Citation: Tu Kunfang, Li Guang, Jiang Yanxia. Effect of Temperature on the Electrocatalytic Oxidation of Ethanol[J]. Acta Physico-Chimica Sinica, ;2020, 36(8): 190602. doi: 10.3866/PKU.WHXB201906026 shu

Effect of Temperature on the Electrocatalytic Oxidation of Ethanol

Department of Chemistry, College of Chemistry and Chemical Engineering, State Key Laboratory of Physical Chemistry of Solid Surfaces, Xiamen University, Xiamen 361005, Fujian Province, P. R. China

Corresponding author: Jiang Yanxia, yxjiang@xmu.edu.cn
Received Date: 26 June 2019
Revised Date: 1 July 2019
Accepted Date: 23 July 2019
Available Online: 31 July 2019
Fund Project: The project was supported by the National Natural Science Foundation of China (21773198, 21621091) and the National Key Research and Development Program of China (2017YFA0206500)

The electrocatalytic activity of commercial Pt/C for ethanol oxidation is relatively low, and the C―C bond is difficult to break. Thus, the complete oxidation process is not easy, and the fuel utilization efficiency becomes considerably reduced. Increasing the temperature can increase the reaction rate and enhance the mass transport; therefore, a temperature-controlled electrode was used during our in situ FTIRS (Fourier Transform Infrared Spectroscopy) investigation. The temperature sensor was placed at a certain distance from the surface of the electrode; thus, the surface temperature needed to be corrected. The temperature was calibrated using the "potentiometric" measurement method, which was because the potential-temperature coefficient of the redox couple is constant under certain conditions, and the electrode surface temperature was obtained by potential conversion at different temperatures during the experiment. The experimental results showed that the relationship between the heating temperature, T_h, and the surface temperature, T_S, was T_S = 0.57T_h + 7.71 (30 ℃ < T_h ≤ 50 ℃) and T_S = 0.62T_h + 5.12 (50 ℃ < T_h ≤ 80 ℃), and according to error analysis, the maximum error was 1 ℃. The temperature-controlled electrode was applied to investigate the electrooxidation of ethanol using both in situ FTIRS and cyclic voltammetry using a commercial Pt/C catalyst at different temperatures. Clearly, based on the CV curve for the oxidation of ethanol, with increasing temperature, the overall oxidation current increased, and the onset potential and peak potential both negatively shifted, indicating that thermal activation allows the oxidation reaction to proceed easier. Electrooxidation of ethanol showed two positive oxidation peaks, and the ratio of the first peak current to the second peak current was used to qualitatively evaluate the selectivity of CO₂. Compared with at 25 ℃, the first peak current increased by 30% at 65 ℃, indicating that the high temperature was conducive to C―C bond cleavage. Comparing the in situ FTIRS recorded at 50 ℃, 35 ℃, and 25 ℃, we found that the onset potential of CO₂ on the commercial Pt/C catalyst was lower by 200 mV, indicating that Pt/C can provide oxygen-containing species at lower potentials at high temperature; however, the onset potentials of CH₃CHO and CH₃COOH did not change with temperature. The CO₂ selectivity was semi-quantitatively calculated by the area of CO₂ compared with the area of CH₃COOH from the FTIRS data. It was found that CO₂ had the highest selectivity at high temperature and low potential, indicating that high temperature is conducive to complete ethanol oxidation during CO₂ formation, possibly because both the ethanol bridge adsorption pattern and adsorbed OH (OH_ad) increased with temperature, enhancing subsequent CO_ad and OH_ad oxidation reactions. The low selectivity of CO₂ at the high potential was due to the adsorption of oxygen-containing species that occupied the surface-active site, blocking the adsorption of ethanol.
- Temperature controlled electrode,
- "Potentiometric" measurement,
- In situ FTIRS,
- Ethanol,
- Electrocatalysis
1. [1]
  Chen, X. B.; Li, C.; Gratzel, M.; Kostecki, R.; Mao, S. S. Chem. Soc. Rev. 2012, 41, 7909. doi: 10.1039/C2CS35230C doi: 10.1039/C2CS35230C
2. [2]
  Antolini, E. J. Power Sources 2007, 170, 1. doi: 10.1016/j.jpowsour.2007.04.009 doi: 10.1016/j.jpowsour.2007.04.009
3. [3]
  An, L.; Zhao, T. S.; Li, Y. S. Renew. Sust. Energ. Rev. 2015, 50, 1462. doi: 10.1016/j.rser.2015.05.074 doi: 10.1016/j.rser.2015.05.074
4. [4]
  Yajima, T.; Uchida, H.; Watanabe, M. J. T. J. Phys. Chem. B 2004, 108 (8), 2654. doi: 10.1021/jp037215q doi: 10.1021/jp037215q
5. [5]
  Ye, J. Y.; Jiang, Y. X.; Sheng, T.; Sun, S. G. Nano Energy 2016, 29, 414. doi: 10.1016/j.nanoen.2016.06.023 doi: 10.1016/j.nanoen.2016.06.023
6. [6]
  Watanabe, M.; Sato, T.; Kunimatsu, K.; Uchida, H. Electrochim. Acta 2008, 53 (23), 6928. doi: 10.1016/j.electacta.2008.02.023 doi: 10.1016/j.electacta.2008.02.023
7. [7]
  Wang, J. Anal. Chim. Acta 1999, 396, 33. doi: 10.1016/S0003-2670(99)00355-4 doi: 10.1016/S0003-2670(99)00355-4
8. [8]
  Zhou, Z. Y.; Wang, Q.; Lin, J. L.; Tian, N.; Sun, S. G. Electrochim. Acta 2010, 55 (27), 7995. doi: 10.1016/j.electacta.2010.02.071 doi: 10.1016/j.electacta.2010.02.071
9. [9]
  Jenkins, D. M.; Song, C. Y.; Fares, S.; Cheng, H.; Barrettino, D. Sens Actu B: Chem. 2009, 137, 222. doi: 10.1016/j.snb.2008.09.046 doi: 10.1016/j.snb.2008.09.046
10. [10]
  Compton, R. G.; Coles, B. A.; Marken, F. Chem. Commun. 1998, 2595. doi: 10.1039/A806511J doi: 10.1039/A806511J
11. [11]
  Yuan, Q.; Zhou, Z. Y.; Zhuang, J.; Wang, X. Chem. Mater. 2010, 22, 2395. doi: 10.1021/cm903844t doi: 10.1021/cm903844t
12. [12]
  Hitmi, H.; Belgsir, E. M.; Léger, J. M.; Lamy, C.; Lezna, R. O. Electrochim. Acta 1994, 39, 407. doi: 10.1016/0013-4686(94)80080-4 doi: 10.1016/0013-4686(94)80080-4
13. [13]
  Rao, L.; Jiang, Y. X.; Zhang, B. W.; Cai, Y. R.; Sun, S. G. Phys. Chem. Chem. Phys. 2014, 16, 13662. doi: 10.1039/C3CP55059A doi: 10.1039/C3CP55059A
14. [14]
  Iwasita, T.; Pastor, E. Electrochim. Acta 1994, 39, 531. doi: 10.1016/0013-4686(94)80097-9 doi: 10.1016/0013-4686(94)80097-9
15. [15]
  Rasch, B.; Iwasita, T. Electrochim. Acta 1990, 35, 989. doi: 10.1016/0013-4686(90)90032-U doi: 10.1016/0013-4686(90)90032-U
16. [16]
  Colmati, F.; Tremiliosi-Filho, G.; Gonzalez, E. R.; Berná, A.; Herrero, E.; Feliu, J, M. Faraday Discuss. 2008, 140, 379. doi: 10.1039/B802160K doi: 10.1039/B802160K
17. [17]
  Liu, H. X.; Tian, N.; Brandon, M. P.; Zhou, Z. Y.; Lin, J. L.; Hardacre, C.; Lin, W. F.; Sun, S. G. ACS Catal. 2012, 2, 708. doi: 10.1021/cs200686a doi: 10.1021/cs200686a
18. [18]
  Lu, G. Q.; Sun, S. G.; Cai, L. R.; Chen, S. P.; Tian, Z. W. Langmuir 2000, 16, 778. doi: 10.1021/la990282k doi: 10.1021/la990282k
19. [19]
  Tian, N.; Xiao, J.; Zhou, Z. Y.; Liu, H. X.; Xu, B. B.; Sun, S. G. Faraday Discuss. 2013, 162, 77. doi: 10.1039/C3FD20146E doi: 10.1039/C3FD20146E
20. [20]
  Ghumman, A.; Pickup, P. G. J. Power Sources.2008, 179, 280. doi: 10.1016/j.jpowsour.2007.12.071 doi: 10.1016/j.jpowsour.2007.12.071
21. [21]
  Rao, V.; Cremers, C.; Stimming, U. J. Eletrochem. Soc. 2007, 154, 1138. doi: 10.1149/1.2777108 doi: 10.1149/1.2777108
22. [22]
  Camara, G.A.; Iwasita, T. J. Eletrochem. Soc. 2005, 578, 315. doi: 10.1016/j.jelechem.2005.01.013 doi: 10.1016/j.jelechem.2005.01.013
23. [23]
  Severson, M. W.; Stuhlmann, C.; Villegas, I.; Weaver, M. J. J. Chem Phys. 1995, 103, 9832. doi: 10.1063/1.469950 doi: 10.1063/1.469950
24. [24]
  Zhang, B. W.; Sheng, T.; Wang, Y. X. ACS Catal. 2017, 7 (1), 892. doi: 10.1021/acscatal.6b03021 doi: 10.1021/acscatal.6b03021
25. [25]
  Wang, H. F; Liu, Z. P. J. Am. Chem. Soc. 2008, 130 (33), 10996. doi: 10.1021/ja801648h doi: 10.1021/ja801648h
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