Growth kinetics of electrochemically generated hydrogen bubbles at increased pressures

Abstract

Bubble growth kinetics has been attracting vast attention in water electrolysis and other gas evolution reactions, but mostly investigated under ambient pressure. For practical scenarios, bubble evolution is usually carried out under high pressure. To better understand the bubble growth kinetics, we monitored the hydrogen bubble evolution process at increased pressures during electrochemical hydrogen production. Unlike the common sense that high pressures could result in smaller bubble size, our results revealed that the increased pressure would increase the aerophilicity of electrode surface, with decreased bubble contact angle from 111° to 89° for 0.1‒2.0 MPa, increased detachment size from 233 to 1207 µm, and reduced growth coefficient from 230 to 10.9 for the high pressures from 0.1 to 3.0 MPa. The steady high-pressure bubble growth kinetics are basically governed by the as-formed supersaturation in bulk solution, which is the balance between the driving force (current density) and the enlarged solubility of bulk solution under high pressure. Insufficient driving force would induce the depletion of bulk supersaturation and stagnate the bubble growth. Further investigation on high-pressure bubble evolution behaviors should shed light on practical industrial electrode design with extended usage life.

References

[1] Chang J, Yang Y. Advancements in seawater electrolysis: progressing from fundamental research to applied electrolyzer application. Renewables. 2023; 1: 415-454.

[2] Zhang W, Liu M, Gu X, Shi Y, Deng Z, Cai N. Water electrolysis toward elevated temperature: advances, challenges and frontiers. Chem Rev. 2023; 123: 7119-7192.

[3] Li M, Xie P, Yu L, Luo L, Sun X. Bubble engineering on micro-/nanostructured electrodes for water splitting. ACS Nano. 2023; 17: 23299-23316.

[4] Ahn SH, Choi I, Park H-Y, et al. Effect of morphology of electrodeposited Ni catalysts on the behavior of bubbles generated during the oxygen evolution reaction in alkaline water electrolysis. Chem Commun. 2013; 49: 9323-9325.

[5] Zhang D, Zeng K. Evaluating the behavior of electrolytic gas bubbles and their effect on the cell voltage in alkaline water electrolysis. Ind Eng Chem Res. 2012; 51: 13825-13832.

[6] Zhao X, Ren H, Luo L. Gas bubbles in electrochemical gas evolution reactions. Langmuir. 2019; 35: 5392-5408.

[7] Wang K, Zhou J, Sun M, et al. Cu-doped heterointerfaced Ru/RuSe₂ nanosheets with optimized H and H₂O adsorption boost hydrogen evolution catalysis. Adv Mater. 2023; 35:2300980.

[8] Chen XH, Li XL, Li T, et al. Enhancing neutral hydrogen production by disrupting the rigid hydrogen bond network on Ru nanoclusters through Nb₂O₅-mediated water reorientation. Energy Environ Sci. 2024; 17: 5091-5101.

[9] Feidenhans'l AA, Regmi YN, Wei C, Xia D, Kibsgaard J, King LA. Precious metal free hydrogen evolution catalyst design and application. Chem Rev. 2024; 124: 5617-5667.

[10] Xu W, Lu Z, Wan P, Kuang Y, Sun X. High-performance water electrolysis system with double nanostructured superaerophobic electrodes. Small. 2016; 12: 2492-2498.

[11] Ren Q, Feng L, Ye C, et al. Nanocone-modified surface facilitates gas bubble detachment for high-rate alkaline water splitting. Adv Energy Mater. 2023; 13:2302073.

[12] Lu Z, Sun M, Xu T, et al. Superaerophobic electrodes for direct hydrazine fuel cells. Adv Mater. 2015; 27: 2361-2366.

[13] Jiang M, Wang H, Li Y, et al. Superaerophobic RuO₂-based nanostructured electrode for high-performance chlorine evolution reaction. Small. 2016; 13:1602240.

[14] Liang X, Kumar V, Ahmadi F, Zhu Y. Manipulation of droplets and bubbles for thermal applications. Droplet. 2022; 1: 80-91.

[15] Brandon NP, Kelsall GH. Growth kinetics of bubbles electrogenerated at microelectrodes. J Appl Electrochem. 1985; 15: 475-484.

[16] Angulo A, van der Linde P. Influence of bubbles on the energy conversion efficiency of electrochemical reactors. Joule. 2020; 4: 555-579.

[17] Rosner DE, Epstein M. Effects of interface kinetics, capillarity and solute diffusion on bubble growth rates in highly supersaturated liquids. Chem Eng Sci. 1972; 27: 69-88.

[18] Westerheide DE, Westwater JW. Isothermal growth of hydrogen bubbles during electrolysis. AlChE J. 1961; 7: 357-362.

[19] Glas JP, Westwater JW. Measurements of the growth of electrolytic bubbles. Int J Heat Mass Transfer. 1964; 7: 1427-1443.

[20] Wang Y, Hu X, Cao Z, Guo L. Investigations on bubble growth mechanism during photoelectrochemical and electrochemical conversions. Colloids Surf A. 2016; 505: 86-92.

[21] Yang X, Karnbach F, Uhlemann M, Odenbach S, Eckert K. Dynamics of single hydrogen bubbles at a platinum microelectrode. Langmuir. 2015; 31: 8184-8193.

[22] Bashkatov A, Hossain SS, Mutschke G, et al. On the growth regimes of hydrogen bubbles at microelectrodes. Phys Chem Chem Phys. 2022; 24: 26738-26752.

[23] Peñas P, Van Der Linde P, Vijselaar W, et al. Decoupling gas evolution from water-splitting electrodes. J Electrochem Soc. 2019; 166: H769-H776.

[24] Van Der Linde P, Peñas-López P, Moreno Soto Á, et al. Gas bubble evolution on microstructured silicon substrates. Energy Environ Sci. 2018; 11: 3452-3462.

[25] She Y, Xu Q, Nie T, et al. In situ investigation of oxygen bubble evolution at photoanode surface affected by reaction temperature. J Phys Chem C. 2023; 127: 14197-14210.

[26] Lu X, Yadav D, Ma B, Ma L, Jing D. Rapid detachment of hydrogen bubbles for electrolytic water splitting driven by combined effects of Marangoni force and the electrostatic repulsion. J Power Sources. 2024; 599:234217.

[27] Xu Q, Liang L, Nie T, She Y, Tao L, Guo L. Effect of electrolyte pH on oxygen bubble behavior in photoelectrochemical water splitting. J Phys Chem C. 2023; 127: 5308-5320.

[28] Wang M. Growth characteristics and the mass transfer mechanism of single bubble on a photoelectrode at different electrolyte concentrations. Phys Chem Chem Phys. 2023; 23: 28497-28509.

[29] Zhao P, Gong S, Zhang C, Chen S, Cheng P. Roles of wettability and wickability on enhanced hydrogen evolution reactions. ACS Appl Mater Interfaces. 2024; 16: 27898-27907.

[30] Li X, Zhang J, Wang X, et al. Bio-inspired spontaneous splitting of underwater bubbles along a superhydrophobic open pathway without perturbation. Droplet. 2022; 1: 65-75.

[31] Park S, Liu L, Demirkır Ç, et al. Solutal Marangoni effect determines bubble dynamics during electrocatalytic hydrogen evolution. Nat Chem. 2023; 15: 1532-1540.

[32] Iwata R, Zhang L, Wilke KL, et al. Bubble growth and departure modes on wettable/non-wettable porous foams in alkaline water splitting. Joule. 2021; 5: 887-900.

[33] Wen R, Ma X, Lee Y-C, Yang R. Liquid-vapor phase-change heat transfer on functionalized nanowired surfaces and beyond. Joule. 2018; 2: 2307-2347.

[34] Qin J, Xie T, Zhou D, et al. Kinetic study of electrochemically produced hydrogen bubbles on Pt electrodes with tailored geometries. Nano Res. 2021; 14: 2154-2159.

[35] Ardron KH, Giustini G, Walker SP. Prediction of dynamic contact angles and bubble departure diameters in pool boiling using equilibrium thermodynamics. Int J Heat Mass Transfer. 2017; 114: 1274-1294.

[36] Bhati J, Paruya S. A semi-analytical method for computing the dynamics of bubble growth: the effect of superheat and operating pressure. Ind Eng Chem Res. 2018; 57: 15159-15171.

[37] Hiroto S. Bubble growth rates and nucleation site densities in saturated pool boiling of water at high pressures. J Nucl Sci Technol. 2011; 48: 734-743.

[38] Michaie S, Rullière R, Bonjour J. Experimental study of bubble dynamics of isolated bubbles in water pool boiling at subatmospheric pressures. Exp Therm Fluid Sci. 2017; 87: 117-128.

[39] Sedev R, Akhondzadeh H, Ali M, Keshavarz A, Iglauer S. Contact angles of a brine on a bituminous coal in compressed hydrogen. Geophys Res Lett. 2022; 49:e2022GL098261.

[40] Song J-W, Fan L-W. Understanding the effects of surface roughness on the temperature and pressure relevancy of water contact angles. Colloids Surf A. 2023; 656:130391.

[41] Song J-W, Fan L-W. Unraveling the synergistic effects of solid surface material and temperature on the contact angle of water under an elevated pressure: an experimental study. J Colloid Interface Sci. 2022; 605: 163-172.

RIGHTS & PERMISSIONS

2025 The Author(s). Droplet published by Jilin University and John Wiley & Sons Australia, Ltd.