Formic acid oxidation on platinum electrodes: a detailed mechanism supported by experiments and calculations on well-defined surfaces

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

doi:10.1039/c7ta07116g

Cited by 91 publications

(159 citation statements)

References 65 publications

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“…However, CO can be also easily to be formed and accumulated on pure Pt(111), which can lead to blocking and poisoning of surface active sites, explaining why the experimentally measured HCOOH oxidation currents are still low on pure Pt electrodes even if at low overpotentials. Thus, our recent study confirmed previous experimental and theoretical conclusions on HCOO as intermediates and CO poison effect on pure Pt electrode . Similarly, three possibilities are considered and the corresponding MEP analyses are carried out on Ru@Pt(111) starting from HCOOH initial oxidation, as shown in Figure (a).…”

Section: Resultssupporting

confidence: 84%

“…The previous experimental studies have concluded that HCOOH oxidation on pure Pt electrodes can evolve via a triple‐path mechanism in acidic electrolyte, namely, a direct pathway, in which HCOOH is oxidized directly into CO 2 by dehydrogenation; an indirect pathway, in which the strongly adsorbed CO is formed through dehydration and further oxidized into CO 2 ; a formate pathway, including formate formation and further oxidation into CO 2 . However, even if on pure Pt electrodes, the measured oxidation current is still low.…”

Section: Introductionmentioning

confidence: 99%

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Mechanistic Understanding of the Effect of Surface Composition of Pt‐Ru Bimetallic Alloy Electrocatalysts on HCOOH Oxidation Pathways at Acid Electrochemical Interface

Zhao

Chen

et al. 2019

ChemistrySelect

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The effect of surface composition of Pt−Ru bimetallic alloy electrocatalysts on HCOOH oxidation mechanisms are first studied systematically at acid electrochemical interface based on DFT in this work. The present studies indicate that the growth of Pt on Ru may be not an optimal electrocatalyst. Instead, the alloying of Pt with Ru can notably enhance the direct electrooxidation activity of HCOOH. The appropriate Ru contents play an important role in determining HCOOH electrooxidation activity and Pt−Ru alloys with low Ru contents are efficient alloy catalysts. The higher Ru contents hinder CO removal and lead to CO poisonous effect on surface active sites, thereby going against HCOOH oxidation. It is also concluded that on Pt−Ru alloys the experimentally observed enhanced oxidation kinetics may be ascribed to improved direct pathways, rather than enhancement of CO tolerance. Two possible descriptors that can scale HCOOH oxidation activity are proposed based on the origin of electrocatalytic activity, which will provide theoretical guidelines for rational design of Pt‐based alloy catalysts with appropriate surface composition.

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Section: Resultssupporting

confidence: 84%

Section: Introductionmentioning

confidence: 99%

Mechanistic Understanding of the Effect of Surface Composition of Pt‐Ru Bimetallic Alloy Electrocatalysts on HCOOH Oxidation Pathways at Acid Electrochemical Interface

Zhao

Chen

et al. 2019

ChemistrySelect

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“…Hence, this study allows for a better understanding of formate adsorption and electrooxidation of formate/formic acid on metallic surfaces. The approach of studying the adsorption behaviour of unreactive adsorbates to understand those of reactive ones has been found to be extremely valuable and can be applied to other surfaces, such as Pt(111) for example …”

Section: Discussionmentioning

confidence: 99%

“…The approach of studying the adsorption behaviour of unreactive adsorbates to understand those of reactive ones has been found to be extremely valuable and can be applied to other surfaces, such as Pt(111) for example. [73] Experimental Section…”

Section: Discussionmentioning

confidence: 99%

Adsorption of Acetate on Au(111): An in‐situ Scanning Tunnelling Microscopy Study and Implications on Formic Acid Electrooxidation

et al. 2019

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The adsorption of acetate on an Au(111) electrode surface in contact with acetic acid at pH 2.7 was imaged in‐situ using scanning tunnelling microscopy (STM). Two different ordered structures were imaged for acetate adsorbed in the bidentate configuration on the unreconstructed ()1×1 surface at 0.95 V (vs. the saturated calomel electrode, SCE). The first structure,(19×19)R23.45∘ , is metastable and transforms at constant potential within 20 minutes to a (2×2) structure, which is thermodynamically more favourable. The (2×2) acetate adlayer starts to form at step edges and propagates via nucleation and growth onto terraces. The findings from in‐situ STM are in agreement with the electrochemical behaviour of acetate on Au(111) characterized by voltammetry. A comparison is made with formate adsorption on Au(111). While acetate is not reactive, in contrast to formate, it can act as a spectator species in formic acid electrooxidation.

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“…The current density was also on the basis of the Pt weight coated on the GC electrode. The formic acid electro‐oxidation over Pt catalysts was in accordance with the dual path, namely, the direct dehydrogenation process (HCOOH→CO 2 +2H + +2e − ) and dehydration process with poisonous CO produced (HCOOH→CO ads +H 2 O).…”

Section: Resultsmentioning

confidence: 73%

Effects of the Synthesis Method and Promoter Content on Bismuth‐Modified Platinum Catalysts in the Electro‐oxidation of Glycerol and Formic Acid

et al. 2019

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Bismuth has an important promotion effect on the catalytic performance of Pt-catalyzed oxidation reactions. Herein, the catalyst structure, Bi content, and catalytic performance of Bimodified Pt catalysts in the electro-oxidation of glycerol and formic acid were researched to unravel the essential promotion role of Bi. The Bi-modification methods included the loading, adsorption, and electrodeposition of Bi on Pt. The electrodeposited Bi-modified Pt had the best performance among the three methods. In a certain range, the lower electrodeposition potential of Bi resulted in a higher Bi content on the Pt catalyst and better performance. The activity of the Pt catalyst with Bi deposited at À 0.15 V was 8.5 times and 27 times that of the monometallic Pt catalyst in the electro-oxidation of glycerol and formic acid, respectively. The selective distribution of Bi adjacent to Pt and a higher percentage of Bi hydroxide were favorable for the catalytic performance.[a] Dr.

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Formic acid oxidation on platinum electrodes: a detailed mechanism supported by experiments and calculations on well-defined surfaces

Abstract: The key elements in the mechanism of the formic acid oxidation reaction on platinum have been completely elucidated, not only for the direct path through an active intermediate, but also for the CO formation route.

Cited by 91 publications

References 65 publications

Mechanistic Understanding of the Effect of Surface Composition of Pt‐Ru Bimetallic Alloy Electrocatalysts on HCOOH Oxidation Pathways at Acid Electrochemical Interface

Mechanistic Understanding of the Effect of Surface Composition of Pt‐Ru Bimetallic Alloy Electrocatalysts on HCOOH Oxidation Pathways at Acid Electrochemical Interface

Adsorption of Acetate on Au(111): An in‐situ Scanning Tunnelling Microscopy Study and Implications on Formic Acid Electrooxidation

Effects of the Synthesis Method and Promoter Content on Bismuth‐Modified Platinum Catalysts in the Electro‐oxidation of Glycerol and Formic Acid

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