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Single-atom Rh/N-doped carbon electrocatalyst for formic acid oxidation


To meet the requirements of potential applications, it is of great importance to explore new catalysts for formic acid oxidation that have both ultra-high mass activity and CO resistance. Here, we successfully synthesize atomically dispersed Rh on N-doped carbon (SA-Rh/CN) and discover that SA-Rh/CN exhibits promising electrocatalytic properties for formic acid oxidation. The mass activity shows 28- and 67-fold enhancements compared with state-of-the-art Pd/C and Pt/C, respectively, despite the low activity of Rh/C. Interestingly, SA-Rh/CN exhibits greatly enhanced tolerance to CO poisoning, and Rh atoms in SA-Rh/CN resist sintering after long-term testing, resulting in excellent catalytic stability. Density functional theory calculations suggest that the formate route is more favourable on SA-Rh/CN. According to calculations, the high barrier to produce CO, together with the relatively unfavourable binding with CO, contribute to its CO tolerance.

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Fig. 1: The synthesis strategy and characterizations.
Fig. 2: Structural characterization by XAFS spectroscopy.
Fig. 3: Electrooxidation of formic acid performance.
Fig. 4: Two CO stripping experiments.
Fig. 5: DFT calculations.

Data availability

The data that support the findings of this paper are available from the corresponding authors upon reasonable request.


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This work was supported by the National Key R&D Program of China (2016YFA0202801 and 2018YFA0702003), the National Natural Science Foundation of China (21671117, 21871159 and 21890383), China Postdoctoral Science Foundation (043260409) and the Jilin Province Science and Technology Development Program (20150101066JC and 20160622037JC). We thank Stanford Synchrotron Radiation Lightsource (SSRL) BL7-3 for providing the beam time. R.C. acknowledges support from the DOE-funded LDRD programme and SSRL. J.D. acknowledges support from the Youth Innovation Promotion Association CAS.

Author information




Y.X. performed the experiments and wrote the paper. Z.-Q.H. and C.-R.C. conducted the DFT calculations and analysis. J.D., R.C., Y.W. and W.C. helped with XANES and EXAFS spectrometry analyses. P.X. and Y.X. collected and analysed the data. Z.L. helped with synthesizing the catalysts. Z.J. and W.X. helped with the single cell test. Z.Z. helped with the data analysis of electrooxidation. X.W., J.Y., S.S. and L.Z. helped with the in situ FTIR analysis. L.G. assisted with taking AC-HAADF-STEM images. X.C., H.Y., C.C. and Q.P. helped with data analyses and discussions. D.W. and Y.L. conceived the experiments, planned synthesis, analysed results and wrote the paper.

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Correspondence to Dingsheng Wang or Yadong Li.

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Supplementary methods, Figs. 1–84 and Tables 1–11.

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Xiong, Y., Dong, J., Huang, ZQ. et al. Single-atom Rh/N-doped carbon electrocatalyst for formic acid oxidation. Nat. Nanotechnol. 15, 390–397 (2020).

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