Cleavage of the C–C Bond in the Ethanol Oxidation Reaction on Platinum. Insight from Experiments and Calculations

Ferre-Vilaplana, Adolfo; Busó-Rogero, Carlos; Feliu, Juan M.; Herrero, Enrique

doi:10.1021/acs.jpcc.6b03117

Cited by 50 publications

(46 citation statements)

References 42 publications

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“…Similar trends in peak intensity can be seen in data reported previously. 55 In 0.1 M HClO4 solution, the main CO oxidation peak appeared at a potential of ~0.763 V, while in sulfuric acid it appeared at ~0.782 V, in agreement with the findings of Herrero et al 30 . In the case of Pt(332), the main CO oxidation peak potentials were at ~0.731 and ~0.745 V for 0.1 M HClO4 and 0.1 M H2SO4, respectively ( Figure 3C).…”

Section: Voltammetric Characterization Of Pt Single Crystals In Electsupporting

confidence: 89%

Site-specific catalytic activity of model platinum surfaces in different electrolytic environments as monitored by the CO oxidation reaction

Farias

Mello

Tanaka

et al. 2017

Journal of Catalysis

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Stepped Pt surfaces having different width (111) terraces interrupted by (110) or (100) monoatomic steps were employed to evaluate the catalytic activity towards CO oxidation at specific sites of these surfaces in HClO4, H2SO4, and H3PO4 solutions, as well as in phosphate buffer and alkaline solution. The catalytic activity at the (111) terraces was sensitive to the nature of the anions derived from the electrolyte dissociation, while no effect on catalytic activity was detected at the monoatomic steps. For the same stepped surface, a change in solution pH, passing from acid to alkaline solutions, had contrasting effects on catalytic activity at the (111) terraces and the step sites, with the catalytic activity of the (111) terraces improving, while catalytic activity at the step sites deteriorated. It was found that the release of CO surface sites occurred preferentially from the (111) terraces of the Pt(s)-[(n-1)(111)×(110)] series, while from Pt(s)-[(n)(111)×(100)] surfaces, (111) terrace and (100) step sites were released simultaneously.

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Section: Voltammetric Characterization Of Pt Single Crystals In Electsupporting

confidence: 89%

Site-specific catalytic activity of model platinum surfaces in different electrolytic environments as monitored by the CO oxidation reaction

Farias

Mello

Tanaka

et al. 2017

Journal of Catalysis

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“…For the C2 pathway, ethanol is incompletely electrooxidized to acetate, with the transfer of 4e − . Although DEFCs have great potential, CH 3 CH 2 OH electrooxidation on most electrocatalysts proceeds through the C2 pathway, leading to the formation of acetate as the final oxidation product; according to previous reports, at room temperature, the percentage of electrocatalysts for CH 3 CH 2 OH oxidation that work through the C1 pathway is only 1%, since breaking the CC bond is kinetically hindered . It is very eager to explore the high activity electrocatalysts, going through the C1 pathway.…”

Section: Application Of Pt Surface Segregation Of Ptm Bimetallic Nanomentioning

confidence: 99%

A Comprehensive Review on Controlling Surface Composition of Pt‐Based Bimetallic Electrocatalysts

Zhang

Yang

Wang

et al. 2018

Advanced Energy Materials

133

104

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version efficiency. [12][13][14][15] Among these metal electrocatalysts, platinum (Pt) exhibits the best activity for formic acid electrooxidation, ethanol electrooxidation, and oxygen reduction. However, pure Pt electrocatalyst faces several severe shortages, which limit its wide application in fuel cells. First, for formic acid and ethanol electrooxidation on pure Pt, the poisoning phenomenon (poison intermediates adsorption) usually happens on the surface of Pt, which will significantly decrease its electrocatalytic performance. [16][17][18][19][20] Second, for cathodic reaction, the oxygen reduction on pure Pt is sluggish. [21][22][23][24] Third, Pt is noble metal, which is limited reserve in nature. Therefore, how to reduce the Pt content and at the same time maintain its electrochemical performance are critical to achieve the commercialization of fuel cell.Bimetallic nanomaterials play an essential role in electrochemical energy conversion and storage, such as in fuel cells and metal-air batteries. [25][26][27] Unlike their monometallic counterparts, bimetallic nanomaterials ordinarily present better performance beneficial from synergistic effects, which means that the electrochemical performance of the whole will be superior than the sum of its parts. [28][29][30] In the case of the noble metals (especially Pt), their high cost and scarcity are obstructing the commercial viability of fuel cells. [31][32][33][34] Reducing the Pt loading without compromising its performance is the target of electrocatalytic investigations. [35][36][37] The typical approach is to incorporate with another metal, which could obtain better performance with much prolonged duration than the traditional commercial Pt/C. There are a great quantity of works on Ptbased bimetallic electrocatalysts, such as alloying Pt with 3d-transition metals, including Fe, [38,39] Co, [40][41][42] Ni, [43,44] and Cu. [45,46] PtM (M = Fe, Co, Ni, etc.) bimetallic nanomaterials have been demonstrated to be promising electrocatalysts, which strategic enhancement and development of the performance of commercial Pt/C electrocatalyst; and fundamental researches have shown that the enhanced catalytic activity originates from the modified electronic structures and geometric structures of Pt in these alloy catalysts. [47][48][49] It is a remarkable fact that these electrocatalytic reactions merely occur on the surface of the electrocatalysts. [28,50] Thus, the surface constituents of electrocatalysts determine the adsorption/desorption behaviors of the reactants and intermediates during the electrochemical reaction. Therefore, the catalytic reactions mechanisms and efficiencies strongly rely on the With increasing energy demands worldwide, significant efforts have been made to develop superior electrocatalysts for efficient energy conversion systems. Among all the electrocatalysts exploited, Pt-based bimetallic nanomaterials stand out by virtue of their high catalytic activity and relatively low cost due to the introduction of a nonprecious metal component. I...

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“…More importantly, ethanol can be directly oxidized into CO 2 in an alkaline medium. [ 7,8 ] This complete ethanol oxidation reaction (EOR) involves the transfer of 12 electrons (Equation ()), leading to a much higher energy density (e.g., 6.34 kWh L −1 for ethanol). Unfortunately, this EOR is kinetically sluggish in that the stable CC bond in ethanol molecules has to be broken.…”

Section: Introductionmentioning

confidence: 99%

“…Based on the numbers of carbon atoms in the products and electrons transferred per ethanol molecule, these EOR pathways are termed as C1‐12e and C2‐4e, respectively. [ 7–10 ] In terms of energy density of the EOR, the C2‐4e pathway has a three times lower efficiency than that of the C1‐12e one. To improve the energy efficiency of direct ethanol fuel cells, advanced electrocatalysts that favor the C1‐12e EOR pathway are thus are highly pursued.…”

Section: Introductionmentioning

confidence: 99%

A Phosphorus‐Doped Ag@Pd Catalyst for Enhanced CC Bond Cleavage during Ethanol Electrooxidation

Yang

Liang

Chen

et al. 2020

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a direct alkaline ethanol fuel cell owns more advantages. [4-6] For example, the production of ethanol from biomass is nonpoisonous and convenient. Ethanol is safe to be stored. More importantly, ethanol can be directly oxidized into CO 2 in an alkaline medium. [7,8] This complete ethanol oxidation reaction (EOR) involves the transfer of 12 electrons (Equation (1)), leading to a much higher energy density (e.g., 6.34 kWh L −1 for ethanol). Unfortunately, this EOR is kinetically sluggish in that the stable CC bond in ethanol molecules has to be broken. Given this fact, ethanol is much easier to be oxidized into acetate rather than CO 2. This oxidation pathway delivers only 4 electrons (Equation (2)). Based on the numbers of carbon atoms in the products and electrons transferred per ethanol molecule, these EOR pathways are termed as C1-12e and C2-4e, respectively. [7-10] In terms of energy density of the EOR, the C2-4e pathway has a three times lower efficiency than that of the C1-12e one. To improve the energy efficiency of direct ethanol fuel cells, advanced electrocatalysts that favor the C1-12e EOR pathway are thus are highly pursued.

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Cleavage of the C–C Bond in the Ethanol Oxidation Reaction on Platinum. Insight from Experiments and Calculations

Cited by 50 publications

References 42 publications

Site-specific catalytic activity of model platinum surfaces in different electrolytic environments as monitored by the CO oxidation reaction

Site-specific catalytic activity of model platinum surfaces in different electrolytic environments as monitored by the CO oxidation reaction

A Comprehensive Review on Controlling Surface Composition of Pt‐Based Bimetallic Electrocatalysts

A Phosphorus‐Doped Ag@Pd Catalyst for Enhanced CC Bond Cleavage during Ethanol Electrooxidation

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