Enhancing hydrogen evolution reaction by harnessing bubble dynamics regulation: Principles, methods, and outlook

Abstract

Electrocatalytic hydrogen evolution reaction (HER) is crucial for green hydrogen production and the transition toward low-carbon energy systems. However, the issues related to electrochemical gas bubbles, particularly at high current densities, have become a critical bottleneck for HER performance, resulting in active site isolation, increased ohmic resistance, and large concentration overpotential. Addressing these bubble-related limitations is therefore essential for advancing HER efficiency. This review aims to provide a comprehensive understanding of bubble manipulation strategies for enhancing HER by (1) exploring the fundamental principles governing bubble dynamics at electrode interfaces, (2) presenting the strategies to mitigate bubble-related issues at electrode interfaces, that is, passive strategies and active strategies, and (3) offering our insights into the challenges and opportunities for bubble dynamics in HER. By consolidating these projects, this review aims to advance the rational design of bubble management strategies and inspire innovative approaches for efficient hydrogen production.

References

[1] IEA. Global Hydrogen Review 2024. International Energy Agency; 2024.

[2] Lagadec MF, Grimaud A. Water electrolysers with closed and open electrochemical systems. Nat Mater. 2020; 19: 1140-1150.

[3] Wang L, Liu W, Sun H, Yang L, Huang L. Advancements and policy implications of green hydrogen production from renewable sources. Energies. 2024; 17: 3548.

[4] Jiang B, Zhu J, Xia Z, et al. Correlating single-atomic ruthenium interdistance with long-range interaction boosts hydrogen evolution reaction kinetics. Adv Mater. 2024; 36:2310699.

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

[6] Blandamer MJ, Franks F, Haywood KH, Tory AC. Effect of added solutes on the size of hydrogen bubbles liberated from a cathodic wire in aqueous solution. Nature. 1967; 216: 783-784.

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

[8] Wu Y, Xu W, Xie P, et al. Growth kinetics of electrochemically generated hydrogen bubbles at increased pressures. Droplet. 2025; 4:e70000.

[9] Young T. An essay on the cohesion of fluids. Philos Trans R Soc Lond A. 1805; 95: 65-87.

[10] Wang J, Zheng Y, Nie F-Q, Zhai J, Jiang L. Air bubble bursting effect of lotus leaf. Langmuir. 2009; 25: 14129-14134.

[11] Ling WYL, Lu G, Ng TW. Increased stability and size of a bubble on a superhydrophobic surface. Langmuir. 2011; 27: 3233-3237.

[12] de Maleprade H, Clanet C, Quéré D. Spreading of bubbles after contacting the lower side of an aerophilic slide immersed in water. Phys Rev Lett. 2016; 117:094501.

[13] Dorrer C, Rühe J. Superaerophobicity: repellence of air bubbles from submerged, surface-engineered silicon substrates. Langmuir. 2012; 28: 14968-14973.

[14] 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.

[15] Yao Y, Lyu J, Li X, et al. A review of efficient electrocatalysts for the oxygen evolution reaction at large current density. DeCarbon. 2024; 5:100062.

[16] Krenz M. Untersuchung des elektrodennahen Raumes gasentwickelnder Elektroden. PhD dissertation. Humboldt-Universität zu Berlin; 1984. (in German)

[17] Neelakantaswamy PS, Rajaratnam A, Kisdnasamy S, Das NP. Systematic errors in conductimetric instrumentation due to bubble adhesions on the electrodes: an experimental assessment. Rev Sci Instrum. 1985; 56: 303-306.

[18] Aldas K. Application of a two-phase flow model for hydrogen evolution in an electrochemical cell. Appl Math Comput. 2004; 154: 507-519.

[19] Vogt H, Balzer RJ. The bubble coverage of gas-evolving electrodes in stagnant electrolytes. Electrochim Acta. 2005; 50: 2073-2079.

[20] Luo L, White HS. Electrogeneration of single nanobubbles at sub-50-nm-radius platinum nanodisk electrodes. Langmuir. 2013; 29: 11169-11175.

[21] Kiuchi D, Matsushima H, Fukunaka Y, Kuribayashi K. Ohmic resistance measurement of bubble froth layer in water electrolysis under microgravity. J Electrochem Soc. 2006; 153: E138.

[22] Janssen LJJ. Effective solution resistivity in beds containing one monolayer or multilayers of uniform spherical glass beads. J Appl Electrochem. 2000; 30: 507-509.

[23] Vogt H. The concentration overpotential of gas evolving electrodes as a multiple problem of mass transfer. J Electrochem Soc. 1990; 137: 1179-1184.

[24] German SR, Edwards MA, Ren H, White HS. Critical nuclei size, rate, and activation energy of H₂ gas nucleation. J Am Chem Soc. 2018; 140: 4047-4053.

[25] German SR, Edwards MA, Chen Q, Liu Y, Luo L, White HS. Electrochemistry of single nanobubbles. Estimating the critical size of bubble-forming nuclei for gas-evolving electrode reactions. Farad Discuss. 2016; 193: 223-240.

[26] Angulo A, van der Linde P, Gardeniers H, Modestino M, Fernández Rivas D. Influence of bubbles on the energy conversion efficiency of electrochemical reactors. Joule. 2020; 4: 555-579.

[27] Chen Q, Luo L, White HS. Electrochemical generation of a hydrogen bubble at a recessed platinum nanopore electrode. Langmuir. 2015; 31: 4573-4581.

[28] Lu Z, Zhu W, Yu X, et al. Ultrahigh hydrogen evolution performance of under-water "superaerophobic" MoS₂ nanostructured electrodes. Adv Mater. 2014; 26: 2683-2687.

[29] Li Y, Zhang H, Xu T, et al. Under-water superaerophobic pine-shaped Pt nanoarray electrode for ultrahigh-performance hydrogen evolution. Adv Funct Mater. 2015; 25: 1737-1744.

[30] Han N, Yang KR, Lu Z, et al. Nitrogen-doped tungsten carbide nanoarray as an efficient bifunctional electrocatalyst for water splitting in acid. Nat Commun. 2018; 9: 924.

[31] Yu X, Yu Z-Y, Zhang X-L, et al. “Superaerophobic” nickel phosphide nanoarray catalyst for efficient hydrogen evolution at ultrahigh current densities. J Am Chem Soc. 2019; 141: 7537-7543.

[32] Li H, Chen S, Zhang Y, et al. Systematic design of superaerophobic nanotube-array electrode comprised of transition-metal sulfides for overall water splitting. Nat Commun. 2018; 9: 2452.

[33] Shan X, Liu J, Mu H, et al. An engineered superhydrophilic/superaerophobic electrocatalyst composed of the supported CoMoS_x chalcogel for overall water splitting. Angew Chem Int Ed. 2020; 59: 1659-1665.

[34] 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.

[35] Wang K, Zhao R, Wang Z, et al. Controlled tuning the morphology of CoNiP catalysts with ultra-high activity for water splitting at large current densities in alkaline medium. Appl Surf Sci. 2023; 626:157218.

[36] Jeong S, Kim U, Lee S, et al. Superaerophobic/superhydrophilic multidimensional electrode system for high-current-density water electrolysis. ACS Nano. 2024; 18: 7558-7569.

[37] Das J, Mandal S, Borbora A, Rani S, Tenjimbayashi M, Manna U. Modulating force of nucleated hydrogen bubble adhesion to boost electrochemical water splitting. Adv Funct Mater. 2024; 34:2311648.

[38] O'Coin D, Ling H. Effect of gas flow rate on bubble formation on superhydrophobic surface. Droplet. 2025; 4:e148.

[39] Jeon D, Park J, Shin C, et al. Superaerophobic hydrogels for enhanced electrochemical and photoelectrochemical hydrogen production. Sci Adv. 2020; 6:eaaz3944.

[40] Bae M, Kang Y, Lee DW, Jeon D, Ryu J. Superaerophobic polyethyleneimine hydrogels for improving electrochemical hydrogen production by promoting bubble detachment. Adv Energy Mater. 2022; 12:2201452.

[41] Kang Y, Lee S, Han S, et al. Versatile, stable, and scalable gel-like aerophobic surface system (GLASS) for hydrogen production. Adv Funct Mater. 2023; 34:2308827.

[42] Sheng S, Shi B, Wang C, et al. Antibuoyancy and unidirectional gas evolution by Janus electrodes with asymmetric wettability. ACS Appl Mater Interfaces. 2020; 12: 23627-23634.

[43] Zhang C, Xu Z, Han N, et al. Superaerophilic/superaerophobic cooperative electrode for efficient hydrogen evolution reaction via enhanced mass transfer. Sci Adv. 2023; 9:eadd6978.

[44] Wang Z, Xiong J, Liao Y, et al. Bionic Janus membranes to manipulate bubbles underwater for hydrogen evolution reactions. Chem Eng J. 2023; 474:145352.

[45] Fu G, Sun X, Zheng Z, et al. Stereolithgraphy of metallic electrode with Janus porosity toward controllable bubble behavior and ultra-stable water electrolysis. Small Struct 2023; 4:2300176.

[46] Wang Z, Wang X, Xiong J, Xie M, Shuai Y. Bionic Janus microfluidic hydrogen production with high gas–liquid separation efficiency. Chem Eng J. 2024; 498:155261.

[47] Sun Y, Zhang C, Guo Z, Liu K, Jiang L, Yu C, Desert beetle inspired heterogeneous electrode for large current density hydrogen evolution reaction. Adv Funct Mater. 2025; 35:2425150.

[48] Zhang C, Teng C, Guo S, et al. Superaerophilic/superaerophobic NiFe-LDHs electrode for enhancing overall water splitting in alkaline media. Nano Lett. 2024; 24: 1959-1966.

[49] Cui Z, Shao Y, Zhang J, Wang Z. Dual-bioinspired Janus mesh membrane with controllable bubbles manipulation property for efficient water splitting and pure gas collection. J Colloid Interface Sci. 2025; 682: 629-642.

[50] Ling H, Rodriguez I, Fanasia FS, Boutin P. Bubble pinch-off on biphilic and superhydrophobic surfaces. Droplet. 2025; 4:e70021.

[51] Yu C, Cao M, Dong Z, et al. Aerophilic electrode with cone shape for continuous generation and efficient collection of H₂ bubbles. Adv Funct Mater. 2016; 26: 6830-6835.

[52] Song Q, Xue Z, Liu C, et al. General strategy to optimize gas evolution reaction via assembled striped-pattern superlattices. J Am Chem Soc. 2020; 142: 1857-1863.

[53] Long Z, Zhao Y, Zhang C, et al. Bioinspired interfacial materials: a multi-bioinspired dual-gradient electrode for microbubble manipulation toward controllable water splitting. Adv Mater. 2020; 32:2070129.

[54] Marozzi CA, Chialvo AC. Development of electrode morphologies of interest in electrocatalysis: part 2: hydrogen evolution reaction on macroporous nickel electrodes. Electrochim Acta. 2001; 46: 861-866.

[55] Kou T, Wang S, Shi R, et al. Periodic porous 3D electrodes mitigate gas bubble traffic during alkaline water electrolysis at high current densities. Adv Energy Mater. 2020; 10:2002955.

[56] Gross SJ, McDevitt KM, Mumm DR, Mohraz A. Mitigating bubble traffic in gas-evolving electrodes via spinodally derived architectures. ACS Appl Mater Interfaces. 2021; 13: 8528-8537.

[57] Wang W, Yu S, Li K, et al. Insights into the rapid two-phase transport dynamics in different structured porous transport layers of water electrolyzers through high-speed visualization. J Power Sources. 2021; 516:230641.

[58] Zhang Y, Cui W, Li L, Zhan C, Xiao F, Quan X, Effect of aligned porous electrode thickness and pore size on bubble removal capability and hydrogen evolution reaction performance. J Power Sources. 2023; 580:233380.

[59] Bu X, Mao Z, Bu Y, et al. Remarkable gas bubble transport driven by capillary pressure in 3D printing-enabled anisotropic structures for efficient hydrogen evolution electrocatalysts. Appl Catal B Environ. 2023; 320:121995.

[60] Chen Y, Chen J, Bai K, Liu J, Xiao Z, Fan S. Microporous structure flowing integrated with electrolytic water splitting based on stacked mesh electrode for hydrogen production. Fuel. 2024; 358:130317.

[61] Jiang X, Kyriakou V, Song C, et al. A novel multi-channel porous structure facilitating mass transport towards highly efficient alkaline water electrolysis. J Energy Chem. 2024; 93: 511-518.

[62] Chen J, Fu G, Tian Y, et al. Three-dimensional-printed Ni-based scaffold design accelerates bubble escape for ampere-level alkaline hydrogen evolution reaction. Interdiscip Mater. 2024; 3: 595-606.

[63] Xie D, Ding L-X, Chen S, Chen G-F, Cheng H, Wang H. High mass transfer rate in electrocatalytic hydrogen evolution achieved with efficient quasi-gas phase system. Angew Chem Int Ed. 2024; 64:e202414493.

[64] Lu Z, Zhang L, Iwata R, Wang EN, Grossman JC. Transport-based modeling of bubble nucleation on gas evolving electrodes. Langmuir. 2020; 36: 15112-15118.

[65] Solymosi T, Geißelbrecht M, Mayer S, et al. Nucleation as a rate-determining step in catalytic gas generation reactions from liquid phase systems. Sci Adv. 2022; 8:eade3262.

[66] Yuan S, Zhao C, Mei X, et al. Bubble management in PEM water electrolysis via imprinting patterned grooves on catalyst layer. Int J Heat Mass Transfer. 2023; 212:124249.

[67] Yang S, Yuan J, Xie P, et al. Macroscopic bubble generation promoted by nanobubble seeds as a traceless anti-fluctuation strategy for water splitting. Nat Commun. 2025; 16: 5732.

[68] 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.

[69] Yuan S, Zhao C, Cai X, et al. Bubble evolution and transport in PEM water electrolysis: mechanism, impact, and management. Prog Energy Combust Sci. 2023; 96:101075.

[70] Pan S, Ye Y, Zhang C, et al. A review of designing hierarchical structure within membrane electrode assembly for water electrolyzer. Adv Sci. 2025; 12:e10546.

[71] Jin C, Liu Y-L, Shan Y, Chen Q-J. Scanning electrochemical cell microscope study of individual H₂ gas bubble nucleation on platinum: effect of surfactants. Chin J Anal Chem. 2021; 49: e21055-e21064.

[72] Park D-H, Park H-K, Chung B-J. Influence of surface tension on the critical current density at sulfuric acid electrolysis. Heat Mass Transf. 2022; 58: 2097-2105.

[73] Kaushik P, Kaur G, Chaudhary GR, Batra U. Interfacial engineering by using Mo based single chain metallosurfactant towards hydrogen evolution reaction. J Electrochem Soc. 2022; 922:116759.

[74] Kaushik P, Kaur G, Chaudhary GR, Batra U. Super-hydrophilic Co- and Mo-based mix-metallomicellar film as an electrocatalyst toward hydrogen evolution reaction. Energy Fuels. 2023; 37: 8500-8511.

[75] Lewis TH, Zhang B. Nanoparticle adhesion and the role of nanobubbles in single-particle collision electrochemistry. J Phys Chem C. 2024; 128: 13074-13082.

[76] Wang H, Xu Z, Lin W, et al. Improving the water electrolysis performance by manipulating the generated nano/micro-bubbles using surfactants. Nano Res. 2023; 16: 420-426.

[77] 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.

[78] Sun C-W, Hsiau S-S. Effect of electrolyte concentration difference on hydrogen production during PEM electrolysis. J Electrochem Sci Technol. 2018; 9: 99-108.

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

[80] Araújo F, Neto RC, Moita AS. Alkaline water electrolysis: ultrasonic field and hydrogen bubble formation. Int J Hydrogen Energy. 2024; 78: 594-603.

[81] Meulenbroek AM, Deen NG, Vreman AW. Marangoni forces on electrolytic bubbles on microelectrodes. Electrochim Acta. 2024; 497:144510.

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

[83] Lee S, Sutomo W, Liu C, Loth E. Micro-fabricated electrolytic micro-bubblers. Int J Multiphase Flow. 2005; 31: 706-722.

[84] Groß TF, Bauer J, Ludwig G, Fernandez Rivas D, Pelz PF. Bubble nucleation from micro-crevices in a shear flow. Exp Fluids. 2017; 59: 12.

[85] Shi T, Feng H, Liu D, Zhang Y, Li Q. High-performance microfluidic electrochemical reactor for efficient hydrogen evolution. Appl Energy. 2022; 325:119887.

[86] Chen Z, Meng C, Ruan H, et al. Removal of bubbles from eletrodes in a planar cyclonic electrolyzer. Chem Eng Process. 2022; 181:109133.

[87] Angulo AE, Frey D, Modestino MA. Understanding bubble-induced overpotential losses in multiphase flow electrochemical reactors. Energy Fuels. 2022; 36: 7908-7914.

[88] Rocha F, Delmelle R, Georgiadis C, Proost J. Electrochemical performance enhancement of 3D printed electrodes tailored for enhanced Gas evacuation during alkaline water electrolysis. Adv Energy Mater. 2023; 13:2203087.

[89] Chen Y, Chen J, Bai K, Xiao Z, Fan S. A flow-through electrode for hydrogen production from water splitting by mitigating bubble induced overpotential. J Power Sources. 2023; 561:232733.

[90] Li S-D, Wang C-C, Chen C-Y. Water electrolysis in the presence of an ultrasonic field. Electrochim Acta. 2009; 54: 3877-3883.

[91] Pollet BG, Foroughi F, Faid AY, Emberson DR, Islam MH. Does power ultrasound (26 kHz) affect the hydrogen evolution reaction (HER) on Pt polycrystalline electrode in a mild acidic electrolyte? Ultrason Sonochem. 2020; 69:105238.

[92] Cho KM, Deshmukh PR, Shin WG. Hydrodynamic behavior of bubbles at gas-evolving electrode in ultrasonic field during water electrolysis. Ultrason Sonochem. 2021; 80:105796.

[93] Foroughi F, Immanuel Bernäcker C, Röntzsch L, Pollet BG. Understanding the effects of ultrasound (408 kHz) on the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) on Raney-Ni in alkaline media. Ultrason Sonochem. 2022; 84:105979.

[94] Su H, Sun J, Wang C, Wang H. Study on the influence of ultrasound on the kinetic behaviour of hydrogen bubbles produced by proton exchange membrane electrolysis with water. Ultrason Sonochem. 2024; 108:106968.

[95] Su H, Sun J, Wang C, Wang H. Temperature impacts on the growth of hydrogen bubbles during ultrasonic vibration-enhanced hydrogen generation. Ultrason Sonochem. 2024; 102:106734.

[96] Saad A, Bai L, Christensen FMS, et al. Ultrasound-enhanced alkaline water splitting with fast bubble release and sustained Ni catalysts. Appl Catal B Environ. 2025; 370:125152.

[97] Fang Z, Wan K-T, Taslim ME. Liquid surface depression and bubble generation by acoustic radiation. Droplet. 2024; 3:e123.

[98] Ji X, Zhong W, Liu K, et al. Extraordinary stability of surfactant-free bubbles suspended in ultrasound. Droplet. 2024; 3:e119.

[99] Feng J, Yang Z. Long-lived yet bare bubbles in ultrasound. Droplet. 2024; 3:e120.

[100] Matsushima H, Iida T, Fukunaka Y. Observation of bubble layer formed on hydrogen and oxygen gas-evolving electrode in a magnetic field. J Solid State Chem. 2012; 16: 617-623.

[101] Matsushima H, Iida T, Fukunaka Y. Gas bubble evolution on transparent electrode during water electrolysis in a magnetic field. Electrochim Acta. 2013; 100: 261-264.

[102] Monzon LMA, Coey JMD. Magnetic fields in electrochemistry: the Lorentz force. A mini-review. Electrochem Commun 2014; 42: 38-41.

[103] Koza JA, Mühlenhoff S, Żabiński P, et al. Hydrogen evolution under the influence of a magnetic field. Electrochim Acta. 2011; 56: 2665-2675.

[104] Lin M-Y, Hourng L-W, Kuo C-W. The effect of magnetic force on hydrogen production efficiency in water electrolysis. Int J Hydrogen Energy. 2012; 37: 1311-1320.

[105] Elias L, Chitharanjan Hegde A. Effect of magnetic field on HER of water electrolysis on Ni–W alloy. Electrocatalysis. 2017; 8: 375-382.

[106] Hu Q, Liu H, Liu Z, Zhong D, Han J, Pan L. A pair of adjacent bubbles evolution at micro-electrode under electrode-normal magnetic field. J Electrochem Soc. 2021; 880:114886.

[107] Baczyzmalski D, Karnbach F, Mutschke G, et al. Growth and detachment of single hydrogen bubbles in a magnetohydrodynamic shear flow. Phys Rev Fluids. 2017; 2:093701.

[108] Sun J, Wang C, Wen H, Yin Q, Fan J. Synergistic effects of magnetic fields and flow velocity on hydrogen bubble dynamics in water electrolysis. Electrochem Commun. 2025; 176:107918.

[109] Cheng H, Scott K, Ramshaw C. Intensification of water electrolysis in a centrifugal field. J Electrochem Soc. 2002; 149: D172.

[110] Cheng H, Scott K. An empirical model approach to gas evolution reactions in a centrifugal field. J Electrochem Soc. 2003; 544: 75-85.

[111] Wang M, Wang Z, Guo Z. Understanding of the intensified effect of super gravity on hydrogen evolution reaction. Int J Hydrogen Energy. 2009; 34: 5311-5317.

[112] Wang M, Wang Z, Guo Z. Water electrolysis enhanced by super gravity field for hydrogen production. Int J Hydrogen Energy 2010; 35: 3198-3205.

[113] Brinkert K, Richter MH, Akay Ö, et al. Efficient solar hydrogen generation in microgravity environment. Nat Commun. 2018; 9: 2527.

[114] Bashkatov A, Yang X, Mutschke G, Fritzsche B, Hossain SS, Eckert K. Dynamics of single hydrogen bubbles at Pt microelectrodes in microgravity. Phys Chem Chem Phys. 2021; 23: 11818-11830.

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