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Internal quantum efficiency higher than 100% achieved by combining doping and quantum effects for photocatalytic overall water splitting

Nature Energy volume 8, pages 504–514 (2023)Cite this article

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Abstract

Multiple exciton generation (MEG), where two or more electron–hole pairs are produced from the absorption of one high-energy photon, could increase the efficiency of light absorbing devices. However, demonstrations of the effect are still scarce in photocatalytic hydrogen production. Moreover, many photocatalytic systems for overall water splitting suffer from poor charge carrier separation. Here we show that a CdTe quantum dot/vanadium-doped indium sulphide (CdTe/V-In2S3) photocatalyst has a built-in electric field and cascade energy band structure sufficient to effectively extract excitons and separate carriers, allowing MEG to be exploited for hydrogen production. We achieve a tunable energy band structure through quantum effects in CdTe and doping engineering of V-In2S3, which induces a 14-fold enhancement in the CdTe/V-In2S3 interfacial built-in electric field intensity relative to pristine CdTe/V-In2S3. We report an internal quantum efficiency of 114% at 350 nm for photocatalytic hydrogen production, demonstrating the utilization of MEG effects. The solar-to-hydrogen efficiency is 1.31%.

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Fig. 1: The energy band structures of the CdTe quantum dots and V-In2S3.
Fig. 2: The morphology and structure of the CdTe/V-In2S3 photocatalysts.
Fig. 3: The interfacial built-in electric field of the CdTe/V-In2S3 photocatalysts.
Fig. 4: The kinetics of interfacial carrier transport and the MEG effect of the CdTe/V-In2S3 photocatalysts.
Fig. 5: The photocatalytic performance of the CdTe/V-In2S3 photocatalysts.

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All data generated in this study are provided in the article, its Supplementary Information and the Source data provided with this paper.

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Acknowledgements

This research is supported by the National Natural Science Foundation of China (22261142666, 52172237), the Shaanxi Science Fund for Distinguished Young Scholars (2022JC-21), the Research Fund of the State Key Laboratory of Solidification Processing (NPU), China (grant no. 2021-QZ-02) and the Fundamental Research Funds for the Central Universities (3102019JC005, D5000220033). All funds were awarded to X.L. We thank the members of the Analytical and Testing Center of Northwestern Polytechnical University for help with X-ray diffraction, XPS and SEM characterization.

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Authors and Affiliations

  1. State Key Laboratory of Solidification Processing, Center for Nano Energy Materials, School of Materials Science and Engineering, Northwestern Polytechnical University, Xi’an, China

    Youzi Zhang, Xu Xin, Yijin Wang, Peng Guo, Ruiling Wang, Bilin Wang & Xuanhua Li

  2. Department of Chemistry and Centre for Scientific Modeling and Computation, Chinese University of Hong Kong, Hong Kong, China

    YuKe Li

  3. Guangzhou Key Laboratory of Low-Dimensional Materials and Energy Storage Devices, Collaborative Innovation Center of Advanced Energy Materials, School of Materials and Energy, Guangdong University of Technology, Guangzhou, China

    Wenjing Huang

  4. Materials Research Institute, School of Engineering and Materials Science, Faculty of Science and Engineering, Queen Mary University of London, London, UK

    Ana Jorge Sobrido

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Contributions

X.L. and Y.Z. proposed the experimental concepts, designed the experiments and prepared the paper. X.L. supervised the project. Y.Z., X.X., Y.W., P.G., R.W. and B.W. carried out the experiments and conducted the materials characterization. W.H. and A.J.S. revised the paper. Y.L. finished the computation. All authors discussed the results and approved the final version of the paper.

Corresponding author

Correspondence to Xuanhua Li.

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Supplementary Figs. 1–49, Discussion, Tables 1–8 and Notes 1 and 2.

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Source Data Fig. 3

Source data for Fig. 3e,f.

Source Data Fig. 4

Source data for averages and error bars in Fig. 4b,c.

Source Data Fig. 5

Source data for averages and error bars in Fig. 5d.

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Zhang, Y., Li, Y., Xin, X. et al. Internal quantum efficiency higher than 100% achieved by combining doping and quantum effects for photocatalytic overall water splitting. Nat Energy 8, 504–514 (2023). https://doi.org/10.1038/s41560-023-01242-7

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