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Phosphorus-doped MoS2 with sulfur vacancy defects for enhanced electrochemical water splitting

具有硫空位的磷掺杂二硫化钼用于增强电化学水分解

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Abstract

MoS2 is a promising electrocatalyst because of its natural abundance and outstanding electrochemical stability. However, the poor conductivity and low activity limit its catalytic performance; furthermore, MoS2 is unable to satisfy the requirements of most industrial applications. In this study, to obtain a P-doped MoS2 catalyst with S vacancy defects, P is inserted into the MoS2 matrix via a solid phase ion exchange at room temperature. The optimal P-doping amount is 11.4 wt%, and the resultant catalyst delivers excellent electrocatalytic properties for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) with the corresponding overpotentials of 93 and 316 mV at 10 mA cm−2 in an alkaline solution; these values surpass the overpotentials of most previously reported MoS2-based materials. Theoretical calculations and results demonstrate that the synergistic effect of the doped P, which forms active centers in the basal plane of MoS2, and S vacancy defects caused by P doping intensifies the intrinsic electronic conductivity and electrocatalytic activity of the catalyst. Density functional theory calculations demonstrate that P optimizes the free energy of the MoS2 matrix for hydrogen adsorption, thereby considerably increasing the intrinsic activity of the doped catalyst for the HER compared with that observed from pristine MoS2. The enhanced catalytic activity of P-doped MoS2 for the OER is attributed to the ability of the doped P which facilitates the adsorption of hydroxyl and hydroperoxy intermediates and reduces the reaction energy barrier. This study provides a new environmentally friendly and convenient solid-phase ion exchange method to improve the electrocatalytic capability of two-dimensional transition-metal dichalcogenides in large-scale applications.

摘要

由于其丰度高、电化学稳定性强, MoS2被认为是一种极具前途的电催化剂. 然而, 其导电性差和活性低, 因此催化性能受到限制. 此外, MoS2无法满足工业化大规模应用的要求. 本工作中, 为了获得具有S空位缺陷的P掺杂MoS2催化剂, 我们在室温下通过固相离子交换将P插入到MoS2基体中. 当P掺杂量为11.4 wt%时为最佳, 所制备的催化剂具有优异的电催化析氢(HER) 和析氧(OER)性能. 碱性条件下, 在10 mA cm−2电流密度下对应的过电位分别为93和316 mV, 这些数值超过了先前报道的大多数二硫化钼基材料的过电位. 理论计算和实验结果都表明, MoS2基面上形成的掺杂P活性中心及由P掺杂引起的S空位缺陷的协同作用增强了催化剂的本征电子电导率和电催化活性. 密度泛函理论计算表明, 与原始的MoS2相比, P优化了MoS2氢吸附自由能,从而显著提高了掺杂后催化剂对HER的固有活性. P掺杂MoS2对OER的催化活性增强归因于掺杂P促进羟基和含氧中间体的吸附及反应能垒的降低. 本研究提出了一种全新、环保、便捷的固相离子交换法来提高二维过渡金属硫族化合物在大规模应用中的电催化能力.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (52072196) and the Major Basic Research Program of the Natural Science Foundation of Shandong Province (ZR2020ZD09). We thank the National Supercomputing Center in Shenzhen, China for their computation assistance.

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Authors and Affiliations

  1. College of Electromechanical Engineering, Qingdao University of Science and Technology, Qingdao, 266061, China

    Hongyao Xue  (薛鸿垚) & Zhenjiang Li  (李镇江)

  2. Key Laboratory of Optic-electric Sensing and Analytical Chemistry for Life Science, MOE, College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao, 266042, China

    Alan Meng  (孟阿兰)

  3. Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Center for Excellence in Molecular Sciences Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China

    Chunjun Chen  (陈春俊)

  4. University of Kent, Canterbury, CT2 7NZ, Kent County, UK

    Hongyan Xue  (薛鸿焱)

  5. College of Materials Science and Engineering, Qingdao University of Science and Technology, Qingdao, 266061, China

    Zhenjiang Li  (李镇江)

  6. National Engineering Laboratory for Advanced Equipments and Key Materials for Tires, Qingdao University of Science and Technology, Qingdao, 266042, China

    Chuansheng Wang  (汪传生)

Authors
  1. Hongyao Xue  (薛鸿垚)
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  2. Alan Meng  (孟阿兰)
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  3. Chunjun Chen  (陈春俊)
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  4. Hongyan Xue  (薛鸿焱)
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  5. Zhenjiang Li  (李镇江)
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  6. Chuansheng Wang  (汪传生)
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Contributions

Xue Hongyao and Li Z conceived the idea. Chen C and Wang C designed the experiments, collected and analyzed the data. Meng A assisted in the theoretical calculations, experiments and characterization. Xue Hongyan assisted in drawing the pictures. Xue Hongyao and Li Z co-wrote the manuscript. All authors discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to Chunjun Chen  (陈春俊), Zhenjiang Li  (李镇江) or Chuansheng Wang  (汪传生).

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Conflict of interest

The authors declare that they have no conflict of interest.

Hongyao Xue received his MSc degree in 2018 from the University of Paderborn. He is studying for his PhD degree at Qingdao University of Science & Technology. His research involves the development and utilization of electrocatalysis materials and energy storage materials.

Zhenjiang Li is a professor of the College of Materials Science and Engineering, Qingdao University of Science & Technology. He received his PhD degree of materials science from the Northwestern Polytechnical University in 2003. Then, he worked as a postdoctoral fellow at Tsinghua University. His research interests mainly focus on the development of novel-type electrode materials for electrocatalysts, photocatalysis, supercapacitors and batteries.

Supplementary Materials

40843_2021_1774_MOESM1_ESM.pdf

Phosphorus-inserted MoS2 with Sulfur Vacancy Defects via a New Solid Phase Ion Exchange Method to boost Electrochemical Water Splitting

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Xue, H., Meng, A., Chen, C. et al. Phosphorus-doped MoS2 with sulfur vacancy defects for enhanced electrochemical water splitting. Sci. China Mater. 65, 712–720 (2022). https://doi.org/10.1007/s40843-021-1774-9

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  • DOI: https://doi.org/10.1007/s40843-021-1774-9

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