Dual metal selenides CoSe/MoSe₂ heterojunction enwrapped in single-atomic-Co doped carbon for electrocatalytic water splitting

Abstract

A novel bifunctional electrocatalyst for water splitting was constructed with the CoSe/MoSe₂ heterojunction encapsulated within a nitrogen-doped carbon matrix (Co₁Mo₂Se/Co‒N‒C). This catalyst was synthesized via a facile one-step high-temperature calcination process. By optimizing the molar ratio of n(Co)/n(Mo) and the calcination temperature, a unique architecture was achieved featuring uniformly dispersed nanoparticles, well-defined heterointerfaces, and isolated Co atoms embedded in the carbon layer. Such structural features facilitated efficient transfer of electrons and maximized exposure of active sites. Electrochemical evaluations in 1.0 mol·L⁻¹ KOH demonstrated that Co₁Mo₂Se/Co‒N‒C exhibited excellent hydrogen evolution reaction performance, requiring an overpotential of only 63 mV to reach 10 mA·cm⁻² with a Tafel slope of 60 mV·dec⁻¹, comparable to that of commercial Pt/C. For oxygen evolution reaction, the catalyst achieved an overpotential of 328 mV at 10 mA·cm⁻² and a Tafel slope of 97 mV·dec⁻¹. Furthermore, a full water splitting cell based on this catalyst reached 10 mA·cm⁻² at an applied voltage of 1.623 V. These results highlight synergistic effects of the heterojunction and the nitrogen-doped carbon matrix, offering a promising strategy for the sustainable hydrogen production.

Graphical abstract

Keywords

transition metal selenides / heterojunction / single atomic catalyst / charge transfer / water splitting

References

[1] Quan L, Jiang H, Mei G L, . Bifunctional electrocatalysts for overall and hybrid water splitting.Chemical Reviews, 2024, 124(7): 3694–3812

[2] Wang J, Gao Y, Kong H, . Non-precious-metal catalysts for alkaline water electrolysis: operando characterizations, theoretical calculations, and recent advances.Chemical Society Reviews, 2020, 49(24): 9154–9196

[3] Zou X, Zhang Y . Noble metal-free hydrogen evolution catalysts for water splitting.Chemical Society Reviews, 2015, 44(15): 5148–5180

[4] Zhu J, Hu L, Zhao P, . Recent advances in electrocatalytic hydrogen evolution using nanoparticles.Chemical Reviews, 2020, 120(2): 851–918

[5] Shi Y M, Zhang B . Recent advances in transition metal phosphide nanomaterials: synthesis and applications in hydrogen evolution reaction.Chemical Society Reviews, 2016, 45(6): 1529–1541

[6] Shi Y, Li M, Yu Y, . Recent advances in nanostructured transition metal phosphides: synthesis and energy-related applications.Energy & Environmental Science, 2020, 13(12): 4564–4582

[7] Qian Q Z, Zhu Y, Ahmad N, . Recent advancements in electrochemical hydrogen production via hybrid water splitting.Advanced Materials, 2024, 36(4): 2306108

[8] Lin Y, Dong Y, Wang X, . Electrocatalysts for the oxygen evolution reaction in acidic media.Advanced Materials, 2023, 35(22): 2210565

[9] Pang B B, Liu X K, Liu T Y, . Laser-assisted high-performance PtRu alloy for pH-universal hydrogen evolution.Energy & Environmental Science, 2022, 15(1): 102–108

[10] Liu Y W, Wu X, Li Z, . Fabricating polyoxometalates-stabilized single-atom site catalysts in confined space with enhanced activity for alkynes diboration.Nature Communications, 2021, 12(1): 4205

[11] Nguyen D C, Doan T L L, Prabhakaran S, . Rh single atoms/clusters confined in metal sulfide/oxide nanotubes as advanced multifunctional catalysts for green and energy-saving hydrogen productions.Applied Catalysis B: Environment and Energy, 2022, 313: 121430

[12] Zhong Y, Lu Y, Pan Z, . Efficient water splitting system enabled by multifunctional platinum-free electrocatalysts.Advanced Functional Materials, 2021, 31(20): 2009853

[13] Jiang Y, Gao S, Liu X, . Recent achievements in selenium-based transition metal electrocatalysts for pH-universal water splitting.Nano Research, 2024, 17(7): 5763–5785

[14] Zhou L H, Yang C M, Zhu W C, . Boosting alkaline hydrogen evolution reaction via an unexpected dynamic evolution of molybdenum and selenium on MoSe₂ electrode.Advanced Energy Materials, 2022, 12(47): 2202367

[15] D’Olimpio G, Nappini S, Vorokhta M, . Enhanced electrocatalytic activity in GaSe and InSe nanosheets: the role of surface oxides.Advanced Functional Materials, 2020, 30(43): 2005466

[16] Jiang F, Wang Y C, Peng H Y, . Triggering asymmetric hybridization via Ni–Se–Co electron bridges on rich amorphous heterostructured nickel selenide for durable alkaline water splitting.Applied Catalysis B: Environment and Energy, 2025, 372: 125326

[17] Kawashima K, Marquez R A, Smith L A, . A review of transition metal boride, carbide, pnictide, and chalcogenide water oxidation electrocatalysts.Chemical Reviews, 2023, 123(23): 12795–13208

[18] Fan H F, Jiao D X, Fan J C, . Kinetically and thermodynamically expediting elementary steps via high-valence Cr-incorporated of nickel selenide for water electrolysis.Nano Research, 2024, 17(3): 1199–1208

[19] Wang Y, Li X P, Zhang M M, . Highly active and durable single-atom tungsten-doped NiS_0.5Se_0.5 nanosheet@NiS_0.5Se_0.5 nanorod heterostructures for water splitting.Advanced Materials, 2022, 34(13): 2107053

[20] Huang L, Wei G, Wang J, . Ion irradiation activated catalytic activity of MoSe₂ nanosheet for high-efficiency hydrogen evolution reaction.Advanced Energy Materials, 2023, 13(28): 2300651

[21] Li D, Li Z Y, Zou R, . Coupling overall water splitting and biomass oxidation via Fe-doped Ni₂P@C nanosheets at large current density.Applied Catalysis B: Environment and Energy, 2022, 307: 121170

[22] Cao X Y, Zhao L L, Wulan B, . Atomic bridging structure of nickel‒nitrogen‒carbon for highly efficient electrocatalytic reduction of CO₂.Angewandte Chemie International Edition, 2022, 61(6): e202113918

[23] Fei H, Dong J, Chen D, . Single atom electrocatalysts supported on graphene or graphene-like carbons.Chemical Society Reviews, 2019, 48(20): 5207–5241

[24] Li J C, Zhang C, Zhang C, . Green electrosynthesis of 5,5′-azotetrazolate energetic materials plus energy-efficient hydrogen production using ruthenium single-atom catalysts.Advanced Materials, 2022, 34(32): 2203900

[25] Jiao Y, Zheng Y, Davey K, . Activity origin and catalyst design principles for electrocatalytic hydrogen evolution on heteroatom-doped graphene.Nature Energy, 2016, 1(10): 16130

[26] Zheng W Q, Zhu R, Wu H J, . Tailoring bond microenvironments and reaction pathways of single-atom catalysts for efficient water electrolysis.Angewandte Chemie International Edition, 2022, 61(41): e202208667

[27] Zhang D D, Li H B, Riaz A, . Unconventional direct synthesis of Ni₃N/Ni with N-vacancies for efficient and stable hydrogen evolution.Energy & Environmental Science, 2022, 15: 185–195

[28] Lei X, Tang Q, Zheng Y, . High-entropy single-atom activated carbon catalysts for sustainable oxygen electrocatalysis.Nature Sustainability, 2023, 6(7): 816–826

[29] Rong C L, Shen X J, Wang Y, . Electronic structure engineering of single-atom Ru sites via Co-N4 sites for bifunctional pH-universal water splitting.Advanced Materials, 2022, 34(21): 2110103

[30] Lyu F, Zeng S, Jia Z, . Two-dimensional mineral hydrogel-derived single atoms-anchored heterostructures for ultrastable hydrogen evolution.Nature Communications, 2022, 13(1): 6249

[31] Yang Q, Liu H, Yuan P, . Single carbon vacancy traps atomic platinum for hydrogen evolution catalysis.Journal of the American Chemical Society, 2022, 144(5): 2171–2178

[32] Luan B B, Chu X Y, Wang Y, . Construction of COF/COF organic S-scheme heterostructure for enhanced overall water splitting.Advanced Materials, 2024, 36(49): 2412653

[33] Lin X L, Liu J L, Qiu X Q, . Ru-FeNi alloy heterojunctions on lignin-derived carbon as bifunctional electrocatalysts for efficient overall water splitting.Angewandte Chemie International Edition, 2023, 62(33): e202306333

[34] Liu Y W, Wang L R, Hubner R, . Cobalt-based Co₃Mo₃N/Co₄N/Co metallic heterostructure as a highly active electrocatalyst for alkaline overall water splitting.Angewandte Chemie International Edition, 2024, 63(14): e202319239

[35] Liu R, Sun M Z, Liu X J, . Enhanced metal-support interactions boost the electrocatalytic water splitting of supported ruthenium nanoparticles on a Ni₃N/NiO heterojunction at industrial current density.Angewandte Chemie International Edition, 2023, 62(46): e202312644

[36] Qin S Y, Sun J P, Meng X C . Modulating the electronic structure at the interface of CoSe and MoSe₂ for enhanced electrocatalytic hydrogen evolution reaction.International Journal of Hydrogen Energy, 2024, 51: 415–422

[37] Yang M, Bao W, Zhang J, . Molybdenum/selenium based heterostructure catalyst for efficient hydrogen evolution: effects of ionic dissolution and repolymerization on catalytic performance.Journal of Colloid and Interface Science, 2024, 658: 32–42

[38] Che S, Ta N, Yang F, . One-pot construction of CoSe nanoparticles anchored on single-atomic-Co doped carbon for pH-universal hydrogen evolution.Materials Chemistry Frontiers, 2022, 6(23): 3577–3588

[39] Che S, Ta N, Yang F, . Interfacial electronic engineering of NiSe-anchored Ni–N–C composite electrocatalyst for efficient hydrogen evolution.Catalysts, 2022, 12(12): 1525

RIGHTS & PERMISSIONS

Higher Education Press