Formic acid oxidation on Bi Pt(1 1 1) electrode in perchloric acid media. A kinetic study

Maciá, M.D.; Herrero, Enrique; Feliu, Juan M.

doi:10.1016/s0022-0728(03)00023-8

Cited by 84 publications

(67 citation statements)

References 51 publications

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“…For the Pt(111) electrode and vicinal surfaces modified with Bi, As, Te, Sb or Pb a clear increase in the currents with respect to those measured in the clean surface is observed [15,44,45,36,46,47,37,48]. For instance, the currents for a Bi modified surface can be 40 times higher than those measured for the unmodified surface in the absence of poison at the same potential.…”

Section: Effect Of the Adatoms In The Route Through The Active Intermmentioning

confidence: 90%

Fundamental aspects of HCOOH oxidation at platinum single crystal surfaces with basal orientations and modified by irreversibly adsorbed adatoms

Boronat-González

Herrero

Feliu

2013

J Solid State Electrochem

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Abstract.Oxidation of formic acid at Pt(hkl) electrodes with basal orientations and modified by irreversibly adsorbed adatoms is revisited. It was shown that the adatoms of the nitrogen group could enhance the electrocatalytic activity through long range electronic effects in the case of Pt (111) substrates or through shorter third body effects when adsorbed at Pt(100) electrodes. In both cases it appears that free platinum sites were required. Special attention is given here to the reactivity at Pt(110) substrates. It is found that maximum electrocatalysis is observed at fully blocked surfaces. This result points out again structure sensitivity effects for this characteristic reaction. Unlike the more compact planes, in which the enhancement of the oxidation rate was explained through essentially rigid models for the adlayer, it is suggested that the resulting enhancement observed at Pt(110) substrates could be explained if some adatom mobility is considered.

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Section: Effect Of the Adatoms In The Route Through The Active Intermmentioning

confidence: 90%

Fundamental aspects of HCOOH oxidation at platinum single crystal surfaces with basal orientations and modified by irreversibly adsorbed adatoms

Boronat-González

Herrero

Feliu

2013

J Solid State Electrochem

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“…Bismuth has given rise to very promising results. [16][17][18] The addition of Bi adatoms to pristine Pt(111) single crystal electrodes diminishes the overpotentials and increase the current density up to 30-40 times that measured for the unmodified surface. 15 Such improvement is clearly related to the deposition of Bi on the terraces, since it reaches the maximum for coverages close to the saturation value.…”

Section: Introductionmentioning

confidence: 99%

“…However, adsorption currents are proportional to the scan rate, being oxidation currents much less affected by the scan rate. 18 By using high scan rates, adsorption currents can dominate the voltammetric profile. 21 For a Bi adatom modified Pt(111) electrode with a coverage 0f 0.25, which is very close to the maximum activity, both types of experiments (low and high scan rate voltammetry) are shown in figure 1.…”

Section: Introductionmentioning

confidence: 99%

Oxidation Mechanism of Formic Acid on the Bismuth Adatom-Modified Pt(111) Surface

et al. 2014

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In order to improve catalytic processes, elucidation of reaction mechanisms is essential. Here, supported by a combination of experimental and computational results, the oxidation mechanism of formic acid on Pt(111) electrodes modified by the incorporation of bismuth adatoms is revealed. In the proposed model, formic acid is first physisorbed on bismuth and then deprotonated and chemisorbed in formate form, also on bismuth, from which configuration the C−H bond is cleaved, on a neighbor Pt site, yielding CO 2 . It was found computationally that the activation energy for the C−H bond cleavage step is negligible, which was also verified experimentally.

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“…In contrast, the activity enhancement of Pt-Pb for formic acid oxidation has been attributed to an electronic interaction between Pb and Pt [90]. The high catalytic activity for a Bi modified Pt catalyst has also been explained by electronic effects working in addition to a 'third-body effect' [91].…”

Section: Anode Catalysts For Electro-oxidation Of Formic Acid Unsuppomentioning

confidence: 99%

The Study of Pt and Pd based Anode Catalysis for Formic Acid Fuel Cell

Uwitonze¹,

Chen²

2017

Chem Sci J

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Detailed investigation of HCOOH electro-oxidation started about five decades ago, with the advent of modern potentiodynamic techniques, driven initially by the purpose of elucidating some of the most interesting and challenging electrode kinetic problems. Many pioneering works that withstood the test of time and the continuous sophistication of surface electrochemistry techniques were published in the 1960s. Stimulated results were obtained, such as: (i) phenomenological interpretation of anodic polarization curves (e.g., Determination of Tafel parameters), HCOOH oxidation on Pd and Pt catalysts; (ii) discovery of the catalytic effect with respect to Pt and Pd for HCCOH oxidation; (iii) investigation of the potential dependent adsorption of HCOOH on Pt and Pd catalysts which are accompanied by a dual pathway mechanism and (iv) formic acid concentration, temperature effects and crossover of nafion membrane.

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Formic acid oxidation on Bi Pt(1 1 1) electrode in perchloric acid media. A kinetic study

Cited by 84 publications

References 51 publications

Fundamental aspects of HCOOH oxidation at platinum single crystal surfaces with basal orientations and modified by irreversibly adsorbed adatoms

Fundamental aspects of HCOOH oxidation at platinum single crystal surfaces with basal orientations and modified by irreversibly adsorbed adatoms

Oxidation Mechanism of Formic Acid on the Bismuth Adatom-Modified Pt(111) Surface

The Study of Pt and Pd based Anode Catalysis for Formic Acid Fuel Cell

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