Rational design of high-performance low-loading oxygen reduction catalysts for alkaline fuel cells
Source abstract
Abstract
The lack of mechanistic understanding and catalyst design principles for alkaline electrolytes, especially for the sluggish oxygen reduction reaction, has impeded the advancement of alkaline fuel cells. Here we propose a modified volcano plot and apply this rationale to strategically design Pt nanosheets with PdHx nanosheets substrates. This catalyst exhibited high stability with a specific activity of 1.71 mA cm-2 at 0.95 V versus the reversible hydrogen electrode, surpassing the benchmark of Pt/C by 49-fold. Spectroscopic, electrochemical and electron microscopic characterizations revealed that such performance enhancement originated from tensile-strained Pt{111} facets, improving oxidative stability and suppressing carbon corrosion. In fuel cell testing, the catalyst enabled a peak power density of 1.67 W cm-2 with a loading of 10 µgPGM Cathode cm-2. Further optimization delivered a peak power density of 21.7 W mg-1PGM Cathode+Anode with a total specific catalyst cost US$1.27 kW-1, surpassing the US Department of Energy's Pt group metal loading and cost targets. This study provides valuable insights into catalyst design for the alkaline oxygen reduction reaction.
Source: europepmc · Quality: candidate unverified · Source record ↗
Research context
OpenAlex topics: Electrocatalysts for Energy Conversion · Fuel Cells and Related Materials · Nanoporous metals and alloys
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (57)
Show source-provided references
1. Britton, B. et al. Perspective—the next decade of AEMFCs: near-term targets to accelerate applied R&D. J. Electrochem. Soc. 167, 084514 (2020).10.1149/1945-7111/ab8c88 ↗
2. Luo, M. & Koper, M. T. M. A kinetic descriptor for the electrolyte effect on the oxygen reduction kinetics on Pt(111). Nat. Catal. 5, 615–623 (2022).10.1038/s41929-022-00810-6 ↗
3. She, Z. W. et al. Combining theory and experiment in electrocatalysis: insights into materials design. Science 355, eaad4998 (2017).10.1126/science.aad4998 ↗
4. Ooka, H., Huang, J. & Exner, K. S. The Sabatier principle in electrocatalysis: basics, limitations, and extensions. Front. Energy Res. 9, 654460 (2021).10.3389/fenrg.2021.654460 ↗
5. Sabatier, P. How I have been led to the direct hydrogenation method by metallic catalysts. Ind. Eng. Chem. 18, 1005–1008 (1926).10.1021/ie50202a005 ↗
6. Kulkarni, A., Siahrostami, S., Patel, A. & Nørskov, J. K. Understanding catalytic activity trends in the oxygen reduction reaction. Chem. Rev. 118, 2302–2312 (2018).10.1021/acs.chemrev.7b00488 ↗
7. 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).10.1021/jp047349j ↗
8. Wang, Y. J. et al. Carbon-supported Pt-based alloy electrocatalysts for the oxygen reduction reaction in polymer electrolyte membrane fuel cells: particle size, shape, and composition manipulation and their impact to activity. Chem. Rev. 115, 3433–3467 (2015).10.1021/cr500519c ↗
9. Lim, C., Fairhurst, A. R., Ransom, B. J., Haering, D. & Stamenkovic, V. R. Role of transition metals in Pt alloy catalysts for the oxygen reduction reaction. ACS Catal. 13, 14874–14893 (2023).10.1021/acscatal.3c03321 ↗
10. Stamenkovic, V. R., Strmcnik, D., Lopes, P. P. & Markovic, N. M. Energy and fuels from electrochemical interfaces. Nat. Mater. 16, 57–69 (2016).10.1038/nmat4738 ↗
11. Li, H. et al. Oxidative stability matters: a case study of pallidum hydride nanosheets for alkaline fuel cells. J. Am. Chem. Soc. 144, 8106–8114 (2022).10.1021/jacs.2c00518 ↗
12. Zhou, M. et al. Improvement of oxygen reduction performance in alkaline media by tuning phase structure of Pd-Bi nanocatalysts. J. Am. Chem. Soc. 143, 15891–15897 (2021).10.1021/jacs.1c08644 ↗
13. Wang, L. et al. Tunable intrinsic strain in two-dimensional transition metal electrocatalysts. Science 363, 870–874 (2019).10.1126/science.aat8051 ↗
14. Luo, M. et al. PdMo bimetallene for oxygen reduction catalysis. Nature 574, 81–85 (2019).10.1038/s41586-019-1603-7 ↗
15. Gómez-Marín, A. M., Rizo, R. & Feliu, J. M. Oxygen reduction reaction at Pt single crystals: a critical overview. Catal. Sci. Technol. 4, 1685–1698 (2014).10.1039/c3cy01049j ↗
16. Li, M. F., Liao, L. W., Yuan, D. F., Mei, D. & Chen, Y. X. pH effect on oxygen reduction reaction at Pt(111) electrode. Electrochim. Acta 110, 780–789 (2013).10.1016/j.electacta.2013.04.096 ↗
17. Jensen, K. D. et al. Elucidation of the oxygen reduction volcano in alkaline media using a copper–platinum(111) alloy. Angew. Chem. Int. Ed. 57, 2800–2805 (2018).10.1002/anie.201711858 ↗
18. 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).10.1038/nchem.1069 ↗
19. Friebel, D. et al. In situ X-ray probing reveals fingerprints of surface platinum oxide. Phys. Chem. Chem. Phys. 13, 262–266 (2010).10.1039/C0CP01434F ↗
20. McCaulley, J. A. In-situ X-ray absorption spectroscopy studies of hydride and carbide formation in supported palladium catalysts. J. Phys. Chem. 97, 10372–10379 (1993).10.1021/j100142a018 ↗
21. Liu, G. et al. Hydrogen-intercalation-induced lattice expansion of Pd@Pt core-shell nanoparticles for highly efficient electrocatalytic alcohol oxidation. J. Am. Chem. Soc. 143, 11262–11270 (2021).10.1021/jacs.1c05856 ↗
22. Sasaki, K., Marinkovic, N., Isaacs, H. S. & Adzic, R. R. Synchrotron-based in situ characterization of carbon-supported platinum and platinum monolayer electrocatalysts. ACS Catal. 6, 69–76 (2016).10.1021/acscatal.5b01862 ↗
23. Takimoto, D. et al. Platinum nanosheets synthesized via topotactic reduction of single-layer platinum oxide nanosheets for electrocatalysis. Nat. Commun. 14, 19 (2023).10.1038/s41467-022-35616-4 ↗
24. Stamenkovic, V. R. et al. Improved oxygen reduction activity on Pt3Ni(111) via increased surface site availability. Science 315, 493–497 (2007).10.1126/science.1135941 ↗
25. Liang, Y., McLaughlin, D., Csoklich, C., Schneider, O. & Bandarenka, A. S. The nature of active centers catalyzing oxygen electro-reduction at platinum surfaces in alkaline media. Energy Environ. Sci. 12, 351–357 (2019).10.1039/C8EE03228A ↗
26. Govindarajan, N., Xu, A. & Chan, K. How pH affects electrochemical processes. Science 375, 379–380 (2022).10.1126/science.abj2421 ↗
27. Kelly, S. R., Kirk, C., Chan, K. & Nørskov, J. K. Electric field effects in oxygen reduction kinetics: rationalizing pH dependence at the Pt(111), Au(111), and Au(100) electrodes. J. Phys. Chem. C 124, 14581–14591 (2020).10.1021/acs.jpcc.0c02127 ↗
28. Briega-Martos, V., Herrero, E. & Feliu, J. M. Effect of pH and water structure on the oxygen reduction reaction on platinum electrodes. Electrochim. Acta 241, 497–509 (2017).10.1016/j.electacta.2017.04.162 ↗
29. Li, H. et al. Analysis of the limitations in the oxygen reduction activity of transition metal oxide surfaces. Nat. Catal. 4, 463–468 (2021).10.1038/s41929-021-00618-w ↗
30. Tian, X. et al. Engineering bunched Pt-Ni alloy nanocages for efficient oxygen reduction in practical fuel cells. Science 366, 850–856 (2019).10.1126/science.aaw7493 ↗
31. Wang, Q. et al. Unveiling the pitfalls of comparing oxygen reduction reaction kinetic data for Pd-based electrocatalysts without the experimental conditions of the current−potential curves. ACS Energy Lett. 7, 952–957 (2022).10.1021/acsenergylett.2c00181 ↗
32. He, T. et al. Mastering the surface strain of platinum catalysts for efficient electrocatalysis. Nature 598, 76–81 (2021).10.1038/s41586-021-03870-z ↗
33. Bugaev, A. L. et al. Palladium carbide and hydride formation in the bulk and at the surface of palladium nanoparticles. J. Phys. Chem. C 122, 12029–12037 (2018).10.1021/acs.jpcc.7b11473 ↗
34. Kabiraz, M. K. et al. Ligand effect of shape-controlled β-palladium hydride nanocrystals on liquid-fuel oxidation reactions. Chem. Mater. 31, 5663–5673 (2019).10.1021/acs.chemmater.9b01561 ↗
35. Zhang, J. et al. Controlling the catalytic activity of platinum-monolayer electrocatalysts for oxygen reduction with different substrates. Angew. Chem. Int. Ed. 44, 2132–2135 (2005).10.1002/anie.200462335 ↗
36. Xu, Y., Ruban, A. V. & Mavrikakis, M. Adsorption and dissociation of O2 on Pt-Co and Pt-Fe alloys. J. Am. Chem. Soc. 126, 4717–4725 (2004).10.1021/ja031701+ ↗
37. Rizo, R., Sitta, E., Herrero, E., Climent, V. & Feliu, J. M. Towards the understanding of the interfacial pH scale at Pt(111) electrodes. Electrochim. Acta 162, 138–145 (2015).10.1016/j.electacta.2015.01.069 ↗
38. Kuo, D. Y., Lu, X., Hu, B., Abruña, H. D. & Suntivich, J. Rate and mechanism of electrochemical formation of surface-bound hydrogen on Pt(111) single crystals. J. Phys. Chem. Lett. 13, 6383–6390 (2022).10.1021/acs.jpclett.2c01734 ↗
39. Editor, G. et al. Stripping voltammetry of carbon monoxide oxidation on stepped platinum single-crystal electrodes in alkaline solution. Phys. Chem. Chem. Phys. 10, 3802–3811 (2008).10.1039/b803503m ↗
40. Jia, Q. et al. Activity descriptor identification for oxygen reduction on platinum-based bimetallic nanoparticles: in situ observation of the linear composition–strain–activity relationship. ACS Nano 9, 387–400 (2015).10.1021/nn506721f ↗
41. Roth, C. et al. Determination of O[H] and CO coverage and adsorption sites on PtRu electrodes in an operating PEM fuel cell. J. Am. Chem. Soc. 127, 14607–14615 (2005).10.1021/ja050139f ↗
42. Teliska, M., O’Grady, W. E. & Ramaker, D. E. Determination of O and OH adsorption sites and coverage in situ on Pt electrodes from Pt L23 X-ray absorption spectroscopy. J. Phys. Chem. B 109, 8076–8084 (2005).10.1021/jp0502003 ↗
43. Meier, J. C. et al. Design criteria for stable Pt/C fuel cell catalysts. Beilstein J. Nanotechnol. 5, 44–67 (2014).10.3762/bjnano.5.5 ↗
44. Zeng, R. et al. Methanol oxidation using ternary ordered intermetallic electrocatalysts: a DEMS study. ACS Catal. 10, 770–776 (2020).10.1021/acscatal.9b04344 ↗
45. Cherstiouk, O. V. et al. Microstructure effects on the electrochemical corrosion of carbon materials and carbon-supported Pt catalysts. Electrochim. Acta 55, 8453–8460 (2010).10.1016/j.electacta.2010.07.047 ↗
46. Wang, X. X., Swihart, M. T. & Wu, G. Achievements, challenges and perspectives on cathode catalysts in proton exchange membrane fuel cells for transportation. Nat. Catal. 2, 578–589 (2019).10.1038/s41929-019-0304-9 ↗
47. Hydrogen and Fuel Cell Technologies Office DOE Technical Targets for Polymer Electrolyte Membrane Fuel Cell Components (US DOE, 2022); https://www.energy.gov/eere/fuelcells/doe-technical-targets-polymer-electrolyte-membrane-fuel-cell-components
48. Setzler, B. P., Zhuang, Z., Wittkopf, J. A. & Yan, Y. Activity targets for nanostructured platinum-group-metal-free catalysts in hydroxide exchange membrane fuel cells. Nat. Nanotechnol. 11, 1020–1025 (2016).10.1038/nnano.2016.265 ↗
49. Douglin, J. C. et al. High-performance ionomerless cathode anion-exchange membrane fuel cells with ultra-low-loading Ag–Pd alloy electrocatalysts. Nat. Energy 8, 1262–1272 (2023).10.1038/s41560-023-01385-7 ↗
50. Kim, D., Resasco, J., Yu, Y., Asiri, A. M. & Yang, P. Synergistic geometric and electronic effects for electrochemical reduction of carbon dioxide using gold–copper bimetallic nanoparticles. Nat. Commun. 5, 4948 (2014).10.1038/ncomms5948 ↗
51. Lima, F. H. B. et al. Catalytic activity–d-band center correlation for the O2 reduction reaction on platinum in alkaline solutions. J. Phys. Chem. C 111, 404–410 (2007).10.1021/jp065181r ↗
52. Mustain, W. E., Chatenet, M., Page, M. & Kim, Y. S. Durability challenges of anion exchange membrane fuel cells. Energy Environ. Sci. 13, 2805–2838 (2020).10.1039/D0EE01133A ↗
53. Wang, H. & Abruña, H. D. IrPdRu/C as H2 oxidation catalysts for alkaline fuel cells. J. Am. Chem. Soc. 139, 6807–6810 (2017).10.1021/jacs.7b02434 ↗
54. Leshchev, D. et al. The Inner Shell Spectroscopy beamline at NSLS-II: a facility for in situ and operando X-ray absorption spectroscopy for materials research. J. Synchrotron Radiat. 29, 1095–1106 (2022).10.1107/S160057752200460X ↗
55. Yang, Y. et al. In situ X-ray absorption spectroscopy of a synergistic Co-Mn oxide catalyst for the oxygen reduction reaction. J. Am. Chem. Soc. 141, 1463–1466 (2019).10.1021/jacs.8b12243 ↗
56. Ravel, B. & Newville, M. ATHENA, ARTEMIS, HEPHAESTUS: data analysis for X-ray absorption spectroscopy using IFEFFIT. J. Synchrotron Radiat. 12, 537–541 (2005).10.1107/S0909049505012719 ↗
57. Yang, Y. et al. High-loading composition-tolerant Co-Mn spinel oxides with performance beyond 1 W/cm2 in alkaline polymer electrolyte fuel cells. ACS Energy Lett. 4, 1251–1257 (2019).10.1021/acsenergylett.9b00597 ↗