Design and Fabrication of the Electrolytic Cell with Silicon-Based Boron-Doped Diamond Electrode and Its Feasibility forin-Situ Nuclear Magnetic Resonance Study

Authors

Hao Peng, 1. College of Chemistry and Chemical Engineering, Xiamen University Xiamen 361005 Fujian, China;
Hui-Jun Sun, 2. School of Electronic Science and Engineering, Xiamen University Xiamen 361005, Fujian;
Zhi-You Zhou, 1. College of Chemistry and Chemical Engineering, Xiamen University Xiamen 361005 Fujian, China;
Lin-Fan Shen, 1. College of Chemistry and Chemical Engineering, Xiamen University Xiamen 361005 Fujian, China;
Long Huang, 3. Kunming Institute of Precious Metals, Kunming 650106, Yunan, China;
Shuo-Hui Cao, 2. School of Electronic Science and Engineering, Xiamen University Xiamen 361005, Fujian;Follow
Shi-Gang Sun, 1. College of Chemistry and Chemical Engineering, Xiamen University Xiamen 361005 Fujian, China;Follow

Corresponding Author

Shuo-Hui Cao(shuohuicao@xmu.edu.cn);
Shi-Gang Sun(sgsun@xmu.edu.cn)

Abstract

In-situ EC-NMR technique can be used to monitor the electrochemical reaction process in real-time and to explain the reaction mechanism at the molecular level, which is a promising and non-destructive online detection technology. This article for the first time reports the design and production of in-situEC-NMR three-electrode single-chamber electrolytic cell using silicon-based boron-doped diamond (Si/BDD) as the working electrode. Research shows that the geometric size of Si/BDD electrode being 12.5 mm 1.2 mm 0.5 mm in the NMR detection zone is small and the thickness of the electrode material is thin, which accounts for the less hindrance to the radio frequency field, and correspondingly the less damage to the uniformity of the magnetic field. The developed EC-NMR electrolytic cell was tested, and a classic electrochemical reaction of electrooxidation from hydroquinone (QH₂) to benzoquinone (Q) was used as a model system to study the entire dynamic process in-situ. After electrolysis of 0.1 mol·L^-1 QH₂ at a constant potential of 1.2 V for 64 min, it is detected that the characteristic peak intensity of QH₂ at 6.58 ppm was gradually decreased, and the characteristic Q peak at 6.83 ppm was gradually generated. The NMR spectrum peak did not split or broaden significantly during the reaction. The results demonstrate that the in-situ EC-NMR electrolytic cell designed and prepared in this paper can be effectively used for the qualitative and quantitative analyses of the reactants and products in electrochemical reactions, which thus will play an important role in the subsequent researches on electrochemical in-situ NMR spectroscopy.

Graphical Abstract

Keywords

Bi/BDD electrode, in-situ EC-NMR, EC-NMR electrolytic cell, electrooxidation, hydroquinone

DOI Link

https://doi.org/10.13208/j.electrochem.200722

Publication Date

2021-06-28

Online Available Date

2021-06-28

Revised Date

2020-08-24

Received Date

2020-07-22

Recommended Citation

Hao Peng, Hui-Jun Sun, Zhi-You Zhou, Lin-Fan Shen, Long Huang, Shuo-Hui Cao, Shi-Gang Sun. Design and Fabrication of the Electrolytic Cell with Silicon-Based Boron-Doped Diamond Electrode and Its Feasibility forin-Situ Nuclear Magnetic Resonance Study[J]. Journal of Electrochemistry, 2021 , 27(3): 332-338.
DOI: In-situ EC-NMR technique can be used to monitor the electrochemical reaction process in real-time and to explain the reaction mechanism at the molecular level, which is a promising and non-destructive online detection technology. This article for the first time reports the design and production of in-situEC-NMR three-electrode single-chamber electrolytic cell using silicon-based boron-doped diamond (Si/BDD) as the working electrode. Research shows that the geometric size of Si/BDD electrode being 12.5 mm 1.2 mm 0.5 mm in the NMR detection zone is small and the thickness of the electrode material is thin, which accounts for the less hindrance to the radio frequency field, and correspondingly the less damage to the uniformity of the magnetic field. The developed EC-NMR electrolytic cell was tested, and a classic electrochemical reaction of electrooxidation from hydroquinone (QH₂) to benzoquinone (Q) was used as a model system to study the entire dynamic process in-situ. After electrolysis of 0.1 mol·L^-1 QH₂ at a constant potential of 1.2 V for 64 min, it is detected that the characteristic peak intensity of QH₂ at 6.58 ppm was gradually decreased, and the characteristic Q peak at 6.83 ppm was gradually generated. The NMR spectrum peak did not split or broaden significantly during the reaction. The results demonstrate that the in-situ EC-NMR electrolytic cell designed and prepared in this paper can be effectively used for the qualitative and quantitative analyses of the reactants and products in electrochemical reactions, which thus will play an important role in the subsequent researches on electrochemical in-situ NMR spectroscopy.

References

[1] Li J T, Chen Q S, Sun S G. In situ microscope FTIR studies of methanol adsorption and oxidation on an individually addressable array of nanostructured Pt microelectrodes[J]. Electrochim. Acta, 2006, 52(18): 5725-5732.
doi: 10.1016/j.electacta.2006.12.082 URL

[2] Kanamura K, Toriyama S, Shiraishi S, Takehara Z. Studies on electrochemical oxidation of nonaqueous electrolytes using in situ FTIR spectroscopy. 1: The effect of type of electrode on on-set potential for electrochemical oxidation of propylene carbonate containing 1.0 mol·dm^-3 LiClO₄[J]. J. Electrochem. Soc., 1995, 142(5): 1383-1389.
doi: 10.1149/1.2048586 URL

[3] Jeanmaire D L, Duyne R P V. Surface Raman spectroelectrochemistry: Part I. Heterocyclic, aromatic, and aliphatic amines adsorbed on the anodized silver electrode[J]. J. Electroanal. Chem. Interfacial Electrochem., 1977, 84(1): 1-20.
doi: 10.1016/S0022-0728(77)80224-6 URL

[4] Diehl G, Karst U. On-line electrochemistry-MS and related techniques[J]. Anal. Bioanal. Chem., 2002, 373(6): 390-398.

[5] Sun S G, Christensen P A, Wieckowski A. In-situ spectroscopic studies of adsorption at the electrode and electrocatalysis[M]. Amsterdam: Elsevier, 2007.

[6] Bard A J, Faulkner L R. Electrochemical methods: fundamentals and applications(2nd ed)[M]. New York: John Wiley & Sons, 2001, 60(1): 669-676.

[7] Tong Y J. In situ electrochemical nuclear magnetic resonance spectroscopy for electrocatalysis: Challenges and prospects[J]. Curr. Opin. Electrochem., 2017, 4(1): 60-68.

[8] Hui Y H, Chng E L K, Chng C Y L, Poh H L, Webster R D. Hydrogen-bonding interactions between water and the one- and two-electron-reduced forms of vitamin K1: Applying quinone electrochemistry to determine the moisture content of non-aqueous solvents[J]. J. Am. Chem. Soc., 2009, 131(4): 1523-1534.
doi: 10.1021/ja8080428 URL

[9] Kim Y O, Jung Y M, Kim S B, Park S M. Two-dimensional correlation analysis of spectroelectrochemical data for p-benzoquinone reduction in acetonitrile[J]. Anal. Chem., 2004, 76(17): 5236-5240.
doi: 10.1021/ac049587g URL

[10] Eggins B R. Interpretation of electrochemical reduction and oxidation waves of quinone-hydroquinone system in acetonitrile[J]. J. Chem. Soc. Chem. Comm., 1969, 21(21): 1267-1268.

[11] Albert K, Dreher E L, Straub H, Rieker A. Monitoring electrochemical reactions by ¹³C NMR spectroscopy[J]. Magn. Reson. Chem., 1987, 25(10): 919-922.
doi: 10.1002/(ISSN)1097-458X URL