The hydrogen evolution reaction on nickel surfaces stabilized by H-absorption

Machado, Sérgio Antônio Spínola; Avaca, Luís Alberto

doi:10.1016/0013-4686(94)e0003-i

Cited by 220 publications

(155 citation statements)

References 24 publications

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“…20 It has since been shown that the primary surface component formed at this potential is indeed α-Ni(OH) 2 . 24 However, the exact thickness of this surface layer has never been determined.…”

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confidence: 88%

An Oxalate Method for Measuring the Surface Area of Nickel Electrodes

Hall

Bock

MacDougall

2014

J. Electrochem. Soc.

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This work establishes a new method to measure the electrochemically active surface area (A ECSA ) of nickel electrodes, in situ. The addition of 0.08 mol L −1 of an oxalate salt to an alkaline electrolyte solution shifts the half-wave potential of the Ni(II)/Ni(III) redox pair by about −80 mV. Further, these peaks are very narrow. The sharpest peak in this work has a full width at half maximum (FWHM) of just 11 mV. This unusual sharpness is attributed to the layered structure of nickel hydroxides and the adsorption of oxalate from the solution on the (001) surface. This is supported by attenuated total reflectance infrared (ATR-IR) peaks measured at 1265 cm −1 , 1655 cm −1 , and 1713 cm −1 , which correspond to mononuclear bidentate oxalate bonded to nickel. At sufficiently fast potential scan rates (≥150 mV s −1 ), the adsorbed oxalate limits growth of the surface hydroxide to a single layer. During the reverse scan, the surface NiOOH/Ni(OH) 2 reduction peak is well-separated from other electrochemical processes and may be used to accurately and precisely measure the A ECSA . The error of this method is estimated at < 10%.

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confidence: 88%

An Oxalate Method for Measuring the Surface Area of Nickel Electrodes

Hall

Bock

MacDougall

2014

J. Electrochem. Soc.

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“…In Equation 5a, c 0 H + denotes the near-surface concentration of H + ions. Here we note that with this assumption we only wish to state that there exists an exponential dependence between the stationary partial currents and the electrode potential; 35 in what follows we shall not draw any conclusion whatsoever about the exact mechanism of hydrogen evolution (and whether it follows a "pure" Volmer, a Volmer-Heyrovsky or a Volmer-Tafel mechanism 35 ).…”

Section: Modellingmentioning

confidence: 99%

Electrochemical Hydrogen Evolution: H⁺or H₂O Reduction? A Rotating Disk Electrode Study

Grozovski

Vesztergom

Ланг

et al. 2017

J. Electrochem. Soc.

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We study the effect of H + and OH − diffusion on the hydrogen evolution reaction in unbuffered aqueous electrolyte solutions of mildly acidic pH values. We demonstrate that the cathodic polarization curves measured on a Ni rotating disk electrode in these solutions can be modeled by assuming two irreversible reactions, the reduction of H + and that of water molecules, both following Erdey-Grúz-Volmer-Butler kinetics. The reduction of H + yields a transport-limited and thus, rotation rate-dependent current at not very negative potentials. At more cathodic potentials the polarization curves are dominated by the reduction of water and no mass transfer limitation seems to apply for this reaction. Although prima facie the two processes may seem to proceed independently, by the means of finite-element digital simulations we show that a strong coupling (due to the recombination of H + and OH − to water molecules) exists between them. We also develop an analytical model that can well describe polarization curves at various values of pH and rotation rates. The key indication of both models is that hydroxide ions can have an infinite diffusion rate in the proximity of the electrode surface, a feature that can be explained by assuming a directed Grotthuss-like shuttling mechanism of transport. A common problem of base metal electroplating is that the deposition of electroactive metals (e.g., Zn, Co, Fe or Ni) is almost inevitably accompanied by hydrogen evolution. In aqueous solutions hydrogen evolution always occurs if current is made high enough to exceed the limiting current of the deposited metal.1 In acidic solutions hydrogen may be formed as a result of H + reduction,while in solutions of pH > 7, the primary source of hydrogen is the electroreduction of water itself:Hydrogen evolution presents several ramifications for electrochemical plating processes. From a strictly technological point of view, the evolution of hydrogen is a serious concern because it reduces the faradaic efficiency of metal deposition, thereby increasing the amount of time and energy utilized to deposit the desired amount of metal at a given total current density. Another problem of hydrogen codeposition is that it can affect the structural and mechanical properties of the metal and can cause embrittlement. 1 Furthermore, hydrogen can also affect the kinetics of layer growth: if hydrogen adsorbs more efficiently on certain crystal planes of the metal, it may block these planes from further deposition so that the metal would preferentially grow on other planes.2 This inhomogeneous growth presents difficulties for the deposition of compact metal layers at the best -that is, if the accumulated gas does not impair the entire plating process. Finally, hydrogen evolution also results in the removal of H + ions from the diffusion layer. Increasing the near-surface pH may alter the intended chemical and electrochemical reactions at the interface. For example, if the solution at the interface becomes sufficiently alkaline, it may cause the solubility of a...

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“…Ni(OH) 2 also forms electrochemically on Ni electrodes in alkaline media, which has importance for the development of Ni-based electrocatalysts [23,105,179,[184][185][186][187]. Consequently, the surface electrochemistry has been extensively studied using atomic force microscopy [188], ellipsometry [181,[189][190][191], IR spectroscopy [192], Raman spectroscopy [166,193,194], UV-Vis spectroscopy [192,195], voltammetry [179,185,[196][197][198][199][200][201], X-ray scattering [176], XPS [179,202] and gravimetry with an electrochemical quartz crystal microbalance [203,204]. During a forward voltammetric sweep, a surface bilayer of α-Ni(OH) 2 underlaid by NiO x forms initially [179].…”

Section: (D) Chemical Ageingmentioning

confidence: 99%

Nickel hydroxides and related materials: a review of their structures, synthesis and properties

et al. 2015

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This review article summarizes the last few decades of research on nickel hydroxide, an important material in physics and chemistry, that has many applications in engineering including, significantly, batteries. First, the structures of the two known polymorphs, denoted as α-Ni(OH) 2 and β-Ni(OH) 2 , are described. The various types of disorder, which are frequently present in nickel hydroxide materials, are discussed including hydration, stacking fault disorder, mechanical stresses and the incorporation of ionic impurities. Several related materials are discussed, including intercalated α-derivatives and basic nickel salts. Next, a number of methods to prepare, or synthesize, nickel hydroxides are summarized, including chemical precipitation, electrochemical precipitation, sol-gel synthesis, chemical ageing, hydrothermal and solvothermal synthesis, electrochemical oxidation, microwaveassisted synthesis, and sonochemical methods. Finally, the known physical properties of the nickel hydroxides are reviewed, including their magnetic, vibrational, optical, electrical and mechanical properties. The last section in this paper is intended to serve as a summary of both the potentially useful properties of these materials and the methods for the identification and characterization of 'unknown' nickel hydroxide-based samples.

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The hydrogen evolution reaction on nickel surfaces stabilized by H-absorption

Cited by 220 publications

References 24 publications

An Oxalate Method for Measuring the Surface Area of Nickel Electrodes

An Oxalate Method for Measuring the Surface Area of Nickel Electrodes

Electrochemical Hydrogen Evolution: H⁺or H₂O Reduction? A Rotating Disk Electrode Study

Nickel hydroxides and related materials: a review of their structures, synthesis and properties

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The hydrogen evolution reaction on nickel surfaces stabilized by H-absorption

Cited by 220 publications

References 24 publications

An Oxalate Method for Measuring the Surface Area of Nickel Electrodes

An Oxalate Method for Measuring the Surface Area of Nickel Electrodes

Electrochemical Hydrogen Evolution: H+or H2O Reduction? A Rotating Disk Electrode Study

Nickel hydroxides and related materials: a review of their structures, synthesis and properties

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Electrochemical Hydrogen Evolution: H⁺or H₂O Reduction? A Rotating Disk Electrode Study