Electrochemical Polarization Research Articles

Eco-friendly spark-generated CoxOy nanoparticle-modified graphite screen-printed sensing surfaces for the determination of H2O2 in energy drinks

The modification of graphite screen-printed electrodes (SPEs) is reported using an eco-friendly and extremely fast method based on the direct cobalt pin electrode-to-SPE spark discharge at ambient conditions. This approach does not utilize any liquids or chemical templates, does not produce any waste, and allows the in-situ generation of CoxOy nanoparticles onto the electrode surface and the development of efficient electrocatalytic sensing surfaces for the determination of H2O2. Co-spark SPEs were characterized using scanning electron microscopy, energy-dispersive X-ray spectroscopy and x-ray photoelectron spectroscopy (XPS), revealing the formation of surface confined CoxOy nanoparticles and the diverse oxidation states of cobalt species. Co-spark SPEs were also characterized with cyclic voltammetry and electrochemical impedance spectroscopy. Redox transitions of the surface confined electrocatalysts are demonstrated by electrochemical polarization studies, showing the formation of different oxides (CoxOy), varying the XPS results. Amperometric measurements at 0.3 V vs. Ag/AgCl revealed a linear relationship between the current response and the concentration of H2O2 over the range 1 − 102 μM, achieving a limit of detection (3σ/m) of 0.6 μM. The interference effect of various electroactive species was effectively addressed by employing dual measurements in the absence and presence of the enzyme catalase. The analytical utility of the method was evaluated in antioxidant rich real-world samples, such as energy drinks, demonstrating sufficient recovery.Graphical

Effect of nitrogen content on grain boundary engineering and corrosion resistance of 316LN stainless steel

Nitrogen solid solution can effectively enhance the strength of steels, but its effect on grain boundary engineering and the corrosion mechanism of steels is still unclear and systematic investigation is needed. In this study, 316LN steel specimens with five nitrogen concentrations were melted and subjected to compression and annealing. The grain boundary character distribution was investigated by electron backscatter diffraction. The corrosion behavior was investigated by the electrochemical polarization curves, electrical impedance spectroscopy, and X-ray photoelectron spectroscopy. The results showed that nitrogen promotes the formation of low-Σ boundaries when the pre-strain is not above 10%. The polarization resistance increases with increasing nitrogen content. The quantitative relationship between the nitrogen content and the pitting potential was obtained. Nitrogen favors the formation of oxides, hydroxides, and NH3/NH4+ on the passivated surface. The effect of planar slip on grain boundary engineering and the influence of NH4+ on the corrosion resistance are discussed.

Decoupling the Kinetic Essence of Iron‐Based Anodes through Anionic Modulation for Rational Potassium‐Ion Battery Design

AbstractPotassium‐ion batteries (PIBs) have favorable characteristics in terms of cell voltage and cost efficiency, making them a promising technology for grid‐scale energy storage. The rational design of suitable electrode materials on a theoretical basis, aiming at high power and energy density, is of paramount importance to bring this battery technology to the practical market. In this paper, a series of iron‐based compounds with different non‐metal anions are selectively synthesized to investigate the nature of kinetic differences induced by anionic modulation. A combination of experimental characterization and theoretical calculation reveals that iron phosphide, with its moderate adsorption energy (Ea) and lowest diffusion barrier (Eb), exhibits the best cycling and rate properties at low electrochemical polarization, which is related to the narrow Δd‐p band center gap that facilitates ion transfer. In addition, the optimization of the electrolyte formula results in the carbon‐supported iron phosphide anode running stably over 2000 cycles at 0.5 A g−1 and exhibiting a high rate capacity of 81.1 mAh g−1 at 2 A g−1. The superior electrochemical properties are attributed to the robust KF‐rich solid electrolyte interphase formed by the highly compatible KFSI in ethylene carbonate (EC)/diethyl carbonate (DEC) configuration.

Sensitive Electrochemical Detection of Carcinoembryonic Antigen Based on Biofunctionalized Nanochannel Modified Carbonaceous Electrode.

The convenient construction of carbon-based electrochemical immunosensors with high performance is highly desirable for the efficient detection of tumor biomarkers. In this work, an electrochemical immunosensor was fabricated by integrating a biofunctionalized mesoporous silica nanochannel film with a carbon-based electrode, which can enable the sensitive determination of carcinoembryonic antigen (CEA) in serum. The commonly used carbonaceous electrode, glassy carbon electrode (GCE), was employed as the supporting electrode and was pre-treated through electrochemical polarization to achieve the stable binding of a vertically ordered mesoporous silica film with amino groups (NH2-VMSF) without the use of any adhesive layer. To fabricate the immunorecognition interface, antibodies were covalently immobilized after the amino groups on the outer surface of NH2-VMSF was derivatized to aldehyde groups. The presence of amino sites within the high-density nanochannels of NH2-VMSF can facilitate the migration of negatively charged redox probes (Fe(CN)63-/4-) to the supporting electrode through electrostatic adsorption, leading to the generation of electrochemical signals. In the presence of CEA, the formation of immunocomplexes on the recognitive interface can reduce the electrochemical signal of Fe(CN)63-/4- on the supporting electrode. Based on this principle, the sensitive electrochemical detection of CEA was achieved. CEA can be determined to range from 0.01 ng mL-1 to 100 ng mL-1 with a limit of detection of 6.3 pg mL-1. The fabricated immunosensor exhibited high selectivity, and the detection of CEA in fetal bovine serum was achieved.

Inhibitive Action of Sulfide Ions on Corrosion and Enhancing Charge‐Discharge Efficiency of Zinc and Zinc‐Indium Alloy as Anode for Alkaline Batteries

AbstractThe obtained data reveal that the coverage of surface (θ) and protection efficiency (η%) for the studied electrodes increases gradually as the inhibitor concentration increases. Tafel plot is carried out at variant temperatures in the investigated basic electrolyte containing 1×10−1 M of S ions. This study reveals that the activation energy barrier of the studied alloy is higher than that of pristine zinc anode at a fixed inhibitor concentration. It is observed that ▵Goads. and η% values rise with rising solution temperature, indicating that S ions adsorption on the studied electrode surfaces occurs by a chemisorption mechanism. Other calculations are made for the additional thermodynamic parameters such as ▵Hoadsand ▵Soads. The zinc anodes get more efficient when S ions are added to the solution, considerably decreasing electrochemical polarization. In addition, the presence of indium sulfide improves the exposed surface area of the alloy, supplying additional improvement in charge‐discharge efficiency. Density functional theory (DFT) is utilized to extract the quantum data to acquire a deeper understanding of the chemical processes between sulfide ions at the interface.

Effect of Graphene on the Performance of Silicon-Carbon Composite Anode Materials for Lithium-Ion Batteries.

(Si/graphite)@C and (Si/graphite/graphene)@C were synthesized by coating asphalt-cracked carbon on the surface of a Si-based precursor by spray drying, followed by heat treatment at 1000 °C under vacuum for 2h. The impact of graphene on the performance of silicon-carbon composite-based anode materials for lithium-ion batteries (LIBs) was investigated. Transmission electron microscopy (TEM) and selected area electron diffraction (SAED) images of (Si/graphite/graphene)@C showed that the nano-Si and graphene particles were dispersed on the surface of graphite, and thermogravimetric analysis (TGA) curves indicated that the content of silicon in the (Si/graphite/graphene)@C was 18.91%. More bituminous cracking carbon formed on the surface of the (Si/graphite/graphene)@C due to the large specific surface area of graphene. (Si/Graphite/Graphene)@C delivered first discharge and charge capacities of 860.4 and 782.1 mAh/g, respectively, initial coulombic efficiency (ICE) of 90.9%, and capacity retention of 74.5% after 200 cycles. The addition of graphene effectively improved the cycling performance of the Si-based anode materials, which can be attributed to the reduction of electrochemical polarization due to the good structural stability and high conductivity of graphene.

Development of a Microwave Sensor for Real-Time Monitoring of a Micro Direct Methanol Fuel Cell

Micro direct methanol fuel cells (μDMFCs) are a promising power source for microelectronic devices and systems. As the operating state and performance of a μDMFC is generally determined by both electrochemical polarization and methanol crossover, it is important to monitor the methanol concentration in μDMFCs. Here, we design and fabricate a microwave sensor and integrate it with a μDMFC for the online detection of methanol concentration in a nonintrusive way. The sensing area is set at the bottom of the anode chamber of a μDMFC which exhibits a maximum output power density of 28.8 mW cm−2 at 30 °C. With a square ring structure, the dual-mode microwave sensor shows a sensitivity of 9.5 MHz mol−1 L. Furthermore, the importance of methanol concentration monitoring is demonstrated in the long term. A relatively smooth methanol decline curve was obtained, which indicated a normal and stable operating status of the μDMFC. Derived from real-time recording data, fuel utilization was additionally calculated as 28.5%.

Preparation and corrosion resistance of polyaniline and waterborne polyurethane composite coating film

AbstractPolyaniline (PANI) particles were synthesized using aniline (AN), dodecyl benzene sulfonic acid (DBSA), and ammonium persulfate (APS). The particles were analyzed using scanning electron microscope (SEM), X‐ray diffraction (XRD), and fourier transform infrared spectroscopy (FTIR). A PANI/waterborne polyurethane composite material (PANI‐WPU) was obtained by combining it with polyethylene glycol (PEG600), diphenylmethane diisocyanate (MDI), dimethylol propionic acid (DMPA), N‐methyl pyrrolidone (NMP), and dibutyltin lauric acid (DBTDL). The structure was characterized by the FTIR spectrum. The mechanical characteristics of the coating film were evaluated with respect to the PANI content, as well as its water absorption, glossiness, electrochemical corrosion resistance, and acid and alkali resistance. The PANI/waterborne polyurethane film has a maximum tensile strength of 23 MPa, an elongation of 1012%, a pencil hardness of 5H, a flexibility of 2 mm, an impact resistance of 50 cm, the water absorption of 14.66%, and the glossiness of 99.9 at 60°. When the PANI content is 0.7%, the mechanical characteristics, glossiness, and anti‐corrosion performance of the composite film improve. The corrosion inhibition efficiency of the aqueous polyurethane coating film with PANI can reach 99.74%, as shown by the examination of electrochemical polarization curves and impedance spectra. The tinplate is coated with a 0.7% PANI‐WPU composite material and edge sealing. This coating provides excellent protection against acid and alkali resistance, as demonstrated by its ability to withstand immersion in 10% H2SO4 and 10% NaOH solution for 90 days without any paint peeling off.

Chemical, electrochemical, and surface studies of Rosa damascene extract as a green corrosion inhibitor for carbon steel in sulfuric acid environment

AbstractTo develop an environmentally acceptable corrosion inhibitor Rosa damascene extract (RD) served as the main ingredient in H2SO4 pickling processes. X‐ray photoelectron spectroscopy (XPS), Fourier‐transform infrared spectroscopy (FT‐IR), technique of electrochemical impedance spectroscopy (EIS), polarization (PP) curves, and tests of weight loss (WL) have all been utilized to examine the inhibitory behavior of Rosa damascene on C‐steel corrosion in 1 M H2SO4 environment. The results show that the extract effectively inhibited the Zn′ corrosion in 1 M H2SO4. The inhibition was more effective at higher concentrations and temperatures. The inhibitory efficiency increased to 93.5% at a higher applied temperature (45°C) and higher Rosa damascene concentration (300 ppm). However, utilizing the weight loss method at potassium iodide addition, the inhibitory effectiveness of 300 ppm of Rosa damascene was synergistically increased from 75.0% to 96.1% at 25°C. Temkin isotherm was congruent with the adsorption process that produced the inhibitory impact on the C‐steel. The chemical adhesion of the Rosa damascene extract to the surface of the C‐steel was determined by the free energy of adsorption (ΔGoads = 40.5 kJ/mol.). In H2SO4 solution, corrosion of C‐steel may be prevented by the powerful inhibitor Rosa damascene extract.

Mechanism and evaluation method of stress corrosion susceptibility of 904L stainless steel with optimized structure in seawater

The stress corrosion cracking (SCC) and the electrochemical behavior of 904 L stainless steel in a simulated seawater environment were investigated using slow strain rate testing (SSRT), electrochemical polarization, electrochemical impedance spectroscopy (EIS) and Mott-Schottky (M-S) curves. The sensitive potential range of 904 L stainless steel was determined by the fast and slow scan potential polarization curve, is − 950 mVSCE ∼ 270 mVSCE. Moreover, with the negative shift of applied potential, the toughness fracture characteristic of the three kinds of steel is reduced, and the sensitization state steel is the most obvious reduction. Finally, a practical formula for evaluating the SCC susceptibility of 904 L stainless steel was developed by integrating data from SSRT and fast and slow scan polarization curves.

Mo doping V0.76Mn0.032Ni0.029O2 vanadium based ternary metal oxides as cathode active materials for lithium-ion hybrid supercapacitor with high lithium storage performance

Lithium-ion hybrid supercapacitors as high-performance energy storage devices are proposed to bridge the electrochemical performances between lithium-ion batteries and supercapacitors. In this paper a novel Mo doping V0.76Mn0.032Ni0.029O2 vanadium based ternary metal oxide is constructed as cathode active material for lithium-ion hybrid supercapacitor. Structural analysis demonstrates Mo doping as interlayer support can ameliorate the V0.76Mn0.032Ni0.029O2 crystal structure and raise the lattice size thus providing more adequate mass transfer channels for lithium-ion storage. In addition, 5 % Mo doping V0.76Mn0.032Ni0.029O2 represents relatively regular crystal particle arrangement with some integrated crystalline form and closely packing together. These structural features enable them to exhibit higher lithium storage performance and when as cathode active material for lithium-ion hybrid supercapacitor, it exhibits the lowest electrochemical and concentration polarization and the highest discharge specific capacities of 150.7, 140.2, 125.4 and 102.5 mAh.g−1 at different current densities along with a high capacity retention rate of 77.3 % at 1000 mA g−1 current density after 2000 cycles.

Aluminum Co-Deposition via DC Magnetron Sputtering for Enhanced Pitting Resistance of Copper–Nickel Alloys

To investigate the improvements in the resistance of Cu–Ni alloys to surface pitting corrosion, Cu–Ni thin films containing Al were fabricated via DC magnetron sputtering. The morphologies of the fabricated samples were obtained using a scanning electron microscopy, which yielded information on the crystal size and sample surface before and after corrosion tests. X-ray diffraction was employed for the structural characterization of the as-deposited films, and vibrational spectroscopy was used to verify the corrosion products. The corrosion behaviors of the Cu–Ni and Cu–Ni–Al samples were examined using electrochemical polarization and cyclic corrosion tests. The Al co-deposited samples showed a refined crystal size as compared to the Cu–Ni sample, suggesting that they are more susceptible to the formation of a passivation film. The corrosion current density of the Cu–Ni–Al was reduced, and the corrosion potential was lower than that without Al content. The negative shift in the corrosion potential of the Al-containing samples indicates that the Al2O3 film suppressed the cathodic reaction, resulting in a decrease in the corrosion rate. These results are consistent with the cyclic corrosion test results, in which no pitting corrosion is observed in the Cu–Ni–Al sample.

Effect of particle dispersion on electrochemical performance of Prussian blue analogues electrode materials for sodium ion batteries.

Prussian blue analogues (PBAs) have advantages such as high voltage and low cost, making them one kind of the promising positive electrode materials for sodium-ion batteries. Particle dispersion is a key physical parameter of electrode materials, and understanding its impact on electrochemical performance is a prerequisite for obtaining high-performance PBAs. In this article, two PBAs samples with different particle dispersion were synthesized through sodium citrate-assisted co-precipitation method by means of staying and stirring. The influence of particle dispersion on electrochemical performance was investigated through polarization curve and AC impedance tests. It was found that PBAs with well-dispersed particles exhibited excellent rate performance, with a capacity of ~120 mAh g-1 at 1 C rate and a capacity retention of 75 % after 100 cycles. The capacity retention rate could reach 63 % at 5 C rate, far higher than that of PBAs samples with poor particle dispersion. From the perspective of electrochemical kinetics analysis, it has been shown that PBAs with well-dispersed particles exhibit smaller electrochemical polarization and faster Na+ diffusion reaction kinetics, which are key factors in achieving excellent rate performance.

Wear and corrosion properties of HVOF sprayed WC-Cr3C2 composite coating for application in polysilicon cyclone separator

The wear and corrosion properties of the cyclone separator play a crucial role for the preparation of high-purity trichlorosilane in the Siemens method polysilicon cold hydrogenation system. In this work, we used fluent simulation technology to determine the optimal spraying process parameters of high velocity oxy-fuel (HVOF) technology, and the Ni60-WC composite coatings with different content of Cr3C2 were prepared on 316L stainless steel surface by using HVOF technology. The microstructure, phase structure and mechanical properties of the coating were characterized, and the wear resistance and corrosion resistance of the coating were studied. By comparing the friction coefficient, wear rate, wear profile and electrochemical polarization and impedance spectrum of the coating, the effects of Cr3C2 content on the microstructure, hardness, wear resistance and corrosion resistance of HVOF sprayed WC composite coating were studied. The results show that the coating prepared by using the simulation parameters are uniform and compact, the coating is tightly bonded to the substrate. The main phases in the coating are WC, W2C and Cr3C2. With the increase of Cr3C2 hard phase, the wear resistance and corrosion resistance gradually improve. Ni60–35WC–20Cr3C2 and Ni60–35WC–30Cr3C2 volume loss rate is the lowest, the friction depth is the shiniest, compared with the substrate, the wear rate is reduced by more than 95 %. Ni60–35WC–20Cr3C2 has the highest corrosion potential, the smallest corrosion current, the smallest corrosion rate and the largest impedance spectrum radius. However, when the content of Cr3C2 reaches 30 %, the corrosion resistance is the worst. Combined with wear resistance and corrosion resistance analysis, the Ni60–35WC–20Cr3C2 coating is selected to provide support for upgrading and prolongating the service life of the cyclone separator.

Electrochemical corrosion behavior of X80 pipeline steel welded joints fabricated by ultrasound-assisted submerged arc welding in CO2-saturated solution

In this study we investigated the electrochemical corrosion behaviors of X80 pipeline steel welded joints fabricated by ultrasound-assisted submerged arc welded (UASAW) joints in CO2-saturated solution. The microstructures of the UASAW joints were analyzed by using metallographic microscopy. Corrosion behavior of UASAW joints was investigated using immersion test, electrochemical polarization, and electrochemical impedance spectroscopy (EIS). The corrosion morphologies and products were characterized by scanning electron microscopy (SEM), energy dispersive spectroscope (EDS) and X-ray diffraction. Metallographic and the corrosion mechanism of UASAW was systematically studied. The investigation results showed that the microstructure of the UASAW weld zone is mainly composed of acicular ferrite and a little granular bainite. The minimum microhardness is obtained in fusion zone (FZ) because of many alloying elements dominated in the final precipitate distribution. Pitting corrosion resistance of the strong vibration region in FZ is attributed to the decline in active sites of the bainite, the UASAW had beneficial effect on the improvement of pitting corrosion resistance of X80 pipeline steel weldment.

Structural evolution and redox chemistry of robust ternary layered oxide cathode for sodium-ion batteries

Nickel/manganese-based O3-type layered oxides have been widely deemed to be a family of promising cathode materials for sodium-ion batteries (SIBs) owing to the large theoretical specific capacity and low manufacturing cost, but being usually challenged by unsatisfied electrochemical performance. In this study, a novel ternary layered oxide NaNi1/2Mn1/4Ti1/4O2 is reported as a robust high-capacity cathode for SIBs, and its structural evolution and redox chemistry in the potential range of 1.5–4.2 V (vs Na+/Na) are carefully explored by coupling X-ray diffraction technique, X-ray photoelectron spectroscopy, transmission electron microscope, FTIR spectroscopy, and galvanostatic measurement. Experimental facts reveal that the material undergoes multiple structural phase evolutions involving two solid-solution regions and one two-phase region based on the redox chemistry of Ni2+/Ni3+ and Ni3+/Ni4+ couples. It exhibits excellent electrochemical performance with a high reversible capacity of 145.2 mAh g−1 and an impressive capacity retention of 85.1% after 100 cycles due to the unique structure with robust ternary composition and stable coating interface. The coating interface is mainly related with formation of the amorphous carbonate layer at preparation step and the CEI film containing alkoxy group during the first charge. In addition, initial Na extraction from the material suffers from a “potential jump” phenomenon owing to severe electrochemical polarization caused by large interfacial impedance and charge-transfer impedance. This work provides new insights on interfacial change, structural evolution and redox reaction of high-capacity O3-type layered oxide cathode during Na extraction/insertion.

Synthesis of hybrid organosilicon materials of various chemistries as efficient protective coatings for mild steels in NaCl media

This study focuses on optimizing the thermal, morphological, scratch resistance, and anti-barrier characteristics of newly developed hybrid sol-gel coatings. The coatings were formulated by varying the synthetic precursors and incorporating a clay additive. The hybrid coatings were prepared using a mixture of organosilane and zirconium propoxide precursors, and further modified with polydimethylsiloxane (PDMS) and Cloisite 20 A (C20A) clay additives. The coatings were applied onto mild steel substrates and their corrosion protection in 3.5 wt% NaCl solutions were evaluated through electrochemical and visual observation testing. Contact angle measurements revealed a hydrophobic nature of the developed coatings on the steel surfaces, primarily attributed to the presence of an organosilane precursor with a long C18-alkyl chain functionality in all formulations. Electrochemical testing data demonstrated that the coating formulation containing the polydimethylsiloxane precursor exhibited good corrosion protection. After 14 days of immersion in a saline medium, this sample exhibited impedance values higher than 106 Ω.cm2 and a low corrosion rate of 3.5 × 10−3 mpy, as determined by electrochemical impedance spectroscopy (EIS) and polarization testing, respectively. Morphological analyzes confirmed the homogeneous and integrated coating layer of this sample, which contributed to its enhanced corrosion protection. Furthermore, the inclusion of the Zr-propoxide precursor in a formulation containing only silane precursors demonstrated favorable effects on the desired coating properties. The hybrid sol-gel coatings exhibited excellent anti-barrier characteristics, which can be attributed to the formation of highly cross-linked Si-O-Si networks. Overall, the reported hybrid coating formulations offer promising alternatives to commercially available toxic conversion coatings, as they exhibit excellent anti-barrier properties and can be considered environmentally friendly.

Improved Test Methods and Models for Localized Corrosion Assessment of Stainless Steels in Aqueous Chloride Media with Low Dissolved Oxygen

Experimental foundation has been established for improving corrosion models for stainless steels exposed to neutral aqueous chloride media with low levels of dissolved oxygen (DO). Accurate repassivation potentials were measured for UNS S31603 and UNS S32205 alloys in chloride electrolytes at room and elevated temperatures using Tsujikawa-Hisamatsu electrochemical (THE) and cyclic potentiodynamic polarization (CPP) methods. It was observed that the repassivation potential values measured using the CPP method were lower than the ones obtained from THE method for the same environmental conditions. Cyclic polarization scans in aqueous chloride media were conducted at different reverse scan rates resulting in varied repassivation potentials. Medium-term corrosion potentials were measured in chloride media with controlled dissolved oxygen levels ranging from 20 ppb to 400 ppb. These results were used as inputs for improving model prediction for repassivation and corrosion potentials. In an extension of previous modeling studies, an improved mechanistic repassivation model was developed based on a new generalized theory that explicitly accounts for the adsorption of water rather than treating it as an ever-present background. With a flexible definition of the repassivation current density, the new repassivation model reproduces the experimental repassivation potentials obtained using THE and CPP methods. The dependence of corrosion potential on DO has been modeled using a mixed-potential model. It has been demonstrated that the effect of agitation (caused by the bubbling of oxygen) needs to be accounted for to describe the corrosion potential, especially at low DO, where mass transport is important. The combined model correctly predicts the occurrence of localized corrosion when tested against exposure data from the literature.

Niobium Carbide and Tantalum Carbide as Nitrogen Reduction Electrocatalysts: Catalytic Activity, Carbophilicity, and the Importance of Intermediate Oxidation States.

Significant interest in the electrocatalytic reduction of molecular nitrogen to ammonia (the nitrogen reduction reaction: NRR) has focused attention on transition metal carbides as possible electrocatalysts. However, a fundamental understanding of carbide surface structure/NRR reactivity relationships is sparse. Herein, electrochemistry, DFT-based calculations, and in situ photoemission studies demonstrate that NbC, deposited by magnetron sputter deposition, is active for NRR at pH 3.2 but only after immersion of an ambient-induced Nb2O5 surface layer in 0.3 M NaOH, which leaves Nb suboxides with niobium in intermediate formal oxidation states. Photoemission data, however, show that polarization to -1.3 V vs Ag/AgCl restores the Nb2O5 overlayer, correlating with electrochemical measurements showing inhibition of NRR activity under these conditions. In contrast, a similar treatment of a sputter-deposited TaC sample in 0.3 M NaOH fails to reduce the ambient-induced Ta2O5 surface layer, and TaC is inactive for NRR at potentials more positive than -1.0 V even though a significant cathodic current is observed. A TaC sample with surface oxide partially reduced by Ar ion sputtering in UHV prior to in situ transfer to UHV exhibits a restored Ta2O5 surface layer after electrochemical polarization to -1.0 V vs Ag/AgCl. The electrochemical and photoemission results are in accord with DFT-based calculations indicating greater N≡N bond activation for N2 bound end-on to Nb(IV) and Nb(III) sites than for N2 bound end-on to Nb(V) sites. Thus, theory and experiment demonstrate that with respect to NbC, the formation and stabilization of intermediate (non-d0) oxidation states for surface transition metal ions is critical for N≡N bond activation and NRR activity. Additionally, the Nb suboxide surface, formed by immersion in 0.3 M NaOH of ambient-exposed NbC, is shown to undergo reoxidation to catalytically inactive Nb2O5 at -1.3 V vs Ag/AgCl, possibly due to hydrolysis or other, as yet not understood, phenomena.

Camphor tree bark extract as green corrosion inhibitor of LCS in 0.5 M H2SO4 with and without salt effect

AbstractThis work tested the ethanol extract of camphor tree Cinnamomum camphora bark (CTBEE) as a green corrosion inhibitor of low carbon steel (LCS) in 0.5 M H2SO4 with and without the synergistic effect of 4000 ppm NaCl or 800 ppm of KI. The corrosion protection of LCS was significantly increased in the presence of CTBEE‐KI and CBWE‐NaCl blends compared with CTBEE alone, according to data performed by electrochemical impedance spectroscopy (EIS) and electrochemical polarization (EP) analyses. The formation of a film by the blends blocks the LCS surface area, preventing corrosive gradients from reaching its surface. Inhibition efficiency (IE%) of 81% and 89% were obtained in the presence of 800 ppm CTBEE‐4000 ppm NaCl and CTBEE‐800 ppm KI, respectively, compared with IE of 65% in the presence of 800 ppm CTBEE only. A maximum IE% of 89% and 97% were reached after 72 h of immersion in the presence of CTBEE‐NaCl and CTBEE‐KI, respectively. Potentiodynamic experiments indicate that the blends act as mixed‐type inhibitors. The inhibition efficiency of CTBEE, CTBEE‐KI, and CTBEE‐NaCl remained effectively high during the testing period of immersion time, which proved the excellent stability of CTBEE in the corrosive acidic media.