Pt-Ni-Cu纳米笼的合成与高效氧还原电催化
Synthesis of Pt-Ni-Cu Nanocages for Efficient Oxygen Reduction Electrocatalysis
DOI: 10.12677/ms.2025.154060, PDF,   
作者: 谢 磊*, 罗水平, 朱金良：广西大学资源环境与材料学院有色金属与材料新加工技术教育部重点实验室，广西 南宁
关键词: 纳米笼；PtNiCu；三元合金；氧还原反应；电催化；Nanocage； PtNiCu； Ternary Alloy； Oxygen Reduction Reaction； Electrocatalysis
摘要: 控制Pt基纳米材料的表面、形状和组成可显著提升氧还原反应的催化性能。由超薄纳米片构成的基于Pt的纳米笼，作为一种新型高效催化剂，具有较高的Pt原子利用率。然而，如何通过简单策略设计多金属纳米笼以扩展催化剂的组成空间仍然是一个挑战。在此，我们提出将溶剂热合成法与室温下的保形腐蚀相结合，实现了壁厚仅为7原子层的Pt-Ni-Cu三元纳米笼的合成。此外，通过调控表面活性剂，能有效控制Pt-Ni-Cu三元纳米笼的结构。由于其独特的结构与组成，Pt-Ni-Cu三元纳米笼在氧还原反应(ORR)中展现出优异的质量活性，0.9 V时质量活性为1411 mA·mgPt−1，是商业Pt/C催化剂的9.0倍，优于近期报道的Pt基纳米笼。
Abstract: Controlling the surface, shape, and composition of Pt-based nanomaterials can greatly boost oxygen reduction catalysis. Pt-based nanocages composed of ultrathin nanosheets have emerged as a new class of efficient catalysts with high atomic utilization efficiency of Pt. However, engineering multimetallic nanocages via facile strategies still remains a challenge to extend compositional space for catalyst development. Here, this work achieves the synthesis of Pt-Ni-Cu ternary nanocages with walls as thin as 7 atomic layers, by developing a general strategy that combines the solvothermal synthesis of highly composition segregated nanocrystals with the conformal corrosion at room temperature. In addition, the structure of Pt-Ni-Cu ternary nanocages can be well controlled by simply changing the surfactants. Benefiting from their unique structure and composition, the Pt-Ni-Cu ternary nanocages exhibit superior mass activity towards oxygen reduction reaction (ORR), with a value of 1411 mA·mgPt−1 at 0.9 V, which is 9.0 times higher than that of commercial Pt/C catalyst and outperforms the recently reported Pt-based nanocages.
文章引用：谢磊, 罗水平, 朱金良. Pt-Ni-Cu纳米笼的合成与高效氧还原电催化[J]. 材料科学, 2025, 15(4): 550-561. https://doi.org/10.12677/ms.2025.154060

参考文献

[1] Yoshida, T. and Kojima, K. (2015) Toyota MIRAI Fuel Cell Vehicle and Progress toward a Future Hydrogen Society. The Electrochemical Society Interface, 24, 45-49. [Google Scholar] [CrossRef] 
[2] Banham, D. and Ye, S. (2017) Current Status and Future Development of Catalyst Materials and Catalyst Layers for Proton Exchange Membrane Fuel Cells: An Industrial Perspective. ACS Energy Letters, 2, 629-638. [Google Scholar] [CrossRef] 
[3] Kongkanand, A. and Mathias, M.F. (2016) The Priority and Challenge of High-Power Performance of Low-Platinum Proton-Exchange Membrane Fuel Cells. The Journal of Physical Chemistry Letters, 7, 1127-1137. [Google Scholar] [CrossRef] [PubMed]
[4] Zhang, L., Roling, L.T., Wang, X., Vara, M., Chi, M., Liu, J., et al. (2015) Platinum-Based Nanocages with Subnanometer-Thick Walls and Well-Defined, Controllable Facets. Science, 349, 412-416. [Google Scholar] [CrossRef] [PubMed]
[5] Chen, C., Kang, Y., Huo, Z., Zhu, Z., Huang, W., Xin, H.L., et al. (2014) Highly Crystalline Multimetallic Nanoframes with Three-Dimensional Electrocatalytic Surfaces. Science, 343, 1339-1343. [Google Scholar] [CrossRef] [PubMed]
[6] Li, M., Zhao, Z., Cheng, T., Fortunelli, A., Chen, C., Yu, R., et al. (2016) Ultrafine Jagged Platinum Nanowires Enable Ultrahigh Mass Activity for the Oxygen Reduction Reaction. Science, 354, 1414-1419. [Google Scholar] [CrossRef] [PubMed]
[7] Bu, L., Zhang, N., Guo, S., Zhang, X., Li, J., Yao, J., et al. (2016) Biaxially Strained PtPb/Pt Core/Shell Nanoplate Boosts Oxygen Reduction Catalysis. Science, 354, 1410-1414. [Google Scholar] [CrossRef] [PubMed]
[8] Debe, M.K., Steinbach, A.J., Vernstrom, G.D., Hendricks, S.M., Kurkowski, M.J., Atanasoski, R.T., et al. (2011) Extraordinary Oxygen Reduction Activity of Pt3Ni7. Journal of The Electrochemical Society, 158, B910. [Google Scholar] [CrossRef] 
[9] Zhu, H., Zhang, S., Guo, S., Su, D. and Sun, S. (2013) Synthetic Control of FePtM Nanorods (M = Cu, Ni) to Enhance the Oxygen Reduction Reaction. Journal of the American Chemical Society, 135, 7130-7133. [Google Scholar] [CrossRef] [PubMed]
[10] Bu, L., Guo, S., Zhang, X., Shen, X., Su, D., Lu, G., et al. (2016) Surface Engineering of Hierarchical Platinum-Cobalt Nanowires for Efficient Electrocatalysis. Nature Communications, 7, Article No. 11850. [Google Scholar] [CrossRef] [PubMed]
[11] Tian, N., Zhou, Z., Sun, S., Ding, Y. and Wang, Z.L. (2007) Synthesis of Tetrahexahedral Platinum Nanocrystals with High-Index Facets and High Electro-Oxidation Activity. Science, 316, 732-735. [Google Scholar] [CrossRef] [PubMed]
[12] Saleem, F., Zhang, Z., Xu, B., Xu, X., He, P. and Wang, X. (2013) Ultrathin Pt-Cu Nanosheets and Nanocones. Journal of the American Chemical Society, 135, 18304-18307. [Google Scholar] [CrossRef] [PubMed]
[13] Yu, X., Wang, D., Peng, Q. and Li, Y. (2011) High Performance Electrocatalyst: Pt-Cu Hollow Nanocrystals. Chemical Communications, 47, 8094. [Google Scholar] [CrossRef] [PubMed]
[14] Gilroy, K.D., Ruditskiy, A., Peng, H., Qin, D. and Xia, Y. (2016) Bimetallic Nanocrystals: Syntheses, Properties, and Applications. Chemical Reviews, 116, 10414-10472. [Google Scholar] [CrossRef] [PubMed]
[15] Luo, S., Tang, M., Shen, P.K. and Ye, S. (2017) Atomic‐Scale Preparation of Octopod Nanoframes with High‐Index Facets as Highly Active and Stable Catalysts. Advanced Materials, 29, Article 1601687. [Google Scholar] [CrossRef] [PubMed]
[16] Peng, X., Zhao, S., Omasta, T.J., Roller, J.M. and Mustain, W.E. (2017) Activity and Durability of Pt-Ni Nanocage Electocatalysts in Proton Exchange Membrane Fuel Cells. Applied Catalysis B: Environmental, 203, 927-935. [Google Scholar] [CrossRef] 
[17] He, D.S., He, D., Wang, J., Lin, Y., Yin, P., Hong, X., et al. (2016) Ultrathin Icosahedral Pt-Enriched Nanocage with Excellent Oxygen Reduction Reaction Activity. Journal of the American Chemical Society, 138, 1494-1497. [Google Scholar] [CrossRef] [PubMed]
[18] Xia, B.Y., Wu, H.B., Wang, X. and Lou, X.W. (2012) One-Pot Synthesis of Cubic PtCU3 Nanocages with Enhanced Electrocatalytic Activity for the Methanol Oxidation Reaction. Journal of the American Chemical Society, 134, 13934-13937. [Google Scholar] [CrossRef] [PubMed]
[19] Yang, X., Roling, L.T., Vara, M., Elnabawy, A.O., Zhao, M., Hood, Z.D., et al. (2016) Synthesis and Characterization of Pt-Ag Alloy Nanocages with Enhanced Activity and Durability toward Oxygen Reduction. Nano Letters, 16, 6644-6649. [Google Scholar] [CrossRef] [PubMed]
[20] Wang, X., Figueroa-Cosme, L., Yang, X., Luo, M., Liu, J., Xie, Z., et al. (2016) Pt-Based Icosahedral Nanocages: Using a Combination of {111} Facets, Twin Defects, and Ultrathin Walls to Greatly Enhance Their Activity toward Oxygen Reduction. Nano Letters, 16, 1467-1471. [Google Scholar] [CrossRef] [PubMed]
[21] Chen, W., Luo, S., Sun, M., Wu, X., Zhou, Y., Liao, Y., et al. (2022) High‐Entropy Intermetallic PtRhBiSnSb Nanoplates for Highly Efficient Alcohol Oxidation Electrocatalysis. Advanced Materials, 34, Article 2206276. [Google Scholar] [CrossRef] [PubMed]
[22] Fan, X., Chen, W., Xie, L., Liu, X., Ding, Y., Zhang, L., et al. (2024) Surface‐Enriched Single‐Bi‐Atoms Tailoring of Pt Nanorings for Direct Methanol Fuel Cells with Ultralow‐Pt‐Loading. Advanced Materials, 36, Article 2313179. [Google Scholar] [CrossRef] [PubMed]
[23] Tang, M., Sun, M., Chen, W., Ding, Y., Fan, X., Wu, X., et al. (2024) Atomic Diffusion Engineered PtSnCu Nanoframes with High‐Index Facets Boost Ethanol Oxidation. Advanced Materials, 36, Article 2311731. [Google Scholar] [CrossRef] [PubMed]
[24] Wang, D., Xin, H.L., Hovden, R., Wang, H., Yu, Y., Muller, D.A., et al. (2013) Structurally Ordered Intermetallic Platinum-Cobalt Core-Shell Nanoparticles with Enhanced Activity and Stability as Oxygen Reduction Electrocatalysts. Nature Materials, 12, 81-87. [Google Scholar] [CrossRef] [PubMed]
[25] Stamenkovic, V.R., Fowler, B., Mun, B.S., Wang, G., Ross, P.N., Lucas, C.A., et al. (2007) Improved Oxygen Reduction Activity on Pt3Ni(111) via Increased Surface Site Availability. Science, 315, 493-497. [Google Scholar] [CrossRef] [PubMed]
[26] Strasser, P., Koh, S., Anniyev, T., Greeley, J., More, K., Yu, C., et al. (2010) Lattice-Strain Control of the Activity in Dealloyed Core-Shell Fuel Cell Catalysts. Nature Chemistry, 2, 454-460. [Google Scholar] [CrossRef] [PubMed]
[27] Noh, S.H., Han, B. and Ohsaka, T. (2015) First-Principles Computational Study of Highly Stable and Active Ternary Ptcuni Nanocatalyst for Oxygen Reduction Reaction. Nano Research, 8, 3394-3403. [Google Scholar] [CrossRef] 
[28] Beermann, V., Gocyla, M., Willinger, E., Rudi, S., Heggen, M., Dunin-Borkowski, R.E., et al. (2016) Rh-Doped Pt-Ni Octahedral Nanoparticles: Understanding the Correlation between Elemental Distribution, Oxygen Reduction Reaction, and Shape Stability. Nano Letters, 16, 1719-1725. [Google Scholar] [CrossRef] [PubMed]
[29] Zhang, P., Dai, X., Zhang, X., Chen, Z., Yang, Y., Sun, H., et al. (2015) One-Pot Synthesis of Ternary Pt-Ni-Cu Nanocrystals with High Catalytic Performance. Chemistry of Materials, 27, 6402-6410. [Google Scholar] [CrossRef] 
[30] Saleem, F., Ni, B., Yong, Y., Gu, L. and Wang, X. (2016) Ultra-Small Tetrametallic Pt-Pd-Rh-Ag Nanoframes with Tunable Behavior for Direct Formic Acid/Methanol Oxidation. Small, 12, 5261-5268. [Google Scholar] [CrossRef] [PubMed]
[31] Gan, L., Cui, C., Heggen, M., Dionigi, F., Rudi, S. and Strasser, P. (2014) Element-Specific Anisotropic Growth of Shaped Platinum Alloy Nanocrystals. Science, 346, 1502-1506. [Google Scholar] [CrossRef] [PubMed]
[32] Cui, C., Gan, L., Heggen, M., Rudi, S. and Strasser, P. (2013) Compositional Segregation in Shaped Pt Alloy Nanoparticles and Their Structural Behaviour during Electrocatalysis. Nature Materials, 12, 765-771. [Google Scholar] [CrossRef] [PubMed]
[33] Carpenter, M.K., Moylan, T.E., Kukreja, R.S., Atwan, M.H. and Tessema, M.M. (2012) Solvothermal Synthesis of Platinum Alloy Nanoparticles for Oxygen Reduction Electrocatalysis. Journal of the American Chemical Society, 134, 8535-8542. [Google Scholar] [CrossRef] [PubMed]
[34] Muzart, J. (2009) N,N-Dimethylformamide: Much More than a Solvent. Tetrahedron, 65, 8313-8323. [Google Scholar] [CrossRef] 
[35] Bai, S., Wang, C., Jiang, W., Du, N., Li, J., Du, J., et al. (2015) Etching Approach to Hybrid Structures of PtPd Nanocages and Graphene for Efficient Oxygen Reduction Reaction Catalysts. Nano Research, 8, 2789-2799. [Google Scholar] [CrossRef] 
[36] Kang, Y., Snyder, J., Chi, M., Li, D., More, K.L., Markovic, N.M., et al. (2014) Multimetallic Core/Interlayer/Shell Nanostructures as Advanced Electrocatalysts. Nano Letters, 14, 6361-6367. [Google Scholar] [CrossRef] [PubMed]
[37] Wang, K., Sriphathoorat, R., Luo, S., Tang, M., Du, H. and Shen, P.K. (2016) Ultrathin PtCu Hexapod Nanocrystals with Enhanced Catalytic Performance for Electro-Oxidation Reactions. Journal of Materials Chemistry A, 4, 13425-13430. [Google Scholar] [CrossRef] 
[38] Mourdikoudis, S. and Liz-Marzán, L.M. (2013) Oleylamine in Nanoparticle Synthesis. Chemistry of Materials, 25, 1465-1476. [Google Scholar] [CrossRef] 
[39] Kong, F., Liu, S., Li, J., Du, L., Banis, M.N., Zhang, L., et al. (2019) Trimetallic Pt-Pd-Ni Octahedral Nanocages with Subnanometer Thick-Wall towards High Oxygen Reduction Reaction. Nano Energy, 64, Article 103890. [Google Scholar] [CrossRef] 
[40] Tian, X., Zhao, X., Su, Y., Wang, L., Wang, H., Dang, D., et al. (2019) Engineering Bunched Pt-Ni Alloy Nanocages for Efficient Oxygen Reduction in Practical Fuel Cells. Science, 366, 850-856. [Google Scholar] [CrossRef] [PubMed]
[41] Zhu, J., Chen, Z., Xie, M., Lyu, Z., Chi, M., Mavrikakis, M., et al. (2019) Iridium‐Based Cubic Nanocages with 1.1‐nm‐Thick Walls: A Highly Efficient and Durable Electrocatalyst for Water Oxidation in an Acidic Medium. Angewandte Chemie International Edition, 58, 7244-7248. [Google Scholar] [CrossRef] [PubMed]
[42] Zhu, J., Xie, M., Chen, Z., Lyu, Z., Chi, M., Jin, W., et al. (2020) Pt‐Ir‐Pd Trimetallic Nanocages as a Dual Catalyst for Efficient Oxygen Reduction and Evolution Reactions in Acidic Media. Advanced Energy Materials, 10, Article 1904114. [Google Scholar] [CrossRef] 
[43] Zhu, J., Xu, L., Lyu, Z., Xie, M., Chen, R., Jin, W., et al. (2021) Janus Nanocages of Platinum‐Group Metals and Their Use as Effective Dual‐Electrocatalysts. Angewandte Chemie International Edition, 60, 10384-10392. [Google Scholar] [CrossRef] [PubMed]
[44] Zheng, Y., Petersen, A.S., Wan, H., Hübner, R., Zhang, J., Wang, J., et al. (2023) Scalable and Controllable Synthesis of Pt‐Ni Bunched‐Nanocages Aerogels as Efficient Electrocatalysts for Oxygen Reduction Reaction. Advanced Energy Materials, 13, Article 2204257. [Google Scholar] [CrossRef] 
[45] Ding, H., Su, C., Wu, J., Lv, H., Tan, Y., Tai, X., et al. (2024) Highly Crystalline Iridium-Nickel Nanocages with Subnanopores for Acidic Bifunctional Water Splitting Electrolysis. Journal of the American Chemical Society, 146, 7858-7867. [Google Scholar] [CrossRef] [PubMed]
[46] Mahmoud, M.A., Saira, F. and El-Sayed, M.A. (2010) Experimental Evidence for the Nanocage Effect in Catalysis with Hollow Nanoparticles. Nano Letters, 10, 3764-3769. [Google Scholar] [CrossRef] [PubMed]

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