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Metal–organic framework coated titanium dioxide nanorod array p–n heterojunction photoanode for solar water-splitting

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Abstract

This paper presents a p–n heterojunction photoanode based on a p-type porphyrin metal–organic framework (MOF) thin film and an n-type rutile titanium dioxide nanorod array for photoelectrochemical water splitting. The TiO2@MOF core–shell nanorod array is formed by coating an 8 nm thick MOF layer on a vertically aligned TiO2 nanorod array scaffold via a layer-by-layer self-assembly method. This vertically aligned core–shell nanorod array enables a long optical path length but a short path length for extraction of photogenerated minority charge carriers (holes) from TiO2 to the electrolyte. A p–n junction is formed between TiO2 and MOF, which improves the extraction of photogenerated electrons and holes out of the TiO2 nanorods. In addition, the MOF coating significantly improves the efficiency of charge injection at the photoanode/electrolyte interface. Introduction of Co(III) into the MOF layer further enhances the charge extraction in the photoanode and improves the charge injection efficiency. As a result, the photoelectrochemical cell with the TiO2@Co-MOF nanorod array photoanode exhibits a photocurrent density of 2.93 mA/cm2 at 1.23 V (vs. RHE), which is ~ 2.7 times the photocurrent achieved with bare TiO2 nanorod array under irradiation of an unfiltered 300 W Xe lamp with an output power density of 100 mW/cm2.

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Author notes

  1. Hui Yang and Joeseph Bright contributed equally to this work.

Authors and Affiliations

  1. Department of Mechanical and Aerospace Engineering, West Virginia University, Morgantown, WV, 26506-6106, USA

    Hui Yang, Joeseph Bright, Peng Zheng, Terence Musho & Nianqiang Wu

  2. C. Eugene Bennett Department of Chemistry, West Virginia University, Morgantown, WV, 26506-6045, USA

    Nianqiang Wu

  3. Department of Pharmaceutical Science, West Virginia University, Morgantown, WV, 26506-9530, USA

    Nianqiang Wu

  4. Lane Department of Computer Science and Electrical Engineering, West Virginia University, Morgantown, WV, 26506, USA

    Sujan Kasani

  5. Department of Chemistry, University of Texas at San Antonio, One UTSA Circle, San Antonio, TX, 78249-1604, USA

    Banglin Chen

  6. Institute of Advanced Materials (IAM), Nanjing Tech University (NanjingTech), 30 South Puzhu Road, Nanjing, 211816, China

    Ling Huang

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  1. Hui Yang
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Correspondence to Ling Huang or Nianqiang Wu.

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Yang, H., Bright, J., Kasani, S. et al. Metal–organic framework coated titanium dioxide nanorod array p–n heterojunction photoanode for solar water-splitting. Nano Res. 12, 643–650 (2019). https://doi.org/10.1007/s12274-019-2272-4

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