Layer-by-Layer Deposition of Pd on Pt(111) Electrode: an Electron Spectroscopy–Electrochemistry Study

Hossain, Mohammad A.; Cummins, Kyle D.; Park, Yeon-Su; Soriaga, Manuel P.; Stickney, John L.

doi:10.1007/s12678-012-0102-5

Cited by 12 publications

(15 citation statements)

References 51 publications

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“…The deposition of Pd on Pt (111) and on Au (111) by the SLRR of a pre-deposited UPD layer of Cu was studied in detail by Soriaga et al [82] and Stickney et al [57], respectively. The results obtained are of significant interest given the applicability of thin Pd coatings in a variety of scenarios associated with fuel-cell catalysis [83,84].…”

Section: Pd and Ru Depositionmentioning

confidence: 99%

“…Ultrathin Pd films, at coverages that ranging from 0.5 to 8 ML, were found completely free of any residual Cu after the displacementby-Pd step. Analysis of the current-potential profiles in the hydrogen-adsorption region seconded by results of a LEED study indicated that at one monolayer coverage, the film was essentially pure terrace, devoid of steps, which did not exhibit hydrogen absorption [82]. At higher coverages, gradual roughness development manifested by the emergence of a voltammetric peak characteristic of hydrogen adsorption-desorption at step sites and weakening of the LEED signal, respectively, was associated with a Stranski-Krastanov transition leading eventually to a 3D growth mode.…”

Section: Pd and Ru Depositionmentioning

confidence: 99%

“…At higher coverages, gradual roughness development manifested by the emergence of a voltammetric peak characteristic of hydrogen adsorption-desorption at step sites and weakening of the LEED signal, respectively, was associated with a Stranski-Krastanov transition leading eventually to a 3D growth mode. Investigating the film thickening the authors of [82] found terrace and step voltammetric peaks still noticeable even at a Pdfilm thickness of 8 ML. However, the diminishing intensity of the latter peaks was clearly exhibited, indicating the growing role of the appreciable absorption into the Pd deposit due to its evolution into a bulk layer.…”

Section: Pd and Ru Depositionmentioning

confidence: 99%

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Recent Advances in the Growth of Metals, Alloys, and Multilayers by Surface Limited Redox Replacement (SLRR) Based Approaches

Dimitrov

2016

Electrochimica Acta

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A B S T R A C TIn the realm of ever increasing importance of nanotechnology, the deposition of ultrathin metal/alloy layers with perfect structure and unique functionality becomes an objective of paramount importance. In the last decade many research groups have been working on the development and application of a new method for epitaxial thin film growth that employs a surface limited redox replacement (SLRR) as a building block reaction. The multiple repetition of this reaction enables the controlled deposition of a monolayer of metal or alloy per cycle. Work in the field has been done on the development of SLRR deposition protocols along with understanding and modelling of the SLRR reaction kinetics, on comparative studies of SLRR based routines, and on other deposition approaches. Most recently, the development of SLRR was extended to the application of all-electroless approaches for carrying out the SLRR (ESLRR). In this paper an overview of all SLRR, ESLRR and related approaches is presented. The description of the background and reaction formalism introduces the method with emphasis on its general applicability and limitations. The discussion then continues with the description of experimental approaches for carrying out a deposition process by SLRR. In this section specific consideration is given to the deposition by shuttling of the working electrode, the flow-cell configuration, the one-cell configuration, and the all-electroless approaches for realizing the repetitive application of a single-cycle SLRR reaction. Next, the ability of these approaches to produce epitaxial, flat and uniform deposits will be discussed through results of electrochemical, in-situ scanning tunneling microscopy, X-ray Photoelectron Spectroscopy and other characterization experiments showing advantages and limitations of SLRR growth in a variety of systems classified into three categories. In the first of these categories Cu, Ag, and Au are used as model systems to introduce the deposition by SLRR. In the second category Pd and Ru deposition by SLRR has been discussed. In the third category all studies concerning a variety of scenarios for Pt deposition by SLRR are presented and in the last part of that section deposition of alloys and multilayers is critically discussed. The paper then continues with a section presenting and discussing modelling approaches of studying the kinetics of a single-cycle SLRR reaction and concludes with the presentation of the extension of modelling to a system where multi-cycle SLRR deposition processes have been investigated. The analysis in this part focuses on the kinetic parameters of the replacement reaction like rate constant, order of the reaction, type of adsorption behavior of the sacrificial metal etc. Finally, this section concludes with a discussion of the mechanistic aspects of the SLRR reaction and more specifically on the factors impacting the deposition process and in turn the resulting structure, morphology, uniformity and continuity of the accordingly grown thin films. The paper a...

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Section: Pd and Ru Depositionmentioning

confidence: 99%

Section: Pd and Ru Depositionmentioning

confidence: 99%

Section: Pd and Ru Depositionmentioning

confidence: 99%

See 1 more Smart Citation

Recent Advances in the Growth of Metals, Alloys, and Multilayers by Surface Limited Redox Replacement (SLRR) Based Approaches

Dimitrov

2016

Electrochimica Acta

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“…Subsequently, Weaver and co-workers [38] used successive applications of the two elementary steps (upd deposition and redox replacement) to create multilayer Pt coatings consisting of epitaxially deposited monolayers. Following these early works, Dimitrov and co-workers [39][40][41][42][43][44][45][46] and Stickney and co-workers [47][48][49][50][51][52][53] fully explored the technique for the preparation of a number of noble metal layers with atomic layer epitaxy. They further advanced practical aspects of the method that include automation of the process using a flow cell [51], a single-cell approach with careful control of upd deposition and ion concentrations [42], the use of adsorbed H as a sacrificial layer [44,53], the electroless deposition of the sacrificial upd layer by short circuiting the substrate with an appropriate counter electrode [45,46] and even some electrocatalytic applications [43,52].…”

Section: Ultrathin Film Applicationsmentioning

confidence: 99%

Electrocatalysts Prepared by Galvanic Replacement

et al. 2017

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Galvanic replacement is the spontaneous replacement of surface layers of a metal, M, by a more noble metal, M noble , when the former is treated with a solution containing the latter in ionic form, according to the general replacement reaction: nM + mM noble n+ → nM m+ + mM noble. The reaction is driven by the difference in the equilibrium potential of the two metal/metal ion redox couples and, to avoid parasitic cathodic processes such as oxygen reduction and (in some cases) hydrogen evolution too, both oxygen levels and the pH must be optimized. The resulting bimetallic material can in principle have a M noble-rich shell and M-rich core (denoted as M noble (M)) leading to a possible decrease in noble metal loading and the modification of its properties by the underlying metal M. This paper reviews a number of bimetallic or ternary electrocatalytic materials prepared by galvanic replacement for fuel cell, electrolysis and electrosynthesis reactions. These include oxygen reduction, methanol, formic acid and ethanol oxidation, hydrogen evolution and oxidation, oxygen evolution, borohydride oxidation, and halide reduction. Methods for depositing the precursor metal M on the support material (electrodeposition, electroless deposition, photodeposition) as well as the various options for the support are also reviewed. 1. Principle of Galvanic Replacement/Deposition 1.1. Thermodynamic Considerations When a metal, M (e.g., Cu, Fe, Co, Ni, Al, etc.), is immersed in a solution containing ions of a more noble metal, M noble n+ (e.g., Pt, Au, Pd, Ag, Ru, Ir, Rh, Os, etc.-i.e., a metal with a higher standard potential) then, due to the difference in their standard electrochemical potentials, E 0 noble − E 0 > 0, and provided that the ionic form of M is stable under the given experimental conditions (of temperatue, pH, complexing agents etc.), the following reaction is thermodynamically favored and can take place spontaneously: M noble n+ + n/m M → M noble + n/m M m+ (1) This reaction, which bears similarities with transmetalation reactions between metal complexes [1] and is also known as immersion plating [2] in the plating industry and galvanic replacement [3] in materials chemistry, can be considered to originate from the coupling of the following two half-reactions: M noble n+ + ne − ↔ M noble (E 0 noble) (2) M m+ + me − ↔ M (E 0) (3)

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“…Platinum group metal (PGM) thin films have gained considerable interest due to their electrocatalytic application [1]. Electrocatalysis on a modified metal surface by foreign metal underpotential deposition (UPD) has been extensively studied [2].…”

Section: Introductionmentioning

confidence: 99%

Electroformation of Pd‐modified Thin Film Electrocatalysts Using E‐ALD Technique

et al. 2021

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Electrochemical atomic layer deposition was used to form bimetallic (BiPd, CuPd) and trimetallic (CuBiPd) thin films via surface‐confined reactions. Pd thin films were characterized by cyclic voltammetry, scanning electron microscopy (SEM) and the alloy formation with preferred Au/Pd(111) orientation was confirmed by XRD. AFM revealed uniform grain distribution, with 3D islands growing on CuBiPd. EDX verified the presence of all deposited elements. Compared to other prepared catalysts, CuBiPd catalyst showed higher activity and stability towards the ethanol oxidation reaction (EOR), as confirmed by the peak current and onset potential trends, respectively: CuBiPd (1.35 mA, −0.450 V)>CuPd (0.6016 mA, −0.442 V)>BiPd (0.275 mA, −0.384 V)>Pd (0.186 mA, −0.350 V). The EOR current on CuBiPd improved by 2.5 folds relative to Pd. The results show that CuBiPd electrocatalyst is a promising material for EOR with enhanced catalytic properties for direct ethanol fuel cell

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Layer-by-Layer Deposition of Pd on Pt(111) Electrode: an Electron Spectroscopy–Electrochemistry Study

Cited by 12 publications

References 51 publications

Recent Advances in the Growth of Metals, Alloys, and Multilayers by Surface Limited Redox Replacement (SLRR) Based Approaches

Recent Advances in the Growth of Metals, Alloys, and Multilayers by Surface Limited Redox Replacement (SLRR) Based Approaches

Electrocatalysts Prepared by Galvanic Replacement

Electroformation of Pd‐modified Thin Film Electrocatalysts Using E‐ALD Technique

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