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Unveiling the Role of the Ti Dopant and Viable Si Doping of Hematite for Practically Efficient Solar Water Splitting

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    Research Article

    Unveiling the Role of the Ti Dopant and Viable Si Doping of Hematite for Practically Efficient Solar Water Splitting
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    • Ki-Yong Yoon
      Ki-Yong Yoon
      School of Energy and Chemical Engineering, Ulsan National Institute of Science and Technology (UNIST), Ulsan 44919, Republic of Korea
      More by Ki-Yong Yoon
    • Juhyung Park
      Juhyung Park
      School of Energy and Chemical Engineering, Ulsan National Institute of Science and Technology (UNIST), Ulsan 44919, Republic of Korea
      More by Juhyung Park
    • Hosik Lee
      Hosik Lee
      School of Energy and Chemical Engineering, Ulsan National Institute of Science and Technology (UNIST), Ulsan 44919, Republic of Korea
      More by Hosik Lee
      Orcidhttps://orcid.org/0000-0003-4667-6551
    • Ji Hui Seo
      Ji Hui Seo
      School of Energy and Chemical Engineering, Ulsan National Institute of Science and Technology (UNIST), Ulsan 44919, Republic of Korea
      More by Ji Hui Seo
    • Myung-Jun Kwak
      Myung-Jun Kwak
      School of Energy and Chemical Engineering, Ulsan National Institute of Science and Technology (UNIST), Ulsan 44919, Republic of Korea
      More by Myung-Jun Kwak
    • Jun Hee Lee
      Jun Hee Lee
      School of Energy and Chemical Engineering, Ulsan National Institute of Science and Technology (UNIST), Ulsan 44919, Republic of Korea
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      Orcidhttps://orcid.org/0000-0001-5121-244X
    • Ji-Hyun Jang*
      Ji-Hyun Jang
      School of Energy and Chemical Engineering, Ulsan National Institute of Science and Technology (UNIST), Ulsan 44919, Republic of Korea
      *Email: [email protected]
      More by Ji-Hyun Jang
      Orcidhttps://orcid.org/0000-0003-4364-6605
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    ACS Catalysis

    Cite this: ACS Catal. 2022, 12, 9, 5112–5122
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    https://doi.org/10.1021/acscatal.1c05106
    Published April 15, 2022
    Copyright © 2022 American Chemical Society
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    Abstract

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    Doping engineering is of key importance for controlling the electrical, optical, and structural properties of a semiconductor. In more expanded doping systems, codoping with deep insight and understanding of interactions between impurities is necessary to make an efficient photoelectrode. Here, we show that the high formation energy of a Si-doped hematite can be decreased with the introduction of a host Ti-dopant, making easy and cost-efficient solution-based Si doping possible. The effect of the positive interaction between dopants lowers the formation energy in a standard atmosphere to the one under extreme conditions of about 10–10 atm. By taking advantage of formation energy control, we achieved a photocurrent density of 4.3 mA cm–2 at 1.23 VRHE in the optimized Si:Ti codoped hematite with a cocatalyst without using any demanding experimental processes. Our study suggests a ground rule for the facile incorporation of the high-formation-energy dopant into photocatalysts, which can be readily extended to other doped systems to achieve a substantial improvement in PEC performance.

    Copyright © 2022 American Chemical Society

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acscatal.1c05106.

    • SEM images, BET measurements, LSV curves, UV–vis absorbance, XPS depth profiles, DFT calculation data, STEM-EDX images, XRD patterns, EIS measurements, electrical conductivity (PDF)

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    Cited By

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    This article is cited by 39 publications.

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    2. Jihun Kang, Balaji G. Ghule, Seung Gyu Gyeong, Seong-Ji Ha, Ji-Hyun Jang. Alleviating Charge Recombination Caused by Unfavorable interaction of P and Sn in Hematite for Photoelectrochemical Water Oxidation. ACS Catalysis 2024, 14 (13) , 10355-10364. https://doi.org/10.1021/acscatal.4c01150
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    33. Gaoteng Zhang, Cheng Lu, Chang Li, Shuo Li, Xiaoquan Zhao, Kaiqi Nie, Jiaou Wang, Kun Feng, Jun Zhong. CoMoO 4 -modified hematite with oxygen vacancies for high-efficiency solar water splitting. Physical Chemistry Chemical Physics 2023, 25 (19) , 13410-13416. https://doi.org/10.1039/D3CP01192E
    34. Qiannan Wu, Kai Zhang, Dejun Wang, Yanhong Lin, Tengfeng Xie. Dual-suppression of bulk and surface charges recombination for hematite photoanode. Electrochimica Acta 2023, 449 , 142241. https://doi.org/10.1016/j.electacta.2023.142241
    35. Jiajia Cai, Xiangxuan Tang, Shiming Zhong, Yongjun Li, Yiyang Wang, Zhi Liao, Jianmin Wang, Keke Mao, Qian Xie. Elucidation the role of Co-MOF on hematite for boosting the photoelectrochemical performance toward water oxidation. International Journal of Hydrogen Energy 2023, 48 (33) , 12342-12353. https://doi.org/10.1016/j.ijhydene.2022.12.165
    36. Xiaoxin Lv, Gaoteng Zhang, Menglian Wang, Guoqing Li, Jiujun Deng, Jun Zhong. How titanium and iron are integrated into hematite to enhance the photoelectrochemical water oxidation: a review. Physical Chemistry Chemical Physics 2023, 25 (3) , 1406-1420. https://doi.org/10.1039/D2CP04969D
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    40. Huan Chai, Lili Gao, Jun Jin. Revealing the Essential Role of Iron Phosphide and its Surface‐Evolved Species in the Photoelectrochemical Water Oxidation by Gd‐Doped Hematite Photoanode. ChemSusChem 2022, 15 (17) https://doi.org/10.1002/cssc.202201030
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    ACS Catalysis

    Cite this: ACS Catal. 2022, 12, 9, 5112–5122
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acscatal.1c05106
    Published April 15, 2022
    Copyright © 2022 American Chemical Society
    Request reuse permissions

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