Solution-phase electrochemistry-nuclear magnetic resonance of small organic molecules

Falck, David; Niessen, W.M.A.

doi:10.1016/j.trac.2015.03.010

Cited by 18 publications

(13 citation statements)

References 37 publications

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“…A different technique for the coupling of electrochemistry and magnetic resonance is hyphenated electrochemical NMR (Albert et al, 1987;Falck et al, 2013;Simon et al, 2012), where the electrochemical cell is physically separated from the NMR spectrometer by passing the electrochemically generated species to an NMR probe by flow. This technique does not suffer from B 0 and B 1 distortions, but there is a time delay between generation and detection of the electrochemical species due to the physical separation.…”

Section: Introductionmentioning

confidence: 99%

“…Despite their first appearance in 1975, electrochemical in operando NMR investigations of liquid-state systems are tested primarily on well-studied, simple redox systems. More recently in operando NMR has been used to study biological systems (Zhang and Zwanziger, 2011;Bussy et al, 2013;Falck et al, 2013). However, this method has not yet been utilized for the investigation of industrial and energy applications, e.g., the electrolytic reduction of CO 2 .…”

Section: Introductionmentioning

confidence: 99%

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An electrochemical cell for in operando 13C nuclear magnetic resonance investigations of carbon dioxide/carbonate processes in aqueous solution

Jovanovic

Schleker

Streun³

et al. 2021

Magn. Reson.

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Abstract. In operando nuclear magnetic resonance (NMR) spectroscopy is one method for the online investigation of electrochemical systems and reactions. It allows for real-time observations of the formation of products and intermediates, and it grants insights into the interactions of substrates and catalysts. An in operando NMR setup for the investigation of the electrolytic reduction of CO2 at silver electrodes has been developed. The electrolysis cell consists of a three-electrode setup using a working electrode of pristine silver, a chlorinated silver wire as the reference electrode, and a graphite counter electrode. The setup can be adjusted for the use of different electrode materials and fits inside a 5 mm NMR tube. Additionally, a shielding setup was employed to minimize noise caused by interference of external radio frequency (RF) waves with the conductive components of the setup. The electrochemical performance of the in operando electrolysis setup is compared with a standard CO2 electrolysis cell. The small cell geometry impedes the release of gaseous products, and thus it is primarily suited for current densities below 1 mA cm−2. The effect of conductive components on 13C NMR experiments was studied using a CO2-saturated solution of aqueous bicarbonate electrolyte. Despite the B0 field distortions caused by the electrodes, a proper shimming could be attained, and line widths of ca. 1 Hz were achieved. This enables investigations in the sub-Hertz range by NMR spectroscopy. High-resolution 13C NMR and relaxation time measurements proved to be sensitive to changes in the sample. It was found that the dynamics of the bicarbonate electrolyte varies not only due to interactions with the silver electrode, which leads to the formation of an electrical double layer and catalyzes the exchange reaction between CO2 and HCO3-, but also due to interactions with the electrochemical setup. This highlights the necessity of a step-by-step experiment design for a mechanistic understanding of processes occurring during electrochemical CO2 reduction.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

An electrochemical cell for in operando 13C nuclear magnetic resonance investigations of carbon dioxide/carbonate processes in aqueous solution

Jovanovic

Schleker

Streun³

et al. 2021

Magn. Reson.

View full text Add to dashboard Cite

show abstract

“…Parallel efforts in flow chemistry have also laid the foundation for promoting HTE electrochemistry, opening another direction for data-driven reaction optimization [ 56 – 58 ]. In the future, the ability to perform such screening in a continuous flow system with tandem NMR or MS analysis would provide a powerful tool for rapid data collection [ 59 , 60 ]. We anticipate that the union of these emerging technologies with data science techniques has the potential to greatly accelerate the pace at which new electrochemical reactions are discovered.…”

Section: High-throughput Experimentation Vs Directed Optimizationsmentioning

confidence: 99%

Working at the interfaces of data science and synthetic electrochemistry

Alvarado¹,

Meinhardt²,

Lin

2022

Tetrahedron Chem

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“…Several experiment setups for the electrochemical reduction and/or oxidation of organic molecules are published (Bussy and Boujtita, 2015;Falck and Niessen, 2015). The first in operando flow cell for the investigation of electrochemical processes was described by Richards et al in 1975 and consisted of a two-electrode setup inside a 5 mm NMR tube (Richards and Evans, 1975).…”

Section: Introductionmentioning

confidence: 99%

An Electrochemical cell for in operando 13C NMR investigations of carbon dioxide/carbonate processes in aqueous solution

Jovanovic

Schleker

Streun

et al. 2021

Preprint

View full text Add to dashboard Cite

Abstract. In operando NMR spectroscopy is a method for the online investigation of electrochemical systems and reactions. It allows a real-time observation of the formation of products and intermediates, and it grants insight into the interactions of substrate and catalyst. An in operando NMR setup for the investigation of the electrolytic reduction of CO2 on silver electrodes has been developed. The electrolysis cell consists of a three-electrode setup using a working electrode of pristine silver, a chlorinated silver wire as reference electrode, and a graphite counter electrode. The setup can be adjusted for the use of different electrode materials and fits inside a 5 mm NMR tube, Additionally, a shielding setup was employed to minimize noise caused by interference of external radio frequency (RF) waves with the conductive components of the setup. The electrochemical performance of the in operando electrolysis setup was investigated in comparison to a standard CO2 electrolysis cell. The small cell geometry impedes the release of gaseous products, and thus it is primarily suited for current densities below 1 mA/cm2. The effect of conductive components on 13C NMR experiments was studied using a CO2 saturated solution of aqueous bicarbonate electrolyte. Despite the B0 field distortions caused by the electrodes, line widths of ca. 1 Hz could be achieved. This enables the investigation of interactions in the sub-Hertz range by NMR spectroscopy. It was found that the dynamics of the bicarbonate electrolyte change due to interaction with the electrochemical setup, by catalyzing the exchange reaction between CO2 and HCO3− and affecting the formation of an electrical double layer.

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Solution-phase electrochemistry-nuclear magnetic resonance of small organic molecules

Cited by 18 publications

References 37 publications

An electrochemical cell for in operando <sup>13</sup>C nuclear magnetic resonance investigations of carbon dioxide/carbonate processes in aqueous solution

An electrochemical cell for in operando <sup>13</sup>C nuclear magnetic resonance investigations of carbon dioxide/carbonate processes in aqueous solution

Working at the interfaces of data science and synthetic electrochemistry

An Electrochemical cell for <i>in operando</i> <sup>13</sup>C NMR investigations of carbon dioxide/carbonate processes in aqueous solution

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Solution-phase electrochemistry-nuclear magnetic resonance of small organic molecules

Cited by 18 publications

References 37 publications

An electrochemical cell for in operando &lt;sup&gt;13&lt;/sup&gt;C nuclear magnetic resonance investigations of carbon dioxide/carbonate processes in aqueous solution

An electrochemical cell for in operando &lt;sup&gt;13&lt;/sup&gt;C nuclear magnetic resonance investigations of carbon dioxide/carbonate processes in aqueous solution

Working at the interfaces of data science and synthetic electrochemistry

An Electrochemical cell for &lt;i&gt;in operando&lt;/i&gt; &lt;sup&gt;13&lt;/sup&gt;C NMR investigations of carbon dioxide/carbonate processes in aqueous solution

Contact Info

Product

Resources

About

An electrochemical cell for in operando <sup>13</sup>C nuclear magnetic resonance investigations of carbon dioxide/carbonate processes in aqueous solution

An electrochemical cell for in operando <sup>13</sup>C nuclear magnetic resonance investigations of carbon dioxide/carbonate processes in aqueous solution

An Electrochemical cell for <i>in operando</i> <sup>13</sup>C NMR investigations of carbon dioxide/carbonate processes in aqueous solution