Change in pH near the Cathode During the Electrodeposition of a Bivalent Metal. Analysis

Harris, Lee B.

doi:10.1149/1.2403622

Cited by 48 publications

(33 citation statements)

References 7 publications

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“…1–11 Thus, to produce metallic films, buffers and complexing agents such as boric acid are commonly added to the electrolyte to mitigate the effects of pH changes. 2,12–14 …”

Section: Introductionmentioning

confidence: 99%

Ultramicroelectrode Studies of Self-Terminated Nickel Electrodeposition and Nickel Hydroxide Formation upon Water Reduction

Ritzert

Moffat

2016

J. Phys. Chem. C

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The interaction between electrodeposition of Ni and electrolyte breakdown, namely the hydrogen evolution reaction (HER) via H3O+ and H2O reduction, was investigated under well-defined mass transport conditions using ultramicroelectrodes (UME’s) coupled with optical imaging, generation/collection scanning electrochemical microscopy (G/C-SECM), and preliminary microscale pH measurements. For 5 mmol/L NiCl2 + 0.1 mol/L NaCl, pH 3.0, electrolytes, the voltammetric current at modest overpotentials, i.e., between −0.6 V and −1.4 V vs. Ag/AgCl, was distributed between metal deposition and H3O+ reduction, with both reactions reaching mass transport limited current values. At more negative potentials, an unusual sharp current spike appeared upon the onset of H2O reduction that was accompanied by a transient increase in H2 production. The peak potential of the current spike was a function of both [Ni(H2O)6]2+(aq) concentration and pH. The sharp rise in current was ascribed to the onset of autocatalytic H2O reduction, where electrochemically generated OH− species induce heterogeneous nucleation of Ni(OH)2(ads) islands, the perimeter of which is reportedly active for H2O reduction. As the layer coalesces, further metal deposition is quenched while H2O reduction continues albeit at a decreased rate as fewer of the most reactive sites, e.g., Ni/Ni(OH)2 island edges, are available. At potentials below −1.5 V vs. Ag/AgCl, H2O reduction is accelerated, leading to homogeneous precipitation of bulk Ni(OH)2·xH2O within the nearly hemispherical diffusion layer of the UME.

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“…1–11 Thus, to produce metallic films, buffers and complexing agents such as boric acid are commonly added to the electrolyte to mitigate the effects of pH changes. 2,12–14 …”

Section: Introductionmentioning

confidence: 99%

Ultramicroelectrode Studies of Self-Terminated Nickel Electrodeposition and Nickel Hydroxide Formation upon Water Reduction

Ritzert

Moffat

2016

J. Phys. Chem. C

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“…Other roles ascribed for boric acid have been to act as a buffer [14,15], catalyst for metal deposition [16,17] and co-adsorbate on the cathode [18,19]. Zech and Landolt [19] reported that the presence of boric acid shifts the potential for proton reduction in the negative direction and lowers the pH rise at the cathode surface.…”

Section: Introductionmentioning

confidence: 99%

Transient and steady-state model of cobalt deposition in borate-sulfate solutions

Vazquez‐Arenas¹,

Pritzker²

2010

Electrochimica Acta

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“…The changes of pH at the cathode during electroplating of transition metals and alloys have been studied by many investigators [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21]. Kuhn and Chan [2] have presented a review of different techniques by which near-surface pH levels have been measured.…”

Section: Introductionmentioning

confidence: 99%

“…Harris [8] developed a mathematical model which predicted hydroxyl ion of OH" concentrations in the diffusion layer during the deposition of a bivalent metal. On the basis of a proposed model, he concluded that the degree of cathode alkalization depends on the rate of H^ consumption at the cathode, buffering reactions in the diffusion layer, and complexation reactions of the metallic ions with the anions present.…”

Section: Introductionmentioning

confidence: 99%

In situ surface pH measurement during electrolysis using a rotating pH electrode

Deligianni

Romankiw

1993

IBM J. Res. & Dev.

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An In situ technique has been developed for measuring the surface pH adjacent to a solid electrode/liquid Interface during electrolysis. Measurements of the surface pH can be used to obtain insights regarding the eiectrodeposltlon of various transition metals and to obtain a better understanding of associated in situ surface chemistry effects. Many transition metals and alloys deposit with simultaneous hydrogen evolution and, as a result, are accompanied by a pH rise near the cathode, thereby affecting the reactivity of the nearby metal-Ion species. Measurements of the surface pH of a solution containing simple salts during hydrogen evolution from a cathode were performed. The surface pl-l of a cathode during Ni and NiFe eiectrodeposltlon was also measured. The experiments demonstrated that, in the absence of buffers or metal ions, the surface pH rises many pH units above the bull( value. During Ni and NiFe eiectrodeposltlon, however, the surface pH of solutions consisting of simple salts and starting from a bulk pl-i level of 2 does not increase more than 3 pH units from the bulk value. In the case of NI and NiFe eiectrodeposltlon, surface buffering occurs because of the hydrolysis of the metal-ion species present. Additionally, it is found that during the anomalous codeposition of NiFe, the surface pH is much lower than that required by the Dahms-Croil hypothesis.^Copyright 1993 by International Business Macliines Corporation. Copying in printed form for private use is permitted without payment of royalty provided that (1) each reproduction is done without alteration and (2) the Journal reference and IBM copyright notice are included on the first page. The title and abstract, but no other portions, of this paper may be copied or distributed royalty free without further permission by computer-based and other information-service systems. Permission to republish any other portion of this paper must be obtained from the Editor.

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Change in pH near the Cathode During the Electrodeposition of a Bivalent Metal. Analysis

Cited by 48 publications

References 7 publications

Ultramicroelectrode Studies of Self-Terminated Nickel Electrodeposition and Nickel Hydroxide Formation upon Water Reduction

Ultramicroelectrode Studies of Self-Terminated Nickel Electrodeposition and Nickel Hydroxide Formation upon Water Reduction

Transient and steady-state model of cobalt deposition in borate-sulfate solutions

In situ surface pH measurement during electrolysis using a rotating pH electrode

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