In situ monitoring multi-carbon alcohol oxidation by combined electrochemistry with spatially selective NMR spectroscopy

doi:10.1016/S1872-2067(23)64526-7

Chinese Journal of Catalysis ›› 2023, Vol. 53: 171-179.DOI: 10.1016/S1872-2067(23)64526-7

In situ monitoring multi-carbon alcohol oxidation by combined electrochemistry with spatially selective NMR spectroscopy

Haolin Zhan^a^,^b^,¹, Lifei Ji^c^,¹, Shuohui Cao^a, Ye Feng^a, Yanxia Jiang^c, Yuqing Huang^a^,^*(), Shigang Sun^c^,^*(), Zhong Chen^a^,^c^,^*()

^aDepartment of Electronic Science, Fujian Provincial Key Laboratory of Plasma and Magnetic Resonance, Xiamen University, Xiamen 361005, Fujian, China
^bDepartment of Biomedical Engineering, Anhui Province Key Laboratory of Measuring Theory and Precision Instrument, Hefei University of Technology, Hefei 230009, Anhui, China
^cDepartment of Chemistry, State Key Laboratory of Physical Chemistry of Solid Surfaces, Xiamen University, Xiamen 361005, Fujian, China

Received:2023-07-24 Accepted:2023-10-03 Online:2023-10-18 Published:2023-10-25
Contact: *E-mail: yqhuangw@xmu.edu.cn (Y. Huang), sgsun@xmu.edu.cn (S. Sun), chenz@xmu.edu.cn (Z. Chen).
About author:
¹Contributed equally to this work.
Supported by:
The National Natural Science Foundation of China(22161142024);The National Natural Science Foundation of China(22204038);The National Natural Science Foundation of China(12275228);The National Natural Science Foundation of China(22073078);The National Natural Science Foundation of China(21974117);The National Key Research and Development Program of China(2021YFA1501504);The Natural Science Foundation of Fujian Province(2021J01053)

Abstract

Abstract:

In situ electrochemical nuclear magnetic resonance (EC-NMR) plays a pivotal role in electrochemical observation on liquid fuel cells, but its applications are generally trapped by insufficient spectral resolution caused by spatiotemporal variations of magnetic fields. Herein, we develop a general spectroelectrochemistry protocol to address this problem and facilitate real-time electrooxidation analyses. This protocol enables the direct extraction of well-resolved and undistorted NMR signals from standard NMR instruments, thus it is commonly applicable to in situ electrochemical studies. The effectiveness for electrooxidation mechanism investigations on multi-carbon alcohols is validated by 1-butanol electrooxidation. It is verified that the direct oxidation of 1-butanol to butyric acid becomes more significant along with higher potentials on Pt/C at 60 °C, while 1-butanol oxidation is more likely to yield gaseous products (mainly CO₂) at lower potentials. Additionally, this protocol reveals that Pt/C rather than PtRu/C is inclined to accomplish the β-C-H bond breaking process for CO₂ generation at a high potential of 1.2 V (vs. SCE). Therefore, this study provides a promising paradigm for electrooxidation investigations on fuel cells, and it may take a meaningful step toward wider electrochemical studies and NMR applications.

Key words: Electrochemical nuclear magnetic resonance, Spatially selective, In situ investigation, 1-Butanol electrooxidation, Liquid fuel cell

Haolin Zhan, Lifei Ji, Shuohui Cao, Ye Feng, Yanxia Jiang, Yuqing Huang, Shigang Sun, Zhong Chen. In situ monitoring multi-carbon alcohol oxidation by combined electrochemistry with spatially selective NMR spectroscopy[J]. Chinese Journal of Catalysis, 2023, 53: 171-179.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64526-7

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Figures/Tables 3

Fig. 1. In situ electrooxidation observation of a blend alcohol sample (containing 0.2 mol L-1 1-butanol, 0.1 mol L-1 ethanol, and 0.1 mol L-1 2-propanol in 0.1 mol L-1 HClO4) on Pt/C at 1.2 V (vs. SCE). (a) Pulse sequences of standard 1D single-pulse NMR, 1D spatially selective NMR methods (SPSE-I and SPSE-II). (b) Schematic in situ electrochemical setups. (c,d) Time-resolved 1D spectra acquired by the 1D single-pulse NMR and SPSE-II sequences. (e) Expanded spectral regions between 0.80 and 1.70 ppm in (d). (f) Predicted electrooxidation mechanism and possible oxidation pathways. The blue region in Fig. 1(d) is expanded to exhibit the fine spectra between 1.90 and 2.50 ppm. The experimental details are given in Supporting Information.

Fig. 2. Experimental results on 0.2 mol L?1 1-butanol and 0.1 mol L?1 HClO4 solution at 60 °C. Quantification results at 1.0 V (a), 0.75 V (b), and 0.5 V (c) on Pt/C, in which the amount of gaseous products (mainly CO2) is calculated by the difference between reactants and products based on the mass conservation law. Normalized conversion rates (d) and product selectivities (e) at three potentials measured form the last in situ SPSE spectra. (f) Possible reaction mechanism of 1-butanol oxidation on Pt/C.

Fig. 3. Experimental results on 1-butanol electrooxidation on two catalysts. Quantitative intensities of 1-butanol, butyric acid, acetic acid, and CO2 during 1-butanol oxidation on Pt/C (a) and PtRu/C (b), respectively. In situ EC-SPSENMR experiments are performed at 1.2 V at 60 °C. (c) Normalized contents of individual molecules were calculated based on the last in situ SPSE spectra. (d) The product selectivities on two electrocatalysts. (e) The predicted schematic diagrams of the 1-butanol oxidation on Pt/C and PtRu/C at 1.2 V.

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In situ monitoring multi-carbon alcohol oxidation by combined electrochemistry with spatially selective NMR spectroscopy

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