Abstract
Platinum is the archetypal electrocatalyst for oxygen reduction—a key reaction in fuel cells and zinc–air batteries. Although dispersing platinum as single atoms on a support is a promising way to minimize the amount required, catalytic activity and selectivity are often low due to unfavourable O2 adsorption. Here we load platinum onto α-Fe2O3 to construct a highly active and stable catalyst with dispersed Pt–Fe pair sites. We propose that the Pt–Fe pair sites have partially occupied orbitals driven by strong electronic coupling, and can cooperatively adsorb O2 and dissociate the O=O bond, whereas OH* can desorb from the platinum site. In alkaline conditions, the catalyst exhibits onset and half-wave potentials of 1.15 V and 1.05 V (versus the reversible hydrogen electrode), respectively, mass activity of 14.9 A mg−1Pt (at 0.95 V) and negligible activity decay after 50,000 cycles. It also shows better performance than 20% Pt/C in a zinc–air battery and H2–O2 fuel cell in terms of specific energy density and platinum utilization efficiency.
This is a preview of subscription content, access via your institution
Access options
Access Nature and 54 other Nature Portfolio journals
Get Nature+, our best-value online-access subscription
$29.99 / 30 days
cancel any time
Subscribe to this journal
Receive 12 digital issues and online access to articles
$119.00 per year
only $9.92 per issue
Buy this article
- Purchase on Springer Link
- Instant access to full article PDF
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
Data availability
The authors declare that all data supporting the findings of this study are available in the article and its Supplementary Information. Source data are provided with this paper.
References
Debe, M. K. Electrocatalyst approaches and challenges for automotive fuel cells. Nature 486, 43–51 (2012).
Chong, L. et al. Ultralow-loading platinum-cobalt fuel cell catalysts derived from imidazolate frameworks. Science 362, 1276–1281 (2018).
Gocyla, M. et al. Shape stability of octahedral PtNi nanocatalysts for electrochemical oxygen reduction reaction studied by in situ transmission electron microscopy. ACS Nano 12, 5306–5311 (2018).
Sun, Y. et al. Ultrathin PtPd-based nanorings with abundant step atoms enhance oxygen catalysis. Adv. Mater. 30, 1802136 (2018).
Stamenkovic, V. R. et al. Improved oxygen reduction activity on Pt3Ni (111) via increased surface site availability. Science 315, 493–497 (2007).
Luo, M. et al. Stable high-index faceted Pt skin on zigzag-like PtFe nanowires enhances oxygen reduction catalysis. Adv. Mater. 30, 1705515 (2018).
Luo, M. & Guo, S. Strain-controlled electrocatalysis on multimetallic nanomaterials. Nat. Rev. Mater. 2, 17059–17072 (2017).
Escudero-Escribano, M. et al. Tuning the activity of Pt alloy electrocatalysts by means of the lanthanide contraction. Science 352, 73–76 (2016).
Bu, L. et al. Biaxially strained PtPb/Pt core/shell nanoplate boosts oxygen reduction catalysis. Science 354, 1410–1414 (2016).
Li, M. et al. Ultrafine jagged platinum nanowires enable ultrahigh mass high activity for the oxygen reduction reaction. Science 354, 1414–1419 (2016).
Jiang, K. et al. Efficient oxygen reduction catalysis by subnanometer Pt alloy nanowires. Sci. Adv. 3, e1601705 (2017).
Huang, H. et al. Achieving remarkable activity and durability toward oxygen reduction reaction based on ultrathin Rh-doped Pt nanowires. J. Am. Chem. Soc. 139, 8152 (2017).
Bu, L. et al. PtPb/PtNi intermetallic core/atomic layer shell octahedra for efficient oxygen reduction electrocatalysis. J. Am. Chem. Soc. 139, 9576 (2017).
Huang, X. et al. High-performance transition metal-doped Pt3Ni octahedra for oxygen reduction reaction. Science 348, 1230 (2015).
Zhang, L. et al. Platinum-based nanocages with subnometer-thick walls and well-defined, controlled facets. Science 349, 412 (2015).
Shen, R. et al. High-concentration single atomic Pt sites on hollow CuSx for selective O2 reduction to H2O2 in acid solution. Chem 5, 2099–2110 (2019).
Choi, C. et al. Tuning selectivity of electrochemical reactions by atomically dispersed platinum catalyst. Nat. Commun. 7, 10922 (2016).
Yang, S., Kim, J., Tak, Y. J., Soon, A. & Lee, H. Single-atom catalyst of platinum supported on titanium nitride for selective electrochemical reactions. Angew. Chem. Int. Ed. 55, 2058–2062 (2016).
Liu, J. et al. High performance platinum single atom electrocatalyst for oxygen reduction reaction. Nat. Commun. 8, 15938 (2017).
Liu, J. et al. Carbon-supported divacancy-anchored platinum single-atom electrocatalysts with superhigh Pt utilization for the oxygen reduction reaction. Angew. Chem. Int. Ed. 58, 1163–1167 (2019).
Huang, Z.-F. et al. Strategies to break the scaling relation toward enhanced oxygen electrocatalysis. Matter 1, 1494–1518 (2019).
Shen, X. et al. Dual-site cascade oxygen reduction mechanism on SnOx/Pt–Cu–Ni for promoting reaction kinetics. J. Am. Chem. Soc. 141, 9463–9467 (2019).
Holby, E. F., Wu, G., Zelenay, P. & Taylor, C. D. Structure of Fe-Nx–C defects in oxygen reduction reaction catalysts from first-principles modeling. J. Phys. Chem. C. 118, 14388–14393 (2014).
Zhang, H. et al. High-performance fuel cell cathodes exclusively containing atomically dispersed iron active sites. Energy Environ. Sci. 12, 2548–2558 (2019).
Cheng, N., Zhang, L., Doyle-Davis, K. & Sun, X. Single-atom catalysts: from design to application. Electrochem. Energy Rev. 2, 539–573 (2019).
Sanson, A. et al. Local structure and spin transition in Fe2O3 hematite at high pressure. Phys. Rev. 94, 014112 (2016).
Shim, S. H. et al. Electronic and magnetic structures of the postperovskite-type Fe2O3 and implications for planetary magnetic records and deep interiors. Proc. Natl Acad. Sci. USA 106, 5508 (2009).
Gao, R. et al. Engineering facets and oxygen vacancies over hematite single crystal for intensified electrocatalytic H2O2 production. Adv. Funct. Mater. 30, 1910539 (2020).
Shen, G. et al. Regulating the spin state of FeIII by atomically anchoring on ultrathin titanium dioxide for efficient oxygen evolution electrocatalysis. Angew. Chem. Int. Ed. 59, 2313–2317 (2020).
Suntivich, J. et al. Design principles for oxygen-reduction activity on perovskite oxide catalysts for fuel cells and metal–air batteries. Nat. Chem. 3, 546–550 (2011).
Suntivich, J., May, K. J., Gasteiger, H. A., Goodenough, J. B. & Shao-Horn, Y. A perovskite oxide optimized for oxygen evolution catalysis from molecular orbital principles. Science 334, 1383–1385 (2011).
Lin, L. et al. A highly CO-tolerant atomically dispersed Pt catalyst for chemoselective hydrogenation. Nat. Nanotechnol. 14, 354–361 (2019).
Zhou, X. et al. Facet-mediated photodegradation of organic dye over hematite architectures by visible light. Angew. Chem. Int. Ed. 51, 178–182 (2012).
Qiao, B. et al. Single-atom catalysis of CO oxidation using Pt1/FeOx. Nat. Chem. 3, 634–641 (2011).
Zhang, H. et al. Dynamic traction of lattice-confined platinum atoms into mesoporous carbon matrix for hydrogen evolution reaction. Sci. Adv. 4, eaao6657 (2018).
Li, J. et al. Highly active and stable metal single-atom catalysts achieved by strong electronic metal-support interactions. J. Am. Chem. Soc. 141, 14515–14519 (2019).
Rodriguez, J. A. & Kuhn, M. Chemical and electronic-properties of Pt in bimetallic surfaces-photoemission and CO-chemisorption studies for Zn/Pt(111). J. Chem. Phys. 102, 4279–4289 (1995).
Zhang, Z. et al. Thermally stable single atom Pt/m-Al2O3 for selective hydrogenation and CO oxidation. Nat. Commun. 8, 16100 (2016).
Luo, M. et al. PdMo bimetallene for oxygen reduction catalysis. Nature 574, 81–85 (2019).
Zhou, Y. et al. Superexchange effects on oxygen reduction activity of edge-sharing [CoxMn1−xO6] octahedra in spinel oxide. Adv. Mater. 30, 1705407 (2018).
Wei, G.-F., Fang, Y.-H. & Liu, Z.-P. First principles Tafel kinetics for resolving key parameters in optimizing oxygen electrocatalytic reduction catalyst. J. Phys. Chem. C. 116, 12696–12705 (2012).
Holewinski, A. et al. Elementary mechanisms in electrocatalysis: revisiting the ORR Tafel slope. J. Electrochem. Soc. 159, H864–H870 (2012).
Castanheira, L. et al. Carbon corrosion in proton-exchange membrane fuel cells: effect of the carbon structure, the degradation protocol, and the gas atmosphere. ACS Catal. 2, 2184–2194 (2015).
Yang, L. et al. Unveiling the high-activity origin of single-atom iron catalysts for oxygen reduction reaction. Proc. Natl Acad. Sci. USA 115, 6626–6631 (2018).
Chen, Y. et al. Enhanced oxygen reduction with single-atomic-site iron catalysts for a zinc–air battery and hydrogen–air fuel cell. Nat. Commun. 9, 5422 (2018).
Xiao, M. et al. A single-atom iridium heterogeneous catalyst in oxygen reduction reaction. Angew. Chem. Int. Ed. 58, 9640–9645 (2019).
Peuckert, M. XPS investigation of surface oxidation layers on a platinum electrode in alkaline solution. Electrochim. Acta 29, 1315–1320 (1984).
Welsh, I. D. & Sherwood, P. M. A. Photoemission and electronic structure of FeOOH: distinguishing between oxide and oxyhydroxide. Phys. Rev. B 40, 6386–6392 (1989).
Chung, D. Y. et al. Highly durable and active PtFe nanocatalysts for electrochemical oxygen reduction reaction. J. Am. Chem. Soc. 137, 15478–15485 (2015).
Nørskov, J. K. et al. Origin of the overpotential for oxygen reduction at a fuel-cell cathode. J. Phys. Chem. B 108, 17886–17892 (2004).
Ravel, B. & Newvile, M. ATHENA, ARTEMIS, HEPHAESTUS: data analysis for X-ray absorption spectroscopy using IFEFFIT. J. Synchrotron Radiat. 12, 537–541 (2005).
Walton, J., Wincott, P., Fairley, N. & Carriick, A. Peak Fitting with CasaXPS (Accolyte Science Press, Knutsford, 2010).
Yang, X., Nash, J., Oliveira, N., Yan, Y. & Xu, B. Understanding the pH dependence of underpotential deposited hydrogen on platinum. Angew. Chem. Int. Ed. 58, 17718–17723 (2019).
Wang, Y. et al. Pt-Ru catalyzed hydrogen oxidation in alkaline media: oxophilic effect or electronic effect? Energy Environ. Sci. 8, 177–181 (2015).
Watzele, S. et al. Determination of electroactive surface area of Ni-, Co-, Fe-, and Ir-based oxide electrocatalysts. ACS Catal. 9, 9222–9230 (2019).
Watzele, S. & Bandarenka, A. S. Quick determination of electroactive surface area of some oxide electrode materials. Electroanalysis 28, 2394–2399 (2016).
Tench, D. & Warren, L. F. Electrodeposition of conducting transition metal oxide/hydroxide films from aqueous solution. J. Electrochem. Soc. 130, 869–872 (1983).
Kresse, G. & Hafner, J. Ab initio molecular dynamics for liquid metals. Phys. Rev. B 47, 558–561 (1993).
Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).
Liao, P. & Carter, E. A. Testing variations of the GW approximation on strongly correlated transition metal oxides: hematite (α-Fe2O3) as a benchmark. Phys. Chem. Chem. Phys. 13, 15189–15199 (2011).
Mathew, K., Sundararaman, R., Letchworth-Weaver, K., Arias, A. A. & Hennig, R. G. Implicit solvation model for density-functional study of nanocrystal surfaces and reaction pathways. J. Chem. Phys. 140, 084106 (2014).
Kiran, M., Chaitanya Kolluru, V. S., Mula, S., Steinmann, S. N. & Hennig, R. G. Implicit self-consistent electrolyte model in plane-wave density-functional theory. J. Chem. Phys. 151, 23401 (2019).
Gauthier, J. A. et al. Unified approach to implicit and explicit solvent simulations of electrochemical reaction energetics. J. Chem. Theory Comput. 15, 6895–6906 (2019).
Acknowledgements
J.-J.Z., L.P. and Z.-F.H. appreciate the support from the National Natural Science Foundation of China (grant nos. 22161142002, 21978200, 22008170). J.L. acknowledges the support from the National Research Foundation of Korea (NRF) grants funded by the Korean government (MSIT) (grant nos. NRF-2019R1A4A1025848 and NRF-2021R1C1C1013953). The wavefunction plots were drawn with the help of the VASPMO program developed by Y. Wang. We also thank the ZK Chemical Research Service Platform.
Author information
Authors and Affiliations
Contributions
J.-J.Z. conceived the idea. J.-J.Z., R.G. and L.P. co-wrote the paper. R.G. and L.P. synthesized the catalysts and performed the catalysis experiments, the theoretical model construction and DFT calculations. J.W. and J.L. contributed to the EXAFS spectroscopy. Z.-F.H. and R.Z. contributed to the EIS measurement and polished the manuscript. W. Wang supplied part of the data and experiments. J.Z. and W.Z. contributed to the fuel cell measurement. All of the authors contributed to the overall scientific interpretation and edited the manuscript.
Corresponding authors
Ethics declarations
Competing interests
The authors declare no competing interests.
Additional information
Peer review information Nature Energy thanks the anonymous reviewers 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.
Supplementary information
Supplementary Information
Supplementary Figs. 1–35, Tables 1–10 and Notes 1–4.
Supplementary Data 1
Numerical source data for Supplementary Fig. 23
Source data
Source Data Fig. 3
Numerical source data for Figs. 3c,d,f.
Rights and permissions
About this article
Cite this article
Gao, R., Wang, J., Huang, ZF. et al. Pt/Fe2O3 with Pt–Fe pair sites as a catalyst for oxygen reduction with ultralow Pt loading. Nat Energy 6, 614–623 (2021). https://doi.org/10.1038/s41560-021-00826-5
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/s41560-021-00826-5
This article is cited by
-
Spin polarized Fe1−Ti pairs for highly efficient electroreduction nitrate to ammonia
Nature Communications (2024)
-
In situ modulating coordination fields of single-atom cobalt catalyst for enhanced oxygen reduction reaction
Nature Communications (2024)
-
Regulating atomic Fe-Rh site distance for efficient oxygen reduction reaction
Science China Chemistry (2024)
-
Atomically dispersed materials: Ideal catalysts in atomic era
Nano Research (2024)
-
Single- and double-atom catalyst anchored on graphene-like C2N for ORR and OER: mechanistic insight and catalyst screening
Carbon Letters (2024)