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Carbon Fiber Supported Binary Metal Sulfide Catalysts with Multi-Dimensional Structures for Electrocatalytic Nitrogen Reduction Reactions Over a Wide pH Range

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Abstract

Green and environmentally friendly electrocatalytic nitrogen (N2) fixation to synthesize ammonia (NH3) is recognized as an effective method to replace the traditional Haber–Bosch process. However, the difficulties in N2 adsorption and fracture of hard N≡N bond still remain major challenges in electrocatalytic N2 reduction reactions (NRR). From the perspectives of enhancing N2 adsorption and providing more catalytic sites, two-dimensional (2D) FeS2 nanosheets and three-dimensional (3D) metal organic framework-derived ZnS embedded within N-doped carbon polyhedras are grown on the carbon cloth (CC) template in this work. Thus, a composite NRR catalyst with multi-dimensional structures, which is signed as FeS2/ZnS-NC@CC, is obtained for using over a wide pH range. The uniform distribution of hollow ZnS-NC frameworks and FeS2 nanosheets on the surface of CC largely increase the N2 enrichment efficiency and offer more active sites, while the CC skeleton acts as an independent conductive substrate and S-doping helps promote the fracture of N≡N bond during the NRR reaction. As a result, the FeS2/ZnS-NC@CC electrode achieves a high Faraday efficiency of 46.84% and NH3 yield of 58.52 μg h−1 mg−1 at -0.5 V vs. Ag/AgCl in 0.1 M KOH. Furthermore, the FeS2/ZnS-NC@CC electrode displays excellent NRR catalytic activity in acidic and neutral electrolytes as well, which outperforms most previously reported electrocatalysts including noble metals. Therefore, this work provides a new way for the design of multi-dimensional electrocatalysts with excellent electrocatalytic efficiency and stability for NRR applications.

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Acknowledgements

The authors are grateful for the financial support from the Natural Science Foundation of Shanghai (20ZR1401400, 18ZR1401600), Shanghai Scientific and Technological Innovation Project (18JC1410600).

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Authors and Affiliations

  1. State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science and Engineering, Innovation Center for Textile Science and Technology, Donghua University, 2999 North Renmin Road, Shanghai, 201620, People’s Republic of China

    Tianyi Zhang, Wei Zong, Yue Ouyang, Yue-E Miao & Tianxi Liu

  2. Research Center for Analysis and Measurement, Donghua University, Shanghai, 201620, People’s Republic of China

    Yue Wu

  3. Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, Wuxi, 214122, People’s Republic of China

    Tianxi Liu

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  1. Tianyi Zhang
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Zhang, T., Zong, W., Ouyang, Y. et al. Carbon Fiber Supported Binary Metal Sulfide Catalysts with Multi-Dimensional Structures for Electrocatalytic Nitrogen Reduction Reactions Over a Wide pH Range. Adv. Fiber Mater. 3, 229–238 (2021). https://doi.org/10.1007/s42765-021-00072-0

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