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

RIGHTS & PERMISSIONS

Higher Education Press