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Purpose The purpose of this paper is to obtain the environmental factor, which has the greatest effect on the corrosion rate of Q235 carbon steel under thin electrolyte layer, and to analyze the effect of this factor on the corrosion morphology, corrosion products and polarization process of Q235 carbon steel. Design/methodology/approach An electrochemical device, which can be used under thin electrolyte layer is designed to measure the corrosion current in different environments. Response surface methodology (RSM) is introduced to analyze the effect of environmental factors on corrosion rate. Scanning electron microscope (SEM) and X-ray diffraction (XRD) technique are used to analyze the results. The Tafel slopes of anode and cathode in different humidity and solution are calculated by least square method. Findings The three environmental factors are ranked according to importance, namely, humidity, temperature and chloride ion deposition rate. In a high humidity environment, the relative content of α-FeOOH in the corrosion product is high and the relative content of β-FeOOH is low. The higher the humidity, the lower the degree of anodic blockage, whereas the degree of cathodic blockage is independent of humidity. The above experiments confirm the effectiveness and efficiency of the device, indicating it can be used for the screening of corrosive environmental factors. Originality/value In this paper, an electrochemical device under thin film is designed, which can simulate atmospheric corrosion well. Subsequent SEM and XRD confirmed the reliability of the data measured by this device. The introduction of a scientific RSM can overcome the limitations of orthogonal experiments and more specifically and intuitively analyze the effects of environmental factors on corrosion rates.

We present a microkinetic model for CO (2) reduction (CO (2) R) on Cu(211) towards C 2 products, based on energetics estimated from an explicit solvent model. We show that the differences in both Tafel slopes and pH dependence for C 1 vs C 2 activity arise from differences in their multi-step mechanisms. We find the depletion in C 2 products observed at high overpotential and high pH to arise from the 2 nd order dependence of C-C coupling on CO coverage, which decreases due to competition from the C 1 pathway. We further demonstrate that CO (2) reduction at a fixed pH yield similar activities, due to the facile kinetics for CO 2 reduction to CO on Cu, which suggests C 2 products to be favored for CO 2 R under alkaline conditions. The mechanistic insights of this work elucidate how reaction conditions can lead to significant enhancements in selectivity and activity towards higher value C 2 products. CO 2 conversion to reduced products provides a use for greenhouse gases, but reaction complexity stymies mechanistic studies. Here, authors present a microkinetic model for CO 2 and CO reduction on copper, based on ab initio simulations, to elucidate pH’s impact on competitive reaction pathways.

Rigorous electrokinetic results are key to understanding the reaction mechanisms in the electrochemical CO reduction reaction (CORR), however, most reported results are compromised by the CO mass transport limitation. In this work, we determined mass transport-free CORR kinetics by employing a gas-diffusion type electrode and identified dependence of catalyst surface speciation on the electrolyte pH using in-situ surface enhanced vibrational spectroscopies. Based on the measured Tafel slopes and reaction orders, we demonstrate that the formation rates of C 2+ products are most likely limited by the dimerization of CO adsorbate. CH 4 production is limited by the CO hydrogenation step via a proton coupled electron transfer and a chemical hydrogenation step of CO by adsorbed hydrogen atom in weakly (7 < pH < 11) and strongly (pH > 11) alkaline electrolytes, respectively. Further, CH 4 and C 2+ products are likely formed on distinct types of active sites. Electrokinetic results are key to understanding the mechanisms in electrochemical CO reduction reaction. Here, the authors determine mass transport free kinetics using a gas-diffusion electrode and identified dependence of copper surface speciation on the electrolyte pH using in situ surface enhanced spectroscopies.

Molybdenum disulfide, as an electronic highly-adjustable catalysts material, tuning its electronic structure is crucial to enhance its intrinsic hydrogen evolution reaction (HER) activity. Nevertheless, there are yet huge challenges to the understanding and regulation of the surface electronic structure of molybdenum disulfide-based catalysts. Here we address these challenges by tuning its electronic structure of phase modulation synergistic with interfacial chemistry and defects from phosphorus or sulfur implantation, and we then successfully design and synthesize electrocatalysts with the multi-heterojunction interfaces (e.g., 1T 0.81 -MoS 2 @Ni 2 P), demonstrating superior HER activities and good stabilities with a small overpotentials of 38.9 and 95 mV at 10 mA/cm 2 , a low Tafel slopes of 41 and 42 mV/dec in acidic as well as alkaline surroundings, outperforming commercial Pt/C catalyst and other reported Mo-based catalysts. Theoretical calculation verified that the incorporation of metallic-phase and intrinsic HER-active Ni-based materials into molybdenum disulfide could effectively regulate its electronic structure for making the bandgap narrower. Additionally, X-ray absorption spectroscopy indicate that reduced nickel possesses empty orbitals, which is helpful for additional H binding ability. All these factors can decrease Mo-H bond strength, greatly improving the HER catalytic activity of these materials. The understanding and regulation of the surface electronic structure of molybdenum disulfide-based catalysts for hydrogen evolution reaction (HER) remains a challenges. Here, the authors design and synthesize electrocatalysts with multi-heterojunction interfaces showing enhanced HER activities and stabilities.

The Tafel slope is a key parameter often quoted to characterize the efficacy of an electrochemical catalyst. In this paper, we develop a Bayesian data analysis approach to estimate the Tafel slope from experimentally-measured current-voltage data. Our approach obviates the human intervention required by current literature practice for Tafel estimation, and provides robust, distributional uncertainty estimates. Using synthetic data, we illustrate how data insufficiency can unknowingly influence current fitting approaches, and how our approach allays these concerns. We apply our approach to conduct a comprehensive re-analysis of data from the CO 2 reduction literature. This analysis reveals no systematic preference for Tafel slopes to cluster around certain \"cardinal values” (e.g. 60 or 120 mV/decade). We hypothesize several plausible physical explanations for this observation, and discuss the implications of our finding for mechanistic analysis in electrochemical kinetic investigations. The Tafel slope in electrochemical catalysis is usually determined from experimental data and remains error-prone. Here, the authors develop a Bayesian approach for Tafel slope quantification, and apply it to study the prevalence of certain \"cardinal\" Tafel slopes in the electrochemical CO 2 reduction literature.

The excellent catalytic activity of metallic MoS 2 edges for the hydrogen evolution reaction (HER) has led to substantial efforts towards increasing the edge concentration. The 2H basal plane is less active for the HER because it is less conducting and therefore possesses less efficient charge transfer kinetics. Here we show that the activity of the 2H basal planes of monolayer MoS 2 nanosheets can be made comparable to state-of-the-art catalytic properties of metallic edges and the 1T phase by improving the electrical coupling between the substrate and the catalyst so that electron injection from the electrode and transport to the catalyst active site is facilitated. Phase-engineered low-resistance contacts on monolayer 2H-phase MoS 2 basal plane lead to higher efficiency of charge injection in the nanosheets so that its intrinsic activity towards the HER can be measured. We demonstrate that onset potentials and Tafel slopes of ∼−0.1 V and ∼50 mV per decade can be achieved from 2H-phase catalysts where only the basal plane is exposed. We show that efficient charge injection and the presence of naturally occurring sulfur vacancies are responsible for the observed increase in catalytic activity of the 2H basal plane. Our results provide new insights into the role of contact resistance and charge transport on the performance of two-dimensional MoS 2 nanosheet catalysts for the HER. Increasing the edge concentration of metallic MoS 2 nanosheets will improve their electrocatalytic performance for hydrogen evolution. The activity of MoS 2 can now be enhanced by facilitating electron injection from the electrode to the catalyst.

Transition metal phosphides (TMPs) are promising candidates for noble metal free electrocatalysts in water splitting applications. In this work, we present the facile synthesis of nickel cobalt phosphide electrocatalyst with three-dimensional nanostructure (3D-NiCoP) on the nickel foam, via hydrothermal reaction and phosphorization. The as-prepared electrocatalyst exhibits an excellent activity for hydrogen evolution reaction (HER) in both acidic and alkaline electrolytes, with small overpotentials to drive 10 mA/cm 2 (80 mV for 0.5 M H 2 SO 4 , 105 mV for 1 M KOH), small Tafel slopes (37 mV/dec for 0.5 M H 2 SO 4 , 79 mV/dec for 1 M KOH), and satisfying durability in long-term electrolysis. 3D-NiCoP also shows a superior HER activity compared to single metal phosphide, such as cobalt phosphide and nickel phosphide. The outstanding performance for HER suggests the great potential of 3D-NiCoP as a highly efficient electrocatalyst for water splitting technology.

The development of high-efficiency electrocatalysts for oxygen evolution reactions (OERs) plays an important role in the water-splitting process. Herein, we report a facile way to obtain two-dimensional (2D) single-unit-cell-thick layered double hydroxide (LDH) nanosheets (NSs, ∼1.3 nm) within only 5 min. These nanosheets presented significantly enhanced OER performance compared to bulk LDH systems fabricated using the conventional co-precipitation method. The current strategy further allowed control over the chemical compositions and electrochemical activities of the LDH NSs. For example, CoFe-LDH NSs presented the lowest overpotential of 0.28 V at 10 mA/cm 2 , and the NiFe-LDHs NSs showed Tafel slopes of 33.4 mV/decade and nearly 100% faradaic efficiency, thus outperforming state-of-the-art IrO 2 water electrolysis catalysts. Moreover, positron annihilation lifetime spectroscopy and high-resolution transmission electron microscopy observations confirmed that rich defects and distorted lattices occurred within the 2D LDH NSs, which could supply abundant electrochemically active OER sites. Periodic calculations based on density functional theory (DFT) further showed that the CoFe- and NiFe-LDHs presented very low energy gaps and obvious spin-polarization behavior, which facilitated high electron mobility during the OER process. Therefore, this work presents a combined experimental and theoretical study on 2D single-unit-cell-thick LDH NSs with high OER activities, which have potential application in water splitting for renewable energy.

Tafel analysis of electrocatalysts is essential in their characterization. This paper analyzes the application of Tafel-like analysis to the four-electron nonelectrochemical oxidation of water by the stoichiometric homogeneous 1-electron oxidant [Ru(bpy)3]3+ to dioxygen catalyzed by homogeneous catalysts, [Ru4O4(OH)2(H2O)4(γ-SiW10O36)2]10− (Ru4POM) and [Co4(H2O)2(PW9O34)2]10– (Co4POM). These complexes have slow electron exchange rates with electrodes due to the Frumkin effect, which precludes the use of known electrochemical methods to obtain Tafel plots at ionic strengths lower than 0.5 M. The application of an electron transfer catalyst, [Ru(bpy)3]3+/2+, increases the rates between the Ru4POM and electrode, but a traditional Tafel analysis of such a complex system is precluded due to a lack of appropriate theoretical models for 4-electron processes. Here, we develop a theoretical framework and experimental procedures for a Tafel-like analysis of Ru4POM and Co4POM, using a stoichiometric molecular oxidant [Ru(bpy)3]3+. The dependence of turnover frequency (TOF) as a function of electrochemical solution potential created by the [Ru(bpy)3]3+/[Ru(bpy)3]2+ redox couple (an analog of the Tafel plot) was obtained from kinetics data and interpreted based on the suggested reaction mechanism.

The transfer coefficient is a quantity that is commonly employed in the kinetic investigation of electrode processes. In the 3 edition of the IUPAC Green Book, the cathodic transfer coefficient is defined as –( )( ln /d ), where is the electroreduction rate constant, is the applied potential, and , and have their usual significance. This definition is equivalent to the other, -( )( ln| |/d ), where is the cathodic current density corrected for any changes in the reactant concentration at the electrode surface with respect to its bulk value. The anodic transfer coefficient is defined similarly, by simply replacing with the anodic current density and the minus sign with the plus sign. It is shown that this definition applies only to an electrode reaction that consists of a single elementary step involving the simultaneous uptake of electrons from the electrode in the case of , or their release to the electrode in the case of . However, an elementary step involving the simultaneous release or uptake of more than one electron is regarded as highly improbable in view of the absolute rate theory of electron transfer of Marcus; the hardly satisfiable requirements for the occurrence of such an event are examined. Moreover, the majority of electrode reactions do not consist of a single elementary step; rather, they are multistep, multi-electron processes. The uncritical application of the above definitions of and has led researchers to provide unwarranted mechanistic interpretations of electrode reactions. In fact, the only directly measurable experimental quantity is ln| |/d , which can be made dimensionless upon multiplication by , yielding ( )( ln| |/d ). One common source of misinterpretation consists in setting this experimental quantity equal to , according to the above definition of the transfer coefficient, and in trying to estimate from , upon ascribing an arbitrary value to , often close to 0.5. The resulting value is then identified with the number of electrons involved in a hypothetical rate-determining step or with that involved in the overall electrode reaction. A few examples of these unwarranted mechanistic interpretations are reported. In view of the above considerations, it is proposed to define the cathodic and anodic transfer coefficients by the quantities = –( )( ln| |/d ) and = ( )( ln /d ), which are independent of any mechanistic consideration.