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Oxygen doping and hollow structure-mediated effects to enable rapid electron transfer during photocatalytic hydrogen peroxide production

氧掺杂和中空结构介导效应在高效光催化过氧化氢 生产中实现快速电子转移

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Abstract

The photocatalytic production of hydrogen peroxide using solar energy is an environment-friendly solution to the energy crisis, but its low efficiency hinders its scale-up feasibility. In this work, a hollow core-shell structure OCN@In2S3 composite photocatalyst was constructed by growing In2S3 ultrathin nanosheets on the surface of O-doped hollow g-C3N4 nanospheres using a two-step hydrothermal method. The hollow structure provided a high specific surface area and enhanced light absorption. O doping increased the number of active sites, and the heterojunction promoted the rapid separation and transfer of photogenerated carriers. Under visible light irradiation, the H2O2 yield of OCN@In2S3 reached 632.5 µmol h−1 g−1, which was 5.7 times higher than that of g-C3N4 and 12.3 times that of In2S3, as well as higher than most g-C3N4-based photocatalysts. Quenching experiments and electron paramagnetic resonance spectroscopy showed that ·O2−was an intermediate product formed during photocatalytic H2O2 generation. The reaction primarily followed a two-step single-electron pathway. The Koutecky-Levich diagram confirmed that the synthesized OCN@In2S3 maintained a high two-electron ORR selectivity during the catalytic reaction (n = 1.67). The photocatalytic mechanism was elucidated by photoluminescence, electrochemical impedance spectroscopy, and ultraviolet photoelectron spectro-scopy, which confirmed that OCN@In2S3 inhibited the recombination of photogenerated carriers. This work provides a simple and attractive strategy for developing highly active energy-conversion photocatalysts.

摘要

因其安全、绿色、低成本的特点, 利用太阳能光催化生产过氧 化氢是解决能源危机的环境友好型方案, 但其效率低下, 严重阻碍了其 规模化可行性. 在这项工作中, 通过使用简单的两步水热法在O掺杂的 空心g-C3N4纳米球表面生长In2S3超薄纳米片, 成功构建了空心核壳结 构OCN@In2S3复合光催化剂. 独特的中空结构提供了更大的比表面积, 增强了光吸收. O掺杂增加了活性位点的数量, 异质结的存在促进了光 生载流子的快速分离和转移. 在可见光照射下, OCN@In2S3的H2O2产率 达到632.5 µmol h−1 g−1, 是普通g-C3N4的5.7倍, 是In2S3的12.3倍, 高于大 多数g-C3N4基光催化剂. 淬灭实验和电子顺磁共振光谱表明, ·O2− 是光 催化产生H2O2的中间产物, 并且反应过程主要遵循两步单电子反应路 径. Koutecky–Levich图证实了合成的OCN@In2S3在催化反应中保持了 较高的两电子ORR选择性(n = 1.67). 通过光致发光、电化学阻抗谱和 紫外光电子能谱等表征手段阐明了可能的光催化机理, 证实了 OCN@In2S3有效抑制光生载流子的复合. 这项工作为开发高活性的能 量转换光催化剂提供了一种简单而有吸引力的策略.

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References

  1. Xu Z, Gong S, Ji W, et al. Photocatalysis coupling hydrogen peroxide synthesis and in-situ radical transform for tetracycline degradation. Chem Eng J, 2022, 446: 137009

    Article  CAS  Google Scholar 

  2. Lin S, Wang Q, Huang H, et al. Piezocatalytic and photocatalytic hydrogen peroxide evolution of sulfide solid solution nano-branches from pure water and air. Small, 2022, 18: e2200914

    Article  Google Scholar 

  3. Jiang Z, Zhang Y, Zhang L, et al. Effect of calcination temperatures on photocatalytic H2O2-production activity of ZnO nanorods. Chin J Catal, 2022, 43: 226–233

    Article  CAS  Google Scholar 

  4. Wang L, Zhang J, Zhang Y, et al. Inorganic metal-oxide photocatalyst for H2O2 production. Small, 2022, 18: e2104561

    Article  Google Scholar 

  5. Che H, Gao X, Chen J, et al. Iodide-induced fragmentation of polymerized hydrophilic carbon nitride for high-performance quasi-homogeneous photocatalytic H2O2 production. Angew Chem Int Ed, 2021, 60: 25546–25550

    Article  CAS  Google Scholar 

  6. Hu J, Yang T, Chen J, et al. Efficient solar-driven H2O2 synthesis in-situ and sustainable activation to purify water via cascade reaction on ZnIn2S4-based heterojunction. Chem Eng J, 2022, 430: 133039

    Article  CAS  Google Scholar 

  7. Xu Y, Liao J, Zhang L, et al. Dual sulfur defect engineering of Z-scheme heterojunction on Ag-CdS1−x@ZnIn2S4−x hollow core-shell for ultra-efficient selective photocatalytic H2O2 production. J Colloid Interface Sci, 2023, 647: 446–455

    Article  CAS  Google Scholar 

  8. Du R, Xiao K, Li B, et al. Controlled oxygen doping in highly dispersed Ni-loaded g-C3N4 nanotubes for efficient photocatalytic H2O2 production. Chem Eng J, 2022, 441: 135999

    Article  CAS  Google Scholar 

  9. Chen L, Chen C, Yang Z, et al. Simultaneously tuning band structure and oxygen reduction pathway toward high-efficient photocatalytic hydrogen peroxide production using cyano-rich graphitic carbon nitride. Adv Funct Mater, 2021, 31: 2105731

    Article  CAS  Google Scholar 

  10. Su L, Wang P, Ma X, et al. Regulating local electron density of iron single sites by introducing nitrogen vacancies for efficient photo-fenton process. Angew Chem Int Ed, 2021, 60: 21261–21266

    Article  CAS  Google Scholar 

  11. Salehi Ghalehsefid E, Ghorbani Jahani Z, Aliabadi A, et al. TiO2 nanotube/ZnIn2S4 nanoflower composite with step-scheme heterojunction for efficient photocatalytic H2O2 production and organic dye degradation. J Environ Chem Eng, 2023, 11: 110160

    Article  CAS  Google Scholar 

  12. Wang K, Li Y, Shi H, et al. Optimizing oxygen and intermediate HOO* adsorption of Cu-Pd alloy cocatalyst for boosting photocatalytic H2O2 production of BiVO4. Adv Sustain Syst, 2022, 6: 2200144

    Article  CAS  Google Scholar 

  13. Liu M, Xing Z, Zhao H, et al. An efficient photo Fenton system for in-situ evolution of H2O2 via defective iron-based metal organic frame-work@ZnIn2S4 core-shell Z-scheme heterojunction nanoreactor. J Hazard Mater, 2022, 437: 129436

    Article  CAS  Google Scholar 

  14. Feng C, Tang L, Deng Y, et al. Synthesis of leaf-vein-like g-C3N4 with tunable band structures and charge transfer properties for selective photocatalytic H2O2 evolution. Adv Funct Mater, 2020, 30: 2001922

    Article  CAS  Google Scholar 

  15. Shiraishi Y, Ueda Y, Soramoto A, et al. Photocatalytic hydrogen peroxide splitting on metal-free powders assisted by phosphoric acid as a stabilizer. Nat Commun, 2020, 11: 3386

    Article  CAS  Google Scholar 

  16. Xie B, Chen D, Li N, et al. Lead-free Cs3Bi2Br9 perovskite in-situ growth on 3D flower-like g-C3N4 microspheres to improve photocatalytic performance. Chem Eng J, 2023, 452: 139662

    Article  CAS  Google Scholar 

  17. Liu W, Wang P, Chen J, et al. Unraveling the mechanism on ultrahigh efficiency photocatalytic H2O2 generation for dual-heteroatom incorporated polymeric carbon nitride. Adv Funct Mater, 2022, 32: 2205119

    Article  CAS  Google Scholar 

  18. Xu X, Wang R, Sun X, et al. Layered perovskite compound NaLaTiO4 modified by nitrogen doping as a visible light active photocatalyst for water splitting. ACS Catal, 2020, 10: 9889–9898

    Article  CAS  Google Scholar 

  19. Xu Y, Guo M, Ge C, et al. Cu single atoms/O doping g-C3N4 mediated photocatalytic activation of peroxymonosulfate for ultrafast carbamazepine removal via high 1O2 yield. Appl Surf Sci, 2023, 640: 158290

    Article  CAS  Google Scholar 

  20. Chang S, Yu J, Wang R, et al. LaTaON2 mesoporous single crystals for efficient photocatalytic water oxidation and Z-scheme overall water splitting. ACS Nano, 2021, 15: 18153–18162

    Article  CAS  Google Scholar 

  21. Yu J, Chang S, Shi L, et al. Single-crystalline Bi2YO4Cl with facet-aided photocarrier separation for robust solar water splitting. ACS Catal, 2023, 13: 3854–3863

    Article  CAS  Google Scholar 

  22. Cao J, Wang H, Zhao Y, et al. Phosphorus-doped porous carbon nitride for efficient sole production of hydrogen peroxide via photocatalytic water splitting with a two-channel pathway. J Mater Chem A, 2020, 8: 3701–3707

    Article  CAS  Google Scholar 

  23. Li X, Ye F, Zhang H, et al. Ternary rGO decorated W18O49@g-C3N4 composite as a full-spectrum-responded Z-scheme photocatalyst for efficient photocatalytic H2O2 production and water disinfection. J Environ Chem Eng, 2023, 11: 110329

    Article  CAS  Google Scholar 

  24. Xia Y, Zhu B, Qin X, et al. Zinc porphyrin/g-C3N4 S-scheme photo-catalyst for efficient H2O2 production. Chem Eng J, 2023, 467: 143528

    Article  CAS  Google Scholar 

  25. Shi H, Li Y, Wang X, et al. Selective modification of ultra-thin g-C3N4 nanosheets on the (110) facet of Au/BiVO4 for boosting photocatalytic H2O2 production. Appl Catal B-Environ, 2021, 297: 120414

    Article  CAS  Google Scholar 

  26. Jiang Z, Long Q, Cheng B, et al. 3D ordered macroporous sulfur-doped g-C3N4/TiO2 S-scheme photocatalysts for efficient H2O2 production in pure water. J Mater Sci Tech, 2023, 162: 1–10

    Article  Google Scholar 

  27. Zhao B, Huang Y, Liu D, et al. Integrating photocatalytic reduction of CO2 with selective oxidation of tetrahydroisoquinoline over InP-In2O3 Z-scheme p-n junction. Sci China Chem, 2020, 63: 28–34

    Article  CAS  Google Scholar 

  28. Chen H, Xing Y, Liu S, et al. Mechanistic insights into efficient photocatalytic H2O2 production of 2D/2D g-C3N4/In2S3 photocatalyst by tracking charge flow direction. Chem Eng J, 2023, 462: 142038

    Article  CAS  Google Scholar 

  29. Liu Y, Chen C, He Y, et al. Rich indium-vacancies In2S3 with atomic p-n homojunction for boosting photocatalytic multifunctional properties. Small, 2022, 18: e2201556

    Article  Google Scholar 

  30. Liu Y, Yu H, Cui X, et al. Synthesis of N-C3N4/Cu/Cu2O: New strategy to tackle the problem of Cu2O photocorrosion with the help of band engineering. Separ Purif Tech, 2022, 282: 119871

    Article  CAS  Google Scholar 

  31. Ren J, Zheng Y, Lin H, et al. Near-infrared light-activated g-C3N4 with effective n → π* electron transition for H2O2 production. Appl Surf Sci, 2023, 638: 158053

    Article  CAS  Google Scholar 

  32. Wan Y, Ma L, Wang T, et al. A g-C3N4/Fe-MOF heterojunction intercalated graphene oxide membrane with persulfate activation self-cleaning property for efficient crude oil in water emulsion separation. J Membrane Sci, 2023, 685: 121922

    Article  CAS  Google Scholar 

  33. Wang Y, Wang H, Chen F, et al. Facile synthesis of oxygen doped carbon nitride hollow microsphere for photocatalysis. Appl Catal B-Environ, 2017, 206: 417–425

    Article  CAS  Google Scholar 

  34. Liu X, Wang S, Yang F, et al. Construction of Au/g-C3N4/ZnIn2S4 plasma photocatalyst heterojunction composite with 3D hierarchical microarchitecture for visible-light-driven hydrogen production. Int J Hydrogen Energy, 2022, 47: 2900–2913

    Article  CAS  Google Scholar 

  35. Hu C, Chu YC, Wang MS, et al. Rapid synthesis of g-C3N4 spheres using microwave-assisted solvothermal method for enhanced photo-catalytic activity. J Photochem Photobiol A-Chem, 2017, 348: 8–17

    Article  CAS  Google Scholar 

  36. Cui Y. In-situ synthesis of C3N4/CdS composites with enhanced photocatalytic properties. Chin J Catal, 2015, 36: 372–379

    Article  CAS  Google Scholar 

  37. Yang Y, Zeng G, Huang D, et al. Molecular engineering of polymeric carbon nitride for highly efficient photocatalytic oxytetracycline degradation and H2O2 production. Appl Catal B-Environ, 2020, 272: 118970

    Article  CAS  Google Scholar 

  38. Zhang X, Yu J, Macyk W, et al. C3N4/PDA S-scheme heterojunction with enhanced photocatalytic H2O2 production performance and its mechanism. Adv Sustain Syst, 2022, 7: 2200113

    Article  Google Scholar 

  39. Hu J, Li X, Qu J, et al. Bifunctional honeycomb hierarchical structured 3D/3D ReS2/ZnIn2S4-Sv heterojunction for efficient photocatalytic H2-evolution integrated with biomass oxidation. Chem Eng J, 2023, 453: 139957

    Article  CAS  Google Scholar 

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Acknowledgements

This work was supported by Hainan Province Science and Technology Special Fund (ZDYF2022SHFZ094), Haikou City Science and Technology Plan Project (2023-012), the National Natural Science Foundation of China (52100038), Hainan Provincial Natural Science Foundation of China (420RC530), the Scientific Research Project of Hainan Higher Education Institutions (Hnky2023-9), and Hainan University Research Start-up Fund (kyqd(zr)22185).

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Authors and Affiliations

  1. Key Laboratory of Agro-Forestry Environmental Processes and Ecological Regulation of Hainan Province, School of Ecology and Environment, Hainan University, Haikou, 570228, China

    Yandong Xu  (徐燕东), Wanyu Tai  (台婉玉), Zhirui Wang  (王沚睿), Linlin Zhang  (张琳琳), Dexin Wang  (王德欣) & Jianjun Liao  (廖建军)

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  1. Yandong Xu  (徐燕东)
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  2. Wanyu Tai  (台婉玉)
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  3. Zhirui Wang  (王沚睿)
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  4. Linlin Zhang  (张琳琳)
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  5. Dexin Wang  (王德欣)
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  6. Jianjun Liao  (廖建军)
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Contributions

Author contributions Xu Y performed the experiments and wrote the paper; Tai W and Wang Z processed and analyzed the data; Zhang L conceived the idea and did the mechanism analysis; Wang D and Liao J guided the experiment arrangement and revised the manuscript. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Linlin Zhang  (张琳琳), Dexin Wang  (王德欣) or Jianjun Liao  (廖建军).

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Conflict of interest The authors declare that they have no conflict of interest.

Additional information

Supplementary information Experimental details and supporting data are available in the online version of the paper.

Yandong Xu is a doctoral student at the School of Ecology and Environment, Hainan University. His main research direction is the preparation of hollow core-shell structure composite photocatalysts and their hydrogen peroxide production performance.

Linlin Zhang is an associate professor at Hainan University. She received a doctorate degree from Harbin Engineering University in 2022. Her main research directions are environmental functional materials and marine anti-fouling and anticorrosion research.

Dexin Wang is an associate professor at the School of Ecological and Environmental Sciences, Hainan University. He received his PhD degree in municipal engineering from Harbin Institute of Technology in 2018. His research interests are focused on sewage treatment and resource utilization.

Jianjun Liao is a professor at the School of Ecological and Environmental Sciences, Hainan University. He received his PhD degree from Hainan University in 2016. His current research interests include nanomaterial-based chemical sensors.

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Oxygen doping and hollow structure-mediated effects to enable rapid electron transfer during photocatalytic hydrogen peroxide production

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Xu, Y., Tai, W., Wang, Z. et al. Oxygen doping and hollow structure-mediated effects to enable rapid electron transfer during photocatalytic hydrogen peroxide production. Sci. China Mater. 67, 153–161 (2024). https://doi.org/10.1007/s40843-023-2659-9

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  • DOI: https://doi.org/10.1007/s40843-023-2659-9

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