Excellent charge separation over NiCo₂S₄/CoTiO₃ nanocomposites improved photocatalytic hydrogen production

Abstract

The rapid migration and separation of photoinduced carriers is a key factor influencing photocatalytic efficiency. Constructing an S-scheme heterojunction is a strategic technique to enhance the separation of photogenerated carriers and boost overall catalytic activity. Herein, a simple physical stirring technique was adopted to successfully fabricate a novel NiCo₂S₄/CoTiO₃ S-scheme heterojunction photocatalyst. Upon exposure to light, the NiCo₂S₄/CoTiO₃-10 specimen demonstrated an outstanding hydrogen evolution rate of 2037.76 μmol·g^–1·h^–1, exceeding twice the rate observed for the pristine NiCo₂S₄ (833.72 μmol·g^–1·h^–1). The experimental outcomes reveal that the incorporation of CoTiO₃ significantly enhances the charge separation and transfer within the system. Concurrently, the formation of the S-scheme mechanism facilitates the separation of carriers while maintaining high redox capabilities. This work introduces an innovative approach to forming S-scheme heterojunctions based on bimetallic sulfides, thereby offering new prospects for the efficient utilization of solar energy.

Graphical abstract

Keywords

NiCo₂S₄ / CoTiO₃ / in situ X-ray photoelectron spectroscopy / S-scheme heterojunction

References

[1] Hai X , Fang L , Xiong M , Zhou X , Wang S , Sun H , Su C , Chen H . Charge density modulation of pyrene-related small molecules by nitrogen heteroatoms precisely regulates photocatalytic generation of hydrogen. ACS Nano, 2023, 17(20): 20570–20579

[2] Zheng X , Song Y , Liu Y , Yang Y , Wu D , Yang Y , Feng S , Li J , Liu W , Shen Y . . ZnIn₂S₄-based photocatalysts for photocatalytic hydrogen evolution via water splitting. Coordination Chemistry Reviews, 2023, 475(15): 214898

[3] Li X , Li Y , Guo X , Jin Z . Design and synthesis of ZnCo₂O₄/CdS for substaitially improved photocatalytic hydrogen production. Frontiers of Chemical Science and Engineering, 2023, 17(5): 606–616

[4] Huang W , Xu F , Li D , Astruc D , Liu X . “On-off” switch for H₂ and O₂ generation from HCOOH resp. H₂O₂. Carbon Energy, 2023, 5(3): e269

[5] Cao Y , Gou H , Zhu P , Jin Z . Ingenious design of CoAl-LDH p-n heterojunction based on CuI as holes receptor for photocatalytic hydrogen evolution. Chinese Journal of Structural Chemistry, 2022, 41(6): 2206079–2206085

[6] Guan C , Liao Y , Xiang Q . Dual-facet engineering of surface carboxyl functionalization and interlayer potassium ions regulation in carbon nitride for enhanced CO₂ photoreduction. Science China Materials, 2024, 679(2): 473–483

[7] Xiao Q , Yang T , Guo X , Jin Z . S-scheme heterojunction constructed by ZnCdS and CoWO₄ nano-ions promotes photocatalytic hydrogen production. Surfaces and Interfaces, 2023, 43: 103577

[8] Li S , Peng S , Li Y . Constructing an open-structured J-type ZnIn₂S₄/In(OH)₃ heterojunction for photocatalytical hydrogen generation. Journal of Physical Chemistry Letters, 2024, 15(19): 5215–5222

[9] Cui E , Hou G , Chen X , Zhang F , Deng Y , Yu G , Li B , Wu Y . In-situ hydrothermal fabrication of Sr₂FeTaO₆/NaTaO₃ heterojunction photocatalyst aimed at the effective promotion of electron-hole separation and visible-light absorption. Applied Catalysis B: Environmental, 2019, 241: 52–65

[10] Zhou Z , Yao H , Wu Y , Li T , Tsubaki N , Jin Z . Synergistic effect of Cu-graphdiyne (C_nH_2n-2)/transition bimetallic tungstate formed S-Scheme heterojunction for enhanced photocatalytic hydrogen evolution. Acta Physico-Chimica Sinica, 2024, 40(10): 2312010

[11] Wang X , Liu B , Ma S , Zhang Y , Wang L , Zhu G , Huang W , Wang S . Induced dipole moments in amorphous ZnCdS catalysts facilitate photocatalytic H₂ evolution. Nature Communications, 2024, 15(1): 2600

[12] Li Y , Li S , Meng L , Peng S . Synthesis of oriented J type ZnIn₂S₄@CdIn₂S₄ heterojunction by controllable cation exchange for enhancing photocatalytic hydrogen evolution. Journal of Colloid and Interface Science, 2023, 650: 266–274

[13] Zhu M , Jiang X , Wang Z , Zhang D , Pu X , Li H , Liu J , Hu H , Guo F , Cai P . Preparation and photocatalytic activity of CoFe₂O₄ nanoparticle modified rod-like Mn_0.3Cd_0.7S photocatalysts with S-scheme heterojunction. Journal of Alloys and Compounds, 2024, 976: 173245

[14] Li Y , Hou Y , Fu Q , Peng S , Hu Y . Oriented growth of ZnIn₂S₄/In(OH)₃ heterojunction by a facile hydrothermal transformation for efficient photocatalytic H₂ production. Applied Catalysis B: Environment and Energy, 2017, 206: 726–733

[15] Zhuang C , Chang Y , Li W , Li S , Xu P , Zhang H , Zhang Y , Zhang C , Gao J , Chen G . . Light-induced variation of lithium coordination environment in g-C₃N₄ nanosheet for highly efficient oxygen reduction reactions. ACS Nano, 2024, 18(6): 5206–5217

[16] Shit S , Jang W , Bolar S , Murmu N , Koo H , Kuila T . Effect of ion diffusion in cobalt molybdenum bimetallic sulfide toward electrocatalytic water splitting. ACS Applied Materials & Interfaces, 2019, 11(24): 21634–21644

[17] Ma L , Hu Y , Chen R , Zhu G , Chen T , Lv H , Wang Y , Liang J , Liu H , Yan C . . Self-assembled ultrathin NiCo₂S₄ nanoflakes grown on ni foam as high-performance flexible electrodes for hydrogen evolution reaction in alkaline solution. Nano Energy, 2016, 24: 139–147

[18] Li F , Xu R , Li Y , Liang F , Zhang D , Fu W , Lv X . N-Doped carbon coated NiCo₂S₄ hollow nanotube as bifunctional electrocatalyst for overall water splitting. Carbon, 2019, 145: 521–528

[19] Zhang L , Zhang J , Yu H , Yu J . Emerging S-scheme photocatalyst. Advanced Materials, 2022, 34(11): 2107668

[20] Wu K , Jiang R , Zhao Y , Mao L , Gu X , Cai X , Zhu M . Hierarchical NiCo₂S₄/ZnIn₂S₄ heterostructured prisms: high-efficient photocatalysts for hydrogen production under visible-light. Journal of Colloid and Interface Science, 2022, 619: 339–347

[21] Xu Y , Mo J , Liu Q , Wang X , Ding S . Self-assembled CoTiO₃ nanorods with controllable oxygen vacancies for the efficient photochemical reduction of CO₂ to CO. Catalysis Science & Technology, 2020, 10(7): 2040–2046

[22] Zhuang C , Li W , Chang Y , Li S , Zhang Y , Li Y , Gao J , Chen G , Kang Z . Coordination environment dominated catalytic selectivity of photocatalytic hydrogen and oxygen reduction over switchable gallium and nitrogen active sites. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2024, 12(10): 5711–5718

[23] Kang E , Kim J . Highly boosted photocatalytic H₂ production from ZnS particles assisted by Cd-Cu co-doping. Journal of Environmental Chemical Engineering, 2023, 11(3): 109833

[24] Li Y , Han P , Hou Y , Peng S , Kuang X . Oriented Zn_mIn₂S_m+3@In₂S₃ heterojunction with hierarchical structure for efficient photocatalytic hydrogen evolution. Applied Catalysis B: Environment and Energy, 2019, 244(5): 604–611

[25] Teng Li T , Noritatsu Tsubaki N , Zhiliang Jin Z . S-scheme heterojunction in photocatalytic hydrogen production. Journal of Materials Science and Technology, 2024, 169(10): 82–104

[26] Xie H , Wang K , Li S , Jin Z . Construction of Co₉S₈/MoS₂/Ni₂P double S-scheme heterojunction for enhanced photocatalytic hydrogen evolution. Surfaces and Interfaces, 2023, 42: 103353

[27] Meng A , Zhou S , Wen D , Han P , Su Y . g-C₃N₄/CoTiO₃ S-scheme heterojunction for enhanced visible light hydrogen production through photocatalytic pure water splitting. Chinese Journal of Catalysis, 2022, 43(10): 2548–2557

[28] Hu Y , Zhang J , Wang D , Sun J , Zhang L , Liu Y , Gao S , Cui Y . Urchin-like NiCo₂S₄ structures synthesized through a one-step solvothermal process for high-performance supercapacitors. Particuology, 2019, 45(4): 66–73

[29] Yang X , Wei S , Ma X , Gao Z , Huang W , Wang D , Liu Z , Wang J . Core-shell CoTiO₃@MnO₂ heterostructure for the photothermal degradation of tetracycline. Journal of Materials Science, 2023, 58(8): 3551–3567

[30] Chen X , Tao H , Jiang Y , Li S , Liu Y , Xie K , Wang Y . P-Doped S vacancy-rich NiCo₂S₄ hollow microspheres for high-performance supercapacitors. Journal of Energy Storage, 2023, 68: 107721

[31] Chen Q , Li H , Wu Z , Li H , Zhu L , Li C , Zhu X , Sun Y . One-step magneto-solvothermal synthesis of porous network NiCo₂S₄ for high-performance supercapacitors. Materials Today. Chemistry, 2023, 30: 101585

[32] Li R , Zhang C , You K , Li B , Bu W , Meng X , Ma B , Ding Y . Molecular confined synthesis of magnetic CoO_x/Co/C hybrid catalyst for photocatalytic water oxidation and CO₂ reduction. Chinese Chemical Letters, 2023, 34(12): 108801

[33] Du G , Fan Y , Jia L , Wang Y , Hao Y , Zhao W , Su Q , Xu B . Sulfur-deficient CoNi₂S₄ nanoparticles-anchored porous carbon nanofibers as bifunctional electrocatalyst for overall water splitting. Frontiers of Chemical Science and Engineering, 2023, 17(11): 1707–1717

[34] Hou T , Chen L , Yang Y , Wang J , Yang T , Rao W . Green and efficient piezocatalytic hydrogen production achieved by modifying SrBi₄Ti₄O₁₅ with CdSe. Journal of Materials Chemistry C: Materials for Optical and Electronic Devices, 2024, 12(14): 5088–5096

[35] Li W , Ma H , Liu Z , Li J , Fang P , Xiong R , Pan C , Wei J . In situ electronic redistribution tuning of ZnIn₂S₄ nanosheets on NiCo₂S₄ hollow tube for boosted photocatalytic hydrogen evolution. Applied Surface Science, 2022, 598: 153801

[36] Jiang K , Iqbal W , Yang B , Rauf M , Ali I , Lu X , Mao Y . Noble metal-free NiCo₂S₄/CN sheet-on-sheet heterostructure for highly efficient visible-light-driven photocatalytic hydrogen evolution. Journal of Alloys and Compounds, 2021, 853: 157284

[37] Bi Z , Guo R , Ji X , Hu X , Wang J , Chen X , Pan W . Direct Z-scheme CoS/g-C₃N₄ heterojunction with NiS co-catalyst for efficient photocatalytic hydrogen generation. International Journal of Hydrogen Energy, 2022, 47(81): 34430–34443

[38] Ma H , Tan Y , Liu Z , Wei J , Xiong R . Construction of CoS_x-ZnIn₂S₄ hollow nanocages derived from metal-organic frameworks for efficient photocatalytic hydrogen production. New Journal of Chemistry, 2021, 45(31): 13860–13868

[39] Ye R , Fang H , Zheng Y , Li N , Wang Y , Tao X . Fabrication of CoTiO₃/g-C₃N₄ hybrid photocatalysts with enhanced H₂ evolution: Z-scheme photocatalytic mechanism insight. ACS Applied Materials & Interfaces, 2016, 8(22): 13879–13889

[40] Zhang L , Wu Y , Tsubaki N , Jin Z . 2D/3D S-scheme heterojunction interface of CeO₂-Cu₂O promotes ordered charge transfer for efficient photocatalytic hydrogen evolution. Acta Physico-Chimica Sinica, 2023, 39(12): 2302051

[41] Yang C , Li X , Jin Z . Square meter lever and durable photocatalytic hydrogen production over manipulating the growth of graphdiyne morphology S-scheme heterojunction. Science China Materials, 2024, 67(2): 493–503

[42] You K , Li B , Li X , Li R , Wu J , Ma B , Ding Y . Efficient photocatalytic hydrogen production over ZnIn₂S₄ by producing sulfur vacancies and coupling with nickel-based polyoxometalate. Chemical Communications, 2023, 59(73): 10972–10975

[43] Fan Z , Guo X , Yang M , Jin Z . Mechanochemically preparation and application of graphdiyne coupled with CdSe nanoparticles for efficient photocatalytic hydrogen production. Chinese Journal of Catalysis, 2022, 43(10): 2708–2719

[44] Hao X , Cui Z , Zhou J , Wang Y , Hu Y , Wang Y , Zou Z . Architecture of high efficient zinc vacancy mediated Z-scheme photocatalyst from metal-organic frameworks. Nano Energy, 2018, 52: 105–116

[45] Jin F , Yang B , Wang X , Li T , Tsubaki N , Jin Z . Facilitating efficient photocatalytic hydrogen evolution via enhanced carrier migration at MOF-on-MOF S-scheme heterojunction interfaces through a graphdiyne (C_nH_2n−2) electron transport layer. Chinese Journal of Structural Chemistry, 2023, 42(12): 100198

[46] Zhang M , Li K , Hu C , Ma K , Sun W , Huang X , Ding Y . Co nanoparticles modified phase junction CdS for photoredox synthesis of hydrobenzoin and hydrogen evolution. Chinese Journal of Catalysis, 2023, 47: 254–264

[47] Chen Y , Chuang C , Qin Z , Shen S , Doane T , Burda C . Electron-transfer dependent photocatalytic hydrogen generation over cross-linked CdSe/TiO₂ type-II heterostructure. Nanotechnology, 2017, 28(8): 084002

[48] Liu J , Yang X , Guo X , Jin Z . Flowered molybdenum base trimetallic oxide decorated by CdS nanorod construct S-scheme heterojunctions for efficient photocatalytic hydrogen evolution. Journal of Materials Science and Technology, 2024, 196: 112–124

[49] Cheng C , He B , Fan J , Cheng B , Cao S , Yu J . An inorganic/organic S-scheme heterojunction H₂-production photocatalyst and its charge transfer mechanism. Advanced Materials, 2021, 33(22): 2100317

[50] Jin Z , Li H , Li J . Efficient photocatalytic hydrogen evolution over graphdiyne boosted with a cobalt sulfide formed S-scheme heterojunctions. Chinese Journal of Catalysis, 2022, 43(2): 303–315

Competing interests

The authors declare that they have no competing interests.

Acknowledgements

This work was financially supported by the Fundamental Research Funds for the Central Universities of the North Minzu University (Grant No. 2023ZRLG20); Innovative Team for Transforming Waste Cooking Oil into Clean Energy and High Value-Added Chemicals; Ningxia Low-Grade Resource High Value Utilization and Environmental Chemical Integration Technology Innovation Team Project. We would also like to express our gratitude to the 2023 Ningxia Hui Autonomous Region Young Scientific and Technological Talents Promotion Project for the financial support.

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