Citation: Qiangqiang SUN, Pengcheng ZHAO, Ruoyu WU, Baoyue CAO. Multistage microporous bifunctional catalyst constructed by P-doped nickel-based sulfide ultra-thin nanosheets for energy-efficient hydrogen production from water electrolysis[J]. Chinese Journal of Inorganic Chemistry, ;2024, 40(6): 1151-1161. doi: 10.11862/CJIC.20230454 shu

Multistage microporous bifunctional catalyst constructed by P-doped nickel-based sulfide ultra-thin nanosheets for energy-efficient hydrogen production from water electrolysis

Shaanxi Key Laboratory of Comprehensive Utilization of Tailings Resources, Shaanxi Engineering Research Center for Mineral Resources Clean & Efficient Conversion and New Materials, Research Centre of Grapheme Technology and Application, School of Chemical Engineering and Modern Materials, Shangluo University, Shangluo, Shaanxi 726000, China

Corresponding author: Baoyue CAO, 231052@slxy.edu.cn
Received Date: 2 December 2023
Revised Date: 27 March 2024

Figures(6)

The multistage microporous electrocatalysts to assist the energy-efficient hydrogen generation from water electrolysis were fabricated on the surface of three-dimensional porous foam (NF) by a one-step hydrothermal synthesis strategy. When the molar ratio of sulfur to phosphorus in the initial mixed solution was 1∶1, an amorphous P-doped nickel-based sulfide (NiSP/NF) electrocatalyst, with Ni₃S₂ and NiPS₃ as the main and secondary crystalline phase, respectively, was obtained by hydrothermal treatment at 120 ℃ for 24 h. Thanks to its unique bi-hierarchy microporous structure composed of interwoven interconnected ultra-thin nanosheets, yielding the nearly 14-fold increased electrochemical active surface area (ECSA), sufficient active sites and interface channels are provided for hydrogen evolution reaction (HER) during water splitting. Meanwhile, benefiting from the lattice defects created by crystalline Ni₃S₂ and the strong electronic interactions with crystalline P doping phases, respectively, the intrinsically catalytic activity of nickel-based electrocatalyst was significantly enhanced. The synergistic effects enable NiSP/NF to exhibit remarkable performances during the whole water splitting, achieving a current density of 10 mA·cm^-2 in 1 mol·L^-1 KOH solution with overpotentials for HER and OER as low as 67 and 212 mV, respectively. Assembled as an electrolyzer for overall water splitting (OWS), a current density of 100 mA·cm^-2 can be achieved only needing a cell voltage of 1.878 V, even at 500 mA·cm^-2 the needed cell voltage was only 2.558 V for NiSP/NF, which is dramatically superior to noble metal catalysts and helpful to improve hydrogen production efficiency for water electrolysis. Particularly, as a bifunctional electrocatalyst, NiSP/NF also exhibited excellent long-term stability and durability, because of less than a 0.03 V cell voltage increase after running a 120-hour chronopotentiometric test at 500 mA·cm^-2.
- P-doping,
- hydrogen evolution reaction,
- oxygen evolution reaction,
- synergistic catalysis
1. [1]
  Bao W W, Yang C M, Ai T T, Zhang J J, Zhou L H, Li Y, Wei X L, Zou X Y, Wang Y. Modulating interfacial charge distribution of NiSe nanoarrays with NiFe-LDH nanosheets for boosting oxygen evolution reaction[J]. Fuel, 2023,332126227. doi: 10.1016/j.fuel.2022.126227
2. [2]
  Vignolo-González H A, Gouder A, Laha S, Duppel V, Carretero-Palacios S, Jiménez-Solano A, Oshima T, Schützendübe P, Lotsch B V. Morphology matters: 0D/2D WO₃ nanoparticle-ruthenium oxide nanosheet composites for enhanced photocatalytic oxygen evolution reaction rates[J]. Adv. Energy Mater., 2023,13(6)2203315. doi: 10.1002/aenm.202203315
3. [3]
  Yuan J J, Huang B J, Lu Y C, Xu H, Qiao Y F, Xu H Q, He G Y, Chen H Q. One-step construction of FeNi LDH/FeNi₂S₄ heterojunctions for boosting electrocatalytic oxygen evolution reaction and hybrid capacitive storage[J]. Appl. Surf. Sci., 2023,610155480. doi: 10.1016/j.apsusc.2022.155480
4. [4]
  Qi J, Zhong X Y, Zeng H Y, Wang C, Liu Z F, Chen J J, Gu L, Hong E, Li M X, Li J, Yang C Z. In-situ study for the elastic structure evolutions of three-dimensional Ir-O framework during the oxygen evolution reaction in acid[J]. Nano Res., 2023,16(7):9022-9030. doi: 10.1007/s12274-023-5668-0
5. [5]
  Zhou Y, Guo Q Y, Luo J B, Wang X Z, Sun F C, Wang C C, Wang S T, Zhang J. The influence of increased content of Ni􀃮 in NiFe LDH via Zn doping on electrochemical catalytic oxygen evolution reaction[J]. Int. J. Hydrog. Energy, 2023,48(13):4984-4993. doi: 10.1016/j.ijhydene.2022.11.075
6. [6]
  Li Y P, Wang W T, Cheng M Y, Qian Q Z, Zhu Y, Zhang G Q. Environmentally benign general synthesis of nonconsecutive carbon-coated RuP₂ porous microsheets as efficient bifunctional electrocatalysts under neutral conditions for energy-saving H₂ production in hybrid water electrolysis[J]. Catal. Sci. Technol., 2022,12(13):4339-4349. doi: 10.1039/D2CY00055E
7. [7]
  Yang J J, Xu L, Zhu W X, Xie M, Liao F, Cheng T, Kang Z H, Shao M W. Rh/RhO_x nanosheets as pH-universal bifunctional catalysts for hydrazine oxidation and hydrogen evolution reactions[J]. J. Mater. Chem. A, 2022,10(4):1891-1898. doi: 10.1039/D1TA09391F
8. [8]
  Yang Y Q, Zhang K, Lin H L, Li X, Chan H C, Yang L C, Gao Q S. MoS₂-Ni₃S₂ heteronanorods as efficient and stable bifunctional electrocatalysts for overall water splitting[J]. ACS Catal, 2017,7(4):2257-2366. doi: 10.1021/acscatal.7b00039
9. [9]
  Stern L A, Feng L G, Song F, Hu X L. Ni₂P as a Janus catalyst for water splitting: The oxygen evolution activity of Ni₂P nanoparticles[J]. Energy Environ. Sci., 2015,8:2347-2351. doi: 10.1039/C5EE01155H
10. [10]
  Deng Y, Xiao Z Y, Wang Z C, Lai J P, Liu X B, Zhang D, Han Y, Li S X, Sun W, Wang L. The rational adjusting of proton-feeding by Pt-doped FeP/C hollow nanorod for promoting nitrogen reduction kinetics[J]. Appl. Catal. B-Environ., 2021,291120047. doi: 10.1016/j.apcatb.2021.120047
11. [11]
  Tang B S, Yang J, Kou Z K, Xu L, Seng H L, Xie Y N, D. Handoko A, Liu X X, Seh Z W, Kawai H, Gong H, Yang W F. Surface-engineered cobalt oxide nanowires as multifunctional electrocatalysts for efficient Zn-air batteries-driven overall water splitting[J]. Energy Storage Mater, 2019,23:1-7.
12. [12]
  Han J, Wu J C, Guan S Q, Xu R, Zhang J, Wang J L, Guan T T, Liu Z C, Li K X. Interference effect of nitrogen-doped CQDs on tailoring nanostructure of CoMoP for improving high-effective water splitting[J]. Electrochim. Acta, 2023,438141595. doi: 10.1016/j.electacta.2022.141595
13. [13]
  Wang J J, Zhang L A, Ren Y M, Wang P. Fluorine-doped nickel oxyhydroxide as a robust electrocatalyst for oxygen evolution reaction[J]. Electrochim. Acta, 2023,437141475. doi: 10.1016/j.electacta.2022.141475
14. [14]
  Che Q J, Li Q, Chen X H, Tan Y, Xu X. Assembling amorphous (Fe-Ni)Co_x-OH/Ni₃S₂ nanohybrids with S-vacancy and interfacial effects as an ultra-highly efficient electrocatalyst: Inner investigation of mechanism for alkaline water-to-hydrogen/oxygen conversion[J]. Appl. Catal. B-Environ, 2020,263118338. doi: 10.1016/j.apcatb.2019.118338
15. [15]
  Miao J W, Xiao F X, Yang H B, Khoo S Y, Chen J Z, Fan Z X, Hsu Y Y, Chen H M, Zhang H, Liu B. Hierarchical Ni-Mo-S nanosheets on carbon fibercloth: A flexible electrode for efficient hydrogen generation in neutral electrolyte[J]. Sci. Adv., 2015,1e1500259. doi: 10.1126/sciadv.1500259
16. [16]
  Gao M R, Liang J X, Zheng Y R, Xu Y F, Jiang J, Gao Q, Li J, Yu S H. An efficient molybdenum disulfide/cobalt diselenide hybrid catalyst for electrochemical hydrogen generation[J]. Nat. Commun., 2015,65982. doi: 10.1038/ncomms6982
17. [17]
  Zhou Y, Li T T, Xi S Q, He C, Yang X G, Wu H J. One-step synthesis of self-standing Ni₃S₂/Ni₂P heteronanorods on nickel foam for efficient electrocatalytic hydrogen evolution over a wide pH range[J]. ChemCatChem, 2018,10:5487-5495. doi: 10.1002/cctc.201801373
18. [18]
  Chen W Z, Liu P Y, Zhang L, Liu Y, Liu Z L, He J L, Wang Y Q. High-efficient and durable overall water splitting performance by interfacial engineering of Fe-doped urchin-like Ni₂P/Ni₃S₂ heterostructure[J]. Chem. Eng. J., 2021,424130434. doi: 10.1016/j.cej.2021.130434
19. [19]
  Zhang X Y, Zhang S, Li J, Wang E. One-step synthesis of well-structured NiS-Ni₂P₂S₆ nanosheets on nickel foam for efficient overall water splitting[J]. J. Mater. Chem. A, 2017,522131. doi: 10.1039/C7TA05285E
20. [20]
  Sun Q Q, Li Y B, Wang J F, Cao B Y, Yu Y, Zhou C S, Zhang G C, Wang Z L, Zhao C. Pulsed electrodeposition of well-ordered nanoporous Cu-doped Ni arrays promotes high efficiency overall hydrazine splitting[J]. J. Mater. Chem. A, 2020,8:21084-21093. doi: 10.1039/D0TA08078K
21. [21]
  Zeng L Y, Sun K A, Wang X B, Liu Y Q, Pan Y, Liu Z, Cao D W, Song Y, Liu S H, Liu C G. Three-dimensional-networked Ni₂P/Ni₃S₂ heteronanoflake arrays for highly enhanced electro-chemical overall-water-splitting activity[J]. Nano Energy, 2018,51:26-36. doi: 10.1016/j.nanoen.2018.06.048
22. [22]
  SUN Q Q, ZHAO P C, WU R Y, CAO B Y, WANG Y M, FAN X M. Porous blade-like cobalt disulfide electrocatalyst boosting hydrazine-assistance energy-efficient hydrogen production[J]. Chinese J. Inorg. Chem., 2023,39(3):422-432.
23. [23]
  Wu Y Y, Liu Y P, Li G D, Zou X, Lian X R, Wang D J, Sun L, Asefa T, Zou X X. Efficient electrocatalysis of overall water splitting by ultrasmall Ni_xCo_3-xS₄ coupled Ni₃S₂ nanosheet arrays[J]. Nano Energy, 2017,35:161-170. doi: 10.1016/j.nanoen.2017.03.024
24. [24]
  Wu Y Y, Li G D, Liu Y P, Yang L, Lian X R, Asefa T, Zou X X. Overall water splitting catalyzed efficiently by an ultrathin nanosheet-built, hollow Ni₃S₂-Based electrocatalyst[J]. Adv. Funct. Mater., 2016,26(27):4839-4847. doi: 10.1002/adfm.201601315
25. [25]
  Hu W, Chen R Q, Xie W, Zou L L, Qin N, Bao D H. CoNi₂S₄ nanosheet arrays supported on nickel foams with ultrahigh capacitance for aqueous asymmetric supercapacitor applications[J]. ACS Appl. Mater. Interfaces, 2014,6(21):19318-19326. doi: 10.1021/am5053784
26. [26]
  Zhang K, Duan Y X, Graham N, Yu W Z. Unveiling the synergy of polymorph heterointerface and sulfur vacancy in NiS/Ni₃S₂ electrocatalyst to promote alkaline hydrogen evolution reaction[J]. Appl. Catal. B-Environ., 2023,323122144. doi: 10.1016/j.apcatb.2022.122144
27. [27]
  Zhang J, Cui R J, Li X A, Liu X H, Huang W. A nanohybrid consisting of NiPS₃ nanoparticles coupled with defective graphene as a pH-universal electrocatalyst for efficient hydrogen evolution[J]. J. Mater. Chem. A, 2017,523536. doi: 10.1039/C7TA07672J
28. [28]
  Li Y B, Tan X, Hocking R K, Bo X, Ren H J, Johannessen B, Smith S C, Zhao C. Implanting Ni-O-VO_x sites into Cu-doped Ni for low-overpotential alkaline hydrogen evolution[J]. Nat. Commun., 2020,112720. doi: 10.1038/s41467-020-16554-5
29. [29]
  Xiao C L, Li Y B, Lu X Y, Zhao C. Bifunctional porous NiFe/NiCo₂O₄/Ni foam electrodes with triple hierarchy and double synergies for efficient whole cell water splitting[J]. Adv. Funct.Mater., 2016,26(20):3515-3523. doi: 10.1002/adfm.201505302
30. [30]
  Zou X, Liu Y P, Li G D, Wu Y Y, Liu D P, Li W, Li H W, Wang D J, Zhang Y, Zou X X. Ultrafast formation of amorphous bimetallic hydroxide films on 3D conductive sulfide nanoarrays for large-current-density oxygen evolution electrocatalysis[J]. Adv. Mater., 2017,291700404. doi: 10.1002/adma.201700404
31. [31]
  Jenjeti R N, Kumar R, Sampath S. Two-dimensional, few-layer NiPS₃ for flexible humidity sensor with high selectivity[J]. J. Mater. Chem. A, 2019,7(24)14545. doi: 10.1039/C9TA03214B
32. [32]
  Zhang J, Wang T, Pohl D, Rellinghaus B, Dong R H, Liu S H, Zhuang X D, Feng X L. Interface engineering of MoS₂/Ni₃S₂ heterostructures for highly enhanced electrochemical overall-water-splitting activity[J]. Angew. Chem. Int. Ed., 2016,128(23):6814-6819. doi: 10.1002/ange.201602237
33. [33]
  Ma L B, Hu Y, Chen R P, Zhu G Y, Chen T, Lv H L, Wang Y R, Liang J, Liu H X, Yan C Z, Zhu H F, Tie Z X, Jin Z, Liu J. Self-assembled ultrathin NiCo₂S₄ nanoflakes grown on Ni foam as high-performance flexible electrodes for hydrogen evolution reaction in alkaline solution[J]. Nano Energy, 2016,24:139-147. doi: 10.1016/j.nanoen.2016.04.024
34. [34]
  Liu Y, Liang X, Gu L, Zhang Y, Li G D, Zou X, Chen J S. Corrosion engineering towards efficient oxygen evolution electrodes with stable catalytic activity for over 6000 h[J]. Nat. Commun., 2018,9:1-10. doi: 10.1038/s41467-017-02088-w
35. [35]
  SHENG Z M, TAO Y R, XU L L, YANG P, WANG W X, WU X C. CoFe‑P catalyst prepared by a facile electrodeposition for high‑efficient oxygen evolution reaction[J]. Chinese J. Inorg. Chem., 2023,39(7):1325-1337.
36. [36]
  Li Q, Wang D W, Han C, Ma X, Lu Q Q, Xing Z C, Yang X R. Construction of amorphous interface in an interwoven NiS/NiS₂ structure for enhanced overall water splitting[J]. J. Mater. Chem. A, 2018,6(18):8233-8237. doi: 10.1039/C8TA01928B
37. [37]
  Lin Y, He L B, Chen T, Zhou D, Wu L, Hou X D, Zheng C B. Cost-effective and environmentally-friendly synthesis of 3D Ni₂P from scrap nickel for highly efficient hydrogen evolution in both acidic and alkaline media[J]. J. Mater. Chem. A, 2018,6(9):4088-4094. doi: 10.1039/C7TA09524D
38. [38]
  Xiao K, Wei J X, Han W K, Liu Z Q. Bimetallic sulfide interfaces: Promoting destabilization of water molecules for overall water splitting[J]. J. Power Sources, 2021,487229408. doi: 10.1016/j.jpowsour.2020.229408
39. [39]
  Gao W, Shi Y Q, Zhang Y F, Zuo L Z, Lu H Y, Huang Y P, Fan W, Liu T X. Molybdenum carbide anchored on graphene nanoribbons as highly efficient all-pH hydrogen evolution reaction electrocatalyst[J]. ACS Sustain. Chem. Eng., 2016,4:6313-6321. doi: 10.1021/acssuschemeng.6b00859
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