Enhanced photocatalytic N₂ fixation using KNbO₃/Bi₄O₅Br₂ type II heterojunction

Abstract

The fabrication of heterojunction catalysts is an effective strategy to enhance charge separation efficiency, thus boosting the performance of photocatalysts. This work presents the synthesis and investigation of a novel KNbO₃/Bi₄O₅Br₂ heterostructure catalyst for photocatalytic N₂–to–NH₃ conversion under light illumination. While morphology analysis revealed KNbO₃ microcubes embedded within Bi₄O₅Br₂ nanosheets, the composite exhibited no significant improvement in specific surface area or optical property compared to Bi₄O₅Br₂ due to the relatively wide band gap and low surface area of KNbO₃. The main contribution lies in the enhanced separation efficiency of photogenerated electrons and holes. Besides, the band structure analysis suggests that KNbO₃ and Bi₄O₅Br₂ exhibit suitable band potentials to form a type II heterojunction. Benefiting from the higher Fermi level of KNbO₃ than Bi₄O₅Br₂, the electron drift at the contact region thus occurs and leads to the formation of a built-in electric field with the direction from KNbO₃ to Bi₄O₅Br₂, accelerating electron migration and improving the operational efficiency of the photocatalysts. Consequently, the KNbO₃/Bi₄O₅Br₂ catalyst shows an increased photoactivity, achieving an NH₃ generation rate 1.78 and 1.58 times those of KNbO₃ and Bi₄O₅Br₂, respectively. This work may offer valuable insights for the design and synthesis of heterojunction composite photocatalysts.

Key words： KNbO₃/Bi₄O₅Br₂; heterojunction; photocatalytic N₂ fixation; charge separation

Competing interests

The authors declare that they have no competing interests.

Acknowledgement

The work was financially supported by the National Natural Science Foundation of China (Grant No. 22172144) and the Key Research and Development Program of Zhejiang Province (Grant No. 2023C03148).

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11705-024-2424-2 and is accessible for authorized users.

References

1 Cherkasov N , Ibhadon A O , Fitzpatrick P . A review of the existing and alternative methods for greener nitrogen fixation. Chemical Engineering and Processing, 2015, 90: 24–33

2 Liao W R , Qi L , Wang Y L , Qin J Y , Liu G Y , Liang S J , He H Y , Jiang L L . Interfacial engineering promoting electrosynthesis of ammonia over Mo/phosphotungstic acid with high performance. Advanced Functional Materials, 2021, 31(22): 2009151

3 Liu D , Yan H P , Lin J W , Lu S W , Xie Y Q , Peng X B , Liang S J , Jiang L L . Regulation of cerium species in Keggin structure of phosphotungstic acid for efficient nitrogen electroreduction to ammonia. Chemical Engineering Science, 2024, 283: 119448

4 Fang H H , Liu D , Luo Y , Zhou Y L , Liang S J , Wang X Y , Lin B Y , Jiang L L . Challenges and opportunities of Ru-based catalysts toward the synthesis and utilization of ammonia. ACS Catalysis, 2022, 12(7): 3938–3954

5 Ren T L , Sheng Y W , Wang M Z , Ren K L , Wang L L , Xu Y . Recent advances of Cu-based materials for electrochemical nitrate reduction to ammonia. Chinese Journal of Structural Chemistry, 2022, 41(12): 2212089–2212106

6 Chen S , Liu D , Peng T . Fundamentals and recent progress of photocatalytic nitrogen-fixation reaction over semiconductors. Solar RRL, 2021, 5(2): 2000487

7 Li X J , Zhao C R , Wang J F , Zhang J Y , Wu Y , He Y M . Cu-doped Bi/Bi₂WO₆ catalysts for efficient N₂ fixation by photocatalysis. Frontiers of Chemical Science and Engineering, 2023, 17(10): 1412–1422

8 Qing X , Yue X P , Feng J Q , Liu J X , Zhang X C , Zhang C M , Wang Y W , Wang Y F , Lv Z P , Li R . . Facile synthesis of 2D Bi₄O₅Br₂/2D thin layer-Ti₃C₂ for improved visible-light photocatalytic hydrogen evolution. Journal of Solid State Chemistry, 2020, 289: 121470

9 Di J , Li Y , Zhang Y , Liu Y L , Wang S W , Wu Y , Li H M , Xia J . Layer-contacted graphene-like BN/ultrathin Bi₃O₄Br stacking for boosting photocatalytic molecular oxygen activation. Transactions of Tianjin University, 2023, 29(3): 235–245

10 Miao Z R , Wang Q L , Zhang Y F , Meng L P , Wang X X . In situ construction of S-scheme AgBr/BiOBr heterojunction with surface oxygen vacancy for boosting photocatalytic CO₂ reduction with H₂O. Applied Catalysis B: Environmental, 2022, 301: 120802

11 Zhao C R , Li X J , Yue L , Ren X J , Yuan S D , Zeng Z H , He Y M . Fabrication of novel BiPO₄/Bi₄O₅Br₂ heterojunctions for improving photoactivity in N₂ fixation and dye degradation. Materials Research Bulletin, 2023, 167: 112377

12 Chawla A , Sudhaik A , Sonu P , Raizada T , Ahamad Q V , Le V H , Nguyen S , Thakur A K , Mishra R , Selvasembian P . Bi-rich Bi_xO_yBr_z-based photocatalysts for energy conversion and environmental remediation: a review. Coordination Chemistry Reviews, 2023, 491: 215246

13 Zhang K F , Chen H X , Pei W B , Dai H X , Li J S , Zhu Y F . Enhanced photocatalytic performance of Bi₄O₅Br₂ with three-dimensionally ordered macroporous structure for phenol removal. Nano Research, 2023, 16(7): 1–11

14 Chachvalvutikul A , Luangwanta T , Inceesungvorn B , Kaowphong S . Bismuth-rich oxyhalide (Bi₇O₉I₃–Bi₄O₅Br₂) solid-solution photocatalysts for the degradation of phenolic compounds under visible light. Journal of Colloid and Interface Science, 2023, 641: 595–609

15 VadivelSGnanasekaranLBalasubramanianN. Revealing the charge transfer mechanism in Er ion-doped Bi₄O₅Br₂/g-C₃N₅ nanocomposite for efficient photocatalytic degradation of antibiotic tetracycline. Carbon Letters, 2023: 1–10

16 Wang B , Zhao J Z , Chen H L , Weng Y X , Tang H , Chen Z R , Zhu W S , She Y B , Xia J X , Li H M . Unique Z-scheme carbonized polymer dots/Bi₄O₅Br₂ hybrids for efficiently boosting photocatalytic CO₂ reduction. Applied Catalysis B: Environmental, 2021, 293: 120182

17 Yi F T , Ma J Q , Lin C W , Wang L Y , Zhang H N , Qian Y X , Zhang K F . Insights into the enhanced adsorption/photocatalysis mechanism of a Bi₄O₅Br₂/g-C₃N₄ nanosheet. Journal of Alloys and Compounds, 2020, 821: 153557

18 Zhao C R , Li X J , Yue L , Ren X J , Yuan S D , Zeng Z H , Hu X , Wu Y , He Y M . Bi₄O₅Br₂ nanoflower and CdWO₄ nanorod heterojunctions for photocatalytic synthesis of ammonia. ACS Applied Nano Materials, 2023, 6(17): 15709–15720

19 Chen X , Li Y , Wu Z , Xu X , Zhu W , Gao X . Bi₄O₅Br₂ anchored on Ti₃C₂ MXene with ohmic heterojunction in photocatalytic NH₃ production: insights from combined experimental and theoretical calculations. Journal of Colloid and Interface Science, 2021, 602: 553–562

20 Wang J , Zhao B , Wang C . TiO₂/KNbO₃ nanocomposite for enhanced humidity sensing performance. Sensors and Actuators. A, Physical, 2023, 349: 114057

21 Li J , Wang R , Bai Z W , Wang G , Zhang X M , Yuan J S , Zhou J Y , Xie E R , Pan X J . Enhanced performance of photoelectrochemical type ultraviolet photodetector by constructing a KNbO₃/ZnO heterojunction. Sensors and Actuators. A, Physical, 2023, 358: 114434

22 Fisher J G , Thuan U T , Farooq M U , Chandrasekaran G , Jung Y D , Hwang E C , Lee J J , Lakshmanan V K . Prostate cancer cell-specific cytotoxicity of sub-micron potassium niobate powder. Journal of Nanoscience and Nanotechnology, 2018, 18(5): 3141–3147

23 Zhang H , Huang Y , Li G , Wang G , Fang D , Song Y , Wang J . Preparation of Er³⁺: Y₃Al₅O₁₂/WO₃-KNbO₃ composite and application in treatment of methamphetamine under ultrasonic irradiation. Ultrasonics Sonochemistry, 2017, 35: 478–488

24 Zhang T T , Zhao K , Yu J G , Jin J , Qi Y , Li H Q , Hou X J , Liu G . Photocatalytic water splitting for hydrogen generation on cubic, orthorhombic, and tetragonal KNbO₃ microcubes. Nanoscale, 2013, 5(18): 8375–8383

25 Huang R , Cai W , Zhang H , Wang Z H , Zhang Q , Gao R L , Chen G , Deng X L , Lei X , Dong J L . . Highly synergistic and polarized KNbO₃/WO₃ heterojunction for piezo-photocatalytic degradation of organic pollutant. Journal of Environmental Chemical Engineering, 2023, 11(3): 110177

26 Shi H F , Zhang C L , Zhou C P , Chen G Q . Conversion of CO₂ into renewable fuel over Pt-gC₃N₄/KNbO₃ composite photocatalyst. RSC Advances, 2015, 5(113): 93615–93622

27 Zhang W Q , Xing P X , Zhang J Y , Chen L , Yang J Y , Hu X , Zhao L H , Wu Y , He Y M . Facile preparation of novel nickel sulfide modified KNbO₃ heterojunction composite and its enhanced performance in photocatalytic nitrogen fixation. Journal of Colloid and Interface Science, 2021, 590: 548–560

28 Xing P X , Zhang W Q , Chen L , Dai X Q , Zhang J Y , Zhao L H , He Y M . Preparation of a NiO/KNbO₃ nanocomposite via a photodeposition method and its superior performance in photocatalytic N₂ fixation. Sustainable Energy & Fuels, 2020, 4(3): 1112–1117

29 Li R , Cai Y Y , Liang S Y , Aihemaiti A , Zhang Z T . Improved piezocatalytic activity with Ag₂O@KNbO₃: mechanisms and performance in organic pollutant degradation. Applied Surface Science, 2024, 644: 158811

30 Wang C Y , Hu C , Chen F , Li H T , Zhang Y H , Ma T Y , Huang H W . Polar layered bismuth-rich oxyhalide piezoelectrics Bi₄O₅X₂ (X = Br, I): efficient piezocatalytic pure water splitting and interlayer anion-dependent activity. Advanced Functional Materials, 2023, 33(29): 2301144

31 Chen L , Wang J F , Li X T , Zhang J Y , Zhao C R , Hu X , Lin H J , Zhao L H , Wu Y , He Y M . Facile preparation of Ag₂S/KTa_0.5Nb_0.5O₃ heterojunction for enhanced performance in catalytic nitrogen fixation via photocatalysis and piezo-photocatalysis. Green Energy & Environment, 2023, 8(6): 1630–1643

32 Xing P X , Wu S J , Chen Y J , Chen P F , Hu X , Lin H J , Zhao L H , He Y M . New application and excellent performance of Ag/KNbO₃ nanocomposite in photocatalytic NH₃ synthesis. ACS Sustainable Chemistry & Engineering, 2019, 7(14): 12408–12418

33 Guo Y Y , Zhang W B , Yang Y N , Wang C . The photocatalytic efficiency enhancement of Bi₄O₅Br₂ by Li-intercalation for NO removal. Journal of Physics and Chemistry of Solids, 2021, 159: 110256

34 Sun J , Li X , Li J , Mu M , Yin X . Fabrication of Bi₄O₅Br₂-decorated rod-like MOF-derived MoS₂ hierarchical heterostructures for boosting photocatalytic CO₂ reduction. Colloids and Surfaces. A, Physicochemical and Engineering Aspects, 2022, 653: 129940

35 Chen L , Dai X Q , Li X J , Wang J F , Chen H F , Hu X , Lin H J , He Y M , Wu Y , Fan M H . A novel Bi₂S₃/KTa_0.75Nb_0.25O₃ nanocomposite with high efficiency for photocatalytic and piezocatalytic N₂ fixation. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2021, 9(22): 13344–13354

36 Schabbach L M , Santos B C D , Bortoli L S D , Fredel M C , Henriques B . Application of Kubelka-Munk model on the optical characterization of translucent dental zirconia. Materials Chemistry and Physics, 2021, 258: 123994

37 Zhang Y , Pan H , Zhang F . Solvothermal synthesis of CDs/Bi₄O₅Br₂ nanocomposites with improved visible-light photocatalytic ciprofloxacin (CIP) decontamination. Materials Letters, 2019, 251: 114–117

38 Scaife D E . Oxide semiconductors in photoelectrochemical conversion of solar energy. Solar Energy, 1980, 25(1): 41–54

39 Yuan S D , Wang J F , Zhao C R , Yue L , Ren X J , Zeng Z H , Hu X , Wu Y , He Y M . S-scheme Bi₂O₃/CdMoO₄ hybrid with highly efficient charge separation for photocatalytic N₂ fixation and tetracycline degradation: fabrication, catalytic optimization, physicochemical studies. Separation and Purification Technology, 2023, 325: 124665

40 Ren X J , Wang J F , Yuan S D , Zhao C R , Yue L , Zeng Z H , He Y M . Decoration of CdMoO₄ micron polyhedron with Pt nanoparticle and their enhanced photocatalytic performance in N₂ fixation and water purification. Frontiers of Chemical Science and Engineering, 2023, 17(12): 1949–1961

41 Wang Y , Li H , Lin Q Y , Zhao J W , Fang X , Wen N , Zhang Z Z , Ding Z X , Yuan R S , Huang X H , Long J . Nanoscale 0D/1D heterojunction of MAPbBr₃/COF toward efficient LED-driven S–S coupling reactions. ACS Catalysis, 2023, 13(23): 15493–15504

42 Wei Y C , Zhang Q Q , Zhou Y , Ma X F , Wang L L , Wang Y J , Sa R J , Long J L , Fu X Z , Yuan R S . Noble-metal-free plasmonic MoO_3‒x-based S-scheme heterojunction for photocatalytic dehydrogenation of benzyl alcohol to storable H₂ fuel and benzaldehyde. Chinese Journal of Catalysis, 2022, 43(10): 2665–2677

43 Su B , Huang H W , Ding Z X , Roeffaers M B J , Wang S B , Long J L . S-scheme CoTiO₃/Cd_9.51Zn_0.49S₁₀ heterostructures for visible-light driven photocatalytic CO₂ reduction. Journal of Materials Science and Technology, 2022, 124: 164–170

44 Lin M , Luo M L , Liu Y Z , Shen J N , Long J L , Zhang Z Z . 1D S-scheme heterojunction of urchin-like SiC-W₁₈O₄₉ for enhancing photocatalytic CO₂ reduction. Chinese Journal of Catalysis, 2023, 50(7): 239–248

45 Zhao J W , Liu F K , Wang W J , Wang Y , Wen N , Zhang Z Z , Dai W X , Yuan R S , Ding Z X , Long J L . S-scheme-heterojunction LaNiO₃/CdLa₂S₄ photocatalyst for solar-driven CO₂-to-CO conversion. ACS Applied Nano Materials, 2023, 6(10): 8927–8936

46 Ray A , Sultana S , Tripathy S P , Parida K . Aggrandizing the photoactivity of ZnO nanorods toward N₂ reduction and H₂ evolution through facile in situ coupling with Ni_xP_y. ACS Sustainable Chemistry & Engineering, 2021, 9(18): 6305–6317

47 ZhaoY XShiRBianX NZhouCZhaoY FZhangSWuFWaterhouseG I NWuL ZTungC H, . Ammonia detection methods in photocatalytic and electrocatalytic experiments: how to improve the reliability of NH₃ production rates? Advanced Science, 2019, 6(8): 1802109

48 Gao X , Wen Y J , Qu D , An L , Luan S L , Jiang W S , Zong X P , Liu X Y , Sun Z C . Interference effect of alcohol on Nessler’s reagent in photocatalytic nitrogen fixation. ACS Sustainable Chemistry & Engineering, 2018, 6(4): 5342–5348

49 ZhaoC RYueLYuanS DRenX JZengZ HHuXZhaoL HWuYHeY M. Enhanced photocatalytic N₂ fixation and water purification using Bi/ZnSnO₃ composite: mechanistic insights and novel applications. Journal of Industrial and Engineering Chemistry, 2024

50 Zhang L L , Ding L X , Chen G F , Yang X F , Wang H H . Ammonia synthesis under ambient conditions: selective electroreduction of dinitrogen to ammonia on black phosphorus nanosheets. Angewandte Chemie International Edition, 2019, 58(9): 2612–2616