Recent Progress in Liquid State Electrochemistry Coupled with NMR Spectroscopy

Pietrzak, Mariusz; Jopa, Sylwia; Mames, Adam; Urbańczyk, Mateusz; Woźny, Mateusz; Ratajczyk, Tomasz

doi:10.1002/celc.202100724

Cited by 15 publications

(10 citation statements)

References 115 publications

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“…Table shows a summary of the main characteristics of some setups used for in situ coupling between NMR and electrochemistry. More information on current developments in the area of coupling between electrochemistry and liquid NMR can be found in the recent review published in 2021 by Pietrzak et al…”

Section: Resultsmentioning

confidence: 99%

Composite Graphite–Epoxy Electrodes for In Situ Electrochemistry Coupling with High Resolution NMR

et al. 2022

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The in situ coupling between electrochemistry and spectrometric techniques can help in the identification and quantification of the compounds produced and consumed during electrochemical reactions. The combination of electrochemistry with nuclear magnetic resonance is quite attractive in this respect, but it has some challenges to be addressed, namely, the reduction in the quality of the NMR signal when the metallic electrodes are placed close to or in the detection region. Since NMR is not a passive technique, the convective effect of the magnetic force (magnetoelectrolysis), which acts by mixing the solution and increasing the mass transport, has to be considered. In seeking to solve the aforementioned problems, we developed a system of miniaturized electrodes inside a 5 mm NMR tube (outer diameter); the working and counter electrodes were prepared with a mixture of graphite powder and epoxy resin. To investigate the performance of the electrodes, the benzoquinone reduction to hydroquinone and the isopropanol oxidation to acetone were monitored. To monitor the alcohol oxidation reaction, the composite graphite–epoxy electrode (CGEE) surface was modified through platinization. The electrode was efficient for in situ monitoring of the aforementioned reactions, when positioned 1 mm above the detection region of the NMR spectrometer. The magnetoelectrolysis effect acts by stirring the solution and increases the reaction rate of the reduction of benzoquinone, because this reaction is limited by mass transport, while no effect on the reaction rate is observed for the isopropanol oxidation reaction.

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Section: Resultsmentioning

confidence: 99%

Composite Graphite–Epoxy Electrodes for In Situ Electrochemistry Coupling with High Resolution NMR

et al. 2022

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“…In this study, the measurement of pH is demonstrated in an electrochemical cell and during electrolysis by in operando nuclear magnetic resonance (NMR), which has proven capable of investigating the (aq)/ / equilibrium in such an environment 25 . The method takes advantage of the high spectral resolution and sensitivity afforded by this cell design even in the presence of electrically conductive material 26 . In contrast to methods that only consider either the (aq)/ 22 or the / equilibrium 24 , the presented method provides data for a wider pH range by considering both equilibria, including an overlap region in-between.…”

Section: Introductionmentioning

confidence: 99%

Quantifying local pH changes in carbonate electrolyte during copper-catalysed $$\hbox {CO}_2$$ electroreduction using in operando $$^{13}\hbox {C}$$ NMR

Schatz

Jovanovic

Eichel

et al. 2022

Sci Rep

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The electrochemical carbon dioxide reduction on copper attracted considerable attention within the last decade, since Cu is the only elemental transition metal that catalyses the formation of short-chain hydrocarbons and alcohols. Research in this field is mainly focused on understanding the reaction mechanism in terms of adsorbates and intermediates. Furthermore, dynamic changes in the micro-environment of the catalyst, i.e. local pH and $$\hbox {CO}_2$$ CO 2 concentration values, play an equivalently important role in the selectivity of product formation. In this study, we present an in operando$$^{13}\hbox {C}$$ 13 C nuclear magnetic resonance technique that enables the simultaneous measurement of pH and $$\hbox {CO}_2$$ CO 2 concentration in electrode vicinity during electroreduction. The influence of applied potential and buffer capacity of the electrolyte on the formation of formate is demonstrated. Theoretical considerations are confirmed experimentally and the importance of the interplay between catalyst and electrolyte is emphasised.

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“…Electrochemical cells for in operando NMR measurements were developed and improved over the past 45 years [26][27][28][29][30] , but high spectral resolution and sensitivity even in the presence of conductive material in the sensitive volume of the NMR setup has been demonstrated only recently. To calculate the pH from in operando 13 C NMR data, we utilize the buffer capability of HCO -3 /CO 2 -3 .…”

Section: Introductionmentioning

confidence: 99%

Quantifying Local pH Changes in Carbonate Electrolyte during Copper-Catalysed CO2 Electroreduction Using In Operando 13C NMR

Schatz

Jovanovic

Eichel

et al. 2022

Preprint

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The electrochemical carbon dioxide reduction on copper attracted considerable attention within the last decade, since Cu is the only elemental transition metal that catalyses the formation of short-chain hydrocarbons and alcohols. Research in that field is mainly concentrated on understanding the reaction mechanism in terms of adsorbates and intermediates. Furthermore, dynamic changes in the microenvironment of the catalyst, i.e. local pH and CO2 concentration values, play an equivalently decisive role in the selectivity of product formation. In this study, we present an in operando 13C Nuclear Magnetic Resonance (NMR) technique that enables the simultaneous measurement of pH and CO2 concentration in electrode vicinity during electroreduction. The influence of applied potential and buffer capacity of the electrolyte on the formation of formate is demonstrated. Herewith, theoretical considerations are confirmed experimentally and the importance of the interplay between catalyst and electrolyte is highlighted.

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Recent Progress in Liquid State Electrochemistry Coupled with NMR Spectroscopy

Cited by 15 publications

References 115 publications

Composite Graphite–Epoxy Electrodes for In Situ Electrochemistry Coupling with High Resolution NMR

Composite Graphite–Epoxy Electrodes for In Situ Electrochemistry Coupling with High Resolution NMR

Quantifying local pH changes in carbonate electrolyte during copper-catalysed $$\hbox {CO}_2$$ electroreduction using in operando $$^{13}\hbox {C}$$ NMR

Quantifying Local pH Changes in Carbonate Electrolyte during Copper-Catalysed CO2 Electroreduction Using In Operando 13C NMR

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