Understanding the hydroxyl adsorption behavior at Pt electrode surface in high-temperature alkaline solutions

Since the application in fuel cell,the electrochemical adsorption of hydroxyl has received considerable attention in recent years.While most research mainly focus on the room temperature,in this paper,the electrochemical adsorption of hydroxyl in alkaline solution at high temperature was investigated.An unusual oxidation peak was observed at-0.27 V,suggesting new behavior of hydroxyl adsorption occurred.As is known two kinds of cation hydrated clusters exist in alkaline solution,(H_(2)O)_(x-1)M^(+)-H_(2)O-O_(ad)H and(H_(2)O)_xM^(+)-O_(ad)H.For K^(+)and Cs^(+),the cluster shows unstable structure due to the weak interaction between hydrated cation and OH^(-)especially at high temperature.However,For Li^(+),Na^(+)the cluster structure would be stable,as the interaction force between the hydrated cation and OH^(-)is so strong.It was revealed that the unusual oxidation peak has some relationship with the(H_(2)O)_(x-1)M^(+)-H_(2)O-O_(ad)H cluster(K^(+)and Cs^(+))absorbed at Pt electrode surface.When the temperature was raised,(H_(2)O)_(x-1)M^(+)-H_(2)O-and-O_(ad)H was disconnected,then the O_(ad)H absorbed at Pt surface got oxidated.Based on the SEM observation,it was showed the unusual electrochemical oxidation reaction would generate platinum oxides,blocking the reactive sites at Pt electrode surface,thus reducing the electrochemical reactivity of Pt electrode.Accordingly,parameters of alkaline concentration and temperature were systematically studied,it was found that increase temperature or alkaline concentration was in favor of the unusual oxidation reaction.This study provides more understanding of hydroxyl adsorption behavior at Pt electrode surface for the high temperature water solution environment.

Selective recovery of lead from zinc oxide dust with alkaline Na_2EDTA solution

The selective recovery of lead from the zinc oxide dust using an alkaline Na2EDTA solution was investigated. The effects of temperature, leaching time, Na2EDTA concentration and initial NaOH concentration on the leaching rates of lead and zinc were studied. The following optimized leaching conditions were obtained： liquid-to-solid ratio 5：1 mL/g, stirring speed 650 r/min, Na2EDTA concentration 0.12 mol/L, initial NaOH concentration 0.5 mol/L, leaching temperature 70 ℃, leaching time 120 min. Under the optimized conditions, the average leaching rates of lead, zinc, fluoride and chloride are 89.92%, 0.94%, 62.84% and 90.02%, respectively. The filtrate was used to electrowin lead powders. The average current efficiency of electrowinning is about 93% and lead content is higher than 98% under the conditions of temperature of 60 ℃, current density of 200 A/m2, H3PO4 concentration of 1.5 g/L, and lead ion concentration of above 5 g/L. The consumption of Na2EDTA and the direct current are about respectively 0.218 kg and 0.958 kW·h for per kilogram of lead powder.

SELECTIVE DISSOLUTION OF GOLD IN AN ALKALINETHIOUREA SOLUTION BY ELECTROLYSIS

Anodic polarization behavior of gold, silver, copper, nickel and iron in potentiostatic condition has been examined in an alkaline aqueous thiourea solution, where gold is hardly dissoluble normally. The addition of Na2SO3 into the solution can accelerate anodic dissolution of gold. The factors affecting selective dissolution of gold in the alkaline thiourea solution by electrolysis have been studied, and the optimum condition was obtained. In 0.1 mol/L thiourea solution of pH 12. 5 containing 0. 5 mol/L Na2SO3 and 2. 5% acetone, at the potential of 0. 34 V vs NHE, at the temperature of 323 K, the dissolved mass of gold anode with the exposed area of 1. 0 cm2 reached more than 300 mg·dm-3 within 30 min, and other metals such as silver, copper, nickel and iron could hardly dissolve.

Polyaniline Formed in Alkaline Solution─A New Luminous Material

Electropolymerization of aniline in KOH solution and properties of the polymer are studied by using in situ reflex ellipsometry, cyclic voltammetry and fluorescence spectroscopic method. The change patterns of ellipsometric parameters and the thickness of film in the process of electropolymerization are investigated. The complex refractive indices and the fluorescence spectra of PAN indicate that the PAN is a new kind of luminous material.

Effects of additives on zinc electrodeposition from alkaline zincate solution

The effects of additives on the surface and cross-sectional morphologies of zinc deposits on iron substrate from alkalinezincate solution were characterized by scanning electron microscope(SEM).The cathodic reaction mechanisms under variousconcentrations of additives were investigated using cyclic voltammetry(CV)and electrochemical impedance spectroscopy(EIS)techniques.It is found that with increasing the additive A content in the bath solution,the nucleation overpotential(NOP)value isobviously increased and the inhibition effect is strengthened.This may be mainly due to the adsorption of additive A on the cathodicelectrode surface,which can cover the active sites and block the discharge reduction.The results of EIS analysis indicate that therate-determining step of zinc electrodeposition process is changed from mixed control step into electrochemical reduction step in thepresence of additive A.However,any quantity of additive B has little effect on the NOP value and the inhibition effect is not obvious.Furthermore,addition of additive A and additive B at the same time displays the strongest inhibition effect and shows a strongsynergism because of their co-adsorption on the cathodic electrode surface.

Effects of applied potential on the stress corrosion cracking behavior of 7003 aluminum alloy in acid and alkaline chloride solutions

Potentiodynamic polarization tests and slow strain rate test（SSRT） in combination with fracture morphology observations were conducted to investigate the stress corrosion cracking（SCC） behavior of 7003 aluminum alloy（AA7003） in acid and alkaline chloride solutions under various applied potentials（Ea）. The results show that AA7003 is to a certain extent susceptible to SCC via anodic dissolution（AD） at open-circuit potential（OCP） and is highly susceptible to hydrogen embrittlement（HE） at high negative Ea in the solutions with p H levels of 4 and 11. The susceptibility increases with negative shift in the potential when Ea is less than-1000 m V vs. SCE. However, the susceptibility distinctly decreases because of the inhibition of AD when Ea is equal to-1000 m V vs. SCE. In addition, the SCC susceptibility of AA7003 in the acid chloride solution is higher than that in the alkaline solution at each potential. Moreover, the effect of hydrogen on SCC increases with increasing hydrogen ion concentration.

Degradation rates and products of fluticasone propionate in alkaline solutions

The apparent degradation rate constant of fluticasone propionate(FLT) in 0.1 M NaOH:methanol=1:1 at 37 °C was previously reported to be 0.169 ± 0.003 h^(-1), and four degradation products(products 1–4) were observed in the solution. The aims of the present study were to assess the degradation rates of FLT in other alkaline solutions and clarify the chemical structures of the four degradation products in order to obtain basic data for designing an enema for inflammatory bowel disease. The apparent degradation rate constants in 0.05 M NaOH and 0.1 M NaOH:CH_3CN=1:1 were 0.472 ± 0.013 h^(-1) and 0.154 ± 0.000 h^(-1)(n=3), respectively. The chemical structures of products 1–4 in 0.1 M NaOH:methanol=1:1 were revealed by nuclear magnetic resonance(NMR)and mass spectrometry data. The chemical structure of products 2 was that the 17-position of the thioester moiety of FLT was substituted by a carboxylic acid. The degradation product in 0.1 M NaOH:CH_3CN=1:1 was found to be product 2 based on ~1H NMR data. The degradation product in 0.05 M NaOH was considered to be product 2 based on the retention time of HPLC. These results are useful for detecting the degradation products of FLT by enzymes of the intestinal bacterial flora in the large intestine after dosing FLT as an enema.

Corrosion behavior of dissimilar copper/brass joints welded by friction stir lap welding in alkaline solution

This study was done to evaluate the nugget zone(NZ)corrosion behavior of dissimilar copper/brass joints welded by friction stir lap welding(FSLW)in a solution of 0.015 mol/L borax(pH 9.3).To this end,dissimilar copper/brass plates were welded with two dissimilar heat inputs(low and high)during the welding procedure.The high and low heat inputs were conducted with 710 r/min,16 mm/min and 450 r/min,25 mm/min,respectively.Using open circuit potential(OCP)measurements,electrochemical impedance spectroscopy(EIS)and Tafel polarization tests,the electrochemical behavior of the specimens in borate buffer solution was assessed.With the help of scanning electron microscope(SEM),the morphology of welded specimen surfaces was examined after immersion in the test solution.According to the results,the NZ grain size and resistance improvement reduced due to the nugget zone corrosion with a decreased heat input.The results obtained from Tafel polarization and EIS indicated the improved corrosion behavior of the welded specimen NZ with a decrease in the heat input during the welding process unlike the copper and brass metals.Furthermore,an increased heat input during the welding process shows a reduction in the conditions for forming the passive films with higher protection behavior.

Alkaline extraction characteristics of steelmaking slag batch in NH_4Cl solution under environmental pressure

In order to obtain better carbonation effect, extraction behavior of slag batch is necessary to study. Relevant parameters like selective extraction yield were originally discussed. The relationship between selective extraction yield and conversion ratio was systemically focused on. The results show that alkaline earth metal conversion ratio is changed with leaching time and NH4CI concentration by first order exponential, and the maximum conversion for calcium keeps about 68% at 120 min in 0.4 mol/L NH4C1 solution, while leaching temperature and particle size have a linear effect on conversion ratio. Selective extraction yield of calcium is more than 93%, and the value of Mg is less than 5%. Apparent layer bands of silicon and calcium appear in the surface area through morphology detection of slag after leaching, and the case for 38-75 μm slag batch is more obvious than 75 150 μm slag and slag with larger particle size when leaching in 0.4 mol/L NH4Cl solution for 90 rain at 60 ℃.

Anodic dissolution of gold in alkaline solutions containing thiourea, thiosulfate and sulfiteions

Gold dissolves electrochemically in alkaline solutions containing ligands to form complex ions with gold ion. Therefore, selective leaching of noble metals is expected without dissolution of base metals such as steels, aluminum alloys in scrap treatment. Gold electrodes were investigated using linear sweep voltammetry, EQCM method and potentiostatic electrolysis in alkaline solutions containing thiourea, Na 2SO 3 and Na 2S 2O 3. The solution composition, electrode potential affect gold dissolution rate and current efficiency. The gold dissolved from anode electrode forms complex ions, suspension particles as compound precipitates and deposits on cathode electrode as a metal. Anodic efficiency for gold dissolution is between 10% and 22%. This is caused by the oxidation decomposition of sulfite ions and thiourea. The stability of the alkaline solution containing these elements was also estimated by capillary electrophoresis technique.

Electrocatalytic Activity of Ni/C Electrodes Prepared by Metal Vapor Synthesis For Hydrogen Evolution in Alkaline Solution

The metal vapor synthesis (MVS) methed was used to prepare activatedcarbon supported nickel electrode. The electrocatalytic activity of the electrode forhydrogen evolution reaction(HGR) in alkaline solution was studied. Cathodicpolarization curves showed the electrocatalytic activity of Ni/C electrode prepared byMVS method was higher than that of the one prepared by conventional method.

Gold leaching with elemental sulfur in alkaline solutions under oxygen pressure

A gold leaching process by using oxidation products of elemental sulfur in alkaline solutions was proposed and investigated. A gold concentrate and a residue from an arsenic refractory gold concentrate by acidic oxidation leaching were tested. The residue contains 16.3% elemental sulfur and no more elemental sulfur was added in tests. For the concentrate elemental sulfur was added before leaching tests. The leaching ratio of gold depends mainly on the initial equivalent ratio of elemental sulfur to hydroxyl ions, the consumption of oxygen and the reaction temperature in the process. Analysis of the experimental results shows that thiosulfate is the majority complexing reagent for gold in the process. Over 90% gold was leached from the residue and 82%87% from the concentrate by using this process.

Corrosion-wear behavior of nanocrystalline Fe88Si12 alloy in acid and alkaline solutions

The corrosion-wear behavior of a nanocrystalline Fe_（88）Si_（12） alloy disc coupled with a Si_3N_4 ball was investigated in acid（pH 3） and alkaline（pH 9） aqueous solutions. The dry wear was also measured for reference. The average friction coefficient of Fe_（88）Si_（12） alloy in the pH 9 solution was approximately 0.2, which was lower than those observed for Fe_（88）Si_（12） alloy in the pH 3 solution and in the case of dry wear. The fluctuation of the friction coefficient of samples subjected to the pH 9 solution also showed similar characteristics. The wear rate in the pH 9 solution slightly increased with increasing applied load. The wear rate was approximately one order of magnitude less than that in the pH 3 solution and was far lower than that in the case of dry wear, especially at high applied load. The wear traces of Fe_（88）Si_（12） alloy under different wear conditions were examined and analyzed by scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy. The results indicated that the tribo-chemical reactions that involve oxidation of the worn surface and hydrolysis of the Si_3N_4 ball in the acid solution were restricted in the pH 9 aqueous solution. Thus, water lubrication can effectively improve the wear resistance of nanocrystalline Fe_（88）Si_（12） alloy in the pH 9 aqueous solution.

Enhancing hydrogen electrocatalytic oxidation on Ni_(3)N/MoO_(2)in-plane heterostructures in alkaline solution

Nickel(Ni)-based materials act as one of the most promising candidates as platinum-group-metal-free(PGM-free)electrocatalysts for hydrogen oxidation reaction(HOR)in alkaline solution.Nevertheless,the electrocatalytic activity of pure Ni is significantly limited due to the sluggish kinetics under alkaline condition.To accelerate the kinetics,constructing heterostructures and nitride structures have been developed as two representative strategies.Here,we combined the two methods and presented a facile synthesis of the sheet-like Ni_(3)N/MoO_(2)in-plane heterostructures for enhanced HOR in alkaline electrolytes.Relative to Ni or Ni_(3)N,the Ni_(3)N/MoO_(2)in-plane heterostructures exhibited a significantly increased mass activity by 8.6-fold or 4.4-fold,respectively.Mechanistic studies revealed that the enhanced activity of Ni_(3)N/MoO_(2)could be attributed to the weakened hydrogen adsorption and strengthened hydroxyl adsorption.This work provides a facile approach to design high-efficiency catalysts for hydrogen-oxidation catalysis and beyond.

Corrosion behavior of Cu/Al casting-rolled clad plates in different alkaline solution

The effect of pH value and different kinds of anions on the corrosion behavior of Cu/Al casting-rolled clad plates in the alkaline solution was evaluated by means of scanning electron microscopy(SEM),energy dispersive spectroscopy(EDS),X-ray diffraction(XRD),weight loss analysis,3D confocal laser scanning microscopy(CLSM)and electrochemical test.Results show the corrosion mainly occurs on the aluminum side.The corrosion resistance of the Cu/Al decreases as the pH value increases.When pH≥12,the dissolution of the film layer is faster than the passivation process.The addition of Cl^(-)ions reduces the corrosion resistance of the Cu/Al clad plates,which leads to pitting corrosion.The higher the concentration of Cl^(-)ions,the more prone the pitting to occur.The addition of SO_(4)^(2-)ions causes the denudation of the samples.The corrosion resistance of the Cu/Al is better in the alkaline solution containing NO_(3)^(-)ions than that in the solution containing Cl^(-)ions or SO_(4)^(2-)ions.When adding SO_(4)^(2-),NO^(3)^(-)and Cl^(-)to the pure alkaline solution,the corrosion resistance of the Cu/Al clad plates decreases.

POLAROGRAPHIC CHARACTERISTICS OF TELLURIUM(Ⅳ)IN ALKALINE DYE-ACID SOLUTION

Polarographic characteristics of Te(Ⅳ)-alkaline dye were investiga- ted at mercury electrode in acidic solution.It was found that the mechanism of the electrode process depended on the concentration of Te(Ⅳ).

The interaction mechanism between zein and folic acid in alkaline aqueous solutions:an experimental and molecular simulation study

Objectives:Folic acid is a vitamin that is not highly soluble in water and is sensitive to the environment.Therefore,it is important to find suitable carriers.This study aimed to exemplify the interaction of folic acid with zein in alkaline aqueous solutions and shed light on how zein can be used as a carrier for folic acid.Materials and Methods:Zein and folic acid were separately dissolved in NaOH solutions with a PH of 11.5.Zein solution and folic acid solution were combined in specific ratios.Various methods including multi-spectroscopy,dynamic light scattering,and electron microscopy combining with molecular dynamics simulations were used to study the interaction mechanism between zein and folic acid in alkaline aqueous solutions.Results:Fluorescence spectroscopy showed that the quenching of zein by folic acid was mainly static,and the main driving force behind this interaction was van der Waals forces and hydrogen bonds.The formation of zein–folic acid complexes was confirmed by ultraviolet–visible spectroscopy,Fourier transform infrared spectroscopy,and circular dichroism spectroscopy.The results also showed that the structure of zein changed when it interacted with folic acid.Dynamic light scattering analysis revealed that the addition of folic acid caused proteins to aggregate.The aggregates of the complexes had an irregular shape and were large,as observed by scanning electron microscopy and transmission electron microscopy.Molecular simulation was used to further investigate the interaction mechanisms.According to these findings,the folic acid molecule interacted with zein in a shallow recess near the protein surface.The dominant forces at play in the zein–folic acid interaction were van der Waals forces and electrostatic forces,including hydrogen bonding.Conclusion:The zein alkali-soluble system is very suitable for folic acid delivery.

Electrolyte-gated SrCoO_(x) FET sensor for highly sensitive detecting pH in extreme alkalinity solution

The pH monitoring is significantly important in chemical industry,biological process,and pollution treatment.However,it remains a great challenge to measure pH in extreme alkalinity conditions.Herein,we employ an electrolyte-gated field-effect-transistor(FET)strategy using non-stoichiometric SrCoO_(x) with rich oxygen-vacancy defects as channel materials for detecting extreme alkalinity.The corresponding channel can provide effective oxygen-ion-migration sites for reversible transformation of OH-↔O_(2)-+H^(+)driven by electric field.The resultant electrolyte-gated FET sensor exhibits a sensitive linear response to high concentrations of alkaline solution,1–20 M.Significantly,the sensor has the ability to directly indicate the pH values ranging from 14.0 to 17.0 in consideration of ion-activity coefficient data.This work offers a great possibility for directly detecting base concentration as well as pH values in extreme alkaline solutions.

Separation of silicon and iron in copper slag by carbothermic reduction-alkaline leaching process

Approximately 2.0-3.0 t of copper slag(CS) containing 35%-45% iron is generated for every ton of copper produced during the pyrometallurgical process from copper concentrate. Therefore, the recovery of iron from CS utilizes a valuable metal and alleviates the environmental stress caused by stockpile. In this paper, a new method has been developed to realize the enrichment of iron in CS through the selective removal of silica. The thermodynamic analyses and experimental results show that the iron in CS can be fully reduced into metallic iron by carbothermic reduction at 1473 K for 60 min. The silica was converted into free quartz solid solution(QSS) and cristobalite solid solution(CSS). QSS and CSS are readily soluble, whereas metallic iron is insoluble, in NaOH solution. Under optimal leaching conditions, a residue containing 87.32% iron is obtained by decreasing the silica content to 6.02% in the reduction roasted product. The zinc content in the residue is less than 0.05%. This study lays the foundation for the development of a new method to comprehensively extract silicon and iron in CS while avoiding the generation of secondary tailing.

PHOTOELECTROCHEMICAL STUDY OF PASSIVE LAYERS ON COPPER ELECTRODES IN SOME ALKALINE MEDIA

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