From Au to Pt via Surface Limited Redox Replacement of Pb UPD in One-Cell Configuration

Fayette, Matthew; Liu, Y.; Bertrand, Didier; Nutariya, Jeerapat; Vasiljević, Nataša; Dimitrov, Nikolay

doi:10.1021/la200348s

Cited by 114 publications

(197 citation statements)

References 51 publications

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“…[11][12][13][14][15][16] On the other hand, the morphology of P deposit is a direct function of SLRR reaction kinetics and stoichiometry. 12,17 They are dependent on experimental conditions.…”

Section: Deposition Via Surface Limited Redox Replacement (Slrr) Of Umentioning

confidence: 99%

Editors' Choice—Reaction Kinetics of Metal Deposition via Surface Limited Redox Replacement of Underpotentially Deposited Monolayer Studied by Surface Reflectivity and Open Circuit Potential Measurements

Bulut

Dole

et al. 2017

J. Electrochem. Soc.

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Presented work studies the relation between kinetics of metal deposition via surface limited redox replacement (SLRR) of underpotentially deposited (UPD) monolayer (ML) and experimental parameters of reaction solution such as meal ions concentrations and supporting electrolyte concentration. The model system is Au deposition on Au(111) via SLRR of Pb UPD ML. The rate constant of the SLRR reaction for different solution designs is determined from temporal change of electrode surface reflectivity and from the open circuit potential transients' analysis. The obtained results show clearly that reaction kinetics of metal deposition via SLRR of UPD ML is significantly affected by the design of the reaction solution i.e. the UPD metal ion, depositing metal ion, and supporting electrolyte concentrations. The ten-fold change of concentration of either solution parameter produces approximately the same change in the value of the rate constants. The presented results have fundamental importance for the future development and application of the metal deposition via SLRR of UPD ML. They offer a link between the reaction solution design and expected trend in SLRR reaction rate, which transposes to successful control of deposition flux, nucleation density and resulting morphology of the deposit. Deposition via Surface Limited Redox Replacement (SLRR) of underpotentially deposited (UPD) monolayer (ML)1 has gained a lot of attention and applications in last two decades.2-4 The main idea is to use an UPD ML as sacrificial material to reduce/deposit a more noble metal (SLRR reaction i.e. galvanic displacement). The basic stoichiometry of the SLRR reaction and deposition process is shown by Equation 1.Here, M and P and S(h,k,l) stand for UPD metal/ion, depositing metal/ion and substrate, while m + /m and p + /p represent the oxidation state of M and P metal ions and corresponding stoichiometry coefficients. Over the years, several experimental protocols for deposition via SLRR of UPD ML have been developed. The first and the basic one, 1,6 involves formation of the UPD ML of M on the substrate S(h,k,l), (potential controlled step) and then subsequent immersion of M UPD /S(h,k,l) into a separate reaction solution where SLRR occurs and deposition of P takes place at open circuit (sample shuffling approach). The second protocol involves the stagnant substrate but sequential application of potential control in solution for UPD ML formation and then application of solution for SLRR reaction and deposition of P at open circuit (solution shuffling approach 7 ). The most recent development has introduced a "one-solution, one-cell" experimental design. 8,9 In this case, the same solution serves for UPD ML formation and subsequent SLRR reaction at open circuit potential. This protocol assumes a sequence of potential controlled step, where co-deposition of UPD ML of M with small amount of P occurs, and the open circuit step, where SLRR reaction and deposition of P proceeds. The very details of these three protocols and their applications hav...

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Section: Deposition Via Surface Limited Redox Replacement (Slrr) Of Umentioning

confidence: 99%

Editors' Choice—Reaction Kinetics of Metal Deposition via Surface Limited Redox Replacement of Underpotentially Deposited Monolayer Studied by Surface Reflectivity and Open Circuit Potential Measurements

Bulut

Dole

et al. 2017

J. Electrochem. Soc.

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“…This process mimics the well known cementation phenomenon, with the only difference that SLRR is limited to the atomic layer level. 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].…”

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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“…7 This fabrication procedure entails Au (1−x) Ag x alloy electrodeposition followed by selective dissolution of Ag ultimately generating the desired NPG structure with a thickness of less than 20 nm. The NPG can be further functionalized with Pt by surface-limited redox replacement (SLRR) 12 to form Pt-NPG, and then applied as the catalyst in the formic acid oxidation and other catalytically relevant reactions. 7 Found to emphasize the enhanced activity boosted by synergism between Pt and Au, 13,14 Pt-NPG was constitutes a cost-effective alternative to Pt or Pt-Au core-shell nanoparticles.…”

Section: Npg Based Catalyst On Glassy Carbon (Gc)mentioning

confidence: 99%

Enhanced Adhesion of Ultrathin Nanoporous Au Deposits by Electrochemical Oxidation of Glassy Carbon

Xia

Rooney

Ambrozik

et al. 2015

J. Electrochem. Soc.

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Electrochemical (EO) and Thermochemical (TO) oxidation have been considered as means for improved adhesion of metals to glassy carbon (GC) substrates. This paper is aimed at studying the effect of EO on the all-electrochemical processing of nanoporous gold (NPG) catalysts with emphasis on their adhesion to a GC substrate. It has been shown by two independent assessment approaches that EO improves twice the amount of retained NPG on GC helping to keep about 90% originally existing material after a two-hour rotation disk electrode test at 1600 rpm. This work also demonstrates that EO modifies the GC in a way making it more passive in the alloy deposition and subsequent dealloying processes. This effect results in a progressive nucleation density decrease with the depth of oxidation which in turn leads to a lack of continuity of the NPG layer. This trend is also accompanied by a decrease in deposition efficiency as a substantial part of the cathodic current is spent on the reduction of the pre-oxidized GC surface. Our study identifies the best outcome of the trade-off scenario between nucleation density, deposition efficiency and adhesion strength to be associated with depth of oxidation in the range 0.10 to 0.25 μm. NPG based catalyst on glassy carbon (GC).-Nanoporous Au (NPG) is a nano-material with three dimensional (3D) continuous structure featuring Au with interconnected nano-sized pores and ligaments.1 NPG and other nanoporous metals have been intensively investigated in recent years. This conductive material has an open, 3D porous framework with surface areas that even in an ultrathin NPG layer configuration could be an order of magnitude larger than the area of planar Au. Besides its continuous crystal lattice throughout the porous network, it has a pore size that is adjustable via simple thermal post-processing, which makes it potentially applicable in various fields such as electro-and gas-phase catalysis, optics, sensors and actuators. [2][3][4][5] It is known that nanoparticulate gold possesses remarkable catalytic activity toward oxidation reactions, should the particles be well supported and smaller than 5 nmin size. 6 Recently, ultrathin films of NPG have been shown to serve as catalysts for fuel cell applications as an alternative to their nanoparticle (NP) counterparts.7-9 These films are generated electrochemically under precise potential/current control, which minimizes material loss and surface contamination over the multi-step NP synthetic routines. 7,10 Compared to nanoparticle synthesis which often lacks control due to the large number of the processing steps, ultra thin films of NPG are cost effective, simple to fabricate, and show better reproducibility in terms of quality and reactivity. Another advantage of NPG films is that the edge effect that lowers the catalytic activity characteristic for NP based catalysts does not exist in NPG films due to its continuous nature. 11In our previous work, we established an all-electrochemical synthetic method for a NPG-based catalyst that maximized t...

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From Au to Pt via Surface Limited Redox Replacement of Pb UPD in One-Cell Configuration

Cited by 114 publications

References 51 publications

Editors' Choice—Reaction Kinetics of Metal Deposition via Surface Limited Redox Replacement of Underpotentially Deposited Monolayer Studied by Surface Reflectivity and Open Circuit Potential Measurements

Editors' Choice—Reaction Kinetics of Metal Deposition via Surface Limited Redox Replacement of Underpotentially Deposited Monolayer Studied by Surface Reflectivity and Open Circuit Potential Measurements

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

Enhanced Adhesion of Ultrathin Nanoporous Au Deposits by Electrochemical Oxidation of Glassy Carbon

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