Electrocatalytic Oxidation of Formic Acid at an Ordered Intermetallic PtBi Surface

Casado-Rivera, Emerilis; Gál, Zoltán A.; Angelo, Antonio; Lind, Cora; DiSalvo, Francis J.; Abruña, Héctor D.

doi:10.1002/cphc.200390030

Cited by 196 publications

(200 citation statements)

References 32 publications

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“…A special focus is on the poisoning of the catalysts by carbon monoxide, and for this, the electrochemical oxidation of formic acid can be studied (see Scheme 1). There are two paths in which formic acid (HCOOH) can be oxidized on the surface of a Pt electrode, namely dehydrogenation and dehydration [6,16]. As shown in Scheme 1, these processes involve either the formation of a reactive intermediate that yields CO 2 as the final product (dehydrogenation) or the formation of CO via the dehydration of formic acid.…”

Section: Cyclic Voltammetrymentioning

confidence: 99%

“…[5]. Furthermore, they have shown that the current densities of PtPb and PtBi electrodes are superior to those of a pure platinum catalyst [6][7][8] and that those intermetallics are almost immune against CO and S poisoning [9,10]. Thus, PtPb and PtBi intermetallic phases are promising materials to replace monometallic platinum nanoparticles in fuel cells.…”

Section: Introductionmentioning

confidence: 99%

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Catalytic Activity of Mono- and Bi-Metallic Nanoparticles Synthesized via Microemulsions

et al. 2014

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Water-in-oil (w/o) microemulsions were used as a template for the synthesis of mono-and bi-metallic nanoparticles. For that purpose, w/o-microemulsions containing H 2 PtCl 6 , H 2 PtCl 6 + Pb(NO 3 ) 2 and H 2 PtCl 6 + Bi(NO) 3 , respectively, were mixed with a w/o-microemulsion containing the reducing agent, NaBH 4 . The results revealed that it is possible to synthesize Pt, PtPb and PtBi nanoparticles of ~3-8 nm in diameter at temperatures of about 30°C. The catalytic properties of the bimetallic PtBi and PtPb nanoparticles were studied and compared with monometallic platinum nanoparticles. Firstly, the electrochemical oxidation of formic acid to carbon monoxide was investigated, and it was found that the resistance of the PtBi and PtPb nanoparticles against the catalyst-poisoning carbon monoxide was significantly higher compared to the Pt nanoparticles. Secondly, investigating the reduction of 4-nitrophenol to 4-aminophenol,we found that the bimetallic NPs are most active at 23 °C, while the order of the activity changes at higher temperatures, i.e., that the Pt nanoparticles are the most active ones at 36 and 49 °C. Furthermore, we observed a strong influence of the support, which was either a polymer or Al 2 O 3 . Thirdly, for the hydrogenation of allylbenzene to propylbenzene, the monometallic Pt NPs turned out to be the most active catalysts, followed by the PtPb and PtBi NPs. Comparing the two bimetallic nanoparticles, one sees that the PtPb NPs are significantly more active than the respective PtBi NPs. OPEN ACCESSCatalysts 2014, 4 257

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Section: Cyclic Voltammetrymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Catalytic Activity of Mono- and Bi-Metallic Nanoparticles Synthesized via Microemulsions

et al. 2014

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“…This modification can consist in deposition of submonolayer amounts of an element [14][15][16], the deposition of metallic monolayer [17] or the formation of alloys or intermetallic compounds [18][19][20]. These modifications of the platinum can act in two different ways: it can prevent the formation of CO through a third body effect, resulting in an increase in the overall reactivity due to the larger availability of active sites for the active intermediate route, or, it can increase the catalytic activity of the active intermediate route through an electronic effect [21].…”

Section: Introductionmentioning

confidence: 99%

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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“…31 In addition, the PtPb intermetallic surface did not show the CO stripping oxidation current after CO exposure to the surface. 34 Abruña et al showed that the intermetallic compounds have a high CO tolerance, 32,34 and presumably, the enhanced CO tolerance is attributed to the changes in the Pt-Pt surface interatomic distance of the compounds. The expanded Pt-Pt interatomic distance in the compounds relative to that of the bulk Pt would change the electronic state of the Pt and hinder CO chemisorptions.…”

Section: Introductionmentioning

confidence: 99%

Ethanol and Methanol Oxidation Activity of PtPb, PtBi, and PtBi2 Intermetallic Compounds in Alkaline Media

Matsumoto

2012

Electrochemistry

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The electrocatalytic activities of a wide range of intermetallic bulk compounds in the ethanol (EtOH) and methanol (MeOH) oxidation reactions in alkaline media have been studied, and the results have been compared to those of pure polycrystalline Pt and Pd electrodes. The PtPb, PtBi, and PtBi 2 intermetallic compounds appeared to be the most promising electrocatalysts among all of the examined bulk electrodes. The current densities at −0.2 V (vs. Ag/AgCl KCl satd.) for PtPb, PtBi, and PtBi 2 in EtOH were 21.4, 7.73, and 6.03 mA cm −2 , respectively. All of the other intermetallic bulk electrodes exhibited current densities less than 2.5 mA cm −2. PtPb had the lowest onset potential of −0.58 V for EtOH oxidation, which was 20-30 mV less than that of pure Pt and Pd. The current densities of PtPb were at least seventeen times larger than those of pure Pt and Pd. PtBi and PtBi 2 , which have onset potentials of −0.51 and −0.45 V, respectively, for the EtOH oxidation reaction exhibited extremely stable oxidation currents of 4.8 and 3.3 mA cm −2 during the constant-potential electrolysis of EtOH. The same behavior was also observed for the MeOH oxidation with PtPb, PtBi, and PtBi 2 intermetallic compounds.

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Electrocatalytic Oxidation of Formic Acid at an Ordered Intermetallic PtBi Surface

Cited by 196 publications

References 32 publications

Catalytic Activity of Mono- and Bi-Metallic Nanoparticles Synthesized via Microemulsions

Catalytic Activity of Mono- and Bi-Metallic Nanoparticles Synthesized via Microemulsions

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

Ethanol and Methanol Oxidation Activity of PtPb, PtBi, and PtBi2 Intermetallic Compounds in Alkaline Media

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