Kinetics and mechanism of electroreduction of Pd(II) complexes

Kravtsov, V. I.

doi:10.1007/s11175-005-0051-x

Cited by 11 publications

(5 citation statements)

References 32 publications

(89 reference statements)

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“…Electrodeposition of palladium behaviour from ammonia based solution has been investigated intensively [5,6,26,30]. A mechanism of palladium electroreduction at pH 5 -13.6 was observed involving an electrochemical reaction (3) [5,6,26]:…”

Section: Fundamentalmentioning

confidence: 99%

Electrochemical polarisation behaviour of palladium electrolyte in a mixed system of Pd/Ni/Cu

Widayatno

2018

AIP Conference Proceedings

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Abstract. The possibility of Pd-plated leadframe fabrication using maskless method was investigated. Palladium metallisation was carried out using a maskless electrochemical patterning process on a substrate of copper disc with deposited nickel pattern on its surface. An appropriate palladium electrolyte required for such system has been previously prepared. Onset potential and current densities for palladium deposition was determined. However, palladium pattern deposit could not be obtained, as the substrates were always entirely covered by palladium. This might be due to an instantaneous palladium deposition caused by displacement reaction between Pd and Cu/Ni. Therefore, a set of voltammetry experiments has been carried out to study polarisation behaviours of the mixed system Pd/Ni/Cu in a threeelectrode RDE system. These experiments were aimed to determine onset potential of palladium deposition at which displacement reaction could be avoided. However, polarisation curves especially for those of palladium and copper indicate that it was not possible to deposit palladium with no copper dissolution. At any potential where palladium deposition was possibly to occur, it was always accompanied by copper dissolution.

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Section: Fundamentalmentioning

confidence: 99%

Electrochemical polarisation behaviour of palladium electrolyte in a mixed system of Pd/Ni/Cu

Widayatno

2018

AIP Conference Proceedings

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“…42 The tetravalent Pd-chloro complex (PdCl 4− ) is a labile complex that is prone to galvanic displacement in aqueous solution. • C for 2.5 h (equivalent to the total time taken to carry out pulsed potentiostatic electrodeposition at duty cycle 0.2).…”

Section: 39mentioning

confidence: 99%

“…Whether the Pd ions displace Ni or not depends upon the Pd complexes. 42 The tetravalent Pd-chloro complex (PdCl 4− ) is a labile complex that is prone to galvanic displacement in aqueous solution. 2).…”

Section: Electrochemical Window (Ew)mentioning

confidence: 99%

Size-Controlled Synthesis of Palladium Nanospheres by Pulse Electrodeposition in 1-Butyl-3-methylimmidazolium Chloride Ionic Liquid

Shrestha¹,

Nagib²,

Biddinger³

2015

J. Electrochem. Soc.

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Pd electrodeposition in ionic liquids has been mostly limited to the formation of thin films, which has restricted its potential application to the electronics and decorative industry only. The electrochemical synthesis of nanostructured Pd could broaden its applications to the catalyst industry as well. In 1-butyl-3-methylimmidazolium chloride, the Pd deposits reported so far have had uncontrolled growth without any well-defined morphology. In this study, we report controlled synthesis of Pd nanoparticles with well-defined morphology on pre-etched Ni electrodes. Potentiostatic pulse deposition was used to synthesize these Pd nanoparticles, which had spherical shape and unimodal size distribution. In contrast, thin film-like morphology was deposited during direct electrodeposition. The size of the Pd nanospheres was controlled by controlling the duty cycle; the size of the Pd nanospheres increased from 14.8 ± 3.5 to 30.8 ± 6.6 nm when the duty cycle decreased from 0.5 to 0.2. The size of the Pd nanospheres showed linear dependence on the duty cycle giving excellent control. X-ray diffraction analysis revealed face-centered cubic crystalline microstructure for the Pd particles. The analysis also suggested that the amount of Pd increased by decreasing the duty cycle. The surface of the Pd deposits was dominated by metallic state as revealed by X-ray photoelectron spectroscopy. Electrodeposited Pd has applications as catalysts, interconnects, jewelry and ornaments.1 Electrodeposition has also been considered for recovery of fission palladium.2 Ionic liquids (ILs) are considered promising electrolytes for Pd electrodeposition because hydrogen embrittlement, which is commonly a problem for Pd electrodeposition in aqueous systems, could be avoided by proper choice of IL. Different types of ILs have been studied for this purpose such as chloroaluminates, 20 Some of the work has also been done with the deep eutectic solvents (DES) choline chloride/urea and choline chloride/ethylene glycol.14,21 Pd-containing liquid metal salts (LMS), which are ILs with metal ions coordinated to the cations are also being explored for Pd electrodeposition. 22 However, these works were mostly limited to the study of Pd thin films. This limits the usability of Pd electrodeposition in ILs to the electronic and decorative industry.Controlled synthesis of nanostructures would make Pd electrodeposition in ILs applicable towards heterogeneous catalysis, where catalysts are usually metal nanoparticles. However, controlling size, shape and distribution of metal nanostructures are not straightforward in either aqueous-based solutions or ILs. Although significant progress has been made in aqueous-based solution regarding the synthesis of Pd nanostructures, the same could not be said for ILs. One of the issues is that the ILs behave differently than that of water; therefore, the knowledge could not be directly transferred from aqueous solutions to ILs. Another prominent issue is that each IL has unique chemistry. Despite these disadvantages, ILs hav...

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“…Palladium electrodeposition in aqueous solution has been extensively studied, and it has been performed in both basic and acidic mediums, among them chloride-based solutions attracted the most attention, 2 references within and the knowledge of palladium electrochemistry in chloride-based aqueous solutions is well established. Although electrodeposition of palladium in aqueous solutions has been performed successfully and is commercially available, hydrogen embrittlement, which is caused by the strong affinity between palladium and hydrogen, is still an intractable issue to be addressed.…”

mentioning

confidence: 99%

Electrochemical Behavior of PdCl₂ in 1-Ethyl-3-Methylimidazolium Chloride Ionic Liquid at Pt-Ir Electrode

Zong-hua

Pešić

2021

J. Electrochem. Soc.

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Electrodeposition of palladium in ionic liquids has not been actively investigated. Herein, the electrochemistry of PdCl2 for electrodeposition of palladium in 1-Ethyl-3-Methylimidazolium Chloride ([EMIM][Cl]) ionic liquid (IL) was studied at a Pt-Ir working electrode. A rotating disc was applied to allow a better understanding of the reaction kinetics. A range of techniques, such as cyclic voltammetry (CV) and current-time transient, were used to elucidate the electrochemistry of palladium of PdCl2 in [EMIM][Cl] IL under both stationary and rotating conditions. Two cathodic waves and two anodic waves were observed in CV. We propose that both of the cathodic peaks, which are separated by the surface alteration of the electrode during the cathodic scan, are produced by the electroreduction of PdCl4 2− to palladium, with their characteristics of mixed kinetics and mass transfer controlled, respectively. Regarding the nucleation of palladium on Pt-Ir electrode, a 3D, instantaneous nucleation mechanism was proved under quiescent conditions. The nucleation of Pd at rotating disc electrode(RDE) was fmodeled, and it was found that RDE promote instantaneous nucleation of Pd.

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Kinetics and mechanism of electroreduction of Pd(II) complexes

Cited by 11 publications

References 32 publications

Electrochemical polarisation behaviour of palladium electrolyte in a mixed system of Pd/Ni/Cu

Electrochemical polarisation behaviour of palladium electrolyte in a mixed system of Pd/Ni/Cu

Size-Controlled Synthesis of Palladium Nanospheres by Pulse Electrodeposition in 1-Butyl-3-methylimmidazolium Chloride Ionic Liquid

Electrochemical Behavior of PdCl₂ in 1-Ethyl-3-Methylimidazolium Chloride Ionic Liquid at Pt-Ir Electrode

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Kinetics and mechanism of electroreduction of Pd(II) complexes

Cited by 11 publications

References 32 publications

Electrochemical polarisation behaviour of palladium electrolyte in a mixed system of Pd/Ni/Cu

Electrochemical polarisation behaviour of palladium electrolyte in a mixed system of Pd/Ni/Cu

Size-Controlled Synthesis of Palladium Nanospheres by Pulse Electrodeposition in 1-Butyl-3-methylimmidazolium Chloride Ionic Liquid

Electrochemical Behavior of PdCl2 in 1-Ethyl-3-Methylimidazolium Chloride Ionic Liquid at Pt-Ir Electrode

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Electrochemical Behavior of PdCl₂ in 1-Ethyl-3-Methylimidazolium Chloride Ionic Liquid at Pt-Ir Electrode