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Au/g-C3N4 heterostructure sensitized by black phosphorus for full solar spectrum waste-to-hydrogen conversion

黑磷敏化的金/氮化碳异质结全光谱废水产氢性能研究

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Abstract

Photocatalytic water splitting with simultaneous degradation of organic pollutants is an effective strategy to alleviate the increasingly serious energy and environmental crisis. However, the photocatalytic activity is restricted by the high charge recombination rate and limited sunlight utilization. Herein, black phosphorus (BP) with a broad sunlight response range was utilized as a photosensitizer to enhance the photocatalytic performance of the Au/carbon nitride (CN) heterostructure. The as-prepared BP/Au/CN exhibited a significantly enhanced H2 generation rate of 1400.8 µmol h−1 g−1 under UV-vis light irradiation, which is almost 70 times higher than that of bare CN and BP/CN and 2 folds higher than that of the Au/CN heterojunction. Specifically, the optimal BP/Au/CN sample presented a waste-to-hydrogen production rate of 195.8 µmol h−1 g−1 with the degradation of bisphenol A, verifying the synergistic effect of the ternary heterojunction. The photocatalytic mechanism was systematically studied by the combination of experiments and theoretical calculations. The improved photocatalytic performance was derived from the overall sunlight absorption ability of BP, effective electron transfer media and plasmonic character of Au nanoparticles, as well as the matched work function and strong interaction of the three components. A unidirectional electron transfer from BP to Au and then to CN was established, which effectively improved the charge transfer capability, resulting from the appropriate Ohmic contact of Au and BP and the Schottky barrier constructed in Au/CN hybrid.

摘要

光催化废水产氢技术是缓解日益严峻的能源和环境危机的有效方法. 然而, 由于载流子复合率较高、太阳光利用率较低, 目前光催化活性仍然难以满足工业发展的需要. 基于以上问题, 本文设计了具有全谱太阳光响应的黑磷敏化的金/氮化碳(BP/Au/CN)异质结光催化剂, 该三元异质结可以在实现降解双酚A的同时, 将水分解为氢气, 其光催化产氢活性可达到195.8 µmol h−1g−1. 此外, 在紫外-可见光照射下, BP/Au/CN的光催化产氢活性可以达到1400.8 µmol h−1g−1, 是CN或BP/CN样品的近70倍, Au/CN异质结的2倍. 光催化活性的提高表明异质结中三种元素具有良好的协同作用. 本文将一系列实验表征与理论计算相结合, 对BP/Au/CN的光催化机理进行了系统研究. 结果表明, 黑磷的全谱太阳光吸收能力、金的电子传输介质作用以及三种材料匹配的功函数是其光催化活性提高的关键因素. 此外, 通过金和黑磷的欧姆接触以及Au/CN杂化体系中肖特基异质结的构筑, 实现了电子从黑磷到金,再到氮化碳的单向转移, 从而提高了载流子的传输性能.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (21801092, 21872001, and U1704140), the Program for the Development of Science and Technology of Jilin Province (20200801040GH), the Science and Technology Research Project of Henan Province (202102210055), the General project of Chinese postdoctoral program (2020M672263), the Key Research Programs in Universities of Henan Province (20A150031), and the Science and Technology Innovation Talent Support Program of Henan Province (19HASTIT034). Eceshi (https://www.eceshi.com) was acknowledged for the EPR analysis.

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Authors and Affiliations

  1. Henan Engineering Center of New Energy Battery Materials, Henan D&A Engineering Center of Advanced Battery Materials, College of Chemistry and Chemical Engineering, Institute of Architectural Engineering, Shangqiu Normal University, Shangqiu, 476000, China

    Lijing Wang  (王立晶), Yafang Qi  (齐亚芳), Hui Li  (李会), Fuli Zhang  (张付力) & Qingfeng Zhou  (周庆峰)

  2. Faculty of Physics, Faculty of Chemistry, Northeast Normal University, Changchun, 130024, China

    Renquan Guan  (关壬铨) & Zhao Zhao  (赵钊)

  3. Center of excellence for environmental safety and biological effects, Beijing Key Lab for Green Catalysis and Separation, Department of Chemistry and Chemical Engineering, College of Environmental and Energy Engineering, Beijing University of Technology, Beijing, 100124, China

    Dandan Wu  (吴丹丹) & Zaicheng Sun  (孙再成)

  4. Key Laboratory of Integrated Regulation and Resource Development on Shallow Lake of Ministry of Education, College of Environment, Hohai University, Nanjing, 210098, China

    Gang Zhou  (周钢)

Authors
  1. Lijing Wang  (王立晶)
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  2. Yafang Qi  (齐亚芳)
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  3. Hui Li  (李会)
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  4. Renquan Guan  (关壬铨)
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  5. Fuli Zhang  (张付力)
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  6. Qingfeng Zhou  (周庆峰)
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  7. Dandan Wu  (吴丹丹)
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  8. Zhao Zhao  (赵钊)
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  9. Gang Zhou  (周钢)
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  10. Zaicheng Sun  (孙再成)
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Contributions

Author contributions Wang L designed and engineered the samples; Sun Z conceived the post-fabrication tuning of random modes; Zhao Z and Qi Y performed the experiments; Zhou G wrote the paper with the support from Zhang F. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Zhao Zhao  (赵钊), Gang Zhou  (周钢) or Zaicheng Sun  (孙再成).

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Conflict of interest The authors declare no conflict of interest.

Additional information

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

Zaicheng Sun is a professor of Beijing Key Lab for Green Catalysis and Separation, Department of Chemistry and Biology, Faculty of Environment and Life, Beijing University of Technology. His research interests are mainly on the photocatalytic nanomaterials for water splitting, H2 production, and self-cleaning optical coating, as well as fluorescent carbon dots for theragnostics.

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Wang, L., Qi, Y., Li, H. et al. Au/g-C3N4 heterostructure sensitized by black phosphorus for full solar spectrum waste-to-hydrogen conversion. Sci. China Mater. 65, 974–984 (2022). https://doi.org/10.1007/s40843-021-1833-1

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