首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 31 毫秒
1.
In this work, the electrochemical behavior of ferrocene (Fc) was investigated by cyclic voltammetry (CV) in room temperature ionic liquids (RTILs) of 1‐ethyl‐3‐methylimidazolium tetrafluoroborate (EMIBF4) on glass carbon (GC), edge plane pyrolytic graphite (EPPG) and multi‐walled carbon nanotube (MWCNTs)‐modified EPPG electrodes, respectively. The results demonstrated that on GC electrode, pairs of well‐defined reversible peaks were observed, while for the electrode of EPPG, the peak potential separation (ΔEp) is obviously larger than the theoretical value of 59 mV, hinting that the electrode of EPPG is distinguished from the commonly used electrode, consistent with the previous proposition that EPPG has many “defects”. To obtain an improved electrochemical response, multi‐walled carbon nanotubes (MWCNTs) were modified on the electrode of EPPG; the increased peak current and promoted peak potential separation not only proved the existence of “defects” in MWCNTs, but also supported that “creating active points” on an electrode is the main contribution of MWCNTs. Initiating the electrochemical research of Fc on the MWCNTs‐modified EPPG electrode in RTILs and verifying the presence of “defects” on both EPPG and MWCNTs using cyclic voltammograms (CVs) of Fc obtained in RTILs of EMIBF4, is the main contribution of this preliminary work.  相似文献   

2.
In this work, for the first time, the direct electron transfer of iron‐containing superoxide dismutase (Fe‐SOD) was observed by cyclic voltammetry on a gold (Au) electrode in three RTILs, i.e., 1‐ethyl‐3‐methylimidazolium tetrafluoroborate (EMIBF4), 1‐n‐propyl‐3‐methylimidazolium tetrafluoroborate (PMIBF4) and 1‐n‐butyl‐3‐methylimidazolium tetrafluoroborate (BMIBF4). And the results demonstrate that when the scan rate was as low as 1 mV/s, a pair of well‐defined quasi‐reversible peaks of Fe‐SOD was presented, while as the potential scan rate was above 10 mV/s, the reduction peak of Fe‐SOD disappeared though its oxidation peak could be clearly observed even as the potential scan rate was up to 400 mV/s, strongly indicating that these CVs we observed were attributable to Fe‐SOD rather than the impurities in RTILs. Its catalysis for oxygen reduction reaction (ORR) was directly verified by the shifting of formal potential, E0′, of ORR, to the positive direction though the value of standard rate constant, κ0, corresponding to ORR, was not much enhanced. In PMIBF4, for the multi‐walled carbon nanotubes (MWCNTs)‐modified gold electrode, both the reduction peak current and oxidation peak current for oxygen redox reaction were all dramatically enhanced compared to the case of a bare gold electrode, and the value of κ0 was also increased from 3.1 × 10?3 cm s?1 for the bare gold electrode, to 17.5 × 10?3 cm s?1. Hence, in the presence of Fe‐SOD in RTILs, MWCNTs, showing catalysis for the electron transfer process of ORR, coupled with Fe‐SOD, leading to the shifting of formal potential corresponding to ORR to the positive direction, presented us a satisfactory catalysis for ORR in RTILs. Some reasons available for this catalysis behavior stemming from Fe‐SOD, and MWCNTs as well, for ORR are discussed based on the previously developed proposition.  相似文献   

3.
Manganese dioxides were prepared onto multi-walled carbon nanotubes (MWCNTs) by cyclic voltammetry (CV). The obtained manganese oxide-MWCNTs (MnO2/MWCNTs) samples were characterized by scanning electron microscope (SEM), X-ray diffraction (XRD), fourier transform infrared spectrometry (FTIR) and thermogravimetry (TG), respectively. The MnO2/MWCNTs-modified graphite electrode was utilized in the electrochemical oxygen reduction reaction (ORR) and the enhanced oxygen reduction peak current strongly suggested that MnO2/MWCNTs has catalysis for ORR when compared to the pure MnO2 or MWCNTs. The catalysis mechanism of MnO2/MWCNTs for ORR was also-discussed.  相似文献   

4.
Catalysis of the electrochemical oxygen reduction reaction (ORR) on a pyrolytic graphite electrode (PGE) by iron-containing superoxide dismutase (Fe-SOD) is investigated for the first time using cyclic voltammetry and electrochemical impedance spectroscopy. The study is carried out in three room-temperature ionic liquids (RTILs), namely, 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIBF4), 1-propyl-3-methylimidazolium tetrafluoroborate (PMIBF4), and 1-butyl-3-methylimidazolium tetrafluoroborate (EMIBF4). The results demonstrate that in EMIBF4, Fe-SOD exhibits the most satisfactory catalysis for ORR, with the standard rate constant of ORR on bare PGE, k s, increasing from 3.9 to 5.1 times 10−3 cm s−1, while in PMIBF4 and BMIBF4 containing Fe-SOD k s increases from 2.6 to 3.6 and from 1.4 to 2.2 times 10−3 cm s−1, respectively. In addition to the increased k s, adding Fe-SOD renders the formal potential of ORR more positive. To accelerate the electron transfer, multi-walled carbon nanotubes (MWCNTs) are employed to modify PGE, consequently, yielding the dramatically increased peak current and k s. For MWCNTs-modified PGE in EMIBF4 free of Fe-SOD, k s increases from 3.9 to ∼7.1 times 10−3 cm s−1. The ORR catalysis by Fe-SOD in the presence of Fe-SOD is also evidenced by the formal-potential shift in the positive direction. With MWCNTs accounting for the larger k s and Fe-SOD being responsible for the formal-potential shift, the catalysis of ORR is satisfactory. Chronocoulmetry experiments proved that some Fe-SOD could be adsorbed on PGE. After analyzing the results, dismutation of superoxide anion O 2 by Fe-SOD is thought to be the main reason for the formal-potential shift. The different polarity of RTILs is probably partly responsible for different k s obtained in different RTILs. Basing on an earlier proposition, the catalysis of ORR by MWCNTs in RTILs is discussed. Published in Russian in Elektrokhimiya, 2007, Vol. 43, No. 9, pp. 1137–1146. The text was submitted by the authors in English.  相似文献   

5.
本文采用溶胶凝胶法制备了一系列不同Ca含量的钙钛矿型氧化物La1-xCaxMnO3(x=0~0.4)纳米颗粒,X射线粉末衍射及精修、扫描电镜表征显示其相纯度和结晶度高,颗粒平均粒径约40 nm。在0.1 mol.L-1KOH水溶液中进行的氧还原电催化性能测试显示,La0.7Ca0.3MnO3样品催化活性最高,表观电子转移数接近4,还原电流密度与Pt/C催化剂相当,而催化稳定性优于Pt/C。进一步研究了La1-xCaxMnO3样品中Mn价态、晶胞参数的改变对氧还原催化活性的影响,结果表明当x=0.3时,催化剂中Mn处于混合价态,Mn-O键长适中,最有利于电催化反应。  相似文献   

6.
For the first time, cobalt particles were electrodeposited on the surface of manganese oxides by cyclic voltammetry (CV) from an aqueous solution of 0.1 M Na2SO4 containing 5 mM CoSO4, and then the samples obtained were characterized by scanning electron microscopy (SEM) and energy dispersive X‐ray analysis (EDAX), respectively. And then, the as‐prepared Co/MnO2‐coated graphite electrode was employed to the oxygen reduction reaction (ORR). Interestingly, the reduction peak potential of ORR on a Co/MnO2‐modified graphite electrode was positively shifted for about 100 mV as compared with that on a MnO2‐modified graphite electrode, indicating that the electrocatalysis of Co/MnO2 composite towards ORR is superior to that of pure MnO2.  相似文献   

7.
本文采用溶胶凝胶法制备了一系列不同Ca含量的钙钛矿型氧化物La1-xCaxMnO3(x=0~0.4)纳米颗粒, X射线粉末衍射及精修、扫描电镜表征显示其相纯度和结晶度高, 颗粒平均粒径约40 nm。在0.1 mol·L-1 KOH水溶液中进行的氧还原电催化性能测试显示, La0.7Ca0.3MnO3样品催化活性最高, 表观电子转移数接近4, 还原电流密度与Pt/C催化剂相当, 而催化稳定性优于Pt/C。进一步研究了La1-xCaxMnO3样品中Mn价态、晶胞参数的改变对氧还原催化活性的影响, 结果表明当x=0.3时, 催化剂中Mn处于混合价态, Mn-O键长适中, 最有利于电催化反应。  相似文献   

8.
A novel organic gel film modified electrode was simply and conveniently fabricated by casting LixMoOy and polypropylene carbonate (PPC) onto the surface of a gold electrode. The cyclic voltammetry and amperometry studies demonstrated that the LixMoOy film modified electrode has a high stability and a good electrocatalytic activity for the reduction of iodate. In amperometry, a good linear relationship between the steady current and the concentration of iodate was obtained in the range from 3×10–7 to 1×10–4 mol L–1 with a correlation coefficient of 0.9997 and a detection limit of 1×10–7 mol L–1.  相似文献   

9.
(Pt–NbPO x )/multi-walled carbon nanotubes (MWCNTs) with different NbPO x MWCNTs were prepared by a simple microwave irradiation method. The (Pt–NbPO x )/MWCNTs catalyst was characterized, and the kinetics toward oxygen reduction reaction (ORR) was determined, compared with that of Pt/MWCNTs catalyst. It was found that 10 wt% NbPO x was the best loading in terms of current density. The number of exchange electrons for the ORR was found to be close to four on both (Pt–NbPO x )/MWCNTs and Pt/MWCNTs.  相似文献   

10.
The Wiener index of a graph G is defined as , where V(G) is the set of all vertices of G and for denotes the length of a minimal path between x and y. A C 4 C 8 net is a trivalent decoration made by alternating squares C 4 and octagons C 8. It can cover either a cylinder or a torus. In this paper, an algorithm for computing the distance matrix of a C 4 C 8(R) nanotorus T = T[p,q] is given. Using this matrix, the Wiener index of T is computed.  相似文献   

11.
二氧化锰(MnO2)材料具有比容量大、电极电位高、储量丰富以及价格低廉等优势,成为水系锌电池正极最受关注的一类材料,然而其仍然存在着结构稳定性差和电化学储存机理复杂的问题。因此,我们通过两步合成法制备了一种花苞状结构的MnO2负载在Ti3C2Tx表面形成Ti3C2Tx/MnO2复合材料,通过X射线粉末衍射(XRD)、X射线光电子能谱(XPS)、透射电子显微镜(TEM)和高分辨透射电子显微镜(HRTEM)对复合样品的结构、成分和形貌进行表征。通过将Ti3C2Tx/MnO2复合材料作为正极,与锌负极匹配组装成水系锌电池,研究了其分别在2 mol·L-1 ZnSO4、2 mol·L-1 ZnSO4+0.1 mol·L-1 MnSO4、30 mol·L-1三氟甲基磺酸四乙基铵(TEAOTf)+1 mol·L-1三氟甲烷磺酸锌(ZnOTf)和3 mol·L-1 ZnOTf四种电解液中的电化学性能。结果表明,Ti3C2Tx/MnO2在2 mol·L-1 ZnSO4中的比容量较高,但循环稳定性很差。将TEAOTf盐和ZnOTf盐共溶于水中,设计了一种新型的含惰性阳离子的超高浓度盐包水电解液(30 mol·L-1 TEAOTf+1 mol·L-1 ZnOTf),不仅提高了Ti3C2Tx/MnO2材料的可逆性,而且有效抑制了电极材料在循环过程中的溶解。  相似文献   

12.
(Y,Yb)MnO3 and HfO2 films were prepared using alkoxy-derived precursor solutions, and (Y,Yb)MnO3/HfO2/Si structures were fabricated. The thickness, surface uniformity and crystallinity of the HfO2 film affect the crystallization of Y0.5Yb0.5MnO3 films. The degree of c-axis orientation and crystallinity of the Y0.5Yb0.5MnO3 films were changed with preparation conditions of HfO2 films. It was difficult to obtain Y0.5Yb0.5MnO3 films with high crystallinity and high degree of c-axis orientation on the HfO2 films thinner than 10 nm. The degree of c-axis orientation and crystallinity of the Y0.5Yb0.5MnO3 films on HfO2 films were improved by using diluted HfO2 precursor solution in the case of 10 nm-thick HfO2 film. Following this, the capacitance-voltage (C-V) characteristics were improved.  相似文献   

13.
Kinetic data for the oxidation of glutathione (reduced, GSH), cysteine, glycine and glutamic acid by colloidal manganese dioxide, (MnO2) n are reported. Colloidal MnO2, oxidized glutathione to disulphide (glutathione, oxidized), was reduced to manganese (II). Glycine and glutamic acid (structural units of glutathione) are not oxidized by colloidal MnO2, but the other structural unit, cysteine, is also oxidized by the same oxidant under similar experimental conditions. This is interpreted in terms of the rate-determining colloidal MnO2-S bonded intermediate. The reactivity of GSH towards colloidal MnO2 is very much higher than cysteine. Kinetics of oxidation of GSH and cysteine by colloidal MnO2 were performed spectrophotometrically as a function of [GSH], [cysteine], colloidal [(MnO2) n ], [HClO4], temperature and trapping agents sodium fluoride and manganese (II) (reduction product of colloidal MnO2). The purpose of this work was to study the role of –NH2, –COOH, –SH groups present in the carbon chain of the above amino acids. It was found that the reactivity of –SH group is higher than –NH2 and –COOH groups. The mechanisms, involving a colloidal MnO2 complex with GSH and cysteine, are proposed. The complexes decompose in a rate-determining step, leading to the formation of free radical and manganese (III), which is also an intermediate. The dimerization of radicals takes place in a subsequent fast step to yield the products.  相似文献   

14.
The electrocatalytic activity of a Prussian blue (PB) film on the aluminum electrode by taking advantage of the metallic palladium characteristic as an electron-transfer bridge (PB/Pd–Al) for electrooxidation of 2-methyl-3-hydroxy-4,5-bis (hydroxyl–methyl) pyridine (pyridoxine) is described. The catalytic activity of PB was explored in terms of FeIII [FeIII (CN)6]/FeIII [FeII (CN)6]1− system. The best mediated oxidation of pyridoxine (PN) on the PB/Pd–Al-modified electrode was achieved in 0.5 M KNO3 + 0.2 M potassium acetate of pH 6 at scan rate of 20 mV s−1. The mechanism and kinetics of the catalytic oxidation reaction of PN were monitored by cyclic voltammetry and chronoamperometry. The results were explained using the theory of electrocatalytic reactions at chemically modified electrodes. The charge transfer-rate limiting reaction step is found to be a one-electron abstraction, whereas a two-electron charge transfer reaction is the overall oxidation reaction of PN by forming pyridoxal. The value of α, k, and D are 0.5, 1.2 × 102 M−1 s−1, and 1.4 × 10−5 cm2 s−1, respectively. Further examination of the modified electrodes shows that the modifying layers (PB) on the Pd–Al substrate have reproducible behavior and a high level of stability after posing it in the electrolyte or Pyridoxine solutions for a long time.  相似文献   

15.
Au/Al2O3 catalysts were modified by different redox metal oxides, such as FeOx, MnOx and CoOx, resulting in a pronounced activity increase in CO oxidation.  相似文献   

16.
A simple procedure was developed to prepare a glassy carbon electrode modified with multi walled carbon nanotubes (MWCNTs) and Celestin blue. Cyclic voltammograms of the modified electrode show stable and a well defined redox couple with surface confined characteristic at wide pH range (2–12). The formal potential of redox couple (E′) shifts linearly toward the negative direction with increasing solution pH. The surface coverage of Celestine blue immobilized on CNTs glassy carbon electrode was approximately 1.95×10?10 mol cm?2. The charge transfer coefficient (α) and heterogeneous electron transfer rate constants (ks) for GC/MWCNTs/Celestine blue were 0.43 and 1.26 s?1, respectively. The modified electrode show strong catalytic effect for reduction of hydrogen peroxide and oxygen at reduced overpotential. The glucose biosensor was fabricated by covering a thin film of sol‐gel composite containing glucose oxides (GOx) on the surface of Celestine blue /MWCNTs modified GC electrode. The biosensor can be used successfully for selective detection of glucose based on the decreasing of cathodic peak current of oxygen. The detection limit, sensitivity and liner calibration rang were 0.3 μM, 18.3 μA/mM and 10 μM–6.0 mM, respectively. The accuracy of the biosensor for glucose detection was evaluated by detection of glucose in a serum sample, using standard addition protocol. In addition biosensor can reach 90% of steady currents in about 3.0 sec and interference effect of the electroactive existing species (ascorbic acid–uric acid and acetaminophen) was eliminated. Furthermore, the apparent Michaelis–Menten constant 2.4 mM, of GOx on the nano composite exhibits excellent bioelectrocatalytic activity of immobilized enzyme toward glucose oxidation. Excellent electrochemical reversibility of redox couple, high stability, technically simple and possibility of preparation at short period of time are of great advantages of this procedure for modification of glucose biosensor.  相似文献   

17.
Influences of α-MnO2, β-MnO2, and δ-MnO2 on the photocatalytic activity of Degussa P-25 TiO2 have been investigated through the photocatalytic degradation of methyl orange. The TiO2 photocatalyst, before and after being contaminated by MnO2, was characterized by UV-visible diffuse reflectance spectroscopy (UV-vis DRS), photoluminescence (PL), and X-ray photoelectron spectroscopy (XPS). The results showed that photocatalytic activity of TiO2 could be inhibited significantly or completely deactivated due to the presence of even a small amount of MnO2 particles. It was found that the poisoning effect varied with the crystal phases of MnO2 and the effect was in the order δ-MnO2 >α-MnO2 >β-MnO2. The poisoning effect was attributed to the formation of heterojunctions between MnO2 and TiO2 particles. The heterojunctions changed the chemical state of Ti4+ and O2− sites in the crystalline phase of TiO2. MnO2 in contact with TiO2 particles also broadens the band-gap of TiO2, which decreases UV absorption of TiO2. It can also create some deep impurity energy levels serving as photoelectron-photohole recombination center, which accelerates the electron-hole recombination. Supported by the National Natural Science Foundation of China (Grant No. 20477009) and the Natural Science Foundation of Hebei Province (Grant No. E2005000183)  相似文献   

18.
In this article, a carbon ionic liquid electrode (CILE) was fabricated by using ionic liquid N-hexylpyridinium hexafluorophosphate as the binder and the modifier. Then urchinlike MnO2 microsphere and chitosan (CTS) was further casted on the CILE surface step-by-step to get a modified electrode that was denoted as CTS/MnO2/CILE. Cyclic voltammetric studies indicated that bisphenol A (BPA) exhibited a well-defined oxidation peak at 0.486 V in 22.83 g L?1 pH 8.0 Britton?Robinson buffer solution, which was attributed to the electro-oxidation of BPA on the modified electrode. The presence of urchinlike MnO2 microsphere on the electrode surface could increase the oxidation peak current (Ipa) greatly, which may be due to the larger surface area that could adsorb more BPA on the electrode surface. Electrochemical parameters of BPA on the modified electrode were calculated with the electron transfer coefficient (α) as 0.66 and the apparent heterogeneous electron transfer rate constant (ks) as 0.50 s?1. Under the optimal conditions, a linear relationship between the Ipa of BPA and its concentration was obtained in the range from 1.37 × 10–1 mg L?1 to 182.6 mg L?1 with the detection limit as 7.31 × 10–3 mg L?1 (3σ). The CTS/MnO2/CILE was applied to the detection of BPA content in different kinds of samples with satisfactory results.  相似文献   

19.
Solid solution phases of a formula Fe8V10W16–xMoxO85 where 0≤x≤4, have been obtained, possessing a structure of the compound Fe8V10W16O85. It was found on the base of XRD and DTA investigations that these solution phases melted incongruently, with increasing the value of x, in the temperature range from 1108 (x=0) to 1083 K (x=4) depositing Fe2WO6 and WO3. The increase of the Mo6+ ions content in the crystal lattice of Fe8V10W16O85 causes the lattice parameters a=b contraction with cbeing almost constant. IR spectra of the Fe8V10W16–xMoxO85 solid solution phases have been recorded.  相似文献   

20.
In this study, to improve the specific capacitance of graphene-based supercapacitor, novel quadri composite of G/PPy/MnOx/Cu(OH)2 was synthesized by using a facile and inexpensive route. First, a two-step method consisting of thermal decomposition and in situ oxidative polymerization was employed to fabricate graphene/polypyrrole/manganese oxide composites. Second, Cu(OH)2 nanowires were deposited on Cu foil. Afterwards, for the electrochemical measurements, composite powders were deposited on Cu(OH)2/Cu foil substrate as working electrodes. The synthesized samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), Fourier transform infrared (FT-IR) spectroscopy, and Raman spectroscopy. The XRD analysis revealed the formation of PPy/graphene, Mn3O4/graphene, and graphene/polypyrrole/MnOx. In addition, the presence of polypyrrole and manganese oxides was confirmed using FT-IR and Raman spectroscopies. Graphene/polypyrrole/MnOx/Cu(OH)2 electrode showed the best electrochemical performance and exhibited the largest specific capacitance of approximately 370 F/g at the scan rate of 10 mV/s in 6 M KOH electrolyte. In addition, other electrochemical measurements (charge–discharge, EIS and cyclical performance) of the G/Cu(OH)2, G/PPy/Cu(OH)2, G/Mn3O4/Cu(OH)2, and G/PPy/MnOx/Cu(OH)2 electrodes suggested that the G/PPy/MnOx/Cu(OH)2 composite electrode is promising materials for supercapacitor application.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号