Voltammetric study of the hydrogen ion/hydrogen couple in acetonitrile/water mixtures

Lanning, John A.; Chambers, James Q.

doi:10.1021/ac60329a002

Cited by 26 publications

(11 citation statements)

References 36 publications

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“…As water is added, the voltammetric form changes drastically, reaching a smaller peak potential separation at the ratio of 4.00 : 1.00 H 2 O : HTFO. This behavior is consistent with the formation of H 9 O 4 + upon addition of water at the ratio of 4.00 : 1.00 H 2 O : HTfO, and peak potential shifts have also been observed in acetonitrile / water mixtures (11). The hydrated proton species would be expected to be more easily reduced than the triflate complex due to the neutral charge of the water ligands.…”

Section: Effect Of Water Additionsupporting

confidence: 81%

Voltammetric Studies of Proton Reduction in 1-Butyl-1-Methylpyrrolidinium Trifluoromethanesulfonate

2013

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The reduction of trifluoromethanesulfonic acid (triflic acid) in the ionic liquid 1-butyl-1-methylpyrrolidinium trifluoromethanesulfonate ( BMPY TfO ) has been investigated at platinum. In the concentration range 7 mM to 55 mM, triflic acid undergoes a broad reduction process at -0.25V vs Ag/AgCl at 100 mV/s, followed by a narrower oxidation process at +0.40V. Addition of water results in shifts of these potentials to more central values, with closer peak spacing ( 340 mV ) at the 4.00 : 1.00 mole ratio H 2 O : triflic acid point. These results suggest that the proton is associated via a three-center bond with two triflate anions in the BMPY TfO / triflic acid solution. Addition of water leads to complexation of the proton by water molecules, with a resulting potential shift for the redox processes.

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Section: Effect Of Water Additionsupporting

confidence: 81%

Voltammetric Studies of Proton Reduction in 1-Butyl-1-Methylpyrrolidinium Trifluoromethanesulfonate

2013

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“…29 Potentiostatic electrolyses were used to ensure selectivity of the reductive processes, with Eapplied and the charge passed chosen based on previously reported optimizations for 1 17 with a shift in the potential scale vs Fc 0/+ due to the use of a mixture of solvents taken into account for accurate comparison of Eapplied. 30 The Eapplied = -0.75 V vs Fc 0/+ used for experiments at Pt is at the onset of the reduction peak observed by CV for all the ANHs under CO2 (Figure 3), while for reticulated vitreous carbon (RVC) electrodes Eapplied = -1.20 V vs Fc 0/+ , at the onset of the reduction peaks observed in CVs…”

Section: H2mentioning

confidence: 99%

Electrochemical Reduction of Carbon Dioxide to Methanol in the Presence of Benzannulated Dihydropyridine Additives

Giesbrecht

Herbert

2017

ACS Energy Lett.

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Dihydropyridines (DHPs) have been postulated as active intermediates in the pyridine-mediated electrochemical conversion of CO2 to methanol, however the ability of isolated DHPs to facilitate methanol production in a similar fashion to their parent aromatic N-heterocycles (ANHs) has not been tested. Here, we use bulk electrolysis to show that 1,2-and 1,4-DHPs (1,2-dihydrophenanthridine and 9,10dihydroacridine) can mediate the sub-stoichiometric electrochemical reduction of CO2 to methanol and formate with similar Faradaic efficiencies as the corresponding ANHs at Pt electrodes. 1,2-dihydrophenanthridine furthermore exhibits improved CO2 reduction activity compared to its parent ANH (phenanthridine) at glassy carbon electrodes. These results provide the first experimental evidence for the participation of DHPs as additives in electrochemical CO2 reduction. TOC GRAPHIC Pt or Glassy CarbonCO 2 HCOO -CH 3 OH (DHP) pH ~ 5 E app

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“…Early work by Lanning and Chambers as well as Barrette and Sawyer demonstrated the high sensitivity to, and even irreproducibility of, electrolyte parameters of HER and HOR activity on a platinum electrode in acetonitrile. More recent findings reported by Suárez‐Herrera et al .…”

Section: Introductionmentioning

confidence: 99%

Hydrogen Oxidation and Hydrogen Evolution on a Platinum Electrode in Acetonitrile

et al. 2015

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This work discusses the kinetics of the hydrogen oxidation reaction (HOR) and hydrogen evolution reaction (HER) on a polycrystalline platinum electrode in acetonitrile, in presence of two different electrolytes. Our findings indicate the sensitivity of the kinetics of these reactions to the presence of small amounts of water. In situ FTIR spectroscopy reveals the ion migration owing to the preferential solvation of protons by residual water, whereas surface‐enhanced Raman spectroscopy confirms that the water leaves the interface under hydrogen oxidation conditions. These observations imply that the kinetic sensitivity of this electrocatalytic reaction towards the preferential solvation processes presents a serious constraint in the establishment of a reference electrode for nonaqueous solvents based on HOR/HER on platinum, and on the comparison of its catalysis in various nonaqueous solvents.

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Voltammetric study of the hydrogen ion/hydrogen couple in acetonitrile/water mixtures

Cited by 26 publications

References 36 publications

Voltammetric Studies of Proton Reduction in 1-Butyl-1-Methylpyrrolidinium Trifluoromethanesulfonate

Voltammetric Studies of Proton Reduction in 1-Butyl-1-Methylpyrrolidinium Trifluoromethanesulfonate

Electrochemical Reduction of Carbon Dioxide to Methanol in the Presence of Benzannulated Dihydropyridine Additives

Hydrogen Oxidation and Hydrogen Evolution on a Platinum Electrode in Acetonitrile

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