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Metal-organic framework-derived nitrogen-doped carbon-coated hollow tubular In2O3/CdZnS heterojunction for efficient photocatalytic hydrogen evolution

金属有机框架衍生的氮掺杂碳包覆空心管In2O3/CdZnS异质结用于高效光催化析氢

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Abstract

Using photocatalytic hydrogen evolution (PHE) technology is a powerful way to solve the energy shortage. In this study, a hexagonal hollow tubular nitrogen-doped carbon (N−C)-coated In2O3/CdZnS heterojunction photocatalyst was in situ synthesized using a simple oil bath heating method. Results show that the PHE rate of N−C/In2O3/CdZnS (∼22.87 µmol h−1) is ∼2.4 times that of pristine CdZnS (∼9.49 µmol h−1) and ∼54.5 times that of pristine In2O3 (∼0.42 µmol h−1). After four cycles, the PHE rate can still retain more than 90% of the original. Its excellent photocatalytic performance is mainly attributed to the following aspects: (1) the N−C layer acts as an electron transport bridge, which ensures the efficient electron transfer of the photocatalytic reaction; (2) the hollow tubular structure enhances the light reflection and absorption; (3) the N−C/In2O3/CdZnS heterostructure improves the carrier recombination and photocorrosion; (4) the large specific surface area and mesoporous structure provide a large number of reactive sites. This study provides a novel idea for designing visible-light-type heterojunction catalysts.

摘要

光催化析氢(PHE)技术是解决当前能源短缺问题的有力途径之一. 本文采用简单的油浴加热方法原位合成了六方空心管状氮掺杂碳包覆的In2O3/CdZnS异质结光催化剂. 结果表明, N−C/In2O3/CdZnS(∼22.87 µmol h−1)的光催化析氢速率是原始CdZnS (∼9.49 µmol h−1)的∼2.4倍, 是原始In2O3(∼0.42µmol h−1)的∼54.5倍. 经过4个循环后, 光催化析氢量仍能达到原来的90%以上. 其优异的光催化性能主要归功于以下几个方面: (1) 氮掺杂碳层作为电子传输桥梁, 保证了光催化反应的高效电子转移; (2) 中空管状结构增强了光的反射, 增强了光吸收性能;(3) 形成N−C/In2O3/CdZnS异质结构, 改善了载流子复合和光腐蚀问题;(4) 大的比表面积和介孔结构提供了大量的反应位点. 因此, 本研究为设计可见光型异质结催化剂提供了新思路.

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References

  1. Wang Q, Domen K. Particulate photocatalysts for light-driven water splitting: Mechanisms, challenges, and design strategies. Chem Rev, 2020, 120: 919–985

    CAS  Google Scholar 

  2. Qi MY, Conte M, Anpo M, et al. Cooperative coupling of oxidative organic synthesis and hydrogen production over semiconductor-based photocatalysts. Chem Rev, 2021, 121: 13051–13085

    CAS  Google Scholar 

  3. Feng L, Pang J, She P, et al. Metal-organic frameworks based on group 3 and 4 metals. Adv Mater, 2020, 32: 2004414

    Google Scholar 

  4. Xia B, Zhang Y, Shi B, et al. Photocatalysts for hydrogen evolution coupled with production of value-added chemicals. Small Methods, 2020, 4: 2000063

    CAS  Google Scholar 

  5. Zuo Q, Liu T, Chen C, et al. Ultrathin metal-organic framework nanosheets with ultrahigh loading of single Pt atoms for efficient visible-light-driven photocatalytic H2 evolution. Angew Chem Int Ed, 2019, 58: 10198–10203

    CAS  Google Scholar 

  6. Hou J, Cao S, Sun Y, et al. Atomically thin mesoporous In2O3-x/In2S3 lateral heterostructures enabling robust broadband-light photo-electrochemical water splitting. Adv Energy Mater, 2018, 8: 1701114

    Google Scholar 

  7. Tan M, Ma Y, Yu C, et al. Boosting photocatalytic hydrogen production via interfacial engineering on 2D ultrathin Z-scheme ZnIn2S4/g-C3N4 heterojunction. Adv Funct Mater, 2022, 32: 2111740

    CAS  Google Scholar 

  8. Khan K, Tao X, Shi M, et al. Visible-light-driven photocatalytic hydrogen production on Cd0.5Zn0.5S nanorods with an apparent quantum efficiency exceeding 80%. Adv Funct Mater, 2020, 30: 2003731

    CAS  Google Scholar 

  9. Zhang W, Zhou X, Huang J, et al. Noble metal-free core-shell CdS/iron phthalocyanine Z-scheme photocatalyst for enhancing photocatalytic hydrogen evolution. J Mater Sci Tech, 2022, 115: 199–207

    Google Scholar 

  10. Zhang W, Zhao S, Xing Y, et al. Sandwich-like P-doped h-BN/ZnIn2S4 nanocomposite with direct Z-scheme heterojunction for efficient photocatalytic H2 and H2O2 evolution. Chem Eng J, 2022, 442: 136151

    CAS  Google Scholar 

  11. Li W, Wang X, Ma Q, et al. CdS@h-BN heterointerface construction on reduced graphene oxide nanosheets for hydrogen production. Appl Catal B-Environ, 2021, 284: 119688

    CAS  Google Scholar 

  12. Zhan X, Zheng Y, Li B, et al. Rationally designed Ta3N5/ZnIn2S4 1D/2D heterojunctions for boosting visible-light-driven hydrogen evolution. Chem Eng J, 2022, 431: 134053

    CAS  Google Scholar 

  13. Hou H, Shao G, Yang W. Recent advances in g-C3N4-based photocatalysts incorporated by MXenes and their derivatives. J Mater Chem A, 2021, 9: 13722–13745

    CAS  Google Scholar 

  14. Wang Q, Astruc D. State of the art and prospects in metal-organic framework (MOF)-based and MOF-derived nanocatalysis. Chem Rev, 2020, 120: 1438–1511

    CAS  Google Scholar 

  15. Nguyen HL. Metal-organic frameworks can photocatalytically split water—Why not?. Adv Mater, 2022, 34: 2200465

    CAS  Google Scholar 

  16. Liu J, Feng J, Lu L, et al. A metal-organic-framework-derived (Zn0.95−Cu0.05)0.6Cd0.4S solid solution as efficient photocatalyst for hydrogen evolution reaction. ACS Appl Mater Interfaces, 2020, 12: 10261–10267

    CAS  Google Scholar 

  17. Song Y, Li Z, Zhu Y, et al. Titanium hydroxide secondary building units in metal-organic frameworks catalyze hydrogen evolution under visible light. J Am Chem Soc, 2019, 141: 12219–12223

    CAS  Google Scholar 

  18. Yang H, Tang J, Luo Y, et al. MOFs-derived fusiform In2O3 mesoporous nanorods anchored with ultrafine CdZnS nanoparticles for boosting visible-light photocatalytic hydrogen evolution. Small, 2021, 17: 2102307

    CAS  Google Scholar 

  19. Shen Q, Zhou S, Yang FL, et al. Engineering one-dimensional hollow beta-In2S3/In2O3 hexagonal micro-tubes for efficient broadband-light photocatalytic performance. J Mater Chem A, 2022, 10: 4974–4980

    CAS  Google Scholar 

  20. Han L, Jing F, Zhang J, et al. Environment friendly and remarkably efficient photocatalytic hydrogen evolution based on metal organic framework derived hexagonal/cubic In2O3 phase-junction. Appl Catal B-Environ, 2021, 282: 119602

    CAS  Google Scholar 

  21. Li R, Sun L, Zhan W, et al. Engineering an effective noble-metal-free photocatalyst for hydrogen evolution: Hollow hexagonal porous microrods assembled from In2O3@carbon core-shell nanoparticles. J Mater Chem A, 2018, 6: 15747–15754

    CAS  Google Scholar 

  22. Zhou X, Luo J, Jin B, et al. Sustainable synthesis of low-cost nitrogen-doped-carbon coated Co3W3C@g-C3N4 composite photocatalyst for efficient hydrogen evolution. Chem Eng J, 2021, 426: 131208

    CAS  Google Scholar 

  23. Wang A, Chen Y, Zheng Z, et al. In situ N-doped carbon-coated mulberry-like cobalt manganese oxide boosting for visible light driving photocatalytic degradation of pharmaceutical pollutants. Chem Eng J, 2021, 411: 128497

    CAS  Google Scholar 

  24. Yang W, Ma G, Fu Y, et al. Rationally designed Ti3C2 MXene@TiO2/CuInS2 Schottky/S-scheme integrated heterojunction for enhanced photocatalytic hydrogen evolution. Chem Eng J, 2022, 429: 132381

    CAS  Google Scholar 

  25. Zhan X, Fang Z, Li B, et al. Rationally designed Ta3N5@ReS2 heterojunctions for promoted photocatalytic hydrogen production. J Mater Chem A, 2021, 9: 27084–27094

    CAS  Google Scholar 

  26. Lin S, Li S, Huang H, et al. Synergetic piezo-photocatalytic hydrogen evolution on CdxZn1−xS solid-solution 1D nanorods. Small, 2022, 18: 2106420

    CAS  Google Scholar 

  27. Lin S, Zhang Y, You Y, et al. Bifunctional hydrogen production and storage on 0D–1D heterojunction of Cd0.5Zn0.5S@halloysites. Adv Funct Mater, 2019, 29: 1903825

    Google Scholar 

  28. Kai S, Xi B, Wang Y, et al. One-pot synthesis of size-controllable core-shell CdS and derived CdS@ZnxCd1−xS structures for photocatalytic hydrogen production. Chem Eur J, 2017, 23: 16653–16659

    CAS  Google Scholar 

  29. Zhong T, Yu Z, Jiang R, et al. Surface-activated Ti3C2Tx MXene cocatalyst assembled with CdZnS-formed 0D/2D CdZnS/Ti3C2−A40 Schottky heterojunction for enhanced photocatalytic hydrogen evolution. Sol RRL, 2022, 6: 2100863

    CAS  Google Scholar 

  30. Ha E, Ruan S, Li D, et al. Surface disorder engineering in ZnCdS for cocatalyst free visible light driven hydrogen production. Nano Res, 2022, 15: 996–1002

    CAS  Google Scholar 

  31. Huang HB, Fang ZB, Yu K, et al. Visible-light-driven photocatalytic H2 evolution over CdZnS nanocrystal solid solutions: Interplay of twin structures, sulfur vacancies and sacrificial agents. J Mater Chem A, 2020, 8: 3882–3891

    CAS  Google Scholar 

  32. Chen J, Lv S, Shen Z, et al. Novel ZnCdS quantum dots engineering for enhanced visible-light-driven hydrogen evolution. ACS Sustain Chem Eng, 2019, 7: 13805–13814

    CAS  Google Scholar 

  33. Liang R, Shen L, Jing F, et al. NH2-mediated indium metal-organic framework as a novel visible-light-driven photocatalyst for reduction of the aqueous Cr(VI). Appl Catal B-Environ, 2015, 162: 245–251

    CAS  Google Scholar 

  34. Hou Q, Li X, Pi Y, et al. Construction of In2S3@NH2−MIL−68(In)@In2S3 sandwich homologous heterojunction for efficient CO2 photoreduction. Ind Eng Chem Res, 2020, 59: 20711–20718

    CAS  Google Scholar 

  35. Zhang Q, Gu H, Wang X, et al. Robust hollow tubular ZnIn2S4 modified with embedded metal-organic-framework-layers: Extraordinarily high photocatalytic hydrogen evolution activity under simulated and real sunlight irradiation. Appl Catal B-Environ, 2021, 298: 120632

    CAS  Google Scholar 

  36. Zhang X, Zhang S, Tang Y, et al. Recent advances and challenges of metal-organic framework/graphene-based composites. Compos Part B-Eng, 2022, 230: 109532

    CAS  Google Scholar 

  37. Pan T, Shen Y, Wu P, et al. Thermal shrinkage behavior of metal-organic frameworks. Adv Funct Mater, 2020, 30: 2001389

    CAS  Google Scholar 

  38. Li F, Liu Y, Mao B, et al. Carbon-dots-mediated highly efficient hole transfer in I–III–VI quantum dots for photocatalytic hydrogen production. Appl Catal B-Environ, 2021, 292: 120154

    CAS  Google Scholar 

  39. Wang Y, Liu X, Liu J, et al. Carbon quantum dot implanted graphite carbon nitride nanotubes: Excellent charge separation and enhanced photocatalytic hydrogen evolution. Angew Chem Int Ed, 2018, 57: 5765–5771

    CAS  Google Scholar 

  40. Wang S, Guan BY, Lou XWD. Construction of ZnIn2S4−In2O3 hierarchical tubular heterostructures for efficient CO2 photoreduction. J Am Chem Soc, 2018, 140: 5037–5040

    CAS  Google Scholar 

  41. Sun L, Zhuang Y, Yuan Y, et al. Nitrogen-doped carbon-coated CuO−In2O3 p−n heterojunction for remarkable photocatalytic hydrogen evolution. Adv Energy Mater, 2019, 9: 1902839

    CAS  Google Scholar 

  42. Zhang Q, Zhang J, Wang X, et al. In-N-In sites boosting interfacial charge transfer in carbon-coated hollow tubular In2O3/ZnIn2S4 heterostructure derived from In-MOF for enhanced photocatalytic hydrogen evolution. ACS Catal, 2021, 11: 6276–6289

    CAS  Google Scholar 

  43. Sun L, Li R, Zhan W, et al. Rationally designed double-shell dodecahedral microreactors with efficient photoelectron transfer: N-doped-C-encapsulated ultrafine In2O3 nanoparticles. Chem Eur J, 2019, 25: 3053–3060

    CAS  Google Scholar 

  44. Fang LJ, Li YH, Liu PF, et al. Facile fabrication of large-aspect-ratio g-C3N4 nanosheets for enhanced photocatalytic hydrogen evolution. ACS Sustain Chem Eng, 2017, 5: 2039–2043

    CAS  Google Scholar 

  45. Zhao S, Li K, Wu J, et al. Metal-organic framework-derived tubular In2O3−C/CdIn2S4 heterojunction for efficient solar-driven CO2 conversion. ACS Appl Mater Interfaces, 2021, 14: 20375–20384

    Google Scholar 

  46. Huang L, Li B, Su B, et al. Fabrication of hierarchical Co3O4@CdIn2S4 p−n heterojunction photocatalysts for improved CO2 reduction with visible light. J Mater Chem A, 2020, 8: 7177–7183

    CAS  Google Scholar 

  47. Wang Q, Chen Y, Liu X, et al. Sulfur doped In2O3−CeO2 hollow hexagonal prisms with carbon coating for efficient photocatalytic CO2 reduction. Chem Eng J, 2021, 421: 129968

    CAS  Google Scholar 

  48. Cao R, Yang H, Zhang S, et al. Engineering of Z-scheme 2D/3D architectures with Ni(OH)2 on 3D porous g-C3N4 for efficiently photocatalytic H2 evolution. Appl Catal B-Environ, 2019, 258: 117997

    CAS  Google Scholar 

  49. Ouyang C, Quan X, Zhang C, et al. Direct Z-scheme ZnIn2S4@MoO3 heterojunction for efficient photodegradation of tetracycline hydrochloride under visible light irradiation. Chem Eng J, 2021, 424: 130510

    CAS  Google Scholar 

  50. Yang YY, Zhang XG, Niu CG, et al. Dual-channel charges transfer strategy with synergistic effect of Z-scheme heterojunction and LSPR effect for enhanced quasi-full-spectrum photocatalytic bacterial inactivation: New insight into interfacial charge transfer and molecular oxygen activation. Appl Catal B-Environ, 2020, 264: 118465

    CAS  Google Scholar 

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Acknowledgements

This work was supported by the Independent Cultivation Program of Innovation Team of Jinan City (2019GXRC011), the Natural Science Foundation of Shandong Province (ZR2021ME143), and the National Natural Science Foundation of China (51908242).

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Authors and Affiliations

  1. School of Physics and Technology, University of Jinan, Jinan, 250022, China

    Weijie Zhang  (张伟杰), Hongjie Qin  (秦鸿杰), Qiling Zheng  (郑其玲), Penghui Zhang  (张鹏辉), Xiaojuan Li  (李晓娟), ChuanLin Li  (李传琳), TongKai Wang  (王同凯), Na Li  (李娜), Shouwei Zhang  (张守伟) & Xijin Xu  (徐锡金)

  2. School of Electronic and Information Engineering (Department of Physics), Qilu University of Technology (Shandong Academy of Sciences), Jinan, 250353, China

    Shunshun Zhao  (赵顺顺)

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  1. Weijie Zhang  (张伟杰)
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  2. Shunshun Zhao  (赵顺顺)
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Contributions

Author contributions Zhang W conducted the experiment and wrote the paper; Zhao S carried out theoretical calculations; Qin H, Zheng Q and Zhang P analyzed the data; Li X and Li C drew the graphs; Wang T and Li N validated the experiment; Xu X provided financial support and useful suggestions; Zhang S put forward useful suggestions.

Corresponding authors

Correspondence to Shouwei Zhang  (张守伟) or Xijin Xu  (徐锡金).

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

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Supplementary information Supporting data are available in the online version of the paper.

Weijie Zhang received a bachelor degree from the School of Physical Science and Technology at the University of Jinan in 2020. He is now pursing his master degree under the supervision of Prof. Xijin Xu at the School of Physics and Technology, University of Jinan, China. His main research interest is the synthesis and characterization of two-dimensional nanomaterials for photocatalytic applications.

Shouwei Zhang received his PhD from Hefei University of Technology in 2015. His main interest is the preparation of photocatalytic materials.

Xijin Xu received his PhD degree from the Institute of Solid State Physics, Chinese Academy of Sciences in 2007. He conducted his postdoctoral research at Nanyang Technological University, Singapore in 2007 and then joined the National Institute for Materials Science, Japan (2008–2010) and Griffith University in Australia (2010–2011). Currently, he is a full professor at the University of Jinan. His most recent research interests include the synthesis and characterization of functional micro/nanostructures and their applications in environmental remediation and energy storage.

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Metal-organic framework-derived nitrogen-doped carbon-coated hollow tubular In2O3/CdZnS heterojunction for efficient photocatalytic hydrogen evolution

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Zhang, W., Zhao, S., Qin, H. et al. Metal-organic framework-derived nitrogen-doped carbon-coated hollow tubular In2O3/CdZnS heterojunction for efficient photocatalytic hydrogen evolution. Sci. China Mater. 66, 1042–1052 (2023). https://doi.org/10.1007/s40843-022-2209-9

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