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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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.
The authors declare no competing interests.
Peer review information Nature Nanotechnology thanks Matteo Cargnello, Sebastian Peter and other, anonymous, reviewer(s) for their contribution to the peer review of this work.
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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). https://doi.org/10.1038/s41565-020-0665-x
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