Electrochemical Synthesis of High-Efficiency Water Electrolysis Catalysts

Abstract

Among the current industrial hydrogen production technologies, electrolysis has attracted widespread attention due to its zero carbon emissions and sustainability. However, the existence of overpotential caused by reaction activation, mass/charge transfer, etc. makes the actual water splitting voltage higher than the theoretical value, severely limiting the industrial application of this technology. Therefore, it is particularly important to design and develop highly efficient electrocatalysts to reduce overpotential and improve energy efficiency. Among the various synthesis methods of electrocatalysts, electrochemical synthesis stands out due to its simplicity, easy reaction control, and low cost. This review article classifies and summarizes the electrochemical synthesis techniques (including electrodeposition, electrophoretic deposition, electrospinning, anodic oxidation, electrochemical intercalation, and electrochemical reconstruction), followed by their application in the field of water electrolysis. In addition, some challenges currently faced by electrochemical synthesis in electrocatalytic hydrogen production, and their potential solutions are discussed to promote the practical application of electrochemical synthesis in water electrolysis.

Graphical Abstract

This review summarizes and classifies commonly used electrochemical synthesis techniques, followed by the application of electrochemical synthesis methods in research on water electrolysis. Additionally, some challenges faced by electrochemical synthesis in the field of water electrolysis and possible solutions are discussed.

Keywords

Electrocatalysts / Electrochemical synthesis / Water splitting / Green hydrogen

References

[1] Nicoletti G, Arcuri N, Nicoletti Get al. . A technical and environmental comparison between hydrogen and some fossil fuels. Energy Convers. Manag.. 2015, 89: 205-213.

[2] Kim JS, Kim B, Kim Het al. . Recent progress on multimetal oxide catalysts for the oxygen evolution reaction. Adv. Energy Mater.. 2018, 8: 1702774.

[3] Xiong Z, Hou YD, Yuan RSet al. . Hollow NiCo₂S₄ nanospheres as a cocatalyst to support ZnIn₂S₄ nanosheets for visible-light-driven hydrogen production. Acta Phys. Chim. Sin.. 2021, 382111021.

[4] Zhang YH, Yang ZC, Zheng DDet al. . Surface cyano groups optimize the charge transfer of poly heptazine imide for enhanced photocatalytic H₂ evolution. Int. J. Hydrog. Energy. 2024, 69372-380.

[5] Huang WH, Bo TT, Zuo SWet al. . Surface decorated Ni sites for superior photocatalytic hydrogen production. SusMat. 2022, 2: 466-475.

[6] IEA: Global Hydrogen Review 2021, IEA, Paris. https://www.iea.org/reports/global-hydrogen-review-2021 (2021). Accessed 25 Nov 2021

[7] Bloor LG, Molina PI, Symes MDet al. . Low pH electrolytic water splitting using earth-abundant metastable catalysts that self-assemble in situ. J. Am. Chem. Soc.. 2014, 136: 3304-3311.

[8] Liu F, Shi CX, Guo XLet al. . Rational design of better hydrogen evolution electrocatalysts for water splitting: a review. Adv. Sci.. 2022, 9: 2200307.

[9] Huang CQ, Zhou JQ, Duan DSet al. . Roles of heteroatoms in electrocatalysts for alkaline water splitting: a review focusing on the reaction mechanism. Chin. J. Catal.. 2022, 432091-2110.

[10] Lu XF, Liao PQ, Wang JWet al. . An alkaline-stable, metal hydroxide mimicking metal-organic framework for efficient electrocatalytic oxygen evolution. J. Am. Chem. Soc.. 2016, 138: 8336-8339.

[11] Lu XF, Yu L, Lou XWD. Highly crystalline Ni-doped FeP/carbon hollow nanorods as all-pH efficient and durable hydrogen evolving electrocatalysts. Sci. Adv.. 2019, 5: eaav6009.

[12] Tomboc GM, Kim J, Wang YTet al. . Hybrid layered double hydroxides as multifunctional nanomaterials for overall water splitting and supercapacitor applications. J. Mater. Chem. A. 2021, 94528-4557.

[13] Ji YR, Guo YF, Liu Xet al. . Insights on rational design and regulation strategies of Prussian blue analogues and their derivatives towards high-performance electrocatalysts. Chem. Eng. J.. 2023, 471. 144743

[14] Dai RR, Dai CY, Hou SJet al. . Opportunities and challenges of hydrotalcite-related electrocatalysts for seawater splitting: a systematic perspective from materials synthesis, characterization and application. J. Mater. Chem. A. 2023, 11: 20383-20407.

[15] Cui ZB, Jiao WS, Huang ZYet al. . Design and synthesis of noble metal-based alloy electrocatalysts and their application in hydrogen evolution reaction. Small. 2023, 19: 2301465.

[16] Zhang XF, Huang WH, Yu Let al. . Enabling heterogeneous catalysis to achieve carbon neutrality: directional catalytic conversion of CO₂ into carboxylic acids. Carbon Energy. 2024, 6. e362

[17] Li SW, Wang YC, Peng SJet al. . Co–Ni-based nanotubes/nanosheets as efficient water splitting electrocatalysts. Adv. Energy Mater.. 2015, 61501661.

[18] Liu YP, Liang X, Gu Let al. . Corrosion engineering towards efficient oxygen evolution electrodes with stable catalytic activity for over 6000 hours. Nat. Commun.. 2018, 92609.

[19] Huang G, Hu M, Xu XTet al. . Optimizing heterointerface of Co₂P-Co_xO_y nanoparticles within a porous carbon network for deciphering superior water splitting. Small Struct.. 2023, 42200235.

[20] Zou Z, Dastafkan K, Shao Yet al. . Electrocatalysts for alkaline water electrolysis at ampere-level current densities: a review. Int. J. Hydrog. Energy. 2024, 51667-684.

[21] Lu XF, Li GR, Tong YX. A review of negative electrode materials for electrochemical supercapacitors. Sci. China Technol. Sci.. 2015, 58: 1799-1808.

[22] Lu XF, Wang AL, Xu Het al. . High-performance supercapacitors based on MnO₂ tube-in-tube arrays. J. Mater. Chem. A. 2015, 3: 16560-16566.

[23] Lu XF, Fang YJ, Luan DYet al. . Metal-organic frameworks derived functional materials for electrochemical energy storage and conversion: a mini review. Nano Lett.. 2021, 21: 1555-1565.

[24] Li GR, Xu H, Lu XFet al. . Electrochemical synthesis of nanostructured materials for electrochemical energy conversion and storage. Nanoscale. 2013, 5: 4056.

[25] Wu XJ, Zhu F, Mu Cet al. . Electrochemical synthesis and applications of oriented and hierarchically quasi-1D semiconducting nanostructures. Coord. Chem. Rev.. 2010, 2541135-1150.

[26] Gafurov ZN, Kantyukov AO, Kagilev AAet al. . Electrochemical methods for synthesis and in situ generation of organometallic compounds. Coord. Chem. Rev.. 2021, 442. 213986

[27] Lv YK, Wang K, Sun WYet al. . A universal electrochemical synthetic strategy for the direct assembly of single-atom catalysts. Adv. Sci.. 2023, 10: 2304656.

[28] Besra L, Liu M. A review on fundamentals and applications of electrophoretic deposition (EPD). Prog. Mater. Sci.. 2007, 521-61.

[29] Yan XH, Xiao X, Au Cet al. . Electrospinning nanofibers and nanomembranes for oil/water separation. J. Mater. Chem. A. 2021, 9: 21659-21684.

[30] Kale MB, Borse RA, Mohamed AGAet al. . Electrocatalysts by electrodeposition: recent advances, synthesis methods, and applications in energy conversion. Adv. Funct. Mater.. 2021, 31: 2101313.

[31] Zhu CY, Wang HW, Guan C. Recent progress on hollow array architectures and their applications in electrochemical energy storage. Nanoscale Horiz.. 2020, 51188-1199.

[32] Cortés-Contreras A, Larios-Durán ER, Antaño-López Ret al. . Simultaneous cathodic and anodic electrodeposition of metal ions from e-waste. Electrochim. Acta. 2023, 464. 142926

[33] Zhang ZR, Feng C, Liu CXet al. . Electrochemical deposition as a universal route for fabricating single-atom catalysts. Nat. Commun.. 2020, 11: 1215.

[34] Zheng DY, Liu KJ, Zhang ZSet al. . Essential features of weak current for excellent enhancement of NO_x reduction over monoatomic V-based catalyst. Nat. Commun.. 2024, 156688.

[35] Yuan WT, Nie XY, Ma GQet al. . Realizing textured zinc metal anodes through regulating electrodeposition current for aqueous zinc batteries. Angew. Chem. Int. Ed.. 2023, 622218386.

[36] He JF, Tong Y, Wang Zet al. . Oxygenate-induced structural evolution of high-entropy electrocatalysts for multifunctional alcohol electrooxidation integrated with hydrogen production. Proc. Natl. Acad. Sci. U. S. A.. 2024, 121. e2405846121

[37] Cao LM, Cao QC, Zhang Jet al. . Electrochemically controlled synthesis of ultrathin nickel hydroxide nanosheets for electrocatalytic oxygen evolution. Inorg. Chem.. 2021, 603365-3374.

[38] Li KX, Zhou GR, Tong Yet al. . Interface engineering of a hierarchical P-modified Co/Ni₃P heterostructure for highly efficient water electrolysis coupled with hydrazine degradation. ACS Sustain. Chem. Eng.. 2023, 11: 14186-14196.

[39] Wang AL, Liang CL, Lu XFet al. . Pt-MoO₃-RGO ternary hybrid hollow nanorod arrays as high-performance catalysts for methanol electrooxidation. J. Mater. Chem. A. 2016, 4: 1923-1930.

[40] Lu XF, Huang ZX, Tong YXet al. . Asymmetric supercapacitors with high energy density based on helical hierarchical porous Na_xMnO₂ and MoO₂. Chem. Sci.. 2016, 7: 510-517.

[41] Lu XF, Chen XY, Zhou Wet al. . α-Fe₂O₃@PANI core-shell nanowire arrays as negative electrodes for asymmetric supercapacitors. ACS Appl. Mater. Interfaces. 2015, 7: 14843-14850.

[42] Lu XF, Lin J, Huang ZXet al. . Three-dimensional nickel oxide@carbon hollow hybrid networks with enhanced performance for electrochemical energy storage. Electrochim. Acta. 2015, 161: 236-244.

[43] Li KX, He JF, Guan XZet al. . Phosphorus-modified amorphous high-entropy CoFeNiCrMn compound as high-performance electrocatalyst for hydrazine-assisted water electrolysis. Small. 2023, 19: 2302130.

[44] Li RP, Li Y, Yang PXet al. . Electrodeposition: synthesis of advanced transition metal-based catalyst for hydrogen production via electrolysis of water. J. Energy Chem.. 2021, 57547-566.

[45] Kim K, Raymond D, Candeago Ret al. . Selective cobalt and nickel electrodeposition for lithium-ion battery recycling through integrated electrolyte and interface control. Nat. Commun.. 2021, 12: 6554.

[46] Lei ZW, Liu P, Yang Xet al. . Monolithic nickel catalyst featured with high-density crystalline steps for stable hydrogen evolution at large current density. Small. 2023, 192301247.

[47] Lee JM, Jung KK, Lee SHet al. . One-step fabrication of nickel nanocones by electrodeposition using CaCl₂·2H₂O as capping reagent. Appl. Surf. Sci.. 2016, 369163-169.

[48] Hang T, Li M, Fei Qet al. . Characterization of nickel nanocones routed by electrodeposition without any template. Nanotechnology. 2008, 19. 035201

[49] Skibińska K, Huang MY, Mutschke Get al. . On the electrodeposition of conically nano-structured nickel layers assisted by a capping agent. J. Electroanal. Chem.. 2022.

[50] Karroubi LB, Patnaik SG, Assresahegn BDet al. . Highly porous scaffolds for Ru-based microsupercapacitor electrodes using hydrogen bubble templated electrodeposition. Energy Storage Mater.. 2022, 47: 134-140.

[51] Hu BM, Jiang SY, Huang CPet al. . A scalable dendritic Si-clad NiSn anode via one-step electrodeposition with ultrahigh areal capacity for micro lithium-ion battery. Small Struct.. 2024, 5: 2300530.

[52] Li XP, Wang Y, Wang JJet al. . Sequential electrodeposition of bifunctional catalytically active structures in MoO₃/Ni-NiO composite electrocatalysts for selective hydrogen and oxygen evolution. Adv. Mater.. 2020, 322003414.

[53] Huang J, Xiong YS, Peng ZYet al. . A general electrodeposition strategy for fabricating ultrathin nickel cobalt phosphate nanosheets with ultrahigh capacity and rate performance. ACS Nano. 2020, 1414201-14211.

[54] Wang Y, Yin ZL, Yan GCet al. . New insight into the electrodeposition of NiCo layered double hydroxide and its capacitive evaluation. Electrochim. Acta. 2020, 336. 135734

[55] Xie SJ, Tan XY, Xue ZHet al. . Cathodic deposition-assisted synthesis of thin glass MOF films for high-performance gas separations. Angew. Chem. Int. Ed.. 2024, 63: 2401817.

[56] Xie SJ, Monnens W, Wan Ket al. . Cathodic electrodeposition of MOF films using hydrogen peroxide. Angew. Chem. Int. Ed.. 2021, 6024950-24957.

[57] Wang MR, Kim Y, Zhang LYet al. . Controllable electrodeposition of ordered carbon nanowalls on Cu(111) substrates. Mater. Today. 2022, 57: 75-83.

[58] Lin D, Chandrasekaran S, Forien JBet al. . 3D-printed graded electrode with ultrahigh MnO₂ loading for non-aqueous electrochemical energy storage. Adv. Energy Mater.. 2023, 13: 2300408.

[59] Jiang ZJ, Du ZJ, Pan Ret al. . Electrosynthesis of metal-organic framework interlayer to realize highly stable and kinetics-enhanced Zn metal anode. Adv. Energy Mater.. 2024, 142402150.

[60] Yao B, Hussain S, Ye ZZet al. . Electrodeposited MOFs membrane with in situ incorporation of charged molecules for osmotic energy harvesting. Small. 2023, 192207559.

[61] Yao SS, Kalami S, Nam Set al. . Development of an electrophoretic deposition method for the in situ fabrication of ultra-thin composite-polymer electrolytes for solid-state lithium-metal batteries. Small. 2023, 192208252.

[62] Sarkar P, Nicholson PS. Electrophoretic deposition (EPD): mechanisms, kinetics, and application to ceramics. J. Am. Ceram. Soc.. 1996, 791987-2002.

[63] Park Y, Kim H, Lee Tet al. . Design of nanocatalyst for electrode structure: Electrophoretic deposition of iron phosphide nanoparticles to produce a highly active hydrogen evolution reaction catalyst. Chem. Eng. J.. 2022, 431. 133217

[64] Tiwari P, Ferson ND, Andrew JS. Elucidating the role of electrophoretic mobility for increasing yield in the electrophoretic deposition of nanomaterials. J. Colloid Interface Sci.. 2020, 570: 109-115.

[65] Atifi S, Mirvakili MN, Williams CAet al. . Fast self-assembly of scalable photonic cellulose nanocrystals and hybrid films via electrophoresis. Adv. Mater.. 2022, 34: 2109170.

[66] Zhang C, Li Y, Li Het al. . Overview of electric-field-induced deposition technology in fabricating organic thin films. J. Mater. Chem. C. 2021, 9374-394.

[67] Dutta P, Deb SK, Patra Aet al. . Electric field guided fast and oriented assembly of MXene into scalable pristine hydrogels for customized energy storage and water evaporation applications. Adv. Funct. Mater.. 2022, 32: 2204622.

[68] Wang RY, Wang WQ, Sun Met al. . Long-lifespan zinc-ion capacitors enabled by anodes integrated with interconnected mesoporous chitosan membranes through electrophoresis-driven phase separation. Angew. Chem. Int. Ed.. 2024, 632317154.

[69] Kasuga T, Saito T, Koga Het al. . One-pot hierarchical structuring of nanocellulose by electrophoretic deposition. ACS Nano. 2022, 1618390-18397.

[70] Wang R, Zhou YS, Zhang Yet al. . Ultrathin covalent organic framework membranes prepared by rapid electrophoretic deposition. Adv. Mater.. 2022, 34: 2204894.

[71] Jamil MF, Biçer E, Yarar Kaplan Bet al. . One-step fabrication of new generation graphene-based electrodes for polymer electrolyte membrane fuel cells by a novel electrophoretic deposition. Int. J. Hydrog. Energy. 2021, 465653-5663.

[72] Hu D, Wu HH, Li YX. Positively charged ultrafiltration membranes fabricated via graft polymerization combined with crosslinking and branching for textile wastewater treatment. Sep. Purif. Technol.. 2021, 264. 118469

[73] Balram A, Santhanagopalan S, Hao BYet al. . Electrophoretically-deposited metal-decorated CNT nanoforests with high thermal/electric conductivity and wettability tunable from hydrophilic to superhydrophobic. Adv. Funct. Mater.. 2016, 26: 2571-2579.

[74] Huang BH, Chen LJ, Chiou YJet al. . Bubble-channeling electrophoresis of honeycomb-like chitosan composites. Adv. Sci.. 2022, 9: 2203948.

[75] Xue JJ, Wu T, Dai YQet al. . Electrospinning and electrospun nanofibers: methods, materials, and applications. Chem. Rev.. 2019, 1195298-5415.

[76] Keirouz A, Wang Z, Reddy VSet al. . The history of electrospinning: Past, present, and future developments. Adv. Mater. Technol.. 2023, 8: 2201723.

[77] Rahmati M, Mills DK, Urbanska AMet al. . Electrospinning for tissue engineering applications. Prog. Mater. Sci.. 2021, 117. 100721

[78] Levitt AS, Vallett R, Dion Get al. . Effect of electrospinning processing variables on polyacrylonitrile nanoyarns. J. Appl. Polym. Sci.. 2018, 13546404.

[79] Szewczyk PK, Stachewicz U. The impact of relative humidity on electrospun polymer fibers: From structural changes to fiber morphology. Adv. Colloid Interface Sci.. 2020, 286. 102315

[80] Halabi M, Mann-Lahav M, Beilin Vet al. . Electrospun anion-conducting ionomer fibers: effect of humidity on final properties. Polymers. 2020, 121020.

[81] Xia CF, Zhou YS, He CHet al. . Recent advances on electrospun nanomaterials for zinc-air batteries. Small Sci.. 2021, 12100010.

[82] Robinson AJ, Pérez-Nava A, Ali SCet al. . Comparative analysis of fiber alignment methods in electrospinning. Matter. 2021, 4821-844.

[83] Wang J, Wang GH, Cheng Bet al. . Sulfur-doped g-C₃N₄/TiO₂ S-scheme heterojunction photocatalyst for Congo red photodegradation. Chin. J. Catal.. 2021, 42: 56-68.

[84] Zhao YF, Guo Y, Lu XFet al. . Exposing single Ni atoms in hollow S/N-doped carbon macroporous fibers for highly efficient electrochemical oxygen evolution. Adv. Mater.. 2022, 34: 2203442.

[85] Liu YF, Wei YZ, Xiong QQet al. . Hollow porous PLA/PBAT composite microfibers with enhanced toughness and prolonged drug release for wound healing. Mater. Des.. 2024, 237. 112624

[86] Chen Y, Liu YD, Li Let al. . Asymmetric bond delta-polarization at the interfacial Se-Ru-O bridge for efficient pH-robust water electrolysis. Adv. Funct. Mater.. 2024, 342406587.

[87] Wang S, Zhu CH, Wang Fet al. . Ultralight and superelastic curly micro/nanofibrous aerogels by direct electrospinning enable high-performance warmth retention. Small. 2023, 192302835.

[88] Guan SJ, Wang JX, Yang Yet al. . Highly stretchable and flexible electrospinning-based biofuel cell for implantable electronic. Adv. Funct. Mater.. 2023, 332303134.

[89] Liu RR, Hou LL, Yue GCet al. . Progress of fabrication and applications of electrospun hierarchically porous nanofibers. Adv. Fiber Mater.. 2022, 4604-630.

[90] Fang YJ, Zeng YX, Jin Qet al. . Nitrogen-doped amorphous Zn-carbon multichannel fibers for stable lithium metal anodes. Angew. Chem. Int. Ed.. 2021, 60: 8515-8520.

[91] Chen Y, Liu YD, Li Let al. . Intensifying the supported ruthenium metallic bond to boost the interfacial hydrogen spillover toward pH-universal hydrogen evolution catalysis. Adv. Funct. Mater.. 2024, 34: 2401452.

[92] Shao ZZ, Zhang X, Song ZHet al. . Simulation guided coaxial electrospinning of polyvinylidene fluoride hollow fibers with tailored piezoelectric performance. Small. 2023, 192303285.

[93] Zeng YX, Sun PX, Pei ZHet al. . Nitrogen-doped carbon fibers embedded with zincophilic Cu nanoboxes for stable Zn-metal anodes. Adv. Mater.. 2022, 342200342.

[94] He XX, Zheng J, Yu GFet al. . Near-field electrospinning: progress and applications. J. Phys. Chem. C. 2017, 1218663-8678.

[95] Huang Y, You XY, Tang ZQet al. . Interface engineering of flexible piezoresistive sensors via near-field electrospinning processed spacer layers. Small Meth.. 2021, 5: 2000842.

[96] Park YS, Kim J, Oh JMet al. . Near-field electrospinning for three-dimensional stacked nanoarchitectures with high aspect ratios. Nano Lett.. 2020, 20441-448.

[97] Wang KY, Liu GH, Hoivik Net al. . Electrochemical engineering of hollow nanoarchitectures: pulse/step anodization (Si, Al, Ti) and their applications. Chem. Soc. Rev.. 2014, 43: 1476-1500.

[98] Macak JM, Tsuchiya H, Ghicov Aet al. . TiO₂ nanotubes: self-organized electrochemical formation, properties and applications. Curr. Opin. Solid State Mater. Sci.. 2007, 11: 3-18.

[99] Dervishi E, McBride M, Edwards Ret al. . Mechanical and tribological properties of anodic Al coatings as a function of anodizing conditions. Surf. Coat. Technol.. 2022, 444. 128652

[100] Lim KG, Guo EJ, Fischer Aet al. . Anodization for simplified processing and efficient charge transport in vertical organic field-effect transistors. Adv. Funct. Mater.. 2020, 30: 2001703.

[101] Kowalski D, Kim D, Schmuki P. TiO₂ nanotubes, nanochannels and mesosponge: self-organized formation and applications. Nano Today. 2013, 8235-264.

[102] Choi J, Wehrspohn RB, Lee Jet al. . Anodization of nanoimprinted titanium: a comparison with formation of porous alumina. Electrochim. Acta. 2004, 49: 2645-2652.

[103] Yan J, Xi ZC, Cong LLet al. . Synergy of platinum single atoms and platinum atomic clusters on sulfur-doped titanium nitride nanotubes for enhanced hydrogen evolution reaction. Small. 2022, 18: 2205603.

[104] Hua SB, Jin T, Guo X. Electrochemical anodic oxidation assisted fabrication of memristors. Int. J. Extrem. Manuf.. 2024, 6. 032008

[105] Xu R, Zeng ZQ, Lei Y. Well-defined nanostructuring with designable anodic aluminum oxide template. Nat. Commun.. 2022, 132435.

[106] Song JN, Zheng MJ, Zhang Bet al. . Fast growth of highly ordered TiO₂ nanotube arrays on Si substrate under high-field anodization. Nano Micro Lett.. 2016, 913.

[107] Yu CP, Zhang WC, Xian MCet al. . Copper azide nanoparticle-encapsulating MOF-derived porous carbon: electrochemical preparation for high-performance primary explosive film. Small. 2022, 182107364.

[108] Yang XY, Kang LY, Wei ZMet al. . A self-sacrificial templated route to fabricate CuFe Prussian blue analogue/Cu(OH)₂ nanoarray as an efficient pre-catalyst for ultrastable bifunctional electro-oxidation. Chem. Eng. J.. 2021, 422. 130139

[109] He YT, Zhang YH, Wang ZHet al. . In situ surface film formed by solid-state anodic oxidation for stable lithium metal anodes. Adv. Funct. Mater.. 2021, 312101737.

[110] Kim JY, Liu GC, Shim GYet al. . Functionalized Zn@ZnO hexagonal pyramid array for dendrite-free and ultrastable zinc metal anodes. Adv. Funct. Mater.. 2020, 302004210.

[111] Zhang W, Peng J, Hua WBet al. . Architecting amorphous vanadium oxide/MXene nanohybrid via tunable anodic oxidation for high-performance sodium-ion batteries. Adv. Energy Mater.. 2021, 112100757.

[112] Yang S, Zhang PP, Nia ASet al. . Emerging 2D materials produced via electrochemistry. Adv. Mater.. 2020, 321907857.

[113] Zhang PL, He P, Yu QKet al. . Delocalized electrochemical exfoliation toward high-throughput fabrication of high-quality graphene. Chem. Eng. J.. 2022, 428. 131122

[114] Lowe SE, Shi G, Zhang YBet al. . The role of electrolyte acid concentration in the electrochemical exfoliation of graphite: mechanism and synthesis of electrochemical graphene oxide. Nano Mater. Sci.. 2019, 1215-223.

[115] Li FW, Xue MQ, Zhang XLet al. . Advanced composite 2D energy materials by simultaneous anodic and cathodic exfoliation. Adv. Energy Mater.. 2018, 8: 1702794.

[116] Liu BB, Zhang QH, Zhang LNet al. . Electrochemically exfoliated chlorine-doped graphene for flexible all-solid-state micro-supercapacitors with high volumetric energy density. Adv. Mater.. 2022, 342106309.

[117] Wang N, Mao NN, Wang ZEet al. . Electrochemical delamination of ultralarge few-layer black phosphorus with a hydrogen-free intercalation mechanism. Adv. Mater.. 2021, 332005815.

[118] Liu YD, Chen Y, Tian YHet al. . Synergizing hydrogen spillover and deprotonation by the internal polarization field in a MoS₂/NiPS₃ vertical heterostructure for boosted water electrolysis. Adv. Mater.. 2022, 342203615.

[119] Mei L, Cao ZL, Ying Tet al. . Simultaneous electrochemical exfoliation and covalent functionalization of MoS₂ membrane for ion sieving. Adv. Mater.. 2022, 342201416.

[120] Liu X, Meng JS, Zhu JXet al. . Comprehensive understandings into complete reconstruction of precatalysts: synthesis, applications, and characterizations. Adv. Mater.. 2021, 332007344.

[121] Yang CF, Zhong WD, Shen Ket al. . Electrochemically reconstructed Cu-FeOOH/Fe₃O₄ catalyst for efficient hydrogen evolution in alkaline media. Adv. Energy Mater.. 2022, 122200077.

[122] Duan Y, Lee JY, Xi SBet al. . Anodic oxidation enabled cation leaching for promoting surface reconstruction in water oxidation. Angew. Chem. Int. Ed.. 2021, 607418-7425.

[123] Han XT, Yu C, Niu YYet al. . Full bulk-structure reconstruction into amorphorized cobalt-iron oxyhydroxide nanosheet electrocatalysts for greatly improved electrocatalytic activity. Small Meth.. 2020, 4: 2000546.

[124] Yuan L, Liu S, Xu SCet al. . Modulation of Volmer step for efficient alkaline water splitting implemented by titanium oxide promoting surface reconstruction of cobalt carbonate hydroxide. Nano Energy. 2021, 82. 105732

[125] Zeng Y, Zhao MT, Huang ZHet al. . Surface reconstruction of water splitting electrocatalysts. Adv. Energy Mater.. 2022, 122201713.

[126] Lee WH, Han MH, Ko YJet al. . Electrode reconstruction strategy for oxygen evolution reaction: maintaining Fe-CoOOH phase with intermediate-spin state during electrolysis. Nat. Commun.. 2022, 13605.

[127] Huang CQ, Zhou QC, Duan DSet al. . The rapid self-reconstruction of Fe-modified Ni hydroxysulfide for efficient and stable large-current-density water/seawater oxidation. Energy Environ. Sci.. 2022, 154647-4658.

[128] Peng DQ, Hu C, Luo XFet al. . Electrochemical reconstruction of NiFe/NiFeOOH superparamagnetic core/catalytic shell heterostructure for magnetic heating enhancement of oxygen evolution reaction. Small. 2023, 19: 2370014.

[129] Zhang LJ, Cai WW, Bao NZ. Top-level design strategy to construct an advanced high-entropy Co-Cu-Fe-Mo (oxy)hydroxide electrocatalyst for the oxygen evolution reaction. Adv. Mater.. 2021, 332100745.

[130] Zheng Y, Jiao Y, Vasileff Aet al. . The hydrogen evolution reaction in alkaline solution: from theory, single crystal models, to practical electrocatalysts. Angew. Chem. Int. Ed.. 2018, 577568-7579.

[131] Lu XF, Zhang SL, Sim WLet al. . Phosphorized CoNi₂S₄ yolk-shell spheres for highly efficient hydrogen production via water and urea electrolysis. Angew. Chem. Int. Ed.. 2021, 60: 22885-22891.

[132] Liu L, Wang Y, Zhao YZet al. . Ultrahigh Pt-mass-activity hydrogen evolution catalyst electrodeposited from bulk Pt. Adv. Funct. Mater.. 2022, 32: 2112207.

[133] Luo Y, Zhang YL, Zhu JYet al. . Material engineering strategies for efficient hydrogen evolution reaction catalysts. Small Meth.. 2024.

[134] Tan YS, Feng JR, Dong HBet al. . The edge effects boosting hydrogen evolution performance of platinum/transition bimetallic phosphide hybrid electrocatalysts. Adv. Funct. Mater.. 2023, 332209967.

[135] Torabinejad V, Aliofkhazraei M, Assareh Set al. . Electrodeposition of Ni-Fe alloys, composites, and nano coatings—a review. J. Alloys Compd.. 2017, 691841-859.

[136] Zuo Y, Bellani S, Saleh Get al. . Ru-Cu nanoheterostructures for efficient hydrogen evolution reaction in alkaline water electrolyzers. J. Am. Chem. Soc.. 2023, 145: 21419-21431.

[137] Tong Y, Chen PZ. Nanostructure engineering of ruthenium-modified electrocatalysts for efficient electrocatalytic water splitting. J. Mater. Chem. A. 2024, 12: 3844-3878.

[138] Li JC, Zhang C, Zhang Cet al. . Green electrosynthesis of 5, 5'-azotetrazolate energetic materials plus energy-efficient hydrogen production using ruthenium single-atom catalysts. Adv. Mater.. 2022, 34: 2203900.

[139] Zhang JC, Gu YN, Lu Yet al. . Each performs its own functions: nickel oxide supported ruthenium single-atoms and nanoclusters relay catalysis with multi-active sites for efficient alkaline hydrogen evolution reaction. Appl. Catal. B Environ.. 2023, 325. 122316

[140] Cao XJ, Gao L, Qu JPet al. . Modulating electronic structure of PtCo-Pt_rich nanowires with Ru atoms for boosted hydrogen evolution catalysis. Small. 2023, 192302639.

[141] Zhang JY, Shu M, Niu YXet al. . Advances in CO catalytic oxidation on typical noble metal catalysts: mechanism, performance and optimization. Chem. Eng. J.. 2024, 495. 153523

[142] Shi Y, Lee C, Tan XYet al. . Atomic-level metal electrodeposition: synthetic strategies, applications, and catalytic mechanism in electrochemical energy conversion. Small Struct.. 2022, 32270012.

[143] Wu HM, Feng CQ, Zhang Let al. . Non-noble metal electrocatalysts for the hydrogen evolution reaction in water electrolysis. Electrochem. Energy Rev.. 2021, 4473-507.

[144] Zhu YL, Lin Q, Zhong YJet al. . Metal oxide-based materials as an emerging family of hydrogen evolution electrocatalysts. Energy Environ. Sci.. 2020, 13: 3361-3392.

[145] Wang LQ, Hao YX, Deng LMet al. . Rapid complete reconfiguration induced actual active species for industrial hydrogen evolution reaction. Nat. Commun.. 2022, 13: 5785.

[146] Xu QC, Zhang JH, Zhang HXet al. . Atomic heterointerface engineering overcomes the activity limitation of electrocatalysts and promises highly-efficient alkaline water splitting. Energy Environ. Sci.. 2021, 145228-5259.

[147] Wei C, Sun YM, Scherer GGet al. . Surface composition dependent ligand effect in tuning the activity of nickel-copper bimetallic electrocatalysts toward hydrogen evolution in alkaline. J. Am. Chem. Soc.. 2020, 142: 7765-7775.

[148] Wang JS, Xin SS, Xiao Yet al. . Manipulating the water dissociation electrocatalytic sites of bimetallic nickel-based alloys for highly efficient alkaline hydrogen evolution. Angew. Chem. Int. Ed.. 2022, 61: 2202518.

[149] Zhang KJ, Wang SX, Li XYet al. . Phase segregation in Cu_0.5Ni_0.5 alloy boosting urea-assisted hydrogen production in alkaline media. Small. 2023, 192300959.

[150] Chai L, Liu SL, Pei STet al. . Electrodeposited amorphous cobalt-nickel-phosphide-derived films as catalysts for electrochemical overall water splitting. Chem. Eng. J.. 2021, 420. 129686

[151] Bai HW, Chen D, Ma QLet al. . Atom doping engineering of transition metal phosphides for hydrogen evolution reactions. Electrochem. Energy Rev.. 2022, 524.

[152] Li KX, Tong Y, He JFet al. . Anion-modulated CoP electrode as bifunctional electrocatalyst for anion-exchange membrane hydrazine-assisted water electrolyser. Mater. Horiz.. 2023, 105277-5287.

[153] Li M, Wang X, Liu Ket al. . Ce-induced differentiated regulation of Co sites via gradient orbital coupling for bifunctional water-splitting reactions. Adv. Energy Mater.. 2023, 13: 2301162.

[154] Khodayar N, Noori A, Rahmanifar MSet al. . An ultra-high mass-loading transition metal phosphide electrocatalyst for efficient water splitting and ultra-durable zinc-air batteries. Energy Environ. Sci.. 2024, 175200-5215.

[155] Jo S, Kang B, Oh Het al. . Reconstruction of a surficial P-rich layer on Ni-P electrocatalysts for efficient hydrogen evolution applicable in acidic and alkaline media. Chem. Eng. J.. 2023, 457. 141138

[156] Li CD, Chen Q, Zheng RBet al. . Regulation of sulfur atoms in MoS_x by magneto-electrodeposition for hydrogen evolution reaction. Small. 2024, 20: 2308729.

[157] Li M, Wang X, Du Het al. . Oxophilic Tm-sites in MoS₂ trigger thermodynamic spontaneous water dissociation for enhanced hydrogen evolution. Adv. Energy Mater.. 2024, 142401716.

[158] Zhong B, Wan SJ, Kuang PYet al. . Crystalline/amorphous Ni/Ni_xS_y supported on hierarchical porous nickel foam for high-current-density hydrogen evolution. Appl. Catal. B Environ.. 2024, 340. 123195

[159] Tsai C, Li H, Park Set al. . Electrochemical generation of sulfur vacancies in the basal plane of MoS₂ for hydrogen evolution. Nat. Commun.. 2017, 815113.

[160] Le FH, Jia W, Shu WTet al. . Deep reconstruction of ruthenate perovskite oxide enables efficient pH-universal hydrogen evolution reaction. Small. 2024, 202404894.

[161] Zhang KX, Zou RQ. Advanced transition metal-based OER electrocatalysts: current status, opportunities, and challenges. Small. 2021, 172100129.

[162] Pei ZH, Zhang HB, Luan DYet al. . Electrocatalytic acidic oxygen evolution: from catalyst design to industrial applications. Matter. 2023, 64128-4144.

[163] Li XM, Hao XG, Abudula Aet al. . Nanostructured catalysts for electrochemical water splitting: current state and prospects. J. Mater. Chem. A. 2016, 4: 11973-12000.

[164] Liu YD, Li L, Wang Let al. . Janus electronic state of supported iridium nanoclusters for sustainable alkaline water electrolysis. Nat. Commun.. 2024, 15: 2851.

[165] Shi QR, Zhu CZ, Du Det al. . Robust noble metal-based electrocatalysts for oxygen evolution reaction. Chem. Soc. Rev.. 2019, 483181-3192.

[166] Qin Y, Yu TT, Deng SHet al. . RuO₂ electronic structure and lattice strain dual engineering for enhanced acidic oxygen evolution reaction performance. Nat. Commun.. 2022, 13: 3784.

[167] Chang B, Cao Z, Ren YFet al. . Electronic perturbation of isolated Fe coordination structure for enhanced nitrogen fixation. ACS Nano. 2024, 18288-298.

[168] Li M, Wang X, Zhang Det al. . Atomic rare earths activate direct O-O coupling in manganese oxide towards electrocatalytic oxygen evolution. Nano Energy. 2024, 128. 109868

[169] Li M, Wang X, Liu Ket al. . Reinforcing Co–O covalency via Ce(4f)–O(2p)–Co(3d) gradient orbital coupling for high-efficiency oxygen evolution. Adv. Mater.. 2023, 35: 2302462.

[170] Wei J, Tang H, Sheng Let al. . Site-specific metal-support interaction to switch the activity of Ir single atoms for oxygen evolution reaction. Nat. Commun.. 2024, 15559.

[171] Ma PY, Cao H, Hao Qet al. . Neighbouring synergy in high-density single Ir atoms on CoGaOOH for efficient alkaline electrocatalytic oxygen evolution. Angew. Chem. Int. Ed.. 2024, 63. e202404418

[172] Mu Y, Wang TT, Zhang Jet al. . Single-atom catalysts: advances and challenges in metal-support interactions for enhanced electrocatalysis. Electrochem. Energy Rev.. 2022, 5145-186.

[173] Sui XL, Zhang L, Li JJet al. . Advanced support materials and interactions for atomically dispersed noble-metal catalysts: from support effects to design strategies. Adv. Energy Mater.. 2022, 12: 2102556.

[174] Liang X, Fu NH, Yao SCet al. . The progress and outlook of metal single-atom-site catalysis. J. Am. Chem. Soc.. 2022, 14418155-18174.

[175] Zeng K, Zheng XJ, Li Cet al. . Recent advances in non-noble bifunctional oxygen electrocatalysts toward large-scale production. Adv. Funct. Mater.. 2020, 30: 2000503.

[176] Kim HJ, Kim HY, Joo Jet al. . Recent advances in non-precious group metal-based catalysts for water electrolysis and beyond. J. Mater. Chem. A. 2022, 1050-88.

[177] Liu JQ, Du YB, Zheng DDet al. . Nickel-based anode electrocatalysts for hydrogen production. ACS Mater. Lett.. 2024, 6: 466-481.

[178] Guo TQ, Li LD, Wang ZC. Recent development and future perspectives of amorphous transition metal-based electrocatalysts for oxygen evolution reaction. Adv. Energy Mater.. 2022, 12: 2200827.

[179] Li JH, Liu YP, Chen Het al. . Design of a multilayered oxygen-evolution electrode with high catalytic activity and corrosion resistance for saline water splitting. Adv. Funct. Mater.. 2021, 312101820.

[180] Liu J, Du W, Guo SYet al. . Iron-locked hydr(oxy)oxide catalysts via ion-compensatory reconstruction boost large-current-density water oxidation. Adv. Sci.. 2023, 102300717.

[181] Wu YJ, Yang J, Tu TXet al. . Evolution of cationic vacancy defects: a motif for surface restructuration of OER precatalyst. Angew. Chem. Int. Ed.. 2021, 6026829-26836.

[182] Hou ZQ, Cui CH, Li YNet al. . Lattice-strain engineering for heterogenous electrocatalytic oxygen evolution reaction. Adv. Mater.. 2023, 35: 2209876.

[183] Zhai PL, Wang C, Zhao YYet al. . Regulating electronic states of nitride/hydroxide to accelerate kinetics for oxygen evolution at large current density. Nat. Commun.. 2023, 141873.

[184] Gawande MB, Goswami A, Asefa Tet al. . Core-shell nanoparticles: synthesis and applications in catalysis and electrocatalysis. Chem. Soc. Rev.. 2015, 447540-7590.

[185] Wang XL, Ma RG, Li SLet al. . In situ electrochemical oxyanion steering of water oxidation electrocatalysts for optimized activity and stability. Adv. Energy Mater.. 2023, 13: 2300765.

[186] Wang J, Liao T, Wei ZZet al. . Heteroatom-doping of non-noble metal-based catalysts for electrocatalytic hydrogen evolution: an electronic structure tuning strategy. Small Meth.. 2021, 52000988.

[187] Sultan S, Tiwari JN, Singh ANet al. . Single atoms and clusters based nanomaterials for hydrogen evolution, oxygen evolution reactions, and full water splitting. Adv. Energy Mater.. 2019, 91900624.

[188] Li L, Wang B, Zhang GWet al. . Electrochemically modifying the electronic structure of IrO₂ nanoparticles for overall electrochemical water splitting with extensive adaptability. Adv. Energy Mater.. 2020, 102001600.

[189] Nong HN, Oh HS, Reier Tet al. . Oxide-supported IrNiO_x core-shell particles as efficient, cost-effective, and stable catalysts for electrochemical water splitting. Angew. Chem. Int. Ed.. 2015, 542975-2979.

[190] Gao JJ, Liu Y, Liu Bet al. . Progress of heterogeneous iridium-based water oxidation catalysts. ACS Nano. 2022, 16: 17761-17777.

[191] Yeo KR, Lee KS, Kim Het al. . A highly active and stable 3D dandelion spore-structured self-supporting Ir-based electrocatalyst for proton exchange membrane water electrolysis fabricated using structural reconstruction. Energy Environ. Sci.. 2022, 15: 3449-3461.

[192] Du M, Li XR, Pang Het al. . Alloy electrocatalysts. EnergyChem. 2023, 5. 100083

[193] Li YJ, Sun YJ, Qin YNet al. . Recent advances on water-splitting electrocatalysis mediated by noble-metal-based nanostructured materials. Adv. Energy Mater.. 2020, 10: 1903120.

[194] Wang J, Xu F, Jin HYet al. . Non-noble metal-based carbon composites in hydrogen evolution reaction: fundamentals to applications. Adv. Mater.. 2017, 291605838.

[195] Wu ZP, Lu XF, Zang SQet al. . Non-noble-metal-based electrocatalysts toward the oxygen evolution reaction. Adv. Funct. Mater.. 2020, 301910274.

[196] Huang CL, Sasaki K, Senthil Raja Det al. . Twinning enhances efficiencies of metallic catalysts toward electrolytic water splitting. Adv. Energy Mater.. 2021, 112170181.

[197] Ning MH, Zhang FH, Wu LBet al. . Boosting efficient alkaline fresh water and seawater electrolysis via electrochemical reconstruction. Energy Environ. Sci.. 2022, 153945-3957.

[198] Singh TI, Rajeshkhanna G, Pan UNet al. . Alkaline water splitting enhancement by MOF-derived Fe-Co-oxide/Co@NC-mNS heterostructure: Boosting OER and HER through defect engineering and in situ oxidation. Small. 2021, 17: 2101312.

[199] Jiang HL, Yu YJ, Duan XQet al. . Heterostructured MoO₃ anchored defect-rich NiFe-LDH/NF as a robust self-supporting electrocatalyst for overall water splitting. Small. 2024, 202307797.

[200] Ren JT, Chen L, Tian WWet al. . Rational synthesis of core-shell-structured nickel sulfide-based nanostructures for efficient seawater electrolysis. Small. 2023, 192300194.

[201] Jiang D, Yang LJ, Yuan HFet al. . Saturated hydrogen regulated ti coordination of metallic TiH₂/Ti electrode via in situ electrochemical hydrogenation for enhanced hydrogen evolution reaction. Nano Energy. 2022, 93. 106892

[202] Li YY, Du XC, Huang JWet al. . Recent progress on surface reconstruction of earth-abundant electrocatalysts for water oxidation. Small. 2019, 151901980.

[203] Hao YR, Xue H, Sun Jet al. . Achieving superior oxygen evolution of perovskite via phase transition and electrochemical reconstruction strategy. Energy Environ. Sci.. 2024, 174044-4054.

[204] Wang KX, Wang S, Hui KSet al. . Dense platinum/nickel oxide heterointerfaces with abundant oxygen vacancies enable ampere-level current density ultrastable hydrogen evolution in alkaline. Adv. Funct. Mater.. 2023, 33: 2211273.

[205] Yan YT, Lin JH, Xu TXet al. . Atomic-level platinum filling into Ni-vacancies of dual-deficient NiO for boosting electrocatalytic hydrogen evolution. Adv. Energy Mater.. 2022, 122270099.

[206] Fan XL, Liu C, Wu MYet al. . Synergistic effect of dual active sites over Ru/α-MoC for accelerating alkaline hydrogen evolution reaction. Appl. Catal. B Environ.. 2022, 318. 121867

[207] Liu HB, Gao J, Xu XCet al. . Oriented construction Cu₃P and Ni2P heterojunction to boost overall water splitting. Chem. Eng. J.. 2022, 448. 137706

[208] Zhu H, Wang YJ, Jiang ZQet al. . Defect engineering promoted ultrafine Ir nanoparticle growth and Sr single-atom adsorption on TiO₂ nanowires to achieve high-performance overall water splitting in acidic media. Adv. Energy Mater.. 2024, 142303987.

[209] You HH, Wu DS, Si DHet al. . Monolayer NiIr-layered double hydroxide as a long-lived efficient oxygen evolution catalyst for seawater splitting. J. Am. Chem. Soc.. 2022, 1449254-9263.

[210] Wang M, Wang YQ, Mao SSet al. . Transition-metal alloy electrocatalysts with active sites modulated by metal-carbide heterophases for efficient oxygen evolution. Nano Energy. 2021, 88. 106216

[211] Li YX, Zhang Z, Zhang ZQet al. . Construction of Ni₂P-NiFe₂O₄ heterostructured nanosheets towards performance-enhanced water oxidation reaction. Appl. Catal. B Environ.. 2023, 339. 123141

[212] Zhao Z, Sun JP, Li Xet al. . Joule heating synthesis of NiFe alloy/MoO₂ and in situ transformed (Ni, Fe)OOH/MoO₂ heterostructure as effective complementary electrocatalysts for overall splitting in alkaline seawater. Appl. Catal. B Environ.. 2024, 340. 123277

[213] Zheng XZ, Qin MK, Ma SXet al. . Strong oxide-support interaction over IrO₂/V₂O₅ for efficient pH-universal water splitting. Adv. Sci.. 2022, 92104636.

Funding

National Natural Science Foundation of China(22250710676)

RIGHTS & PERMISSIONS

Shanghai University and Periodicals Agency of Shanghai University