Acetic acid adsorption on smooth Pt electrodes

Krauskopf, E.K.; Wiȩckowski, Andrzej

doi:10.1016/0022-0728(89)80083-x

Cited by 20 publications

(12 citation statements)

References 17 publications

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“…The carboxylate group itself interacts only weakly with Pt and does not support stable adsorption. Apparently, the lifetime of the weakly adsorbed oxalate is too low to allow C-C bond breaking, similar to the behavior of acetic acid [55,56]. For adsorption in the H upd region, especially at high H upd coverage at 0.06 V, slow reduction of oxalic acid to CO ad is possible as well, comparable to the reduction of CO 2 [57].…”

Section: Adsorption/oxidation Of Oxalic Acid On a Pt/c Catalyst Electmentioning

confidence: 79%

Adsorption and electrooxidation of ethylene glycol and its C2 oxidation products on a carbon-supported Pt catalyst: A quantitative DEMS study

Wang

Jusys

Behm

2009

Electrochimica Acta

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Section: Adsorption/oxidation Of Oxalic Acid On a Pt/c Catalyst Electmentioning

confidence: 79%

Adsorption and electrooxidation of ethylene glycol and its C2 oxidation products on a carbon-supported Pt catalyst: A quantitative DEMS study

Wang

Jusys

Behm

2009

Electrochimica Acta

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“…While the stable carboxylate can desorb from the particle, freeing sites for further reaction, small molecule carboxylates are known to adsorb weakly to Pt − with different binding characteristics depending upon the structure of the surface plane. − It is possible the carbamic acid formed following DMF oxidation can serve as a capping agent for Pt particles (step 3, Scheme ) and affect the rate of Pt ion reduction at different crystallographic planes. Greater blocking of (100) planes by carbamic acid species may inhibit Pt ion reduction (step 4, Scheme ) and enable a relatively faster rate of Pt addition to (111) planes, leading to the preferential growth of cubes over long reaction periods (vide infra). − Deeper understanding of the factors that control carboxylate adsorption at different types of structural sites on Pt surface planes is needed to develop a more detailed model for the role carbamic acid may play in the shape-selective Pt particle growth processes.…”

Section: Resultsmentioning

confidence: 99%

Solvothermal Synthesis and Electrochemical Characterization of Shape-Controlled Pt Nanocrystals

et al. 2014

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A simple, surfactant-free solvothermal method is reported for the preparation of <10 nm shape-controlled platinum crystallites. Reactions were carried out in N,Ndimethyformamide (DMF) and DMF−water mixtures. Effects of reaction time and temperature, DMF−water ratio, and metal precursor salt were examined. When the reaction conditions were tuned, ensembles of Pt particles with dominant truncated octahedral/ cuboctahedral or cubic shapes could be formed from the metal acetylacetonate (acac) precursor salt. Metal nanocrystal development was monitored through the use of highresolution transmission electron microscopy (HR-TEM) and X-ray and electrochemical analysis methods. Voltammograms probing CO and formic acid oxidation over shapecontrolled nanocrystals adsorbed to a glassy carbon electrode displayed expected features characteristic of extended ( 111) and (100) facets, confirming the stability and surface cleanliness of particles taken directly from the reaction mixture. A mechanism for Pt reduction and the growth and stabilization of preferentially shaped Pt nanocrystals in the DMF−water solvent system is proposed. The involvement of DMF as a reducing agent and carboxylate ions as weakly coordinating, and hence easily displaced, nanoparticle capping ligands is discussed.

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“…Ultimately, the role of the anion depends on how strongly it interacts with the electrode surface. Strongly adsorbed anions such as (bi)sulfate and chloride expectedly impede metal deposition. , On Rh(111), it is believed that a pseudomorphic Cu adlayer was deposited underneath a well-ordered (√3 × √7)−(bi)sulfate structure . More recently, Hoyer et al examined electrochemical deposition of Pd on Rh(111) in an effort to alter the electrcatalytic property of Rh electrodes by depositing foreign metals …”

Section: Introductionmentioning

confidence: 99%

Role of the Anion in the Underpotential Deposition of Cadmium on a Rh(111) Electrode: Probed by Voltammetry and in Situ Scanning Tunneling Microscopy

et al. 2005

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In situ scanning tunneling microscopy (STM) and cyclic voltammetry (CV) were employed to examine the underpotential deposition (UPD) of cadmium on a rhodium(111) electrode in sulfuric and hydrochloric acids. The (bi)sulfate and chloride anions in the electrolytes played a main role in controlling the number and arrangement of Cd adatoms. Deposition of Cd along with hydrogen adsorption occurred near 0.1 V (vs reversible hydrogen electrode) in either 0.05 M H2SO4 or 0.1 M HCl containing 1 mM Cd(ClO4)2. These coupled processes resulted in an erroneous coverage of Cd adatoms. The process of Cd deposition shifted positively to 0.3 V and thus separated from that of hydrogen in 0.05 M H2SO4 containing 0.5 M Cd2+. The amount of charge (80 microC/cm2) for Cd deposition in 0.5 M Cd2+ implied a coverage of 0.17 for the Cd adatoms, which agreed with in situ STM results. Regardless of [Cd2+], in situ STM imaging revealed a highly ordered Rh(111)-(6 x 6)-6Cd + HSO4- or SO42- structure in sulfuric acid,. In hydrochloric acid, in situ STM discerned a (2 x 2)-Cd + Cl structure at potentials where Cd deposition commenced. STM atomic resolution showed roughly one-quarter of a monolayer of Cd adatoms were deposited, ca. 50% more than in sulfuric acid. Dynamic in situ STM imaging showed potential dependent, reversible transformations between the (6 x 6) Cd adlattices and (square root 3 x square root 7)-(bi)sulfate structure, and between (2 x 2) and (square root 7 x square root 7)R19.1 degrees -Cl structures. The fact that different Cd structures observed in H2SO4 and HCl entailed the involvement of anions in Cd deposition, i.e. (bi)sulfate and chloride anions were codeposited with Cd adatoms on Rh(111).

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Acetic acid adsorption on smooth Pt electrodes

Cited by 20 publications

References 17 publications

Adsorption and electrooxidation of ethylene glycol and its C2 oxidation products on a carbon-supported Pt catalyst: A quantitative DEMS study

Adsorption and electrooxidation of ethylene glycol and its C2 oxidation products on a carbon-supported Pt catalyst: A quantitative DEMS study

Solvothermal Synthesis and Electrochemical Characterization of Shape-Controlled Pt Nanocrystals

Role of the Anion in the Underpotential Deposition of Cadmium on a Rh(111) Electrode: Probed by Voltammetry and in Situ Scanning Tunneling Microscopy

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