Abstract
Single-atom catalysts have shown promising performance in various catalytic reactions. Catalytic metal sites supported on oxides or carbonaceous materials are usually strongly coordinated by oxygen or heteroatoms, which naturally affects their electronic environment and consequently their catalytic activity. Here, we reveal the stabilization of single-atom catalysts on tungsten carbides without the aid of heteroatom coordination for efficient catalysis of the oxygen evolution reaction (OER). Benefiting from the unique structure of tungsten carbides, the atomic FeNi catalytic sites are weakly bonded with the surface W and C atoms. The reported catalyst shows a low overpotential of 237 mV at 10 mA cm−2, which can even be lowered to 211 mV when the FeNi content is increased, a high turnover frequency value of 4.96 s−1 (η = 300 mV) and good stability (1,000 h). Density functional theory calculations show that either metallic Fe/Ni atoms or (hydro)oxide FeNi species are responsible for the high OER activity. We suggest that the application of inexpensive and durable WCx supports opens up a promising pathway to develop further single-atom catalysts for electrochemical catalytic reactions
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Acknowledgements
We thank C. Eichenauer and M. Unterweger for assistance with TGA and X-ray diffraction analysis; we are also grateful to the high-performance computing centre and J. Zhou of Nanjing Tech University for support with computational resources. The authors also thank Ceshigo for technical support with DFT calculations and XAS data. We also thank ZELMI, TU-Berlin for supporting SEM measurements. This work is funded by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) under Germany’s Excellence Strategy-EXC 2008/1 (UniSysCat)-390540038 and Basismodul, Eigene Stelle (LI 3545/1-1)-449814841, postdoctoral funding from TU-Berlin (3-1323552-07-01, 3-2323552-07-01), National Key R&D Programme of China (2019YFA0110600, 2019YFA0110601), National Natural Science Foundation of China (11902144), Science and Technology Project of Sichuan Province (2020YFH0087) and Natural Science Foundation of the Jiangsu Higher Education Institutions (19KJB430022). This project has also received funding from the European Union’s Horizon 2020 Research and Innovation Programme under grant agreement no. 823717−ESTEEM3.
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S.L. and A.T. conceived and designed the experiments. S.L. synthesized the materials and performed catalytic tests. Y.W. and P.A.v.A. performed STEM imaging and analytical characterization, and analysed the STEM data. B.C., S.L. and C.C. conceived the module structure and carried out the DFT calculations. C.C. assisted with measurement of XAS and data analysis. M.-Y.Y. performed the SEM measurements. S.L., C.C. and A.T. wrote the whole paper together.
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S.L. and A.T. have filed a provisional patent application regarding the synthesis of WCx-supported single-atom catalysts. The remaining authors declare no competing interests.
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Supplementary Information
Chemical reagents and materials. Characterizations and methods. Experimental sections. Electrochemical measurements. Calculation methods. Supplementary Figs. 1–44 and Tables 1–6. Captions for Videos 1–3.
Supplementary Video 1
The active atoms on WCx under STEM.
Supplementary Video 2
The active atoms at the edge of WCx under STEM.
Supplementary Video 3
The production of O2 on the electrode.
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Li, S., Chen, B., Wang, Y. et al. Oxygen-evolving catalytic atoms on metal carbides. Nat. Mater. 20, 1240–1247 (2021). https://doi.org/10.1038/s41563-021-01006-2
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DOI: https://doi.org/10.1038/s41563-021-01006-2
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