Growth of Pt by surface limited redox replacement of underpotentially deposited hydrogen

Nutariya, Jeerapat; Fayette, Matthew; Dimitrov, Nikolay; Vasiljević, Nataša

doi:10.1016/j.electacta.2013.01.052

Cited by 62 publications

(68 citation statements)

References 66 publications

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“…5 Several sacrificial materials, like Cu, 68 Pb,7,9 and H,10 have been studied for the deposition of Pt monolayers. In addition to Pt, the SLRR was extended to the monolayer deposition of other metals, such as Pd, 11 Ru, 12 and Ag.…”

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confidence: 99%

“…2,4 Brankovic et al developed a method for Pt monolayer deposition by galvanic displacement of a layer of sacrificial underpotential deposition (UPD) metal, which is called surface-limited redox replacement (SLRR). 5 Several sacrificial materials, like Cu, 68 Pb, 7,9 and H, 10 have been studied for the deposition of Pt monolayers. In addition to Pt, the SLRR was extended to the monolayer deposition of other metals, such as Pd, 11 Ru, 12 and Ag.…”

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confidence: 99%

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Polarization-dependent Total Reflection Fluorescence X-ray Absorption Fine Structure (PTRF-XAFS) Studies on the Structure of a Pt Monolayer on Au(111) Prepared by the Surface-limited Redox Replacement Reaction

et al. 2017

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We studied the initial stage of a Pt monolayer produced by surface-limited redox replacement (SLRR) using polarizationdependent total reflection fluorescence X-ray absorption fine structure (PTRF-XAFS). Different from the widely accepted understanding that metallic monolayer islands are formed, our XAFS showed that the Pt monolayer, initially present on the Au(111) substrate, was mainly in the form of a planar [PtCl 4 ] 2¹ complex with its molecular plane parallel to Au(111). This result provides a new insight into the mechanism of SLRR.Keywords: X-ray absorption fine structure (XAFS) | Surface-limited redox replacement reaction | Pt monolayerPolymer electrolyte fuel cells (PEFCs), which emit no greenhouse gases, have attracted much attention because of the necessity for the modern society to shift from fossil fuels to clean energy. However, several issues concerning electrocatalysts, including their cost and durability, have greatly inhibited the practical use of PEFCs.1 To reduce the cost of the electrocatalyst, we need to increase the surface area of Pt, which is the main component of the fuel cell catalyst currently. Considerable effort has been devoted to investigating the electrodeposition of Pt. 24Owing to the high surface energy and low wettability of Pt, it is difficult to obtain monolayer deposition on a flat surface with conventional electrodeposition methods.2,4 Brankovic et al. developed a method for Pt monolayer deposition by galvanic displacement of a layer of sacrificial underpotential deposition (UPD) metal, which is called surface-limited redox replacement (SLRR).5 Several sacrificial materials, like Cu, 68 Pb,7,9 and H,10 have been studied for the deposition of Pt monolayers. In addition to Pt, the SLRR was extended to the monolayer deposition of other metals, such as Pd, 11 Ru, 12 and Ag. 5,13 Furthermore, bimetallic monolayer depositions were also achieved by the SLRR.14,15 However, there are only limited numbers of studies regarding the mechanism of the deposition process on atomic levels. In situ scanning tunneling microscopy (STM) was used to study the structure of Pt submonolayers.8 Brankovic et al. systematically studied the reaction mechanism of SLRR to replace the UPD Cu with Pt. They proposed a kinetic model, 16 based on the stoichiometry of SLRR, 6 and also proposed the nucleation mechanism of the Pt monolayer clusters, 17 and the UPD procedure on the Pt monolayer modified surface. 9,15 However, some aspects remain unclear. For example, what is the chemical state and structure of the Pt submonolayers and Pt submonolayerAu interaction, which are very important parameters since they are related to the catalytic properties? To examine the Pt initial structure created by the SLRR of the Cu UPD layer, we applied polarization-dependent total reflection fluorescence-X-ray absorption fine structure (PTRF-XAFS) techniques. 1820PTRF-XAFS is a powerful way of characterizing the surface structure and electronic state of less than a monolayer of adsorbate on atomically flat surfaces even und...

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Polarization-dependent Total Reflection Fluorescence X-ray Absorption Fine Structure (PTRF-XAFS) Studies on the Structure of a Pt Monolayer on Au(111) Prepared by the Surface-limited Redox Replacement Reaction

et al. 2017

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“…In some cases, SLRR can be simplified by first performing UPD of the metal M, followed by injection of the metal N in the electrolyte, using a one-pot process [76]. SLRR has also been extended to the use of non-metallic sacrificial monolayers; for example, a UPD hydrogen layer has been used as a sacrificial layer to perform metal replacement [77]. Repetition of this process leads ideally to a homo-or hetero-epitaxial layer of high quality that could be used for particular functional applications.…”

Section: Surface-limited Electrochemical Processes For Materials Syntmentioning

confidence: 99%

Electrodeposition of Alloys and Compounds in the Era of Microelectronics and Energy Conversion Technology

Zangari

2015

Coatings

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Electrochemical deposition methods are increasingly being applied to advanced technology applications, such as microelectronics and, most recently, to energy conversion. Due to the ever growing need for device miniaturization and enhanced performance, vastly improved control of the growth process is required, which in turn necessitates a better understanding of the fundamental phenomena involved. This overview describes the current status of and latest advances in electrodeposition science and technology. Electrochemical growth phenomena are discussed at the macroscopic and atomistic scale, while particular attention is devoted to alloy and compound formation, as well as surface-limited processes. Throughout, the contribution of Professor Foresti and her group to the understanding of electrochemical interfaces and electrodeposition, is highlighted.

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“…Because of this, strategies such as surface limited redox replacement (SLRR), 6,[18][19][20][21][22][23][24][25][26][27][28][29][30] or limited ion adsorption on the substrate. [18][19][20][21][22][23][24][25][26]28,29,50,51 These factors ultimately result in the operation of a cyclic process that allows for the deposition of a strict amount of material (usually limited to a ML) per cycle rendering the deposit thickness finely controllable. An additional benefit of these methods is associated with the naturally existing short period of deposition inactivity between cycles that prevents the establishment steady mass transport controlled growth.…”

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confidence: 99%

“…16,17 Therefore, complete coverage of the substrate can be ensured, only by the deposition of films of significant thicknesses that, in turn, can be controlled solely by charge calculations over the course of deposition. Because of this, strategies such as surface limited redox replacement (SLRR), 6,[18][19][20][21][22][23][24][25][26][27][28][29][30] Defect-Mediated Growth (DMG), 31 Surfactant Mediated Growth (SMG), 32 Self-Terminating Growth (STG), 33,34 Forced Deposition (FD) 12,[35][36][37] and Spontaneous Deposition (SD) 11,[37][38][39][40][41][42][43][44][45][46][47][48][49] have * Electrochemical Society Student Member. * * Electrochemical Society Member.…”

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The Spontaneous Deposition of Au on Pt (111) and Polycrystalline Pt

Ambrozik

Mitchell

Dimitrov

2016

J. Electrochem. Soc.

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Gold is epitaxially grown by spontaneous deposition (SD) on Pt(111) and Pt [poly]. It has been demonstrated that in the system of interest the SD takes place as a hybrid process, consisting of the potential-controlled reduction of an adsorbed [AuCl 4 ] − complex along with an electroless reduction of the same complex coupled with Pt surface oxidation over the course of adsorption. This hybrid deposition process is shown to promote an outstanding layer-by-layer growth mode on Pt(111) that involves the formation of smooth films with virtually no surface roughness increase. This finding is seconded by in-situ STM experiments demonstrating that the SD of Au on Au(111) leads to similar growth results. In addition, an adlattice structure of √ 7 × √ 7 r19.1 • is determined for the [AuCl 4 ] − adsorbate on Au (111) suggesting a theoretical deposited amount of about 15% Au surface coverage per SD cycle. It has been shown that a Pt(111) substrate is completely masked after five cycles of SD followed by layer densification in continuity development. It has also been shown that the Au amount deposited specifically through the electroless route can be controlled by the amount of initial Pt oxidation, the concentration of dissolved O 2 , and the duration of [AuCl 4 The deposition of thin noble metal films is an area of significant interest for the fundamental and applied communities alike. Noble metal monolayer, to multilayer structures on a sacrificial substrate allows for the utilization of the beneficial properties of electropositive metals or alloys such as; corrosion resistance and catalytic activity, while minimizing the metals use, thus promoting cost effectiveness. In addition it has been shown that monolayer to bilayer metal films on foreign substrates exhibit different electronic properties and chemisorption trends when compared to the bulk material. This is explained through the alteration of the d-band center and orbital mixing resulting from epitaxial strain and electron ligand effects.1-4 Overall, these unique properties can ultimately enhance a material's catalytic usefulness. 5,6 In addition to this it has also been shown that if a metal substrate is decorated by a sub-monolayer of a foreign metal in a controllable way, a synergism can result between the substrate and the foreign metal. This synergy results in enhanced properties, that in some cases are accompanied by the stabilization of the underlying substrate. [7][8][9][10][11] Adzic et al. have demonstrated that the electrodepostion of 0.26 to 0.33 layers of Au on an underlying Pt substrate not only results in steady oxygen reduction reaction activity but also, after 30,000 cycles, the accordingly decorated catalyst is proven significantly more durable than the Pt catalyst on its own.10 Hazzazi et al. have also shown that Au deposited via forced deposition on Pt with coverages up to 0.73 layers improve a catalysts activity toward the ethanol oxidation reaction. 12The above listed sample of advantages of ultrathin epitaxial and continuous noble metal f...

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Growth of Pt by surface limited redox replacement of underpotentially deposited hydrogen

Cited by 62 publications

References 66 publications

Polarization-dependent Total Reflection Fluorescence X-ray Absorption Fine Structure (PTRF-XAFS) Studies on the Structure of a Pt Monolayer on Au(111) Prepared by the Surface-limited Redox Replacement Reaction

Polarization-dependent Total Reflection Fluorescence X-ray Absorption Fine Structure (PTRF-XAFS) Studies on the Structure of a Pt Monolayer on Au(111) Prepared by the Surface-limited Redox Replacement Reaction

Electrodeposition of Alloys and Compounds in the Era of Microelectronics and Energy Conversion Technology

The Spontaneous Deposition of Au on Pt (111) and Polycrystalline Pt

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