Enhanced Electrochemical Oxidation of BH4− on Pt Electrode in Alkaline Electrolyte with the Addition of Thiourea

2010 ◽  
Vol 132 ◽  
pp. 271-278 ◽  
Author(s):  
Dan Mei Yu ◽  
Chang Guo Chen ◽  
Shu Lei ◽  
Xiao Yuan Zhou ◽  
Guo Zhong Cao

The electrochemical oxidation of sodium borohydride (NaBH4) on Pt electrode in alkaline electrolyte with the addition of thiourea has been studied by means of cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and chronopotentiometry (CP). NaBH4 is readily to react with hydroxyl groups to release hydrogen through either direct oxidation or catalytic hydrolysis. The experimental results demonstrated that the addition of an appropriate amount of thiourea to the alkaline electrolyte resulted in the suppression of catalytic hydrolysis and diffusion of borohydride ions through the separation membrane.

2020 ◽  
Vol ahead-of-print (ahead-of-print) ◽  
Author(s):  
Belkis Ustamehmetoğlu ◽  
Nesrin Köken ◽  
Nilgun Kizilcan ◽  
Ahmet Akar ◽  
Şebnem Tayyar

Purpose The purpose of this paper is to produce non-conductive copolymers of N-vinyl carbazole (NVCz) and methyl ethyl ketone formaldehyde resin (MEKFR) by the electroinduced Ce (IV) polymerization method and the electrochemical oxidization of the formed copolymer to produce their conductive green form. The non-conductive and conductive copolymers were characterized by using Fourier transform infrared, solid-state conductivity and spectroelectrochemical, chronoamperometric, cyclovoltammetric and electrochemical impedance spectroscopic measurements. Design/methodology/approach The chronoamperometric electropolymerization of white, insulator form of the copolymer of NVCz and MEKFR (copolymer 1) on to Pt electrode was carried out and the green coloured film of the MEKFR-ox-NVCz copolymer (copolymer 11) was produced in the doped and conductive form. All reactions were performed in dichloromethane containing 0.1 M BU4NClO4. Copolymer 11 films obtained on the surface of the working electrode were removed and washed in acetonitrile and dried at room temperature before characterization. The results were compared with the copolymer obtained by electrochemical oxidation of MEKF-R and NVCz (copolymer 2). Findings The insulating copolymer of NVCz and MEKFR (copolymer 1) was produced by the electroinduced Ce (IV) polymerization method and converted into the conductive form electrochemically on the surface of the Pt electrode (copolymer 11). The polymers were characterized by electrochemical, spectrophotometric and conductivity measurements. The ionization potentials, optical band gap, peak potentials Ep, doping degree and specific capacitance of the copolymer 11 were obtained. The conductivity of the copolymer 11 is lower than the PNVCz and higher than the copolymer obtained by electrochemical oxidation of MEKF-R and NVCz (copolymer 2). The copolymer 11 has a lower onset potential than PNVCz and the copolymer 1 and slightly higher band gap than PNVCz. The capacitive behaviours of the copolymer 11 were very close to PNVCz. Research limitations/implications This study focuses on obtaining a green and conductive form of the copolymer of NVCz and MEKFR with the electrochemical method by using a white and insulator form of the same copolymer. Practical implications This work provides technical information for the synthesis of conducting copolymer of NVCz and MEKFR. Social implications These copolymers may be in the field of PNVCz applications such as photoconductivity and corrosion inhibition. Originality/value Electroinduced Ce (IV) MEKFR redox system was applied for the polymerization of NVCz monomer to produce the copolymer 1. The conductive copolymer 11 was synthesized through electrochemical oxidative coupling of the carbazole groups of the copolymer 1.


2012 ◽  
Vol 588-589 ◽  
pp. 90-94 ◽  
Author(s):  
Hua Li Zhao ◽  
Qun Chu You ◽  
An Ma Chun

Electrochemical behaviors of Ce3+/Ce4+ couple in mixed acid (H2SO4 and CH3SO3H) were investigated on Pt electrode. Polarization curves and electrochemical impedance spectroscopy (EIS) were used to optimize mixed acid composition, and the mixed acid consisting of 1.0 M methanesulfonic acid (MSA) and 0.8 M sulfuric acid is singled out as the optimum electrolyte. Subsequently, the effects of current density and electrolyte temperature on the electrochemical oxidation of Ce3+ to Ce4+ were researched. A 92.2% current efficiency was achieved at 40 mA•cm-2 in cerium (III) solution with the optimum mixed acid electrolyte above at 313 K. It can satisfy the application of mediated electrochemical oxidation process with Ce3+/Ce4+ mediator.


2011 ◽  
Vol 347-353 ◽  
pp. 3264-3267 ◽  
Author(s):  
Dong Hong Duan ◽  
Yi Fang Zhao ◽  
Shi Bin Liu ◽  
Ai Lian Wu

The electrochemical behavior of BH4- on Cu electrode in 1M NaOH was investigated by cyclic voltammetry(CV) in the potential range of -1.2V to 0.4V versus Hg/HgO. The CV results show that Cu electrode has obvious catalytic activities to the BH4- hydrolysis which belongs to ‘catalytic’ electrode materials. The BH4- electro-oxidation process on Cu is complex and it could associate with the BH4- hydrolysis reaction, followed by oxidation of the intermediate H, then, the intermediate product (e.g. BH3OH−) oxidized, and direct oxidation of BH4- at more positive potentials.


2001 ◽  
Vol 73 (12) ◽  
pp. 1929-1940 ◽  
Author(s):  
Z. Ezerskis ◽  
Z. Jusys

Potentiodynamic investigations on a platinum electrode show that oxidation of phenol, monochlorophenols, dichlorophenols, 2,3,6-, 2,4,5-, 2,4,6-trichlorophenols, and pentachlorophenol in 1 M NaOH solution, containing 1 mM of phenols, proceeds in the potential region of Pt oxide formation. The oxidation rate of phenols decreases with the increase in the number of chlorine atoms in the benzene ring in the row: phenol > monochlorophenols > dichlorophenols > trichlorophenols > pentachlorophenol. The electrochemical stability of phenols, as studied using a cyclic voltammetry, depends on their chlorination degree and isomerism. Galvanostatic oxidation of 1 M NaOH solutions containing 1 mM of phenol, monochlorophenols, dichlorophenols, 2,3,6-, 2,4,5-, 2,4,6-trichlorophenols, and pentachlorophenol were carried out on a platinum electrode using 30 mA cm­2 current density. The electrolysis of the solutions was performed in the course of 10 h, and concentration of phenols in the anolytes was monitored during oxidation. The concentration of phenolic compounds diminishes from 1 mM to 10­50 mM during 4­5 h of electrooxidation and does not change during further galvanostatic oxidation. A decrease in concentration of phenols during galvanostatic electrolysis weakly depends on the isomerism and a chlorination degree of the compounds. A rapid decrease in concentration of studied phenols during the first 4­5 h of electrolysis and a nonselective oxidation of different chlorophenols suggest that the oxidation proceeds via electrochemically generated oxidants. Further decrease in concentration of phenols is rather small due to deactivation of the electrode as a result of polymerization of corresponding phenols and diffusion limitations.


2015 ◽  
Vol 3 (2) ◽  
pp. 267-271
Author(s):  
Richa Sharma ◽  
Sushma Dave

Electrochemical oxidation of methyl substituted aniline (anisidine) has been done on both gold and platinum electrode using cyclic voltammetry. The results were compared in different supporting electrolytes such as KCl, KNO3, H2SO4, HCl. Effect of pH was observed on electrochemical oxidation of o- & p- anisidine at gold and platinum electrode. During various scan single oxidation peak during first forward scan with no corresponding cathodic peak was obtained while a new anodic cathodic couple peak appears in subsequent scan obtained. Kinetic parameters like heterogeneous rate constant, transfer co-efficient and diffusion co-efficient were also calculated. A sensitive method was developed for estimation of micro quantities of anisidine by linear sweep voltammetry and hydrodynamic voltammetry.Int J Appl Sci Biotechnol, Vol 3(2): 267-271 DOI: http://dx.doi.org/10.3126/ijasbt.v3i2.12615 


Author(s):  
Nadica Abazovic ◽  
Tatjana Savic ◽  
Tatjana Novakovic ◽  
Mirjana Comor ◽  
Zorica Mojovic

Solvothermaly synthesized zirconium oxide nanopowders, pure and doped with various amounts of iron ions (1 - 20 %), were used as modifiers of glassy carbon electrode. The modified electrodes were tested in the reaction of electrochemical oxidation of 2,4,6-trichlorophenol (TCP) in order to investigate the influence of doping on electrochemical performance of zirconia matrix. The techniques of cyclic voltammetry and electrochemical impedance spectroscopy were employed. Cyclic voltammetry showed that electrooxidation of TCP proceeded through oxidation of hydroxyl group. Possible pathway included formation of quinones and formation of polyphenol film on the electrode surface leading to the electrode fouling. Iron doping enhanced the activity of zirconia matrix towards TCP electrooxidation. Electrochemical impedance spectroscopy showed the importance of iron content in zirconia matrix for preferable pathway of TCP electrooxidation. Quinone formation pathway was favored by low iron doped zirconia (doped with 1% of iron), while polyphenol film formation on the electrode surface was more pronounced at samples with higher iron ion content (for doping with 10 and 20 % of iron). The sample with 5 % of added iron ions, showed intermediate behavior where formed polyphenol film showed slight degradation.


1989 ◽  
Vol 54 (1) ◽  
pp. 64-69 ◽  
Author(s):  
Roland Meier ◽  
Gerhard Werner ◽  
Matthias Otto

Electrochemical oxidation of [V(IV)O(nta)(H2O)]- (H3nta nitrilotriacetic acid) was studied in aqueous solution by means of cyclic voltammetry, differential pulse polarography, and current sampled DC polarography on mercury as electrode material. In the pH-range under study (5.5-9.0) the corresponding V(V) complex is produced by one-electron oxidation of the parent V(IV) species. The oxidation product is stable within the time scale of cyclic voltammetry. The evaluation of the pH-dependence of the half-wave potentials leads to a pKa value for [V(IV)O(nta)(H2O)]- which is in a good agreement with previous determinations. The measured value for E1/2 is very close to the formal potential E0 calculated via the Nernst equation on the basis of known literature values for log Kox and log Kred, the complex stability constants for the oxidized and reduced form, respectively.


2001 ◽  
Vol 66 (1) ◽  
pp. 139-154 ◽  
Author(s):  
M. Fátima C. Guedes Da Silva ◽  
Luísa M. D. R. S. Martins ◽  
João J. R. Fraústo Da Silva ◽  
Armando J. L. Pombeiro

The organonitrile or carbonyl complexes cis-[ReCl(RCN)(dppe)2] (1) (R = 4-Et2NC6H4 (1a), 4-MeOC6H4 (1b), 4-MeC6H4 (1c), C6H5 (1d), 4-FC6H4 (1e), 4-ClC6H4 (1f), 4-O2NC6H4 (1g), 4-ClC6H4CH2 (1h), t-Bu (1i); dppe = Ph2PCH2CH2PPh2), or cis-[ReCl(CO)(dppe)2] (2), as well as trans-[FeBr(RCN)(depe)2]BF4 (3) (R = 4-MeOC6H4 (3a), 4-MeC6H4 (3b), C6H5 (3c), 4-FC6H4 (3d), 4-O2NC6H4 (3e), Me (3f), Et (3g), 4-MeOC6H4CH2 (3h); depe = Et2PCH2CH2PEt2), novel trans-[FeBr(CO)(depe)2]BF4 (4) and trans-[FeBr2(depe)2] (5) undergo, as revealed by cyclic voltammetry at a Pt-electrode and in aprotic non-aqueous medium, two consecutive reversible or partly reversible one-electron oxidations assigned as ReI → ReII → ReIII or FeII → FeIII → FeIV. The corresponding values of the oxidation potentials IE1/2ox and IIE1/2ox (waves I and II, respectively) correlate with the Pickett's and Lever's electrochemical ligand and metal site parameters. This allows to estimate these parameters for the various nitrile ligands, depe and binding sites (for the first time for a FeIII/IV couple). The electrochemical ligand parameter show dependence on the "electron-richness" of the metal centre. The values of IE1/2ox for the ReI complexes provide some supporting for a curved overall relationship with the sum of Lever's electrochemical ligand parameter. The Pickett parametrization for closed-shell complexes is extended now also to 17-electron complexes, i.e. with the 15-electron ReII and FeIII centres in cis-{[ReCl(dppe)2]}+ and trans-{FeBr(depe)2}2+, respectively.


Sign in / Sign up

Export Citation Format

Share Document