In situ FT-IR and ex situ EPR analysis for the study of the electroreduction of carbon dioxide in N,N-dimethylformamide on a gold interface

Pérez, Eliseo García; Garcia, Jarem Raul; Cardoso, Daniel; McGarvey, Bruce R.; Batista, Eduardo Augusto Caldas; Rodrigues-Filho, Ubirajara P.; Vielstich, W.; Franco, Douglas Wagner

doi:10.1016/j.jelechem.2004.11.044

Cited by 19 publications

(4 citation statements)

References 24 publications

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“…The upward band at 1271 cm –1 is attributed to the C–N stretching vibration, and that at 1241 cm –1 is attributed to the N–O stretching vibration of the intermediate product. In addition, the absorption peak at 1371 cm –1 is attributed to CO 3 2– generated during the reaction. , The 3D infrared images are significantly different from those in Figure , showing that the electrochemical reduction of NB, PNT, and PNA in DMSO is changed from a reversible single-electron process in the absence of CO 2 to an irreversible four-electron process in its presence.…”

Section: Resultsmentioning

confidence: 84%

“…In addition, the absorption peak at 1371 cm −1 is attributed to CO 3 2− generated during the reaction. 28,29 The 3D infrared images are significantly different from those in Figure 2, showing that the electrochemical reduction of NB, PNT, and PNA in DMSO is changed from a reversible singleelectron process in the absence of CO 2 to an irreversible fourelectron process in its presence.…”

Section: ■ Results and Discussionmentioning

confidence: 85%

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Effect of Electron-Donating Groups on the Electrochemical Degradation of Aromatic Nitro Compounds in Aprotic Media Containing CO₂

Meng

Wang

et al. 2021

J. Phys. Chem. C

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The electrochemical degradation of p-nitrochlorobenzene in aprotic media containing CO2 is reported. Little is known about the effects of electron-donating groups on electrochemical degradation of aromatic nitro compounds. Accordingly, electrochemical behavior of nitrobenzene (NB), para-nitrotoluene (PNT), and para-nitroanisole (PNA), in an aprotic solvent containing CO2, was investigated by cyclic voltammetry (CV), in situ Fourier transform infrared (FT-IR) spectroscopy, and potenstiostatic electrolysis. It was established that their electrochemical reduction was an irreversible four-electron transfer process. Based on cyclic voltabsorptometry (CVA), derivative cyclic voltabsorptometry (DCVA), and chronoamperometry (CA), a mechanism of electroreduction of aromatic nitro compounds in the presence of CO2 was proposed. The products of potenstiostatic electrolysis, in the presence of CO2, were characterized by X-ray single-crystal diffraction, 13C NMR, and 1H NMR. NB and PNT gave only the corresponding azo compound with a 99% conversion rate. However, the conversion rate of PNA was lower (78%) due to the effect of the strong electron-donating methoxy group. The intermediate reduction product 4,4′-dimethoxyazoxybenzene was formed along 4,4′-dimethoxyazobenzene. In the process, CO2 was converted to CO3 2–. This constitutes a new way of carbon sequestration.

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Section: Resultsmentioning

confidence: 84%

Section: ■ Results and Discussionmentioning

confidence: 85%

Effect of Electron-Donating Groups on the Electrochemical Degradation of Aromatic Nitro Compounds in Aprotic Media Containing CO₂

Meng

Wang

et al. 2021

J. Phys. Chem. C

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“…The weak band at 1456 cm À1 is due to the bending vibration of the N-H bond in aminosilane. 46 This demonstrates that aminosilane has been successfully graed onto the pretreated MWCNTs by the silylation reactions.…”

Section: Compositional Analysismentioning

confidence: 85%

Pretreated multiwalled carbon nanotube adsorbents with amine-grafting for removal of carbon dioxide in confined spaces

Yang

et al. 2014

RSC Adv.

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“…The CO 2 reduction products were characterized in situ by Fourier transform infraredattenuated total reflectance (FTIR-ATR) spectroscopy (Figure 6a) after the passage of 1 F. The IR data show new peaks at frequencies υ = 1594 cm À 1 , υ = 1380 cm À 1 , and υ = 1337 cm À 1 , which would correspond with the formation of formate, HCOO À . [38][39][40] The reduction process was monitored by cyclic voltammetry (Figure 6b). The cyclic voltammogram recorded at the end of the electrolysis showed two new peaks at anodic scan and cathodic scan related to the oxalate oxidation (E pa = + 0.25 V vs SCE), and a formate radical reduction formed on the oxalate oxidation (E pc = À 0.89 V vs SCE), respectively.…”

Section: The First Reduction Electron Transfer Processmentioning

confidence: 99%

Electrochemical Reduction of 4‐Nitrobenzyl Phenyl Thioether for Activation and Capture of CO₂

et al. 2021

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In this work, a new simple molecule, 4-nitrobenzyl phenyl thioether (1), is prepared and used for controlling and tuning CO 2 reactivity in function of the electrode potential. The first part of the study is devoted to determining the electrochemical reduction mechanism of 1 in N,N-dimethylformamide under nitrogen. The compound shows a first reversible one-electron transfer process, whereas the reaction cleavage of the CÀ S bond takes place after a second electron transfer process through a stepwise mechanism (thermodynamic and kinetic parameters are conveniently determined). In the second part of the study, the inert atmosphere was replaced by a CO 2 atmosphere. At low potential values, compound 1 acts as a redox mediator that allows the reduction of CO 2 at ca. À 1.2 V vs. SCE. The electrochemical generation of 1 2À at more negative potential values leads to a CÀ S bond cleavage reaction that yields the corresponding nitrobenzyl and thiosulfate anions, which react with CO 2 . The nitro aromatic anion derivative makes it possible to obtain electrocarboxylated derivatives, whereas the thiophenolate anion captures CO 2 reversibly. Hence, this research opens a new way of tuning and controlling the reaction processes associated with CO 2 from homogenous catalysis at low negative potentials, to electrocarboxylation processes passing to CO 2 reversible electrochemically triggered adsorption processes.

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In situ FT-IR and ex situ EPR analysis for the study of the electroreduction of carbon dioxide in N,N-dimethylformamide on a gold interface

Cited by 19 publications

References 24 publications

Effect of Electron-Donating Groups on the Electrochemical Degradation of Aromatic Nitro Compounds in Aprotic Media Containing CO₂

Effect of Electron-Donating Groups on the Electrochemical Degradation of Aromatic Nitro Compounds in Aprotic Media Containing CO₂

Pretreated multiwalled carbon nanotube adsorbents with amine-grafting for removal of carbon dioxide in confined spaces

Electrochemical Reduction of 4‐Nitrobenzyl Phenyl Thioether for Activation and Capture of CO₂

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In situ FT-IR and ex situ EPR analysis for the study of the electroreduction of carbon dioxide in N,N-dimethylformamide on a gold interface

Cited by 19 publications

References 24 publications

Effect of Electron-Donating Groups on the Electrochemical Degradation of Aromatic Nitro Compounds in Aprotic Media Containing CO2

Effect of Electron-Donating Groups on the Electrochemical Degradation of Aromatic Nitro Compounds in Aprotic Media Containing CO2

Pretreated multiwalled carbon nanotube adsorbents with amine-grafting for removal of carbon dioxide in confined spaces

Electrochemical Reduction of 4‐Nitrobenzyl Phenyl Thioether for Activation and Capture of CO2

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Effect of Electron-Donating Groups on the Electrochemical Degradation of Aromatic Nitro Compounds in Aprotic Media Containing CO₂

Effect of Electron-Donating Groups on the Electrochemical Degradation of Aromatic Nitro Compounds in Aprotic Media Containing CO₂

Electrochemical Reduction of 4‐Nitrobenzyl Phenyl Thioether for Activation and Capture of CO₂