A New Hyphenated Technique of in Situ Electrochemical NMR and the Application Progress

doi:10.19894/j.issn.1000-0518.220184

Chinese Journal of Applied Chemistry ›› 2023, Vol. 40 ›› Issue (3): 317-328.DOI: 10.19894/j.issn.1000-0518.220184

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A New Hyphenated Technique of in Situ Electrochemical NMR and the Application Progress

Xiao-Ping ZHANG(), Si-Yue ZHANG, Ming-Chang WANG, Yu-Tong ZHANG, Sha-Lin MIAO, Yu WANG, Wei SUN()

College of Chemistry and Chemical Engineering，Key Lab of Functional Materials and Photoelectrochemistry of Haikou，Hainan Normal University，Haikou 571158，China

Received:2022-05-18 Accepted:2022-10-12 Published:2023-03-01 Online:2023-03-27
Contact: Xiao-Ping ZHANG,Wei SUN
About author:swyy26@hotmail.com
25478885@qq.com；
Supported by:
the National Natural Science Foundation of China Youth Science Foundation Project(22102043);Hainan Provincial Natural Science Foundation of High Level-talent Project(220RC594)

Abstract

Abstract:

The microscopically dynamic mechanism of electrochemical reaction on electrode-surfaces fails to uncover by isolated traditional electrochemical method. Nuclear magnetic resonance（NMR） technology provides the message of sample's chemical shift and the tiny split produced by J coupling at a molecular level， it can be easier to identify isomer，molecular construct and electronic change. Hence， in situ electrochemical NMR hyphenated technique （EC-NMR technique） permits to monitor the reaction pathway and dynamic mechanism of the electrochemical reactions nondestructively at a molecular level. It seems to be more performing technique to reveal the reaction mechanism， structure-function relationship， and to discover unstable chemical intermediates which the ex-situ technique will never be. However， for the incompatibility between electrochemical cells and NMR， the study and application of the in situ EC-NMR technique is relatively lack. In order to understand the new technique for much more people， the article explains the development aboard and at home of the EC-NMR technology， working principle， challenge， and application which in electrochemical catalysis， the reaction mechanisms， fuel cell， and medication research. Future key issues of EC-NMR technology are also predicted.

Key words: In situ electrochemical cell, Nuclear magnetic resonance, Electrochemistry-NMR technique

CLC Number:

O652.7

Xiao-Ping ZHANG, Si-Yue ZHANG, Ming-Chang WANG, Yu-Tong ZHANG, Sha-Lin MIAO, Yu WANG, Wei SUN. A New Hyphenated Technique of in Situ Electrochemical NMR and the Application Progress[J]. Chinese Journal of Applied Chemistry, 2023, 40(3): 317-328.

Figures/Tables 12

Fig.1 Electrochemical cell designed for in situ EC-NMR

Fig.2 Richards′s electrochemical flow cell for insertion in NMR probe［9］

Fig.3 Schematic diagram of the experimental arrangement used in the Alber′s continuous flow experiment［10］

Fig.4 Electrochemical cell inside Varian A-60 probe assembly［11］Note： a.l.8-mm capillary tube； b.Plexlglas cap； c.copper wire leads； d.5-mm NMR tube； e.NMR spinner turbine； f.NMR spinner assembly； g. glass NMR probe tube； h.reference and auxiliary electrode assembly； i.Sb-SnO2 film； j.detector coil length； k.graphite plug； I.narrow graphite rod； m.mercury pool； n.graphite cup

Fig.5 （A） Coaxial three-electrode assembly inserted in normal 10-mm NMR sample tube；（B） Effects of the intruding WE on the lineshape of a high-field 1H NMR signal for HOD at 300 MHz［12］Note： A： a.Reference electrode capillary （emerging below working electrode， WE）； b.cylindrical Pt-mesh counter electrode （CE）； c.pinholes （=4） connecting CE/WE compartments； d.Teflon plugs； e.tubular WE （Au film on glass）； f.receiver coils. B： a.spiral Pt wire； b. cylindrical Pt mesh； c.thin Au film

Fig.6 （a） Schematic of the interdigitated gold electrode EC-NMR system setup. The system can be incorporated into a 5-mm commercial NMR tube and thus used in standard high-resolution solution NMR probes. The components are： A. 200 μh inductors as RF chokes， B. Counter electrode electrical finger， C. Working electrode electrical finger， D. Copper tape， E. Counter electrode interdigitated electrode， F. Working electrode interdigitated electrode， G. electrolyte level in NMR tube， H. catalyst， and I.NMR coil. （b） The polyimide （Kapton） strip shown before the mask is removed to reveal the interdigitated gold electrodes. （c） The NMR cap in place on an empty NMR tube. The electrodes in （b） will be rolled lengthwise into a cylinder and inserted into the NMR tube for an experiment［14］

Fig.7 Klod′s electrochemical cell design for in situ NMR spectroelec-trochemistry［16］

Fig.8 （a） Huang′s schematic of the EC-NMR cell adapted from Dunsch et al.′s work；（b） Normal （blue） and ethanol oxidation reaction （EOR）（red） CVs on the activated Pt black；（c） Normal （blue） and EOR （red） CVs on the activated PtRu black［18］

Fig.9 Zhang et al.′s Electrochemical cell designed for in situ EC-NMR［20］

Fig.10 Pollyana′s electrochemical cell illustration［22］

Fig.11 （A） Real-time 2D COSY NMR spectra recorded in situ during the electrochemical reduction of 9-chloroanthracene；（B） Redox behavior of 9-chloroanthracene based on these spectra［26］

Fig.12 Summary of the electrochemical generation of NAPQI through the cleavage of phenacetin aromatic［17］

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A New Hyphenated Technique of in Situ Electrochemical NMR and the Application Progress

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