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.
Subscribe to Journal
Get full journal access for 1 year
only $4.92 per issue
All prices are NET prices.
VAT will be added later in the checkout.
Tax calculation will be finalised during checkout.
Rent or Buy article
Get time limited or full article access on ReadCube.
All prices are NET prices.
The data that support the findings of this paper are available from the corresponding authors upon reasonable request.
Arico, A. S., Bruce, P., Scrosati, B., Tarascon, J. M. & van Schalkwijk, W. Nanostructured materials for advanced energy conversion and storage devices. Nat. Mater. 4, 366–377 (2005).
Lai, J. et al. Concave and duck web-like platinum nanopentagons with enhanced electrocatalytic properties for formic acid oxidation. J. Mater. Chem. A 4, 807–812 (2016).
Vidal-Iglesias, F. J., López-Cudero, A., Solla-Gullón, J. & Feliu, J. M. Towards more active and stable electrocatalysts for formic acid electrooxidation: antimony‐decorated octahedral platinum nanoparticles. Angew. Chem. Int. Ed. 52, 964–967 (2013).
Su, N. et al. The facile synthesis of single crystalline palladium arrow-headed tripods and their application in formic acid electro-oxidation. Chem. Commun. 51, 7195–7198 (2015).
Yang, S. et al. One-pot synthesis of graphene-supported monodisperse Pd nanoparticles as catalyst for formic acid electro-oxidation. Sci. Rep. 4, 4501 (2014).
Sial, M. A. Z. G., Ud Din, M. A. & Wang, X. Multimetallic nanosheets: synthesis and applications in fuel cells. Chem. Soc. Rev. 47, 6175–6200 (2018).
Li, C. et al. Dendritic defect-rich palladium-copper-cobalt nanoalloys as robust multifunctional non-platinum electrocatalysts for fuel cells. Nat. Commun. 9, 3702 (2018).
Chen, S., Su, H., Wang, Y., Wu, W. & Zeng, J. Size-controlled synthesis of platinum–copper hierarchical trigonal bipyramid nanoframes. Angew. Chem. Int. Ed. 54, 108–113 (2015).
Fu, Q., Li, H., Ma, S., Hu, B. & Yu, S. A mixed-solvent route to unique PtAuCu ternary nanotubes templated from Cu nanowires as efficient dual electrocatalysts. Sci. China Mater. 59, 112–121 (2016).
Dong, L. et al. Pd–Ag alloy hollow nanostructures with interatomic charge polarization for enhanced electrocatalytic formic acid oxidation. Nano Res. 9, 1590–1599 (2016).
Ji, X. et al. Nanocrystalline intermetallics on mesoporous carbon for direct formic acid fuel cell anodes. Nat. Chem. 2, 286–293 (2010).
Xu, H. et al. Ultra-uniform PdBi nanodots with high activity towards formic acid oxidation. J. Power Sources 356, 27–35 (2017).
Chang, J., Feng, L., Liu, C., Xing, W. & Hu, X. An effective Pd-Ni2P/C anode catalyst for direct formic acid fuel cells. Angew. Chem. Int. Ed. 53, 122–126 (2014).
Wang, X., Yang, J., Yin, H., Song, R. & Tang, Z. ‘Raisin bun’‐like nanocomposites of palladium clusters and porphyrin for superior formic acid oxidation. Adv. Mater. 25, 2728–2732 (2013).
Li, H. et al. Shape-controlled synthesis of surface-clean ultrathin palladium nanosheets by simply mixing a dinuclear PdI carbonyl chloride complex with H2O. Angew. Chem. Int. Ed. 52, 8368–8372 (2013).
Huang, X. et al. Freestanding palladium nanosheets with plasmonic and catalytic properties. Nat. Nanotechnol. 6, 28–32 (2011).
He, T. et al. Inflating hollow nanocrystals through a repeated Kirkendall cavitation process. Nat. Commun. 8, 1261 (2017).
Li, C. et al. Surfactant-directed synthesis of mesoporous Pd films with perpendicular mesochannels as efficient electrocatalysts. J. Am. Chem. Soc. 137, 11558–11561 (2015).
Xia, B. et al. Ultrathin and ultralong single-crystal platinum nanowire assemblies with highly stable electrocatalytic activity. J. Am. Chem. Soc. 135, 9480–9485 (2013).
Guo, X. et al. Direct, nonoxidative conversion of methane to ethylene, aromatics and hydrogen. Science 344, 616–619 (2014).
Yang, X. F. et al. Single-atom catalysts: a new frontier in heterogeneous catalysis. Acc. Chem. Res. 46, 1740–1748 (2013).
Chen, Y. et al. Single-atom catalysts: synthetic strategies and electrochemical applications. Joule 2, 1242–1264 (2018).
Liu, J. Catalysis by supported single metal atoms. ACS Catal. 7, 34–59 (2017).
Jones, J. et al. Thermally stable single-atom platinum-on-ceria catalysts via atom trapping. Science 353, 150–154 (2016).
Liu, P. et al. Photochemical route for synthesizing atomically dispersed palladium catalysts. Science 352, 797–800 (2016).
Wang, L. et al. Atomic-level insights in optimizing reaction paths for hydroformylation reaction over Rh/CoO single-atom catalyst. Nat. Commun. 7, 14036 (2016).
Zitolo, A. et al. Identification of catalytic sites in cobalt–nitrogen–carbon materials for the oxygen reduction reaction. Nat. Commun. 8, 957 (2017).
Wu, H. et al. Highly doped and exposed Cu(i)–N active sites within graphene towards efficient oxygen reduction for zinc–air batteries. Energy Environ. Sci. 9, 3736–3745 (2016).
Gao, G., Jiao, Y., Waclawik, E. R. & Du, A. Single atom (Pd/Pt) supported on graphitic carbon nitride as an efficient photocatalyst for visible-light reduction of carbon dioxide. J. Am. Chem. Soc. 138, 6292–6297 (2016).
Liu, W. et al. Single-site active cobalt-based photocatalyst with a long carrier lifetime for spontaneous overall water splitting. Angew. Chem. Int. Ed. 56, 9312–9317 (2017).
Cao, Y. et al. Atomic-level insight into optimizing the hydrogen evolution pathway over a Co1-N4 single-site photocatalyst. Angew. Chem. Int. Ed. 56, 12191–12196 (2017).
Wei, S. et al. Direct observation of noble metal nanoparticles transforming to thermally stable single atoms. Nat. Nanotechnol. 13, 856–861 (2018).
Funke, H. & Scheinost, A. C. Wavelet analysis of extended X-ray absorption fine structure data. Phys. Rev. B 71, 094110 (2005).
Zitolo, A. et al. Identification of catalytic sites for oxygen reduction in iron- and nitrogen-doped graphene materials. Nat. Mater. 14, 937–942 (2015).
Liu, W. et al. Single-atom dispersed Co–N–C catalyst: structure identification and performance for hydrogenative coupling of nitroarenes. Chem. Sci. 7, 5758–5764 (2016).
Fei, H. et al. General synthesis and definitive structural identification of MN4C4 single-atom catalysts with tunable electrocatalytic activities. Nat. Catal. 1, 63–72 (2018).
Sarangi, R., Cho, J., Nam, W. & Solomon, E. I. XAS and DFT investigation of mononuclear cobalt(iii) peroxo complexes: electronic control of the geometric structure in CoO2 versus NiO2 systems. Inorg. Chem. 50, 614–620 (2011).
Koningsberger, D. C. & Prins, R. (eds.) X-ray Absorption: Principles, Applications, Techniques of EXAFS, SEXAFS and XANES Vol. 92 (Wiley, 1988).
Vaughan, B. A. et al. Mechanistic studies of single-step styrene production using a rhodium(i) catalyst. J. Am. Chem. Soc. 139, 1485–1498 (2017).
Jiang, B. et al. A stepwise-designed Rh-Au-Si nanocomposite that surpasses Pt/C hydrogen evolution activity at high overpotentials. Nano Res. 10, 1749–1755 (2017).
Sateke, S. et al. Pentamethylcyclopentadienyl rhodium(iii)–chiral disulfonate hybrid catalysis for enantioselective C–H bond functionalization. Nat. Catal. 1, 585–591 (2018).
Herron, J. A., Scaranto, J., Ferrin, P., Li, S. & Mavrikakis, M. Trends in formic acid decomposition on model transition metal surfaces: a density functional theory study. ACS Catal. 4, 4434–4445 (2014).
Cho, J. et al. Role of heteronuclear interactions in selective H2 formation from HCOOH decomposition on bimetallic Pd/M (M = late transition FCC metal) catalysts. ACS Catal. 7, 2553–2562 (2017).
Lović, J. D. et al. Catalytic activities of Pt thin films electrodeposited onto Bi coated glassy carbon substrate toward formic acid electrooxidation. J. Electroanal. Chem. 735, 1–9 (2014).
Chen, Y.-X., Heinen, M., Jusys, Z. & Behm, R. J. Bridge-bonded formate: active intermediate or spectator species in formic acid oxidation on a Pt film electrode? Langmuir 22, 10399–10408 (2006).
Neurock, M., Janik, M. & Wieckowski, A. A first principles comparison of the mechanism and site requirements for the electrocatalytic oxidation of methanol and formic acid over Pt. Faraday Discuss. 140, 363–378 (2009).
Chen, Q., Liu, Z. & Wong, C. H. An ab initio molecular dynamics study on the solvation of formate ion and formic acid in water. J. Theor. Comput. Chem. 11, 1019–1032 (2012).
Lee, J. G. et al. Deprotonation of solvated formic acid: Car–Parrinello and metadynamics simulations. J. Phys. Chem. B 110, 2325–2331 (2006).
Ravel, B. & Newville, M. ATHENA, ARTEMIS, HEPHAESTUS: data analysis for X-ray absorption spectroscopy using IFEFFIT. J. Synchrotron Radiat. 12, 537–541 (2005).
Bunău, O. & Joly, Y. Self-consistent aspects of X-ray absorption calculations. J. Phys. Condens. Matter 21, 345501 (2009).
Zhu, F. et al. High selectivity PtRh/RGO catalysts for ethanol electro-oxidation at low potentials: enhancing the efficiency of CO2 from alcoholic groups. Electrochim. Acta 292, 208–216 (2018).
Zhi, W. S. et al. Combining theory and experiment in electrocatalysis: insights into materials design. Science 355, eaad4498 (2017).
Wyckoff, R. W. G. Cubic Closest Packed, CCP, Structure Crystal Structures 2nd edn, Vol. 1, 7–83 (Interscience Publishers, 1963).
Kresse, G. & Hafner, J. Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium. J. Phys. Rev. B 49, 14251–14269 (1994).
Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. J. Phys. Rev. B 54, 11169–11186 (1996).
Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).
Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 59, 1758–1775 (1999).
Monkhorst, H. J. & Pack, J. D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 13, 5188–5192 (1976).
Grimme, S., Antony, J., Ehrlich, S. & Krieg, H. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J. Chem. Phys. 132, 154104 (2010).
Jónsson, H., Mills, G. & Jacobsen, K. W. in Classical and Quantum Dynamics in Condensed Phase Simulations 385–404 (World Scientific, 1998).
Henkelman, G. & Jónsson, H. A dimer method for finding saddle points on high dimensional potential surfaces using only first derivatives. J. Chem. Phys. 111, 7010–7022 (1999).
Huang, B., Xiao, L., Lu, J. & Zhuang, L. Spatially resolved quantification of the surface reactivity of solid catalysts. Angew. Chem. Int. Ed. 55, 6239–6243 (2016).
Hoover, W. G. Canonical dynamics: equilibrium phase-space distributions. Phys. Rev. A 31, 1695–1697 (1985).
Nosé, S. A unified formulation of the constant temperature molecular dynamics methods. J. Chem. Phys. 81, 511–519 (1984).
Yeh, K. Y., Restaino, N. A., Esopi, M. R., Maranas, J. K. & Janik, M. J. The adsorption of bisulfate and sulfate anions over a Pt(111) electrode: a first principle study of adsorption configurations, vibrational frequencies and linear sweep voltammogram simulations. Catal. Today 202, 20–35 (2013).
Mathew, K., Sundararaman, R., Letchworth-Weaver, K., Arias, T. A. & Hennig, R. G. Implicit solvation model for density-functional study of nanocrystal surfaces and reaction pathways. J. Chem. Phys. 140, 084106 (2014).
Man, I. C. et al. Universality in oxygen evolution electrocatalysis on oxide surfaces. ChemCatChem 3, 1159–1165 (2011).
Yu, L., Pan, X., Cao, X., Hu, P. & Bao, X. Oxygen reduction reaction mechanism on nitrogen-doped graphene: a density functional theory study. J. Catal. 282, 183–190 (2011).
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.
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
About this article
Cite this article
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
Science China Materials (2021)
Decorating Metal Organic Framework on Nickel Foam for Efficient Cu2+ Removal Based on Adsorption and Electrochemistry
Environmental Technology (2021)
Regulating nitrogenous adsorption and desorption on Pd clusters by the acetylene linkages of hydrogen substituted graphdiyne for efficient electrocatalytic ammonia synthesis
Nano Energy (2021)
Catalytic Nanomaterials toward Atomic Levels for Biomedical Applications: From Metal Clusters to Single-Atom Catalysts
ACS Nano (2021)
New Journal of Chemistry (2021)