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![](https://wqketang.oss-cn-beijing.aliyuncs.com/unzip/large-zip/zip-5a068380-fdb5-4345-9543-0bd4a1959756/4577/files/4577-TOC.jpg?Expires=1722046244&OSSAccessKeyId=STS.NTg9w9ZxPFrLAp9YmcBB8sSBr&Signature=N4kHDGNtwl1u2oFQC92%2FcK2XvjQ%3D&security-token=CAISywJ1q6Ft5B2yfSjIr5fScs2Nt6dx8bCnQ1aIvW02Ts0UnJbpkDz2IHtKenhsBOsbtfk1mG5W5%2FgZlqJ9SptIAEfJa9d99MzBNe5rhNCT1fau5Jko1beHewHKeTOZsebWZ%2BLmNqC%2FHt6md1HDkAJq3LL%2Bbk%2FMdle5MJqP%2B%2FUFB5ZtKWveVzddA8pMLQZPsdITMWCrVcygKRn3mGHdfiEK00he8TouufTinpHMskGA1Aell7Mvyt6vcsT%2BXa5FJ4xiVtq55utye5fa3TRYgxowr%2Fwo0v0YpGya5YzHXwcPskvdKZbo78UqLQlla6w%2BGqFJqvPxr%2Fp8t%2Fx5fWJKAezhVgs8cVM8JOjIqKOscIsipskwWrEswgzSyCaJL7f%2FhREKa7znWGyxgyLY25K9yOXNh%2FA7x25WFZknm%2BbJoNLmr0pOOvEupw7sdK3UTzDnGoABbXzkp4UHTVH%2BGO8Cix75xu4gRnbl4cQw5QDCjOqKCxANISW%2FCqmpa6f7NSAHDskKVsje8ChsVrBv8k%2B2VKSvupc4KH%2BU6JW5S%2BAftIHa0LcxylOfoBazklITVqYoMuSijS8cG6eAPRpVBK%2FHFGjxX9TMl21N3PtJeLYvVWJ0MJQgAA%3D%3D)
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It is challenging and desirable to construct Pt-based nanocomposites with oxygen storage function as efficient oxygen reduction reaction (ORR) catalysts for practical proton exchange membrane fuel cells (PEMFCs). Herein, we achieve novel porous nanocomposites of PtCu3 nanoalloys-embedded in the PWOx matrix (PtCu3@PWOx), which has an oxygen container feature. The PtCu3@PWOx/C exhibits an ultrahigh mass activity (MA) of 3.94 A·mgPt−1 for ORR, which is 26.3 times as high as the commercial Pt/C and the highest value ever reported for PtCu-based binary system. Theoretical calculations reveal that the compressive strain and d-band center downshift of Pt intrinsically contribute to the excellent ORR performance. In H2-air PEMFCs at room temperature, furthermore, the PtCu3@PWOx/C delivers a high power density (218.6 mW·cm−2), much superior to commercial Pt/C (131.6 mW·cm−2). In H2-O2 PEMFCs, PtCu3@PWOx/C outputs a maximum power density of 420.1 mW·cm−2. This work provides an effective idea for designing oxygen-storing ORR catalysts used for practical room-temperature H2-air fuel cells.
Wang, X. Q.; Li, Z. J.; Qu, Y. T.; Yuan, T. W.; Wang, W. Y.; Wu, Y. E.; Li, Y. D. Review of metal catalysts for oxygen reduction reaction: From nanoscale engineering to atomic design. Chem. 2019, 5, 1486–1511.
Sun, Y. Y.; Polani, S.; Luo, F.; Ott, S.; Strasser, P.; Dionigi, F. Advancements in cathode catalyst and cathode layer design for proton exchange membrane fuel cells. Nat. Commun. 2021, 12, 5984.
Kulkarni, A.; Siahrostami, S.; Patel, A.; Nørskov, J. K. Understanding catalytic activity trends in the oxygen reduction reaction. Chem. Rev. 2018, 118, 2302–2312.
Zhang, J. W.; Yuan, Y. L.; Gao, L.; Zeng, G. M.; Li, M. F.; Huang, H. W. Stabilizing Pt-based electrocatalysts for oxygen reduction reaction: Fundamental understanding and design strategies. Adv. Mater. 2021, 33, 2006494.
Shi, Y. F.; Lyu, Z. H.; Zhao, M.; Chen, R. H.; Nguyen, Q. N.; Xia, Y. N. Noble-metal nanocrystals with controlled shapes for catalytic and electrocatalytic applications. Chem. Rev. 2021, 121, 649–735.
Huang, L.; Zaman, S.; Wang, Z. T.; Niu, H. T.; You, B.; Xia, B. Y. Synthesis and application of platinum-based hollow nanoframes for direct alcohol fuel cells. Acta Phys. Chim. Sin. 2021, 37, 2009035.
Zhu, E. B.; Xue, W.; Wang, S. Y.; Yan, X. C.; Zhou, J. X.; Liu, Y.; Cai, J.; Liu, E. S.; Jia, Q. Y.; Duan, X. F. et al. Enhancement of oxygen reduction reaction activity by grain boundaries in platinum nanostructures. Nano Res. 2020, 13, 3310–3314.
Zhao, F. L.; Zheng, L. R.; Yuan, Q.; Yang, X. T.; Zhang, Q. H.; Xu, H.; Guo, Y. L.; Yang, S.; Zhou, Z. Y.; Gu, L. et al. Ultrathin PdAuBiTe nanosheets as high-performance oxygen reduction catalysts for a direct methanol fuel cell device. Adv. Mater. 2021, 33, 2103383.
Li, J. R.; Sharma, S.; Liu, X. M.; Pan, Y. T.; Spendelow, J. S.; Chi, M. F.; Jia, Y. K.; Zhang, P.; Cullen, D. A.; Xi, Z. et al. Hard-magnet L10-CoPt nanoparticles advance fuel cell catalysis. Joule 2019, 3, 124–135.
Luo, L. X.; Fu, C. H.; Wu, A. M.; Zhuang, Z. C.; Zhu, F. J.; Jiang, F. L.; Shen, S. Y.; Cai, X. Y.; Kang, Q.; Zheng, Z. F. et al. Hydrogen-assisted scalable preparation of ultrathin Pt shells onto surfactant-free and uniform Pd nanoparticles for highly efficient oxygen reduction reaction in practical fuel cells. Nano Res. 2022, 15, 1892–1900.
Tian, X. L.; Lu, X. F.; Xia, B. Y.; Lou, X. W. Advanced electrocatalysts for the oxygen reduction reaction in energy conversion technologies. Joule 2020, 4, 45–68.
Xia, Y. N.; Campbell, C. T.; Cuenya, B. R.; Mavrikakis, M. Introduction: Advanced materials and methods for catalysis and electrocatalysis by transition metals. Chem. Rev. 2021, 121, 563–566.
Wang, Y.; Zheng, X. B.; Wang, D. S. Design concept for electrocatalysts. Nano Res. 2022, 15, 1730–1752.
Ott, S.; Orfanidi, A. ; Schmies, H.; Anke, B.; Nong, H. N.; Hübner, J.; Gernert, U.; Gliech, M.; Lerch, M.; Strasser, P. Ionomer distribution control in porous carbon-supported catalyst layers for high-power and low Pt-loaded proton exchange membrane fuel cells. Nat. Mater. 2020, 19, 77–85.
Garlyyev, B.; Watzele, S.; Fichtner, J.; Michalička, J.; Schökel, A.; Senyshyn, A.; Perego, A.; Pan, D. J.; El-Sayed, H. A.; Macak, J. M. et al. Electrochemical top-down synthesis of C-supported Pt nanoparticles with controllable shape and size: Mechanistic insights and application. Nano Res. 2021, 14, 2762–2769.
Song, J. J.; Yang, Y. X.; Liu, S. J.; Li, L.; Yu, N.; Fan, Y. T.; Chen, Z. M.; Kuai, L.; Geng, B. Y. Dispersion and support dictated properties and activities of Pt/metal oxide catalysts in heterogeneous CO oxidation. Nano Res. 2021, 14, 4841–4847.
Long, P.; Du, S. Q.; Liu, Q.; Tao, L.; Peng, C.; Wang, T. H.; Gu, K. Z.; Xie, C.; Zhang, Y. Q.; Chen, R. et al. Fluorination-enabled interface of PtNi electrocatalysts for high-performance high-temperature proton exchange membrane fuel cells. Sci. China Mater. 2022, 65, 904–912.
Greeley, J.; Stephens, I. E. L.; Bondarenko, A. S.; Johansson, T. P.; Hansen, H. A.; Jaramillo, T. F.; Rossmeisl, J.; Chorkendorff, I.; Nørskov, J. K. Alloys of platinum and early transition metals as oxygen reduction electrocatalysts. Nat. Chem. 2009, 1, 552–556.
Lei, W. J.; Li, M. G.; He, L.; Meng, X.; Mu, Z. J.; Yu, Y. S.; Ross, F. M.; Yang, W. W. A general strategy for bimetallic Pt-based nano-branched structures as highly active and stable oxygen reduction and methanol oxidation bifunctional catalysts. Nano Res. 2020, 13, 638–645.
Liang, Y. Y.; Lei, H.; Wang, S. J.; Wang, Z. L.; Mai, W. J. Pt/Zn heterostructure as efficient air-electrocatalyst for long-life neutral Zn-air batteries. Sci. China Mater. 2021, 64, 1868–1875.
Huang, L.; Zaman, S.; Tian, X. L.; Wang, Z. T.; Fang, W. S.; Xia, B. Y. Advanced platinum-based oxygen reduction electrocatalysts for fuel cells. Acc. Chem. Res. 2021, 54, 311–322.
Stamenkovic, V. R.; Mun, B. S.; Arenz, M.; Mayrhofer, K. J. J.; Lucas, C. A.; Wang, G. F.; Ross, P. N.; Markovic, N. M. Trends in electrocatalysis on extended and nanoscale Pt-bimetallic alloy surfaces. Nat. Mater. 2007, 6, 241–247.
Wang, P. T.; Shao, Q.; Huang, X. Q. Updating Pt-Based electrocatalysts for practical fuel cells. Joule 2018, 2, 2514–2516.
Stamenkovic, V. R.; Fowler, B.; Mun, B. S.; Wang, G. F.; Ross, P. N.; Lucas, C. A.; Markovic, N. M. Improved oxygen reduction activity on Pt3Ni (111) via increased surface site availability. Science 2007, 315, 493–497.
Wang, D. L.; Xin, H. L.; Hovden, R.; Wang, H. S.; Yu, Y. C.; Muller, D. A.; DiSalvo1, F. J.; Abruña, H. D. Structurally ordered intermetallic platinum-cobalt core–shell nanoparticles with enhanced activity and stability as oxygen reduction electrocatalysts. Nat. Mater. 2013, 12, 81–87.
Kong, F. P.; Ren, Z. H.; Banis, M. N.; Du, L.; Zhou, X.; Chen, G. Y.; Zhang, L.; Li, J. J.; Wang, S. Z.; Li, M. S. et al. Active and stable Pt-Ni alloy octahedra catalyst for oxygen reduction via near-surface atomical engineering. ACS Catal. 2020, 10, 4205–4214.
Chaudhari, N. K.; Hong, Y. J.; Kim, B.; Choi, S. I.; Lee, K. Pt-Cu based nanocrystals as promising catalysts for various electrocatalytic reactions. J. Mater. Chem. A. 2019, 7, 17183–17203.
Yan, W. J.; Zhang, D. P.; Zhang, Q. X.; Sun, Y.; Zhang, S. X.; Du, F.; Jin, X. Synthesis of PtCu-based nanocatalysts: Fundamentals and emerging challenges in energy conversion. J. Energy Chem. 2022, 64, 583–606.
Hannagan, R. T.; Giannakakis, G.; Flytzani-Stephanopoulos, M.; Sykes, E. C. H. Single-atom alloy catalysis. Chem. Rev. 2020, 120, 12044–12088.
Kim, H. Y.; Kwon, T.; Ha, Y.; Jun, M.; Baik, H.; Jeong, H. Y.; Kim, H.; Lee, K.; Joo, S. H. Intermetallic PtCu nanoframes as efficient oxygen reduction electrocatalysts. Nano Lett. 2020, 20, 7413–7421.
Guo, N. K.; Xue, H.; Bao, A.; Wang, Z. H.; Sun, J.; Song, T. S.; Ge, X.; Zhang, W.; Huang, K. K.; He, F. et al. Achieving superior electrocatalytic performance by surface copper vacancy defects during electrochemical etching process. Angew. Chem., Int. Ed. 2020, 59, 13778–13784.
Gatalo, M.; Ruiz-Zepeda, F.; Hodnik, N.; Dražić, G.; Bele, M.; Gaberšček, M. Insights into thermal annealing of highly-active PtCu3/C oxygen reduction reaction electrocatalyst: An in-situ heating transmission electron microscopy study. Nano Energy 2019, 63, 103892.
Luo, S. P.; Tang, M.; Shen, P. K.; Ye, S. Y. Atomic-scale preparation of octopod nanoframes with high-index facets as highly active and stable catalysts. Adv. Mater. 2017, 29, 1601687.
Park, J.; Kabiraz, M. K.; Kwon, H.; Park, S.; Baik, H.; Choi, S. I.; Lee, K. Radially phase segregated PtCu@PtCuNi dendrite@frame nanocatalyst for the oxygen reduction reaction. ACS Nano 2017, 11, 10844–10851.
Li, W. Q.; Hu, Z. Y.; Zhang, Z. W.; Wei, P.; Zhang, J. N.; Pu, Z. H.; Zhu, J. W.; He, D. P.; Mu, S. C.; Van Tendeloo, G. Nano-single crystal coalesced PtCu nanospheres as robust bifunctional catalyst for hydrogen evolution and oxygen reduction reactions. J. Catal. 2019, 375, 164–170.
Ahn, C. Y.; Park, J. E.; Kim, S.; Kim, O. H.; Hwang, W.; Her, M.; Kang, S. Y.; Park, S.; Kwon, O. J.; Park, H. S. et al. Differences in the electrochemical performance of Pt-based catalysts used for polymer electrolyte membrane fuel cells in liquid half- and full-cells. Chem. Rev. 2021, 121, 15075–15140.
Choi, J.; Lee, Y. J.; Park, D.; Jeong, H.; Shin, S.; Yun, H.; Lim, J.; Han, J. H.; Kim, E. J.; Jeon, S. S. et al. Highly durable fuel cell catalysts using crosslinkable block copolymer-based carbon supports with ultralow Pt loadings. Energy Environ. Sci. 2020, 13, 4921–4929.
Yarlagadda, V.; Carpenter, M. K.; Moylan, T. E.; Kukreja, R. S.; Koestner, R.; Gu, W. B.; Thompson, L.; Kongkanand, A. Boosting fuel cell performance with accessible carbon mesopores. ACS Energy Lett. 2018, 3, 618–621.
Lee, Y. J.; Kim, H. E.; Lee, E.; Lee, J.; Shin, S.; Yun, H.; Kim, E. J.; Jung, H.; Ham, H. C.; Kim, B. J. et al. Ultra-low Pt loaded porous carbon microparticles with controlled channel structure for high-performance fuel cell catalysts. Adv. Energy Mater. 2021, 11, 2102970.
Qin, Y. C.; Zhang, W. L.; Guo, K.; Liu, X. B.; Liu, J. Q.; Liang, X. Y.; Wang, X. P.; Gao, D. W.; Gan, L. Y.; Zhu, Y. T. et al. Fine-tuning intrinsic strain in penta-twinned Pt-Cu-Mn nanoframes boosts oxygen reduction catalysis. Adv. Funct. Mater. 2020, 30, 1910107.
Fang, D. H.; Wan, L.; Jiang, Q. K.; Zhang, H. J.; Tang, X. J.; Qin, X. P.; Shao, Z. G.; Wei, Z. D. Wavy PtCu alloy nanowire networks with abundant surface defects enhanced oxygen reduction reaction. Nano Res. 2019, 12, 2766–2773.
Wang, D. D.; Chen, Z. W.; Huang, Y. C.; Li, W.; Wang, J.; Lu, Z. L.; Gu, K. Z.; Wang, T. H.; Wu, Y. J.; Chen, C. et al. Tailoring lattice strain in ultra-fine high-entropy alloys for active and stable methanol oxidation. Sci. China Mater. 2021, 64, 2454–2466.
Lu, B. A.; Sheng, T.; Tian, N.; Zhang, Z. C.; Xiao, C.; Cao, Z. M.; Ma, H. B.; Zhou, Z. Y.; Sun, S. G. Octahedral PtCu alloy nanocrystals with high performance for oxygen reduction reaction and their enhanced stability by trace Au. Nano Energy 2017, 33, 65–71.
Strasser, P.; Koh, S.; Anniyev, T.; Greeley, J.; More, K.; Yu, C. F.; Liu, Z. C.; Kaya, S.; Nordlund, D.; Ogasawara, H. et al. Lattice-strain control of the activity in dealloyed core–shell fuel cell catalysts. Nat. Chem. 2010, 2, 454–460.
Yang, X. T.; Yao, K. X.; Ye, J. Y.; Yuan, Q.; Zhao, F. L.; Li, Y. F.; Zhou, Z. Y. Interface-rich three-dimensional Au-doped PtBi intermetallics as highly effective anode catalysts for application in alkaline ethylene glycol fuel cells. Adv. Funct. Mater. 2021, 31, 2103671.
Zhao, T.; Luo, E. G.; Li, Y.; Wang, X.; Liu, C. P.; Xing, W.; Ge, J. J. Highly dispersed L10-PtZn intermetallic catalyst for efficient oxygen reduction. Sci. China Mater. 2021, 64, 1671–1678.
Liu, H. P.; Liu, K.; Zhong, P.; Qi, J.; Bian, J. H.; Fan, Q. K.; Ren, K.; Zheng, H. Q.; Han, L.; Yin, Y. D. et al. Ultrathin Pt-Ag alloy nanotubes with regular nanopores for enhanced electrocatalytic activity. Chem. Mater. 2018, 30, 7744–7751.
Zhou, T. P.; Shan, H.; Yu, H.; Zhong, C. A.; Ge, J. K.; Zhang, N.; Chu, W. S.; Yan, W. S.; Xu, Q.; Wu, H. A. et al. Nanopore confinement of electrocatalysts optimizing triple transport for an ultrahigh-power-density zinc-air fuel cell with robust stability. Adv. Mater. 2020, 32, 2003251.
Feng, Y.; Cheng, C. Q.; Zou, C. Q.; Zheng, X. L.; Mao, J.; Liu, H.; Li, Z.; Dong, C. K.; Du, X. W. Electroreduction of carbon dioxide in metallic nanopores through a pincer mechanism. Angew. Chem., Int. Ed. 2020, 59, 19297–19303.
Shi, S.; Wen, X. L.; Sang, Q. Q.; Yin, S.; Wang, K. L.; Zhang, J.; Hu, M.; Yin, H. M.; He, J.; Ding, Y. Ultrathin nanoporous metal electrodes facilitate high proton conduction for low-Pt PEMFCs. Nano Res. 2021, 14, 2681–2688.
Feng, Y. G.; Huang, B. L.; Yang, C. Y.; Shao, Q.; Huang, X. Q. Platinum porous nanosheets with high surface distortion and Pt utilization for enhanced oxygen reduction catalysis. Adv. Funct. Mater. 2019, 29, 1904429.
Peng, X. W.; Zhang, L.; Chen, Z. X.; Zhong, L. X.; Zhao, D. K.; Chi, X.; Zhao, X. X.; Li, L. G.; Lu, X. H.; Leng, K. et al. Hierarchically porous carbon plates derived from wood as bifunctional ORR/OER electrodes. Adv. Mater. 2019, 31, 1900341.
Li, M. F.; Zhao, Z. P.; Cheng, T.; Fortunelli, A.; Chen, C. Y.; Yu, R.; Zhang, Q. H.; Gu, L.; Merinov, B. V.; Lin, Z. Y. et al. Ultrafine jagged platinum nanowires enable ultrahigh mass activity for the oxygen reduction reaction. Science 2016, 354, 1414–1419.
Gao, Y.; Kong, D. B.; Liang, J. X.; Han, D. L.; Wang, B.; Yang, Q. H.; Zhi, L. J. Inside-out dual-doping effects on tubular catalysts: Structural and chemical variation for advanced oxygen reduction performance. Nano Res. 2022, 15, 361–367.
Chen, C.; Kang, Y. J.; Huo, Z. Y.; Zhu, Z. W.; Huang, W. Y.; Xin, H. L. L.; Snyder, J. D.; Li, D. G.; Herron, J. A.; Mavrikakis, M. et al. Highly crystalline multimetallic nanoframes with three-dimensional electrocatalytic surfaces. Science 2014, 343, 1339–1343.
Fidiani, E.; Thirunavukkarasu, G.; Li, Y.; Chiu, Y. L.; Du, S. F. Au integrated AgPt nanorods for the oxygen reduction reaction in proton exchange membrane fuel cells. J. Mater. Chem. A 2021, 9, 5578–5587.
Park, C.; Lee, E.; Lee, G.; Tak, Y. Superior durability and stability of Pt electrocatalyst on N-doped graphene-TiO2 hybrid material for oxygen reduction reaction and polymer electrolyte membrane fuel cells. Appl. Catal. B Environ. 2020, 268, 118414.
Ahn, S. H.; Klein, M. J.; Manthiram, A. 1D Co- and N-doped hierarchically porous carbon nanotubes derived from bimetallic metal organic framework for efficient oxygen and tri-iodide reduction reactions. Adv. Energy Mater. 2017, 7, 1601979.
Peng, L.; Hung, C. T.; Wang, S. W.; Zhang, X. M.; Zhu, X. H.; Zhao, Z. W.; Wang, C. Y.; Tang, Y.; Li, W.; Zhao, D. Y. Versatile nanoemulsion assembly approach to synthesize functional mesoporous carbon nanospheres with tunable pore sizes and architectures. J. Am. Chem. Soc. 2019, 141, 7073–7080.
Liang, J.; Zheng, Y.; Chen, J.; Liu, J.; Hulicova-Jurcakova, D.; Jaroniec, M.; Qiao, S. Z. Facile oxygen reduction on a three-dimensionally ordered macroporous graphitic C3N4/carbon composite electrocatalyst. Angew. Chem., Int. Ed. 2012, 51, 3892–3896.
Wen, Z.; Liu, J.; Li, J. Core/shell Pt/C nanoparticles embedded in mesoporous carbon as a methanol-tolerant cathode catalyst in direct methanol fuel cells. Adv. Mater. 2008, 20, 743–747.
Asset, T.; Job, N.; Busby, Y.; Crisci, A.; Martin, V.; Stergiopoulos, V.; Bonnaud, C.; Serov, A.; Atanassov, P.; Chattot, R. et al. Porous hollow PtNi/C electrocatalysts: Carbon support considerations to meet performance and stability requirements. ACS Catal. 2018, 8, 893–903.
Chong, L. N.; Wen, J. G.; Kubal, J.; Sen, F. G.; Zou, J. X.; Greeley, J.; Chan, M.; Barkholtz, H.; Ding, W. J.; Liu, D. J. Ultralow-loading platinum-cobalt fuel cell catalysts derived from imidazolate frameworks. Science 2018, 362, 1276–1281.
Zhao, J. J.; Fu, C. H.; Ye, K.; Liang, Z.; Jiang, F. L.; Shen, S. Y.; Zhao, X. R.; Ma L.; Shadike, Z.; Wang, X. M. et al. Manipulating the oxygen reduction reaction pathway on Pt-coordinated motifs. Nat. Commun. 2022, 13, 685.
Hammer, B.; Nørskov, J. K. Theoretical surface science and catalysis-calculations and concepts. Adv. Catal. 2000, 45, 71–129.
Xu, F.; Cai, S. B.; Lin, B. F.; Yang, L.; Le, H. F.; Mu, S. C. Geometric engineering of porous PtCu nanotubes with ultrahigh methanol oxidation and oxygen reduction capability. Small 2022, 18, 2107387.
Tian, X. L.; Zhao, X.; Su, Y. Q.; Wang, L. J.; Wang, H. M.; Dang, D.; Chi, B.; Liu, H. F.; Hensen, E. J. M.; Lou, X. W. et al. Engineering bunched Pt-Ni alloy nanocages for efficient oxygen reduction in practical fuel cells. Science 2019, 366, 850–856.