Electrocarboxylation of CO_(2) with Organic Substrates:Toward Cathodic Reaction

Electrocarboxylation of carbon dioxide(CO_(2))using organic substrates has emerged as a promising method for the sustainable synthesis of value-added carboxylic acids due to its renewable energy source and mild reaction conditions.The reactivity and product selectivity of electrocarboxylation are highly dependent on the cathodic behavior,involving a sequence of electron transfers and chemical reactions.Hence,it is necessary to understand the cathodic reaction mechanisms for optimizing reaction performance and product distribution.In this work,a review of recent advancements in the electrocarboxylation of CO_(2)with organic substrates based on different cathodic reaction pathways is presented to provide a reference for the development of novel methodologies of CO_(2)electrocarboxylation.Herein,cathodic reactions are particularly classified into two categories based on the initial electron carriers(i.e.,CO_(2)radical anion and substrate radical anion).Furthermore,three cathodic pathways(ENE(N),ENED,and EDEN)of substrate radical anion-induced electrocarboxylation are discussed,which differ in their electron transfer sequence,substrate dissociation,and nucleophilic reaction,to highlight their implications on reactivity and product selectivity.

Plasma diagnosis of tetrahedral amorphous carbon films by filtered cathodic vacuum arc deposition

Filtered cathodic vacuum arc(FCVA)deposition is regarded as an important technique for the synthesis of tetrahedral amorphous carbon(ta-C)films due to its high ionization rate,high deposition rate and effective filtration of macroparticles.Probing the plasma characteristics of arc discharge contributes to understanding the deposition mechanism of ta-C films on a microscopic level.This work focuses on the plasma diagnosis of an FCVA discharge using a Langmuir dualprobe system with a discrete Fourier transform smoothing method.During the ta-C film deposition,the arc current of graphite cathodes and deposition pressure vary from 30 to 90 A and from 0.3 to 0.9 Pa,respectively.The plasma density increases with arc current but decreases with pressure.The carbon plasma density generated by the arc discharge is around the order of10^(10)cm^(-3).The electron temperature varies in the range of 2-3.5 eV.As the number of cathodic arc sources and the current of the focused magnetic coil increase,the plasma density increases.The ratio of the intensity of the D-Raman peak and G-Raman peak(I_(D)/I_(G))of the ta-C films increases with increasing plasma density,resulting in a decrease in film hardness.It is indicated that the mechanical properties of ta-C films depend not only on the ion energy but also on the carbon plasma density.

Optical and electrical properties of BaSnO_(3) and In_2O_(3) mixed transparent conductive films deposited by filtered cathodic vacuum arc technique at room temperature

For the crystalline temperature of BaSnO_(3)(BTO)was above 650℃,the transparent conductive BTO-based films were always deposited above this temperature on epitaxy substrates by pulsed laser deposition or molecular beam epitaxy till now which limited there application in low temperature device process.In the article,the microstructure,optical and electrical of BTO and In_(2)O_(3) mixed transparent conductive BaInSnO_(x)(BITO)film deposited by filtered cathodic vacuum arc technique(FCVA)on glass substrate at room temperature were firstly reported.The BITO film with thickness of 300 nm had mainly In_(2)O_(3) polycrystalline phase,and minor polycrystalline BTO phase with(001),(011),(111),(002),(222)crystal faces which were first deposited at room temperature on amorphous glass.The transmittance was 70%–80%in the visible light region with linear refractive index of 1.94 and extinction coefficient of 0.004 at 550-nm wavelength.The basic optical properties included the real and imaginary parts,high frequency dielectric constants,the absorption coefficient,the Urbach energy,the indirect and direct band gaps,the oscillator and dispersion energies,the static refractive index and dielectric constant,the average oscillator wavelength,oscillator length strength,the linear and the third-order nonlinear optical susceptibilities,and the nonlinear refractive index were all calculated.The film was the n-type conductor with sheet resistance of 704.7Ω/□,resistivity of 0.02Ω⋅cm,mobility of 18.9 cm2/V⋅s,and carrier electron concentration of 1.6×10^(19) cm^(−3) at room temperature.The results suggested that the BITO film deposited by FCVA had potential application in transparent conductive films-based low temperature device process.

Effect of 10% Si addition on cathodic arc evaporated TiAlSiN coatings

The effect of 10% Si （mole fraction） addition on TiAlSiN coatings was studied. Ti0.5Al0.5N, Ti0.5Al0.4Si0.1N and Ti0.55Al0.35Si0.1N coatings were deposited on WC？Co substrates by cathodic arc evaporation. The microstructure and mechanical properties were characterized by X-ray diffraction （XRD）, X-ray photoelectron spectroscopy （XPS）, scanning electron microscopy （SEM）, nano-indentation measurement and scratch test. The mechanisms of how Si affects the properties and failure modes of TiAlSiN coatings were also discussed. The results show that the addition of 10% Si results in the formation of nc-（Ti,Al,Si）N/a-Si3N4 nano-composite structure. The hardness and toughness of TiAlSiN coatings increase, whereas the coating adhesion strength decreases. Compared with Ti0.55Al0.35Si0.1N coating, Ti0.5Al0.4Si0.1N coating has higher hardness but lower toughness. The dominant failure mode of TiAlN coating is wedging spallation due to low toughness and strong interfacial adhesion. The dominant failure mode of TiAlSiN coatings is buckling spallation due to improved toughness and weakened interfacial adhesion.

Pseudo-capacitive Behavior of Cobalt Hydroxide/Carbon Nanotubes Composite Prepared by Cathodic Deposition

A novel type of composite electrode based on nmltiwalled carbon nanotubes coated with sheet-like cobalt hydroxide particles was used in supercapacitors. Cobalt hydroxide cathodlcally deposited fiom Co（NO3）O2 solution with carbon nanotubes as matrix exhibited large pseudo-capacitance of 322 F/g in 1 mol/L KOH. To characterize the cobalt hydroxide nanocomposite electrode, a charge-discharge cycling test, cyclic voltammetry, and an impedance test were done. This cobalt hydroxide composite exhibiting excellent pseudo-capacitive behavior （i.c. high reversibility, high specific capacitance, low impedance）, was demonstrated to be a candidate for the application of electrochemical supercapacitors. A combined capacitor consisting of cobalt hydroxide composite as a cathode and activated carbon fiber as an anode was reported. The electrochemical pcrformance of the combined capacitor was characterized by cyclic voltammetry and a dc charge/discharge test. The combined capacitor showed ideal capacitor behavior with an extended operating voltage of 1.4 V. According to the extended operating voltage, the energy density of the combined capacitor at a current density of 100 mA/cm^2 was found to be 11 Wh/kg. The combined capacitor exhibited high-energy density and stable power characteristics,

CATHODIC PROCESS AND WEAR RESISTANCE OF ELECTRO-DEPOSITED RE-Ni-W-P-SiC COMPOSITE COATING

Cathodic deposition current density of the composite coatings increases when SiC par-ticles and rare earth (RE) were added in the bath, which is profitable for Ni- W-P alloy to deposit in the cathod, forming Ni-W-P-SiC and RE-Ni-W-P-SiC composite coatings. On the contrary, the addition of PTFE in the bath decreases cathodic deposition current density of the coatings. The current density increases a little when the amount of RE is 7-9g/l; however, the current density increases greatly when the amount of RE is increased to 11-13g/l. Bui ij the amount of RE is raised further, the current density decreases. Hardness and wear resistance of RE-Ni-W-P-SiC composite coating have been studied, and the results show that the hardness and wear resistance of RE-Ni-W-P-SiC composite coating increase with increasing heat treatment tempera-ture, which reach peak values at 400℃; while the hardness and wear resistance of the coating decrease with the rise of heat treated temperature continuously.

Effect of Zn/Mg ratio on cathodic protection of carbon steel using Al-Zn-Mg sacrificial anodes

Al-Zn-Mg alloys with different Zn/Mg mass ratios were evaluated as sacrificial anodes for cathodic protection of carbon steel in 3.5 wt.%Na Cl solution.The anodes were fabricated from pure Al,Zn and Mg metals using casting technique.Optical microscopy,SEM-EDS,XRD and electrochemical techniques were used.The results indicated that with decreasing Zn/Mg mass ratio,the grain size ofα(Al)and the particle size of the precipitates decreased while the volume fraction of the precipitates increased.The anode with Zn/Mg mass ratio>4.0 exhibited the lowest corrosion rate,while the anode with Zn/Mg mass ratio<0.62 gave the highest corrosion rate and provided the highest cathodic protection efficiency for carbon steel(AISI 1018).Furthermore,the results showed that the anode with Zn/Mg mass ratio<0.62 exhibited a porous corrosion product compared to the other anodes.

A review on photoelectrochemical cathodic protection semiconductor thin films for metals

Photoelectrochemical(PEC) cathodic protection is considered as an environment friendly method for metals anticorrosion. In this technology, a n-type semiconductor photoanode provides the photogenerated electrons for metal to achieve cathodic protection. Comparing with traditional PEC photoanode for water splitting, it requires the photoanode providing a suitable cathodic potential for the metal, instead of pursuit ultimate photon to electric conversion efficiency, thus it is a more possible PEC technology for engineering application. To date, great efforts have been devoted to developing novel n-type semiconductors and advanced modification method to improve the performance on PEC cathodic protection metals. Herein, recent progresses in this field are summarized. We highlight the fabrication process of PEC cathodic protection thin film, various nanostructure controlling, doping, compositing methods and their operation mechanism. Finally, the current challenges and future potential works on improving the PEC cathodic protection performance are discussed.

CREVICE CORROSION BEHAVIOR OF X70 STEEL IN HCO_3^- SOLUTION UNDER CATHODIC POLARIZATION

The crevice corrosion behavior of XTO steel was investigated with a wedge-shaped crevice assembly under -1000 m V （SCE） cathodic polarization in the solutions with various HCO3 concentrations. The potential, current, pH and the oxygen content within the crevice were measured with or without outside coupled specimen. The results indicated that the polarization potential of XTO steel in the crevice dropped with the increase of time under the cathodic polarization. There was a remarkable influence of HCO3 concentration on the potential of XTO steel in the crevice. When HCO3 concentration was up to 0.125%, the surface of the metal was covered with the corrosion products that resulted in the polarization extent of XTO steel decreased. The pH value in the crevice rose and it dropped gradually from the crevice mouth to the bottom under the cathodic polarization. With the increasing of HCO3 concentration, the hydrolyzation reaction of metal in the crevice bottom aggravated. Most of the dissolved oxygen in the crevice was consumed by the cathodic current. The maximum cathodic current on the metal surface was at the crevice mouth and it was much more than that at the crevice bottom.

Cathodic reaction mechanisms in CO2 corrosion of low-Cr steels

The cathodic reaction mechanisms in CO2 corrosion of low-Cr steels were investigated by potentiodynamic polarization and galvanostatic measurements.Distinct but different dominant cathodic reactions were observed at different p H levels.At the higher p H level(p H>~5),H2 CO3 reduction was the dominant cathodic reaction.The reaction was under activation control.At the lower pH level(pH<~3.5),H+reduction became the dominant one and the reaction was under diffusion control.In the intermediate area,there was a transition region leading from one cathodic reaction to another.The measured electrochemical impedance spectrum corresponded to the proposed cathodic reaction mechanisms.

Effect of cathodic potential on stress corrosion cracking behavior of 21Cr2NiMo steel in simulated seawater

This study aims at providing systematically insights to clarify the impact of cathodic polarization on the stress corrosion cracking(SCC)behavior of 21 Cr2 NiMo steel.Slow-strain-rate tensile tests demonstrated that 21 Cr2 NiMo steel is highly sensitive to hydrogen embrittlement at strong cathodic polarization.The lowest SCC susceptibility occurred at-775 mV vs.SCE,whereas the SCC susceptibility was remarkably higher at potentials below-950 mV vs.SCE.Scanning electron microscopy(SEM)and electron backscattered diffraction(EBSD)revealed that the cathodic potential decline caused a transition from transgranular to intergranular mode in the fracture path.The intergranular mode transformed from bainite boundaries separation to prior austenitic grain boundaries separation under stronger cathodic polarization.Furthermore,corrosion pits promoted the nucleation of SCC cracks.In conclusion,with the decrease in the applied potential,the SCC mechanism transformed from the combination of hydrogen embrittlement and anodic dissolution to typical hydrogen embrittlement.

Experience on offshore cathodic protection retrofitting in the northern South China Sea

Platforms I and II are steel structures located in offshore areas southeast of the Zhujiang (Pearl) River Delta, the northern South China Sea,. in about 110 in water depth. The jackets, with aluminum sacrificial anodes for cathodic protection (CP) of the immersed zone, were launched in March 1995. In May 096 a CP survey showed that, after almost one year of service, a low polarization level had been achieved and some extended unprotected zones existed; mainly in the deepest part of the Platform II. Further to this, a joint activity was decided in order to assess the need of a possible retrofitting of the CP systems. The results of the activity carried out are dealt with, including technical and economical comparisons amongst several retrofitting options, both with sacrificial anodes and with impressed current systems. The adopted solution is illustrated and data are reported on the level of protection presently achieved.

Effects of cathodic polarization on SCC behavior of AA7003 under various aging treatments

In this paper,the effect of cathodic polarization on corrosion behavior of AA7003 under three kinds of aging treatments(including peak aging(PA),double peak aging(DPA)and regression re-aging(RRA))was studied in 3.5 wt%sodium chloride solution through slow strain rate testing(SSRT)and electrochemical testing.X-ray diffraction(XRD)and scanning electron microscopy(SEM)methods were also applied to investigating corrosion behavior and fracture morphology.The results showed that under open circuit,stress corrosion cracking(SCC)of AA7003 might by classified as anodic dissolution.In this case,the extent of SCC susceptibility(ISCC)of AA7003 alloy with different aging treatments was as follows:ISCC(PA)>ISCC(DPA)>ISCC(RRA).On the other hand,stress corrosion cracking(SCC)of AA7003 under cathodic polarization might be classified as hydrogen embrittlement(HE)which had been proved in this paper by presence of AlH3 diffraction peak in XRD patterns.In this case,for AA7003 with any of the three aging treatments,hydrogen embrittlement susceptibility(IHE)increases with negatively shifting of cathodic polarization.

Composition demixing effect on cathodic arc ion plating

The composition demixing effect has been found often in alloy coatings deposited by cathodic arc ion plating using various alloy cathode targets. The characteristics of composition demixing phenomena were summarized. Beginning with the ionization zone near the surface of the cathode target, a physical model in terms of the ions generated in the ionization zone and their movement in the plating room modified by bias electric field was proposed. Based on the concept of electric charge state, the simulation calculation of the composition demixing effect was carried out. The percentage of atoms of an element in coating and from the alloy target was demonstrated by direct comparison. The influences of the composition change of the alloy target and the bias electric field on the composition demixing effect were discussed in detail. It is also proposed that the average charge states of the elements may be used to calculate the composition demixing effect and to design the composition of the alloy target.

Cathodic micro-arc electro-deposition of ZrO_2 coatings in an aqueous solution containing colloidal particles

By a novel technique-cathodic micro-arc electro-deposition (CMED), ZrO_2coatings were deposited on an FeCrAl alloy. Experimental results show that the necessary conditionsfor obtaining ZrO_2 coatings are to apply a pulse peak voltage over a critical value and addmoderate amounts of ZrO_2 colloidal particles and Zr(NO_3)_4 in the aqueous solution. Theas-deposited coatings are porous because hydrogen, water, and other vapors are generated andreleased from the coatings to the solution during the spark reaction. The coatings containmonoclinic and tetragonal crystalline ZrO_2 with certain degree of amorphous structure. Theprocessing parameters and mechanism of CMED were discussed.

EFFECT OF CATHODIC PROTECTION ON FRACTURE BEHAVIOUR OF LOWALLOY STEELS IN SEAWATER

Fracture behaviour of low-alloy steels AIST4340,HY100,Welten60,AISIA537 and A131 in artificial seawater under static,cyclic loading and at cathodic protection potential has been investigated by using the techniques of fracture mechanics, electrochemistry and electronfractography.The results reveal that at hydrogen evolution potentials(cathodic pro- tection potential)the critical yield strength required for the occurrance of SCC decreases from 985 at corrosion potential(E_c)to 872 MPa.The effect of cathodic protection on crack propagation of corrosion fatigue(CF)is not simple,it is closely related to the yield strength of steels and their SCC behaviour.For the steels with high yield strength,cathodic protection promotes(da/dN)_Ⅱ evidently,and reduces △K_(th) value.The(da/dN)-△K curves dis- play a plateau at the third stage of CF for steels with medium or low yield strength.It is men- tioned that the cathodic protection potential for oceaneering constructures should be control- led at top level of the protective range.It seems reasonable that the strength of steel for oceaneeing use might be increased by 200 or 300 MPa.

Effect of pulsed bias on the properties of ZrN/TiZrN films deposited by a cathodic vacuum arc

ZrN/TiZrN multilayers are deposited by using the cathodic vacuum arc method with different substrate bias（from 0 to 800 V）,using Ti and Zr plasma flows in residual N 2 atmosphere,combined with ion bombardment of sample surfaces.The effect of pulsed bias on the structure and properties of films is investigated.Microstructure of the coating is analyzed by X-ray diffraction（XRD）,and scanning electron microscopy（SEM）.In addition,nanohardness,Young＇s modulus,and scratch tests are performed.The experimental results show that the films exhibit a nanoscale multilayer structure consisting of TiZrN and ZrN phases.Solid solutions are formed for component TiZrN films.The dominant preferred orientation of TiZrN films is（111） and（220）.At a pulsed bias of 200 V,the nanohardness and the adhesion strength of the ZrN/TiZrN multilayer reach a maximum of 38 GPa,and 78 N,respectively.The ZrN/TiZrN multilayer demonstrates an enhanced nanohardness compared with binary TiN and ZrN films deposited under equivalent conditions.

An electrochemical method for evaluating the resistance to cathodic disbondment of anti-corrosion coatings on buried pipelines

Methods for evaluating the resistance to cathodic disbondment （RCD） of anti-corrosion coatings on buried pipelines were reviewed. It is obvious that these traditional cathodic disbondment tests （CDT） have some disadvantages and the evaluated results are only simple figures and always rely on the subjective experience of the operator. A new electrochemical method for evaluating the RCD of coatings, that is, the potentiostatic evaluation method （PEM）, was developed and studied. During potentiostatic anodic polarization testing, the changes of stable polarization current of specimens before and after cathodic disbonding （CD） were measured, and the degree of cathodic disbondment of the coating was quantitatively evaluated, among which the equivalent cathodic disbonded distance AD was suggested as a parameter for evaluating the RCD. A series of testing parameters of the PEM were determined in these experiments.

THE EFFECTS OF NEGATIVE BIAS AND FLUX RATIO ON THE PROPERTIES OF TiN THIN FILMS FORMED BY FILTERED CATHODIC ARC PLASMA TECHNIQUE

The filtered cathodic vacuum-arc (FCVA) technique is a supplementary and alterna tive technique with respect to convendtional physical and chemical vapour deposi tion which can remove macro-particles effectively and make the deposition proces s at ambient temperature. In this work, high quality TiN thin films were deposi ted on silicon substrates at low temperature using the improved filtered cathodi c arc plasma (FCAP) technique. AFM, XRD, TEM were employed to characterize the T iN thin films. The effects of the negative substrate bias on the grain size, pre ferred crystalline orientation, surface roughness of TiN thin films were discuss ed.

Kinetics of Zn cathodic deposition in alkaline zincate solution

Kinetic parameters of the electrode reactions were measured by investigating steady-state current-potential behaviors. The Tafel slopes of cathodic and anodic processes are -0.113 8 V and -0.041 18 V, the anodic and cathodic apparent transfer coefficients are 0.519 3 and 1.435 2, respectively, and the stoichiometric number of rate-deterrnining step is 1. The theoretical kinetics equation of electrode reaction was deduced, from which the dynamic parameters can be calculated as follows： the cathodic and anodic Tafel slopes are -0.118 V and -0.039 4 V, respectively, consisting with the experimental values, Finally, the correctness of the mechanism was further demonstrated using apparent transfer coefficient according to the electrochemical dynamic equation of multi-electron reaction.