Effect of pretreatments on the hydrogen evolution kinetics of pure titanium using impedance and SECM technologies

Li, Xinran; Zhang, Qinhao; Meng, Xianze; Wu, Lian-Kui; Cao, Fahe

doi:10.1016/j.corsci.2021.109726

Cited by 20 publications

(21 citation statements)

References 90 publications

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“…The experimental solutions were prepared using ultrapure water (18.2 MΩ·cm), where 1 mM FcMeOH + 0.1 M NaClO 4 was used for the approach curve, and 5 mM HClO 4 + 0.1 M NaClO 4 (pH 2.3) was used for other tests due to no observable effect of FcMeOH and ClO 4 – on the electrochemical behavior of Ti . Under the naturally aerated condition, the test solution was used as prepared, and the measurement was conducted in the atmospheric environment.…”

Section: Methodsmentioning

confidence: 99%

“…In this work, a dual Pt/Ti (25/50 μm in diameter) UME tip with an RG value (the diameter ratio of the glass sheath to metal wire) of five and a Pt (125 μm in diameter) UME substrate with an RG value of more than 10 were prepared for SECM experiments. The Pt UME in the tip was to assist the alignment of the Ti UME to the Pt substrate . The Ti UME (50 μm in diameter) and Ti planar electrode (2 mm in diameter) were also made.…”

Section: Methodsmentioning

confidence: 99%

“…Pre-reduction was conducted by polarizing P-Ti at −0.903 V for 400 s in 5 mM HClO 4 + 0.1 M NaClO 4 with corresponding DO contents to reduce its surface oxide film . The polarization potential should not be too negative to prevent a large amount of hydrogen absorption into the underlying Ti and should be removed when the OCP of Ti has no further reduction with prolonged time. , After such activation by electro-reduction, the obtained sample was denoted as EA-Ti.…”

Section: Methodsmentioning

confidence: 99%

“…Titanium (Ti) has excellent corrosion resistance owing to its naturally formed oxide layer at the interface of metal/oxidizing media, including air and H 2 O. Therefore, the electrochemical behavior at the Ti/solution interface is significantly sensitive to the nature of the oxide film . However, under its service or experimental conditions, this film tends to be reduced by cathodic polarization.…”

Section: Introductionmentioning

confidence: 99%

“…In this setup, the Pt UME substrate quantitatively separates the reaction current or intermediate species produced by the active metal UME tips with a high collection efficiency (around or more than 90%). For Ti covered with the spontaneous oxide film, we have studied the HER behavior and kinetics under deaerated conditions after different pretreatments . However, DO is inevitable in a natural environment; therefore, its influence on the film features of Ti, and its competitive reduction with H + cannot be ignored.…”

Section: Introductionmentioning

confidence: 99%

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In Situ Studies of Hydrogen Evolution Kinetics on Pure Titanium Surface: The Effects of Pre-Reduction and Dissolved Oxygen

Meng

Zhang

et al. 2022

J. Phys. Chem. C

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The apparent cathodic current on the Ti surface in acidic solution is composed of three reactions: the reductions of the oxide film, H+, and O2. However, classical electrochemical tests usually provide coupled multi-reaction currents. Furthermore, dissolved oxygen makes in situ measurements significant due to the thermodynamic instability of Ti. In this study, the effects of pre-reduction and dissolved oxygen on hydrogen evolution reaction (HER) kinetics on the Ti surface were investigated by electrochemical and composition characterizations. The HER current was quantitatively separated from the apparent cathodic current from Ti, including the reductions of the oxide film, H+, and O2 by scanning electrochemical microscopy. The HER transfer coefficient and standard rate constant for Ti spontaneously passivated in air (P-Ti) are both 0.48/4.9 × 10–12 cm/s in aerated and O2-saturated solutions, while those for Ti activated by electro-reduction (EA-Ti) are 0.25/3.6 × 10–7 cm/s and 0.25/3.1 × 10–7 cm/s, respectively. The variable HER behavior is caused by the changes in the film electronic structure and composition except for the competition reduction between O2 and H+ as indicated by Mott–Schottky and surface-enhanced Raman spectroscopy. The deviation from 0.5 in the transfer coefficient implies that the Tafel slope and HER mechanism should be analyzed with caution.

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

In Situ Studies of Hydrogen Evolution Kinetics on Pure Titanium Surface: The Effects of Pre-Reduction and Dissolved Oxygen

Meng

Zhang

et al. 2022

J. Phys. Chem. C

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Probing passivity of corroding metals using scanning electrochemical probe microscopy

Skaanvik

Gateman

2023

Electrochemical Science Adv

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Passive films are essential for the longevity of metals and alloys in corrosive environments. A great deal of research has been devoted to understanding and characterizing passive films, including their chemical composition, thickness, uniformity, thickness, porosity, and conductivity. Many characterization techniques are conducted under vacuum, which do not portray the true in‐service environments passive films will endure. Scanning electrochemical probe microscopy (SEPM) techniques have emerged as necessary tools to complement research on characterizing passive films to enable the in situ extraction of passive film parameters and monitoring of local breakdown events of compromised films. Herein, we review the current research efforts using scanning electrochemical microscopy, scanning electrochemical cell microscopy (or droplet cell measurements), and local electrochemical impedance spectroscopy techniques to advance the knowledge of local properties of passivated metals. The future use of SEPM for quantitative extraction of local film characteristics within in‐service environments (i.e., with varying pH, solution composition, and applied potential) is promising, which can be correlated to nanostructural and microstructural features of the passive film and underlying metal using complementary microscopy and spectroscopy methods. The outlook on this topic is highlighted, including exciting avenues and challenges of these methods in characterizing advanced alloy systems and protective surface films.

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An innovative approach for atrazine electrochemical oxidation modelling: Process parameter effect, intermediate formation and kinetic constant assessment

Iovino,

Chianese,

Fenti

et al. 2023

Chemical Engineering Journal

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Effect of pretreatments on the hydrogen evolution kinetics of pure titanium using impedance and SECM technologies

Cited by 20 publications

References 90 publications

In Situ Studies of Hydrogen Evolution Kinetics on Pure Titanium Surface: The Effects of Pre-Reduction and Dissolved Oxygen

In Situ Studies of Hydrogen Evolution Kinetics on Pure Titanium Surface: The Effects of Pre-Reduction and Dissolved Oxygen

Probing passivity of corroding metals using scanning electrochemical probe microscopy

An innovative approach for atrazine electrochemical oxidation modelling: Process parameter effect, intermediate formation and kinetic constant assessment

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