Cyclic Voltammetry Coupled with Faradic Adsorption/Desorption Processes: A Finite Element Simulation

Authors

Jia-yao GUO, 1. Chemistry and Chemical Engineering Innovation and Entrepreneurship Education Center of Hunan Province, School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan, 411201, Hunan, China;
Duan CHEN, 1. Chemistry and Chemical Engineering Innovation and Entrepreneurship Education Center of Hunan Province, School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan, 411201, Hunan, China;
Jie ZHANG, 1. Chemistry and Chemical Engineering Innovation and Entrepreneurship Education Center of Hunan Province, School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan, 411201, Hunan, China;Follow
Dong-ping ZHAN, 2. Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian, China;

Corresponding Author

Jie ZHANG(jiezhang@hnust.edu.cn)

Abstract

Heterogeneous electron transfer (HET) coupled with Faradic adsorption/desorption is the fundamental processes involved in hydrogen evolution reaction, oxygen reduction reaction, carbon dioxide reduction reaction, and methanol oxidation reaction. However, the electrochemical behaviors of HET coupled with Faradic adsorption/desorption are complicated, and difficult to get the interface reaction kinetics quantitatively. In this paper, finite element method was adopted to simulate the cyclic voltammetric behaviors of HET coupled with Faradic adsorption/desorption processes by using the Fick’s second law and Langmuir isotherm. The cyclic voltammograms when reactant or product adsorbed weakly or strongly were simulated, and they agreed well with the classical results. In addition, taking the reactant adsorption for example, the effects of scanning rate, saturated adsorption and adsorption equilibrium constant on cyclic voltammograms were investigated. The simulation demonstrates that weak adsorption can be magnified with the increasing scanning rate, and the peak current changes gradually from being proportional to the square root of scanning rate to being proportional to the scanning rate. The difference between anodic and cathodic peak currents is linearly related to saturated adsorption. Therefore, the quantitative characterization of saturated adsorption is realized by correlating the difference between anodic and cathodic peak currents to the saturated adsorption. With the increasing adsorption equilibrium constant, the weak adsorption transfers to strong adsorption, and the adsorption/desorption peaks separate from diffusion peaks to form prepeaks or postpeaks. The potential-dependent adsorption equilibrium constant was also simulated, which demonstrates that it can further change the shape and position of adsorption/desorption peaks. The quantitative method based on this model can help researchers to obtain saturated adsorption and adsorption equilibrium constant quantitatively from the cyclic voltammograms coupled with Faradic adsorption/desorption processes. The simulation can also help researchers to understand the different cyclic voltammetric behaviors between surface processes and diffusion processes, and would be constructive for the study of electrocatalysis involving adsorption/desorption processes.

Graphical Abstract

Keywords

adsorption/desorption, heterogeneous electron transfer, electrode process, cyclic voltammetry, finite element simulation

DOI Link

https://doi.org/10.13208/j.electrochem.190411

Publication Date

2020-04-28

Online Available Date

2019-11-06

Revised Date

2019-06-20

Received Date

2019-04-10

Recommended Citation

Jia-yao GUO, Duan CHEN, Jie ZHANG, Dong-ping ZHAN. Cyclic Voltammetry Coupled with Faradic Adsorption/Desorption Processes: A Finite Element Simulation[J]. Journal of Electrochemistry, 2020 , 26(2): 281-288.
DOI: 10.13208/j.electrochem.190411
Available at: https://jelectrochem.xmu.edu.cn/journal/vol26/iss2/14

References

[1] Coleman E J, Co A C . The complex inhibiting role of surface oxide in the oxygen reduction reaction[J]. ACS Catalysis, 2015,5(12):7299-7311.
doi: 10.1021/acscatal.5b02122 URL

[2] Adzic R R, Tripkovic A V, O'Grady W E . Structural effects in electrocatalysis[J]. Nature, 1982,296(5853):137-138.
doi: 10.1038/296137a0 URL

[3] Wang W, Zhang J, Wang F F , et al. Mobility and reactivity of oxygen adspecies on platinum surface[J]. Journal of the American Chemical Society, 2016,138(29):9057-9060.
doi: 10.1021/jacs.6b05259 URL

[4] Zhou X S, Dong Z R, Zhang H M , et al. Self-assembly of a Rh(I) complex on Au(111) surfaces and its electrocatalytic activity toward the hydrogen evolution reaction[J]. Langmuir, 2007,23(12):6819-6826.
doi: 10.1021/la062949q URL

[5] Li K, Peng B S, Peng T Y . Recent advances in heterogeneous photocatalytic CO₂ conversion to solar fuels[J]. ACS Catalysis, 2016,6(11):7485-7527.
doi: 10.1021/acscatal.6b02089 URL

[6] Sun S G( 孙世刚), Chen S L( 陈胜利 ). Electrocatalysis[M]. Chemical Industry Press Co., Ltd.( 化学工业出版社), 2016.

[7] Yang J H, Cooper J K, Toma F M , et al. A multifunctional biphasic water splitting catalyst tailored for integration with high-performance semiconductor photoanodes[J]. Nature Materials, 2016,16(3):335-341.

[8] Merki D, Vrubel H, Rovelli L , et al. Fe, Co, and Ni ions promote the catalytic activity of amorphous molybdenum sulfide films for hydrogen evolution[J]. Chemical Science, 2012,3(8):2515-2525.

[9] Yin Y, Han J C, Zhang Y M , et al. Contributions of phase, sulfur vacancies, and edges to the hydrogen evolution reaction catalytic activity of porous molybdenum disulfide nanosheets[J]. Journal of the American Chemical Society, 2016,138(25):7965-7972.

[10] Li G Q, Zhang D, Qiao Q , et al. All the catalytic active sites of MoS₂ for hydrogen evolution[J]. Journal of the American Chemical Society, 2016,138(51):16632-16638.

[11] Bard A J, Faulkner L R . Electrochemical methods: Fundamentals and applications(2nd Ed.)[M]. New York, Wiley, 2001.

[12] Jiang Y F, Jiang B, Yang L K , et al. Determination of adsorbed species of hypophosphite electrooxidation on Ni electrode by in situ infrared with shell-isolated nano-particle-enhanced Raman spectroscopy[J]. Electrochemistry Communications, 2014,48:5-9.

[13] Li C Y, Chen S Y, Zheng Y L , et al. In-situ electrochemical shell-isolated Ag nanoparticles-enhanced Raman spectroscopy study of adenine adsorption on smooth Ag electrodes[J]. Electrochimica Acta, 2016,199:388-393.

[14] Li J F, Zhang Y J, Rudnev A V , et al. Electrochemical shell-isolated nanoparticle-enhanced raman spectroscopy: correlating structural information and adsorption processes of pyridine at the Au(hkl) single crystal/solution interface[J]. Journal of the American Chemical Society, 2015,137(6):2400-2408.
doi: 10.1021/ja513263j URL

[15] Chen C H, Meadows K E, Cuharuc A , et al. High resolution mapping of oxygen reduction reaction kinetics at polycrystalline platinum electrodes[J]. Physical Chemistry Chemical Physics, 2014,16(34):18545-18552.
doi: 10.1039/c4cp01511h URL

[16] Zuliani C, Walsh D A, Keyes T E , et al. Formation and growth of oxide layers at platinum and gold nano- and microelectrodes[J]. Analytical Chemistry, 2010,82(17):7135-7140.

[17] Su Y Z, Yan J W, Li M G , et al. Adsorption of solvent cations on Au(111) and Au(100) in alkylimidazolium-based ionic liquids-worm-like versus micelle-like structures[J]. Zeitschrift Fur Physikalische Chemie-International Journal of Research in Physical Chemistry & Chemical Physics, 2012,226(9/10):979-994.

[18] Tang Y G, Yan J W, Zhu F , et al. Comparative electrochemical scanning tunneling microscopy study of nonionic fluorosurfactant zonyl FSN self-assembled monolayers on Au(111) and Au(100): a potential-induced structural transition[J]. Langmuir, 2011,27(3):943-947.

[19] Rodríguez-López J, Alpuche-Avilés M A, Bard A J . Interrogation of surfaces for the quantification of adsorbed species on electrodes: Oxygen on gold and platinum in neutral media[J]. Journal of the American Chemical Society, 2008,130(50):16985-16995.

[20] Liang Z X, Ahn H S, Bard A J . A study of the mechanism of the hydrogen evolution reaction on nickel by surface interrogation scanning electrochemical microscopy[J]. Journal of the American Chemical Society, 2017,139(13):4854-4858.

[21] Ahn H S, Bard A J . Assessment of the stability and operability of cobalt phosphide electrocatalyst for hydrogen evolution[J]. Analytical Chemistry, 2017,89(16):8574-8579.
doi: 10.1021/acs.analchem.7b02799 URL

[22] Wopschall R H, Shain I . Effects of adsorption of electroactive species in stationary electrode polarography[J]. Analytical Chemistry, 1967,39(13):1514-1527.

[23] Cuharuc A S, Zhang G, Unwin P R . Electrochemistry of ferrocene derivatives on highly oriented pyrolytic graphite (HOPG): quantification and impacts of surface adsorption[J]. Physical Chemistry Chemical Physics, 2016,18(6):4966-4977.

[24] Zhang J, Jia J C, Han L H , et al. Kinetic investigation on the confined etching system of n-type gallium arsenide by scanning electrochemical microscopy[J]. Journal of Physical Chemistry C, 2014,118(32):18604-18611.
doi: 10.1021/jp5056446 URL

[25] Güell A G, Ebejer N, Snowden M E , et al. Structural correlations in heterogeneous electron transfer at monolayer and multilayer graphene electrodes[J]. Journal of the American Chemical Society, 2012,134(17):7258-7261.

[26] Zheng Q, Huang X M, Liu Y , et al. Electrochemical quantification of intermolecular hydrogen bonding between ferrocenemethanol and 3-mercaptopropanoic acid on gold[J]. Journal of Physical Chemistry C, 2017,121(40):22123-22129.

[27] Kobayashi K, Fujisaki F, Yoshimine T , et al. An analysis of the voltammetric adsorption waves of methyl viologen[J]. Bulletin of the Chemical Society of Japan, 1986,59(12):3715-3722.

[28] He P X, Crooks R M, Faulkner L R . Adsorption and electrode reactions of disulfonated anthraquinones at mercury electrodes[J]. Journal of Physical Chemistry, 1990,94(3):1135-1141.

[29] Zheng Q, Zhang J, Yang Y F , et al. Regulating the intermolecular hydrogen bonding: The reversible assembly and disassembly in the diffusion layer[J]. Journal of The Electrochemical Society, 2017,164(2):H97-H103.