Effects of pH and a hydrogenation stimulator on rate constants of cathodic evolution of hydrogen and its diffusion into steel in acid sulfate solutions

From steady-state and non-steady-state polarization measurements, kinetics parameters for the hydrogen evolution reaction at carbon steel in acid sulfate solutions in the absence and in the presence of KCNS are calculated. Based on the results obtained by an electrochemical diffusion method and using the Iyer-Pickering-Zamanzadeh analysis, apparent rate constants for the principal stages of the hydrogen evolution reaction are calculated.     

Kinetics of the hydrogen evolution reaction on chromium,chromium oxide coated steel

The kinetics of the hydrogen evolution reaction (h.e.r.) on tin-free-steels chromium-type (TFS-CT) in citric acid solutions between pH 2.0 to 5.0 have been investigated. TFS-CT materials consist of steel sheets electrolytically plated with light metallic chromium coatings which in turn are covered by much thinner films of chromium oxide. Anomalously high cathodic Tafel slopes for the h.e.r. have been found and explained utilizing the Meyer dual barrier model. A mechanism for the h.e.r. based on Langmuir (?→1) adsorption behaviour, electrochemical desorption as the rate-determining electrode reaction step and the dual barrier model is consistent with the experimental results.     

Bifunctional Near-Neutral Electrolyte Enhances Oxygen Evolution Reaction

Performance of electrocatalytic reactions depends on not only the composition and structure of the active sites, but also their local environment, including the surrounding electrolyte. In this work, we demonstrate that BF₂(OH)₂⁻ anion is the key fluoroborate species formed in the mixed KBi/KF (KBi=potassium borate) electrolyte to enhance the rate of the oxygen evolution reaction (OER) at near-neutral pH. Through a combination of electrokinetic and in situ spectroscopic studies, we show that the mixed KBi/KF electrolyte promotes the OER via two pathways: 1) stabilizing the interfacial pH during the proton-producing reaction with its high buffering capacity; and 2) activating the interfacial water via strong hydrogen bonds with F-containing species. With the KBi/KF electrolyte, electrodeposited Co(OH)₂ is able to achieve 100 mA/cm² at 1.74 V, which is among the highest reported activities with earth-abundant electrocatalysts at near neutral conditions. These findings highlight the potential of leveraging electrolyte-engineering for improving the electrochemical performance of the OER.     

Numerical Simulation for Crevice Corrosion of 304 Stainless Steel in Sodium Chloride Solution

The authors presented a mechanistic model describing the chemical reactions within a corroded thin, nar-row crevice. In the mathematical model, a two-dimensional steady-state was used to predict the crevice pH profile by taking into account dissolved oxygen and hydrogen ions within the crevice. It consists of six parallel electrochemical reactions: multi anodic reactions(Fe, Cr, Ni dissolution reactions) and three cathodic reactions(the oxygen reduction, the hydrogen reaction and water dissociation). Current density distribution and oxygen concentration distribution were determined to be corresponding to the evolution of potential distribution within the crevice. The contribution of each metal reaction to the overall corrosion process was in proportion to the mole fraction, and the simulation pro-vided a good agreement with published experimental results for the crevice corrosion of stainless steel in sodium chloride solution.     

Activity volcanoes for the electrocatalysis of homolytic and heterolytic hydrogen evolution

This paper derives a simple kinetic model for the electrochemical current generated by a heterolytic model for hydrogen evolution, as it would apply to the reaction taking place on molecular catalysts, and compares the activity trends to the classical Volmer-Heyrovsky-Tafel models. It is demonstrated that in the heterolytic mechanism, pH plays a crucial role in optimizing the overall activity.     

In-situ characterization of the electrochemistry of grain and grain boundary of an X70 steel in a near-neutral pH solution

An in-situ scanning vibrating electrode technique (SVET) was used to characterize microscopically the local electrochemistry of grain and grain boundary in an X70 steel in a near-neutral pH solution. It was found that the grain was anodic relative to the grain boundary. Localized corrosion, such as pitting, preferentially occurs on the grain, rather than on the grain boundary. Once a stress corrosion crack initiates from the corrosion pit, there is a higher electrochemical driving force for the crack growth within a grain than that at grain boundary. Therefore, the stress corrosion cracking follows a transgranular mode.     

Ceforanide: a new and efficient corrosion inhibitor for mild steel in HCl solution

The corrosion inhibition properties of ceforanide for mild steel in HCl solution were analyzed by electrochemical impedance spectroscopy, potentiodynamic polarization, and gravimetric methods. The increase in inhibitor concentration and immersion time showed a positive effect on inhibition efficiency. The experimental data showed a frequency distribution and therefore a modeling element with frequency dispersion behavior and a constant phase element have been used. In aqueous acid solution, mild steel reacts by evolution of hydrogen. Visual observations showed that the hydrogen evolution decreased (i.e., corrosion inhibition effect increased) with increasing concentration of ceforanide. Potentiodynamic polarization study revealed that ceforanide acted as a mixed type of inhibitor. The results obtained from different methods are in good agreement. The adsorption behavior of ceforanide is experimentally investigated by contact angle measurement on metal surface. The contact angle of metal surface to the acid solution increased with inhibitor concentration; thereby confirming the increased hydrophobic nature of metal surface to the acid solution having inhibitors.     

Combining phosphate species and stainless steel cathode to enhance hydrogen evolution in microbial electrolysis cell (MEC)

Microbial electrolysis cells (MEC) must work around neutral pH because of microbial catalysis at the anode. To develop a hydrogen evolution cathode that can work at neutral pH remains a major challenge in MEC technology. Voltammetry performed at pH 8.0 on rotating disk electrodes showed that the presence of phosphate species straightforwardly multiplied the current density of hydrogen evolution, through the so-called cathodic deprotonation reaction. The mechanism was stable on stainless steel cathodes whereas it rapidly vanished on platinum. The phosphate/stainless steel system implemented in a 25 L MEC with a marine microbial anode led to hydrogen evolution rates of up to 4.9 L/h/m² under 0.8 V voltage, which were of the same order than the best performance values reported so far.     

1,3-二甲基-5-亚硝基-6-氨基脲嘧啶铂电极电化学加氢机理研究

采用稳态极化法、循环伏安法和恒电位库仑法对1,3-二甲基-5-亚硝基-6-氨基脲嘧啶在铂电极上的电化学加氢机理进行了研究,研究介质为硫酸和硫酸钾水溶液.结果表明,pH=3时,1,3-二甲基-5-亚硝基-6-氨基脲嘧啶在铂电极析氢电位(-600～-800mV,vs.饱和硫酸钾的硫酸亚汞参比电极)前,发生加氢还原反应,氢离子在铂电极表面得到电子生成原子态的氢参与反应.随着pH值降低,加氢反应速度增大,还原电位正移.在铂电极上的电化学加氢过程受扩散控制,增大搅拌速度和提高温度都可提高反应速度.     

pH effect on electrocatalytic reduction of CO2 over Pd and Pt nanoparticles

Adsorbed hydrogen participates in electrocatalytic reduction of CO₂ and competitive hydrogen evolution reaction (HER) simultaneously, and its reaction pathway greatly affects the activity and selectivity of CO₂ reduction. In this work, we investigate pH effect on electrocatalytic reduction of CO₂ over Pd and Pt nanoparticles (NPs) with a similar size in a pH range from 1.5 to 4.2. Pt NPs completely contribute to HER in the pH range. Over Pd NPs, Faradaic efficiency for CO production at − 1.19 V (vs. reversible hydrogen electrode) varies from 3.2% at pH of 1.5 to 93.2% at pH of 4.2, and current density for CO production reaches maximum at pH of 2.2. The significant enhancement of Faradaic efficiency and current density for CO production over Pd NPs at high pH values is attributed to decreased kinetics of hydrogen evolution reaction by increasing hydrogen binding energy and lowered adsorption affinity of CO-like intermediate compared to Pt.     

In‐Operando Mapping of pH Distribution in Electrochemical Processes

In aqueous electrochemical processes, the pH evolves spatially and temporally, and often dictates the process performance. Herein, a new method for the in‐operando monitoring of pH distribution in an electrochemical cell is demonstrated. A combination of pH‐sensitive fluorescent dyes, encompassing a wide pH range from ≈1.5 to 8.5, and rapid electrochemically coupled laser scanning confocal microscopy is used to observe pH changes in the cell. Using electrocoagulation as an example process, we show that the method provides new insights into the reaction mechanisms. The pH close to the aluminium electrode surface is influenced by the applied current density, hydrolysis of aluminium cations, and gas evolution. Through quantification of the pH at the anode, along with gas analysis, we find that hydrogen is evolved at the anode due to a non‐Faradaic chemical reaction. This leads to increased production of coagulant, which may open new routes to enhance the process performance. This method for in‐operando dynamic visualization of pH paves the way for studies of electrochemical processes, including other water treatment, electrosynthesis, and batteries.     

Biomimetic hydrogen evolution: MoS2 nanoparticles as catalyst for hydrogen evolution

The electrochemical hydrogen evolution reaction is catalyzed most effectively by the Pt group metals. As H2 is considered as a future energy carrier, the need for these catalysts will increase and alternatives to the scarce and expensive Pt group catalysts will be needed. We analyze the ability of different metal surfaces and of the enzymes nitrogenase and hydrogenase to catalyze the hydrogen evolution reaction and find a necessary criterion for high catalytic activity. The necessary criterion is that the binding free energy of atomic hydrogen to the catalyst is close to zero. The criterion enables us to search for new catalysts, and inspired by the nitrogenase active site, we find that MoS2 nanoparticles supported on graphite are a promising catalyst. They catalyze electrochemical hydrogen evolution at a moderate overpotential of 0.1-0.2 V.     

(Ni-Co)-WC复合电极的析氢催化性能

采用 复合电沉 积方法获 得了（ Ｎｉ Ｃｏ） Ｗ Ｃ 复合电极 ,考 察了 复合 电极 在弱 酸性、碱性 和中性介质 中的析 氢电催化 性能,并 在弱酸性 介质中 进行了电 化学稳定 性实验 ． 结果 表明,复 合电极具有优越 的析氢 电催化性 能和良好 的电化 学稳定性 ．     

Flow injection electrochemical enzyme immunoassay for theophylline using a protein A immunoreactor and p-aminophenyl phosphate-p-aminophenol as the detection system.

A competitive electrochemical enzyme immunoassay has been developed for the antiasthmatic drug theophylline, utilizing a controlled-pore glass-protein A immunoreactor and flow injection techniques. p-Aminophenyl phosphate, a substrate for alkaline phosphatase, has been used in this assay, and its hydrolysis product p-aminophenol was determined at +0.2 V versus the saturated calomel electrode. For each sample the antibody-protein A reaction takes place at near-neutral pH, and the complexes are eluted at acid pH. Serum theophylline has been determined by this method, and good relative standard deviations and percentage recoveries have been achieved.     

Hydrogen effects on microstructural evolution and passive film characteristics of a duplex stainless steel

We revealed the effects of hydrogen on the microstructural evolution and passive film properties of a 2205 duplex stainless steel by the joint use of electron backscatter diffraction (EBSD), electron channeling contrast imaging (ECCI), X-ray photoelectron spectroscopy (XPS) and electrochemical measurements. The microstructural analysis results show that effects of hydrogen on the two phases are different: (i) in austenite, stacking faults are induced by hydrogen, and (ii) in ferrite, hydrogen causes an increase of the dislocation density. The XPS analysis revealed that hydrogen reduced the occurrence of Cr₂O₃ and nitrogen in the passive film, leading to the reduction of their overall thickness. Furthermore, for the first time we demonstrated that the hydrogen release time plays an important role in the electrochemical behavior of the hydrogen charged steel.     

Thin-layer spectroelectrochemical kinetic study of viologen cation radicals reacting at hydrogen-evolving gold and nickel electrodes

The kinetics of viologen cation radicals reacting at hydrogen-evolving gold and nickel electrodes in pH 6–8 electrolytes have been investigated. Visible absorption spectroscopy was used to follow the course of the reaction in an optically transparent thin-layer electrochemical cell under quasi-steady-state conditions. The spectroelectrochemical data were analyzed using classical kinetics and yielded zero-order behavior with respect to the viologen cation radical. For methyl viologen cation radical at gold, a formal zero-order rate constant evaluated at zero hydrogen overpotential was found to be 1.0 × 10^?13 mol s^?1 cm^?2. At nickel the comparable rate constant was nearly two orders of magnitude larger than at gold. Increasing pH from 6 to 8 at gold electrodes shifted both the hydrogen evolution and the methyl viologen cation radical reaction 60–70 mV/pH unit in a negative direction. The diquat cation radical behaved in a similar manner. The proposed mechanism involves a fast, non-rate-limiting, chemical reaction between the viologen cation radical and adsorbed hydrogen atom(s). Results are interpreted in terms of previous proposed hydrogen evolution reaction mechanisms.     

H_2S环境中UNS J91540不锈钢的电化学行为对SCC的影响

应用慢应变速率拉伸试验和电化学方法研究了湿硫化氢溶液中UNS J91450不锈钢的电化学行为对应力腐蚀开裂的影响.结果表明,本实验条件下UNS J91540不锈钢具有较高的SCC敏感性,并随着溶液pH的降低而明显增大.该不锈钢的电化学行为对它的腐蚀开裂(SCC)敏感性具有重要影响.开路电位下该不锈钢的SCC行为同时受氢脆作用和裂纹尖端阳极溶解作用的影响.在pH较低的介质中析氢电流较高而裂纹尖端阳极溶解作用略低,而在pH较高的介质中析氢电流较低而裂纹尖端的阳极溶解作用相对增强.氢脆作用对UNS J91540不锈钢SCC敏感性影响更显著.     

Cu/CdCO3 catalysts for efficient electrochemical CO2 reduction over the wide potential window

High efficiency and low-cost catalyst-driven electrocatalytic CO₂ reduction to CO production are of great significance for energy storage and development. The severe competitive hydrogen evolution reaction occurs at large negative potential window limits the achievement of the target product from CO₂ at high efficiency. Here, we successfully prepared Cu_x/CdCO₃ composite catalyst rich in interfaces, in which achieved high CO Faraday efficiency exceeded 90% in a wide potential window of 700 mV and highest value up to 97.9% at −0.90 V vs. RHE. The excellent performance can be ascribed to the positive contribution of Cu_x/CdCO₃, which maintains a suitable high local pH value during electrochemical reduction, thus inhibiting the competitive hydrogen evolution reaction. Moreover, the compact structure between Cu and CdCO₃ ensures fast electron transfer both inside catalysts and interface, thus speeding up the reaction kinetics of CO₂ to CO conversion. Theoretically calculations further prove that the combination of Cu and CdCO₃ provides the well-defined electronic structure for intermediates adsorption, significantly reducing the reaction barrier for the formation of CO. This work provides new insights into the design of efficient electrochemical CO₂ reduction catalysts for inhibiting hydrogen evolution by adjusting the local pH effect.     

Application of metal chalcogenide-based anodic electrocatalyst toward substituting oxygen evolution reaction in water splitting

Electrochemical water splitting for producing hydrogen has received increasing attention. However, the large overpotential of oxygen evolution reaction (OER) is a bottleneck in water splitting. Exploiting value-added alternative reactions to replace the OER semi-reaction in water splitting can not only produce valuable products at both electrodes, but also reduce the overpotential of water splitting. Recently, metal chalcogenides (sulfides and selenides) have been widely studied in electrocatalytic reactions. This review concentrates on the recent application of metal chalcogenides in value-added anodic reactions by replacing the OER during electrochemical water splitting, including urea oxidation reaction (UOR), 5-hydroxymethylfurfural electrochemical oxidation reaction (HMF-EOR), which provides the guidance for the rational design of advanced metal chalcogenide electrocatalysts in renewable energy.     

Corrosion-wear monitoring of TiN coated ASP23 steel by electrochemical noise measurements

A modified electrochemical noise (EN) technique has been applied to monitor corrosion-wear of TiN coated ASP23 steel sliding against corundum in 0.5 M H₂SO₄. Experimental results show that corrosion-wear mechanisms of TiN coatings depend on their substrate properties. When the substrate is active, such as ASP23 tool steel, the electrochemical noise is dominated by dissolution of the substrate at the pinholes and the hydrogen evolution all over the exposed surface.