电单体间的静电排斥增强,PDMAEMA刷的构象呈现了从塌缩到溶胀的UCST转变行为,并且在较高[Fe(CN)_6]~(3-)浓度条件下,PDMAEMA刷构象转变的UCST增高.在较低p H值条件下,较多的PDMAEMA单体被质子化,[Fe(CN)_6]~(3-)与PDMAEMA带正电单体的结合增强,PDMAEMA刷构象转变的UCST增大.基于pH和[Fe(CN)_6]~(3-)对PDMAEMA刷体系中的静电调控效应,可以预言,在较小p H和较大[Fe(CN)_6]~(3-)浓度条件下,PDMAEMA链在垂直培基表面沿着链方向形成结节状结构.这是由于以[Fe(CN)_6]~(3-)为中介的链内带电单体间的静电吸引作用增强,导致临近单体间汇聚结节.我们的理论结果符合实验观测,由此表明,pH调节PDMAEMA单体的带电状态,以及[Fe(CN)_6]~(3-)在PDMAEMA链内凝聚导致的静电屏蔽效应,决定着PDMAEMA刷的UCST构象转变和结构特性.     

Reversible valence tautomerism induced by a single-shot laser pulse in a cobalt-iron Prussian blue analog

Reversible valence tautomeric conversion induced by a single-shot laser pulse (8 ns duration) with a photon excitation energy of 2.38 eV has been observed in Na0.36Co1.32Fe(CN)(6).5.6H(2)O. A photoswitching process with accompanying magnetization and color changes was successfully achieved within the pulse duration at high temperature (above 200 K) in a thermal hysteresis loop. This unusual photoeffect originates from an optical charge transfer between Fe and Co atoms and evolves due to a cooperative interaction among the local photoexcited sites.     

几种Fe（Ⅵ）化合物的物理性质、电化学性能及稳定性研究

为深入认识高铁化合物的物理性质和电化学性能,采用化学法合成了K2FeO4、BaFeO4、SrFeO4和 K2Sr(FeO4)2等几种高铁化合物,比较研究了这几种高铁化合物的形貌、结构、在不同浓度KOH溶液中的溶解度 及其放电性能.研究结果显示,在这几种高铁化合物中,BaFeO4具有较好的电化学性能.但在实验过程中发现,除 K2FeO4外,其余几种高铁化合物均不稳定,在干燥环境中放置时会发生分解.采用量子化学从头算方法从理论上 分析了高铁化合物的稳定性变化规律.研究结果表明,高铁化合物的稳定性与阳离子对FeO42-的极化作用有很 大关系,极化作用越强,高铁化合物就越不稳定.