Enhanced hydrogen evolution reaction performance of manganese-doped vanadium disulfide nanosheet across full pH spectrum and in simulated seawater

Abstract

Hydrogen production technologies that can efficiently operate across the entire pH range hold great promise for diverse application scenarios, especially in seawater electrolysis. In this work, we report a facile colloidal-chemistry synthesis of manganese-doped vanadium disulfide (Mn-VS₂) monolayer nanosheets with superior hydrogen evolution reaction performance. The incorporation of manganese lowers the formation energy of sulfur vacancies and modifies electronic states, thereby creating additional catalytic sites and enhancing reaction kinetics. Benefiting from these features, Mn-VS₂ achieves an overpotential of 40 mV at -10 mA·cm^-2 in simulated seawater and maintains excellent operational stability for over 100 h. These findings underscore the potential of Mn-VS₂ as a robust electrocatalyst for direct seawater electrolysis, providing a viable avenue for exploring sustainable hydrogen production in practical marine environments.

Keywords

Hydrogen evolution / Mn doping / VS₂ nanosheets / full pH range / defects / electronic regulation

References

[1] Zhai P,Wu Y.Engineering single-atomic ruthenium catalytic sites on defective nickel-iron layered double hydroxide for overall water splitting.Nat Commun2021;12:4587 PMCID:PMC8319438

[2] Zheng Y,Li LH.Toward design of synergistically active carbon-based catalysts for electrocatalytic hydrogen evolution.ACS Nano2014;8:5290-6 PMCID:PMC4046781

[3] Zhou Z,Wei L,Jian X.Electrocatalytic hydrogen evolution under neutral pH conditions: current understandings, recent advances, and future prospects.Energy Environ Sci2020;13:3185-206

[4] Lang C,Yan X,Zhu M.Molecular chemisorption: a new conceptual paradigm for hydrogen storage.Chem Synth2022;2:1

[5] Wang Y,Yun Y,Huang Y.CoMoP hole transfer layer functionally enhances efficiency and stability of BiVO₄ based photoanode for solar water splitting.Appl Catal B-Environ2024;358:124375

[6] McCrory CC,Peters JC.Electrocatalytic hydrogen evolution in acidic water with molecular cobalt tetraazamacrocycles.J Am Chem Soc2012;134:3164-70

[7] Chen Y,Yang H.Systematic constructing FeOCl/BiVO₄ hetero-interfacial hybrid photoanodes for efficient photoelectrochemical water splitting.Small2024;20:e2402406

[8] Wu H,Yang B.Carbon-dot-enhanced electrocatalytic hydrogen evolution.Acc Mater Res2022;3:319-30

[9] Yang F,Du Y.A monodisperse Rh₂ P-based electrocatalyst for highly efficient and pH-universal hydrogen evolution reaction.Adv Energy Mater2018;8:1703489

[10] Callejas JF,Read CG.Electrocatalytic and photocatalytic hydrogen production from acidic and neutral-pH aqueous solutions using iron phosphide nanoparticles.ACS Nano2014;8:11101-7

[11] He Y,Zhu Z.High-performance multidimensional-structured N-doped nickel modulated Mo₂N/FeO_xN_y bifunctional electrocatalysts for efficient alkaline seawater splitting.Chem Eng J2024;489:151348

[12] Meng L,Liu S.Cooperative effects between NiMo alloy enable highly efficient for all-pH-value and alkaline seawater hydrogen evolution.Appl Catal B-Environ2024;358:124388

[13] Wang L,Cheng X.ZIF-derived carbon nanoarchitecture as a bifunctional pH-universal electrocatalyst for energy-efficient hydrogen evolution.ACS Sustainable Chem Eng2019;7:10044-51

[14] Zhang X,Rao R.Defects materials of institut lavoisier-125(Ti) materials enhanced photocatalytic activity for toluene and chlorobenzene mixtures degradation: mechanism study.J Colloid Interface Sci2024;660:423-39

[15] Jiao Y,Davey K.Activity origin and catalyst design principles for electrocatalytic hydrogen evolution on heteroatom-doped graphene.Nature Energy2016;1:16130

[16] Trasatti, S. Electrocatalysis of Hydrogen Evolution: Progress in Cathode Activation. In Advances in Electrochemical Science and Engineering; Gerischer, H., Tobias, C. W., Eds.; Wiley, 1991; pp 1-85.

[17] Lu Q,Ma Q,Zhang H.2D transition-metal-dichalcogenide-nanosheet-based composites for photocatalytic and electrocatalytic hydrogen evolution reactions.Adv Mater2016;28:1917-33

[18] Guo F,Sobrido AJ,Feng J.Recent advances in ultralow-Pt-loading electrocatalysts for the efficient hydrogen evolution.Adv Sci2023;10:e2301098 PMCID:PMC10375096

[19] Li C.Recent advances in noble metal (Pt, Ru, and Ir)-based electrocatalysts for efficient hydrogen evolution reaction.ACS Omega2020;5:31-40 PMCID:PMC6963895

[20] Xia L,Pan K.Dual Co_xS_y-modified tungsten disulfide double-heterojunction electrocatalyst for efficient hydrogen evolution in all-pH media.ACS Appl Mater Interfaces2023;15:11765-76

[21] Sun L,Cheng Z.A heterostructured WS₂/WSe₂ catalyst by heterojunction engineering towards boosting hydrogen evolution reaction.Chem Eng J2022;443:136348

[22] Wang R,Tan X.Atmosphere plasma treatment and Co heteroatoms doping on basal plane of colloidal 2D VSe₂ nanosheets for enhanced hydrogen evolution.Int J Hydrogen Energy2021;46:32425-34

[23] Husain A,Danish M.Elevated symmetric supercapacitor performance and simulated solar light-functioning H₂O₂ production using single-step fabricated 2D/2D NiAl-based LDH/CoNi-based MOF nanohybrid.Surf Interfaces2024;51:104749

[24] Guo Z,Wang W,Dong B.Ultrathin VS₂ nanoplate with in-plane and out-of-plane defects for an electrochemical supercapacitor with ultrahigh specific capacitance.J Mater Chem A2018;6:14681-8

[25] Kim HJ,Lee IH.Electronic structure and charge-density wave transition in monolayer VS₂.Current Applied Physics2021;30:8-13

[26] Luo N,Duan W.Structural and electronic phase transitions in ferromagnetic monolayer VS₂ induced by charge doping. Phys. Rev. B. 2017,95,205432.

[27] Wang R,Liu X,Cao L.Synergistic effects of dual-doping with Ni and Ru in monolayer VS₂ nanosheet: unleashing enhanced performance for acidic HER through defects and strain.Small2024;20:e2311217

[28] Wang R,Liu X,Hu Y.Anchoring Pt nanoparticle onto monolayer VS₂ nanosheets boost efficient acidic hydrogen evolution.Int J Hydrogen Energy2024;74:384-91

[29] Feng J,Wu C.Metallic few-layered VS₂ ultrathin nanosheets: high two-dimensional conductivity for in-plane supercapacitors.J Am Chem Soc2011;133:17832-8

[30] Cui Y,Liu X,Gao Y.Electronic conductivity of two-dimensional VS₂ monolayers: a first principles study.Comput Mater Sci2021;200:110767

[31] Zhang J,Wang Z.Synergistic interlayer and defect engineering in VS₂ nanosheets toward efficient electrocatalytic hydrogen evolution reaction.Small2018;14:1703098

[32] Zhang H,Lau W.Dimension-dependent phase transition and magnetic properties of VS₂.J Mater Chem A2013;1:10821

[33] Du C,Shang M.In situ engineering MoS₂ NDs/VS₂ lamellar heterostructure for enhanced electrocatalytic hydrogen evolution.ACS Sustainable Chem Eng2018;6:15471-9

[34] Guo T,Sun Z.Bio-templated formation of defect-abundant VS₂ as a bifunctional material toward high-performance hydrogen evolution reactions and lithium-sulfur batteries.J Energy Chem2020;42:34-42

[35] van Efferen C,Hall J.A full gap above the Fermi level: the charge density wave of monolayer VS₂.Nat Commun2021;12:6837 PMCID:PMC8617271

[36] Liang H,Zhang D.Solution growth of vertical VS₂ nanoplate arrays for electrocatalytic hydrogen evolution.Chem Mater2016;28:5587-91

[37] Su J,Li Y.Sub-millimeter-scale monolayer p-type H-phase VS₂.Adv Funct Mater2020;30:2000240

[38] Peng X,Liu Y.Strain engineering of two-dimensional materials for energy storage and conversion applications.Chem Synth2023;3:47

[39] Wang T,Yu X.Modulating the electronic structure of VS₂via Ru decoration for an efficient pH-universal electrocatalytic hydrogen evolution reaction.Nanoscale2024;16:11250-61

[40] Dong S,Liu B.Guiding transition metal-doped hollow cerium tandem nanozymes with elaborately regulated multi-enzymatic activities for intensive chemodynamic therapy.Adv Mater2022;34:e2107054

[41] Yang Z,Zhang Q.Bulk-phase reconstruction enables robust zinc metal anodes for aqueous zinc-ion batteries.Angew Chem Int Ed Engl2023;62:e202308017

[42] Kuraganti V,Bar-Ziv R,Bar-Sadan M.Manganese doping of MoSe₂ promotes active defect sites for hydrogen evolution.ACS Appl Mater Interfaces2019;11:25155-62

[43] Wang L,Chen X.Charge-modulated VS₂ monolayer for effective hydrogen evolution reaction.J Phys Chem C2021;125:12004-11

[44] Zhao R,Zhou J.Dual glutathione depletion enhanced enzyme catalytic activity for hyperthermia assisted tumor therapy on semi-metallic VSe₂/Mn-CS.ACS Nano2022;16:10904-17

[45] Zhang W,Zhang J.Exposure of active edge structure for electrochemical H₂ evolution from VS₂/MWCNTs hybrid catalysts.Int J Hydrogen Energy2018;43:22949-54

[46] Bao D,Gao Y,Zheng Y.Dynamic creation of a local acid-like environment for hydrogen evolution reaction in natural seawater.J Am Chem Soc2024;146:34711-9

[47] Xu R,Cao L.VS₂ microflowers with in situ embedded few-layer MoS₂ nanobelts for enhanced hydrogen evolution reaction at high current density.J Electrochem Soc2020;167:026508

[48] He W,Peng J,Wang J.Mo-dopant-strengthened basal-plane activity in VS₂ for accelerating hydrogen evolution reaction.Chem Eng J2020;396:125227

[49] Xu J,Yu B,Zhang J.Metallic 1T-VS₂ nanosheets featuring V²⁺ self-doping and mesopores towards an efficient hydrogen evolution reaction.Inorg Chem Front2019;6:3510-7

[50] Feng T,Zhan Z,Yin P.Cobalt doping VS₂ on nickel foam as a high efficient electrocatalyst for hydrogen evolution reaction.Int J Hydrogen Energy2022;47:10646-53

[51] Bolar S,Jang W,Murmu NC.Regulating the metal concentration for selective tuning of VS₂/MoS₂ heterostructures toward hydrogen evolution reaction in acidic and alkaline media.ACS Appl Energy Mater2022;5:10086-97

[52] Zhang J,Huang H.Spatial relation controllable Di-defects synergy boosts electrocatalytic hydrogen evolution reaction over VSe₂ nanoflakes in all pH electrolytes.Small2022;18:e2204557

[53] Feng L,He D.Heterostructured VN/Mo₂C nanoparticles as highly efficient pH-universal electrocatalysts toward the hydrogen evolution reaction.ACS Sustainable Chem Eng2021;9:15202-11

[54] Xie Z,Ding D.Accelerating hydrogen evolution at neutral pH by destabilization of water with a conducting oxophilic metal oxide.J Mater Chem A2020;8:12169-76

[55] Ni Y,Wang S.Heterostructured nickel/vanadium nitrides composites for efficient electrocatalytic hydrogen evolution in neutral medium.J Power Sources2022;521:230934

[56] Chhowalla M,Eda G,Loh KP.The chemistry of two-dimensional layered transition metal dichalcogenide nanosheets.Nat Chem2013;5:263-75

[57] Voiry D,Li J.Enhanced catalytic activity in strained chemically exfoliated WS₂ nanosheets for hydrogen evolution.Nat Mater2013;12:850-5

[58] Xu P,Guo S.Atomic Ru-doped Ni_0.85Se nanosheets as efficient electrocatalysts toward simulated seawater hydrogen evolution.Energy Fuels2023;37:18204-9

[59] Penders J,Horgan CC.Single particle automated raman trapping analysis.Nat Commun2018;9:4256 PMCID:PMC6189196