Alloy nanocrystals （NCs） of Pt with 3d transition metals, especially Ni, are excellent catalysts for the oxygen reduction reaction （ORR）. In this work, we, for the first time, demonstrated the water phase colloida...Alloy nanocrystals （NCs） of Pt with 3d transition metals, especially Ni, are excellent catalysts for the oxygen reduction reaction （ORR）. In this work, we, for the first time, demonstrated the water phase colloidal synthesis of Pt-M （M = Ni, Co and Fe） alloy NCs with tunable composition and morphology through a facile hydrothermal method. Pt-Ni alloy NCs synthesized with this method presented better ORR activity than commercial Pt/C catalysts. The X-ray energy dispersive spectra （EDS） mapping technique revealed that Pt-enriched shells existed on the as-synthesized Pt-Ni alloy NCs. About two atom thick layered Pt-enriched shells formed on Pts0Nis0 NCs and the thickness of the Pt-enriched shells increased as the Ni content increased. Furthermore, X-ray photoelectron spectroscopy analysis revealed that the oxidation level of the surface Pt atoms on the Pt-Ni alloy NCs decreased compared with monometallic Pt NCs, implying a decrease in the oxophilicity of the surface Pt atoms. Pt-Ni alloy NCs with lower oxophilicity of the surface Pt atoms give higher ORR activity. The most active alloy sample showed 13 times higher specific activity and six times higher mass activity at 0.9 V vs. a reversible hydrogen electrode when compared with commercial Pt/C. Pt-Ni alloy NCs also showed better durability than commercial Pt/C in long term ORR tests.展开更多
基金supported as part of the Catalysis Center for Energy Innovation, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Basic Energy Sciences under Award Number DE-SC0001004Program for New Century Excellent Talents in University of China (NCET-12-0297)~~
基金We thank Prof. Dechun Zou and Mr. Ming Peng for their help with electrochemical characterization. This work was supported by the National Natural Science Foundation of China （Nos. 21025101, 21271011, and 21321001）. Y. W. Z. particularly appreciates the financial aid from the China National Funds for Distinguished Young Scientists from the National Natural Science Foundation of China （NSFC）. The work on micros- copy was partly carried out in the Center of Electron Microscopy of Zhejiang University, which was financially supported by the National Natural Science Foundation of China （No. 51222202）, the National Basic Research Program of China （No. 2014CB932500） and the Program for Innovative Research Teams in Universities of Ministry of Education of China （No. IRT13037） and the Fundamental Research Funds for the Central Universities （No. 2014XZZX003-07）.
文摘Alloy nanocrystals （NCs） of Pt with 3d transition metals, especially Ni, are excellent catalysts for the oxygen reduction reaction （ORR）. In this work, we, for the first time, demonstrated the water phase colloidal synthesis of Pt-M （M = Ni, Co and Fe） alloy NCs with tunable composition and morphology through a facile hydrothermal method. Pt-Ni alloy NCs synthesized with this method presented better ORR activity than commercial Pt/C catalysts. The X-ray energy dispersive spectra （EDS） mapping technique revealed that Pt-enriched shells existed on the as-synthesized Pt-Ni alloy NCs. About two atom thick layered Pt-enriched shells formed on Pts0Nis0 NCs and the thickness of the Pt-enriched shells increased as the Ni content increased. Furthermore, X-ray photoelectron spectroscopy analysis revealed that the oxidation level of the surface Pt atoms on the Pt-Ni alloy NCs decreased compared with monometallic Pt NCs, implying a decrease in the oxophilicity of the surface Pt atoms. Pt-Ni alloy NCs with lower oxophilicity of the surface Pt atoms give higher ORR activity. The most active alloy sample showed 13 times higher specific activity and six times higher mass activity at 0.9 V vs. a reversible hydrogen electrode when compared with commercial Pt/C. Pt-Ni alloy NCs also showed better durability than commercial Pt/C in long term ORR tests.
