Combined scanning tunnelling microscopy and in situ Fourier transform infrared study of dioxygen reduction on gold

Brooker, J.; Christensen, Paul; Hamnett, A.; He, Run-xi; Paliteiro, Carlos

doi:10.1039/fd9929400339

Cited by 30 publications

(24 citation statements)

References 12 publications

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“…The high activity of Au(100) face toward the four‐electron ORR in alkaline medium was mainly attributed to structural effects, allowing for more facile O−O bond splitting, and for a stronger adsorption of OH . Earlier spectro‐electrochemical in situ studies on the ORR at Au electrodes were either performed under conditions where mass transport to/from the electrode is severely hindered, as in measurements in an external reflection configuration, or where it is limited over macroscopic distances, as in an internal reflection configuration without enforced mass transport . The external reflection in situ IR studies claimed to see the adsorbed superoxide at ca.…”

Section: Introductionmentioning

confidence: 99%

The Effect of Anions and pH on the Activity and Selectivity of an Annealed Polycrystalline Au Film Electrode in the Oxygen Reduction Reaction‐Revisited

Jusys

Behm

2019

ChemPhysChem

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Aiming at a better understanding of correlations between the activity and selectivity of Au electrodes in the oxygen reduction reaction (ORR) under controlled transport conditions, we have investigated this reaction by combined electrochemical and in situ FTIR measurements, performed in a flow cell set‐up in an attenuated total reflection (ATR) configuration in acid and alkaline electrolytes. The formation of incomplete reduction products (hydrogen peroxyde/peroxyls) was detected by a collector electrode, the onset of OHad formation was probed by bulk CO oxidation. Using an electroless‐deposited, annealed Au film on a Si prism as working electrode and three different electrolytes for comparison (sulfuric acid, perchloric acid, sodium hydroxide solution), we could derive detailed information on the anion adsorption behavior, and could correlate this with the ORR characteristics. The data reveal pronounced effects of the anions and the pH on the ORR characteristics, indicated e. g., by a grossly different activity and selectivity for the 4‐electron pathway to water/hydroxyls, with the onset ranging from ca. 1.0 V in alkaline electrolyte to 0.6 V in sulfuric acid electrolyte, and the selectivity for the 4‐electron pathway ranging from 100 % (alkaline electrolyte, low overpotentials) to 40 % (acidic electrolytes, alkaline electrolyte at high overpotentials). In contrast, the effect of the ORR on the anion adsorption characteristics is small. Anion effects as well as correlations between anion adsorption and ORR are discussed.

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Section: Introductionmentioning

confidence: 99%

The Effect of Anions and pH on the Activity and Selectivity of an Annealed Polycrystalline Au Film Electrode in the Oxygen Reduction Reaction‐Revisited

Jusys

Behm

2019

ChemPhysChem

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“…The polycrystalline Au electrode used in this work was a disc of 99.99% Au from Johnson Matthey with a geometric area of 0.150 cm 2 and formed as a RDE with Te¯on. The disc was polished with diamond paste to a 0.25 mm ®nish, sonicated in an ultrasonic bath and carefully cleaned with AnalaR ethanol and pyrodistilled water.…”

Section: Methodsmentioning

confidence: 99%

“…The upd of lead is a convenient example of this process because it was studied in detail on pc-Au and Au single crystals (mainly in HClO 4 ) so that a sort of atlas of lead upd spectra on most of the Au planes is available in the literature [3,4]; data on the electroreduction of O 2 by pc-Au modi®ed by lead upd are also available [5±9]. Since all this work is a good basis for comparison, we decided to look at the upd of lead on the`100'-Au surface and to investigate the in¯uence of such deposit upon the reduction of O 2 and of HO 2 À in 1 M NaOH. The results obtained, which this paper reports and discusses, appear to show that the`100'-Au surface is structurally dierent from the (100) gold plane.…”

Section: Introductionmentioning

confidence: 99%

“…One may wonder, for example, whether the (100)-like behavior of the`100'-Au surface is due to the presence on it of patches of the (100) plane. One experimental approach to this problem is to examine the surface directly by applying in-situ STM [2]. Another approach is to use the upd of metals as a probe, since such a process is quite sensitive to surface structure.…”

Section: Introductionmentioning

confidence: 99%

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Electroreduction of oxygen on a (100)-like polycrystalline gold surface in an alkaline solution containing Pb(II)

Paliteiro

Martins

1998

Electrochimica Acta

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In a previous work from this laboratory, it was shown that it is possible to electrochemically modify a polycrystalline surface of gold so that it behaves towards O 2 reduction like the (100) gold plane. To check whether this similarity in behavior is due to the presence on the (100)-like surface of suciently large (100) spots, the process of the upd of Pb(II) was used in this work as a probe of the surface crystallographic orientations both in deaerated and in O 2 À saturated solutions. The observed cyclic voltammograms (CV) and polarization curves were entirely dierent from those reported in the literature for a typical polycrystalline gold surface. The CV data were analyzed in an attempt to gain insight on the crystallography of the (100)-like surface. The in¯uence of adsorbed lead on the electroreduction of oxygen in 1 M NaOH on the (100)-like surface was also scrutinised. It was found that the reduction is dierently aected by adsorbed Pb(II) ions and by underpotential deposited Pb adatoms. Adsorbed Pb(II) do not change the reduction mechanism, it only alters the rate constant for HO 2 À disproportionation, whereas the surface becomes able to reduce O 2 to OH À without desorption of HO 2 À to the solution bulk when modi®ed by Pb adatoms. The details of the electroreduction of O 2 and of HO 2 À are thoroughly discussed in relation to the surface processes underneath. Together with the CV data, they show that there are no signi®cant (100) spots on the (100)-like surface and that this surface is structurally dierent from the gold (100) plane. #

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“…[42,43] Aband at 1210 cm À1 was assigned to adsorbed superoxide on aG es urface, [35] while ab and at the slightly higher wavenumber of 1250 cm À1 was assigned to the same species on Au foil. [44] Ab and at 1162 cm À1 was assigned to adsorbed superoxide on ar ough Bi/Aus urface. [45] Interestingly, ab and at 1223 cm À1 was observed by Kunimatsu and coworkers for aN afion-coated Pt thin film in O 2 atmosphere, but was assigned to the strong CF 2 stretching mode from Nafion.…”

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confidence: 99%

Adsorbed Intermediates in Oxygen Reduction on Platinum Nanoparticles Observed by In Situ IR Spectroscopy

2018

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The sluggish kinetics of oxygen reduction to water remains a significant limitation in the viability of proton-exchange-membrane fuel cells, yet details of the four-electron oxygen reduction reaction remain elusive. Herein, we apply in situ infrared spectroscopy to probe the surface chemistry of a commercial carbon-supported Pt nanoparticle catalyst during oxygen reduction. The IR spectra show potential-dependent appearance of adsorbed superoxide and hydroperoxide intermediates on Pt. This strongly supports an associative pathway for oxygen reduction. Analysis of the adsorbates alongside the catalytic current suggests that another pathway must also be in operation, consistent with a parallel dissociative pathway.

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Combined scanning tunnelling microscopy and in situ Fourier transform infrared study of dioxygen reduction on gold

Cited by 30 publications

References 12 publications

The Effect of Anions and pH on the Activity and Selectivity of an Annealed Polycrystalline Au Film Electrode in the Oxygen Reduction Reaction‐Revisited

The Effect of Anions and pH on the Activity and Selectivity of an Annealed Polycrystalline Au Film Electrode in the Oxygen Reduction Reaction‐Revisited

Electroreduction of oxygen on a (100)-like polycrystalline gold surface in an alkaline solution containing Pb(II)

Adsorbed Intermediates in Oxygen Reduction on Platinum Nanoparticles Observed by In Situ IR Spectroscopy

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