Graphical Abstract

We report a facile strategy to synthesize intermetallic nanoparticle (iNP) electrocatalysts via one-pot pyrolysis of a zeolitic imidazolate framework, ZIF-8, encapsulating precious metal nanoparticles (NPs). ZIF-8 serves not only as precursor for N-doped carbon (NC), but also as Zn source for the formation of intermetallic or alloy NPs with the encapsulated metals. The resulting sub-4 nm PtZn iNPs embedded in NC exhibit high sintering resistance up to 1, 000 ℃. Importantly, the present methodology allows fine-tuning of both composition (e.g., PdZn and RhZn iNPs, as well as AuZn and RuZn alloy NPs) and size (2.4, 3.7, and 5.4 nm PtZn) of the as-formed bimetallic NPs. To the best of our knowledge, this is the first report of a metal-organic framework (MOF) with multiple functionalities, such as secondary metal source, carbon precursor, and size-regulating reagent, which promote the formation of iNPs. This work opens a new avenue for the synthesis of highly uniform and stable iNPs.
Wang, Y. J.; Zhao, N. N.; Fang, B. Z.; Li, H.; Bi, X. T. T.; Wang, H. J. 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. 2015, 115, 3433-3467.
Shao, M. H.; Chang, Q. W.; Dodelet, J. P.; Chenitz, R. Recent advances in electrocatalysts for oxygen reduction reaction. Chem. Rev. 2016, 116, 3594-3657.
Wu, J. B.; Yang, H. Platinum-based oxygen reduction electrocatalysts. Acc. Chem. Res. 2013, 46, 1848-1857.
You, H. J.; Yang, S. C.; Ding, B. J.; Yang, H. Synthesis of colloidal metal and metal alloy nanoparticles for electrochemical energy applications. Chem. Soc. Rev. 2013, 42, 2880-2904.
Furukawa, S.; Komatsu, T. Intermetallic compounds: Promising inorganic materials for well-structured and electronically modified reaction environments for efficient catalysis. ACS Catal. 2017, 7, 735-765.
Bing, Y. H.; Liu, H. S.; Zhang, L.; Ghosh, D.; Zhang, J. J. Nanostructured Pt-alloy electrocatalysts for PEM fuel cell oxygen reduction reaction. Chem. Soc. Rev. 2010, 39, 2184-2202.
Watanabe, M.; Tsurumi, K.; Mizukami, T.; Nakamura, T.; Stonehart, P. Activity and stability of ordered and disordered Co-Pt alloys for phosphoric-acid fuel-cells. J. Electrochem. Soc. 1994, 141, 2659-2668.
Wu, J. F.; Yuan, X. Z.; Martin, J. J.; Wang, H. J.; Zhang, J. J.; Shen, J.; Wu, S. H.; Merida, W. A review of PEM fuel cell durability: Degradation mechanisms and mitigation strategies. J. Power Sources 2008, 184, 104-119.
Yan, Y. C.; Du, J. S. S.; Gilroy, K. D.; Yang, D. R.; Xia, Y. N.; Zhang, H. Intermetallic nanocrystals: Syntheses and catalytic applications. Adv. Mater. 2017, 29, 1605997.
Bu, L. Z.; Zhang, N.; Guo, S. J.; Zhang, X.; Li, J.; Yao, J. L.; Wu, T.; Lu, G.; Ma, J. Y.; Su, D. et al. Biaxially strained PtPb/Pt core/shell nanoplate boosts oxygen reduction catalysis. Science 2016, 354, 1410-1414.
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.
Huang, X. Q.; Zhao, Z. P.; Cao, L.; Chen, Y.; Zhu, E. B.; Lin, Z. Y.; Li, M. F.; Yan, A. M.; Zettl, A.; Wang, Y. M. et al. High-performance transition metal-doped Pt3Ni octahedra for oxygen reduction reaction. Science 2015, 348, 1230-1234.
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.
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.
Kang, Y. J.; Pyo, J. B.; Ye, X. C.; Gordon, T. R.; Murray, C. B. Synthesis, shape control, and methanol electro-oxidation properties of Pt-Zn alloy and Pt3Zn intermetallic nanocrystals. ACS Nano 2012, 6, 5642-5647.
Qi, Z. Y.; Xiao, C. X.; Liu, C.; Goh, T. W.; Zhou, L.; Maligal-Ganesh, R.; Pei, Y. C.; Li, X. L.; Curtiss, L. A.; Huang, W. Y. Sub-4 nm PtZn intermetallic nanoparticles for enhanced mass and specific activities in catalytic electrooxidation reaction. J. Am. Chem. Soc. 2017, 139, 4762-4768.
Xiao, C. X.; Maligal-Ganesh, R. V.; Li, T.; Qi, Z. Y.; Guo, Z. Y.; Brashler, K. T.; Goes, S.; Li, X. L.; Goh, T. W.; Winans, R. E. et al. High-temperature-stable and regenerable catalysts: Platinum nanoparticles in aligned mesoporous silica wells. ChemSusChem 2013, 6, 1915-1922.
Joo, S. H.; Park, J. Y.; Tsung, C. K.; Yamada, Y.; Yang, P. D.; Somorjai, G. A. Thermally stable Pt/mesoporous silica core-shell nanocatalysts for high-temperature reactions. Nat. Mater. 2009, 8, 126-131.
Pei, Y. C.; Maligal-Ganesh, R. V.; Xiao, C. X.; Goh, T. W.; Brashler, K.; Gustafson, J. A.; Huang, W. Y. An inorganic capping strategy for the seeded growth of versatile bimetallic nanostructures. Nanoscale 2015, 7, 16721-16728.
Maligal-Ganesh, R. V.; Xiao, C. X.; Goh, T. W.; Wang, L. L.; Gustafson, J.; Pei, Y. C.; Qi, Z. Y.; Johnson, D. D.; Zhang, S. R.; Tao, F. et al. A ship-in-a-bottle strategy to synthesize encapsulated intermetallic nanoparticle catalysts: Exemplified for furfural hydrogenation. ACS Catal. 2016, 6, 1754-1763.
Li, X. L.; Goh, T. W.; Xiao, C. X.; Stanton, A. L. D.; Pei, Y. C.; Jain, P. K.; Huang, W. Y. Synthesis of monodisperse palladium nanoclusters using metal-organic frameworks as sacrificial templates. ChemNanoMat 2016, 2, 810-815.
Yang, Q. H.; Xu, Q.; Yu, S. H.; Jiang, H. L. Pd nanocubes@ZIF-8: Integration of plasmon-driven photothermal conversion with a metal-organic framework for efficient and selective catalysis. Angew. Chem., Int. Ed. 2016, 55, 3685-3689.
Li, X. L.; Goh, T. W.; Li, L.; Xiao, C. X.; Guo, Z. Y.; Zeng, X. C.; Huang, W. Y. Controlling catalytic properties of Pd nanoclusters through their chemical environment at the atomic level using isoreticular metal-organic frameworks. ACS Catal. 2016, 6, 3461-3468.
Li, X. L.; Van Zeeland, R.; Maligal-Ganesh, R. V.; Pei, Y. C.; Power, G.; Stanley, L.; Huang, W. Y. Impact of linker engineering on the catalytic activity of metal-organic frameworks containing Pd(Ⅱ)-bipyridine complexes. ACS Catal. 2016, 6, 6324-6328.
Lu, G.; Li, S. Z.; Guo, Z.; Farha, O. K.; Hauser, B. G.; Qi, X. Y.; Wang, Y.; Wang, X.; Han, S. Y.; Liu, X. G. et al. Imparting functionality to a metal-organic framework material by controlled nanoparticle encapsulation. Nat. Chem. 2012, 4, 310-316.
Zhu, Q. L.; Xu, Q. Metal-organic framework composites. Chem. Soc. Rev. 2014, 43, 5468-5512.
Furukawa, H.; Cordova, K. E.; O'Keeffe, M.; Yaghi, O. M. The chemistry and applications of metal-organic frameworks. Science 2013, 341, 1230444.
Liu, B.; Shioyama, H.; Akita, T.; Xu, Q. Metal-organic framework as a template for porous carbon synthesis. J. Am. Chem. Soc. 2008, 130, 5390-5391.
Zhao, S. L.; Yin, H. J.; Du, L.; He, L. C.; Zhao, K.; Chang, L.; Yin, G. P.; Zhao, H. J.; Liu, S. Q.; Tang, Z. Y. Carbonized nanoscale metal-organic frameworks as high performance electrocatalyst for oxygen reduction reaction. ACS Nano 2014, 8, 12660-12668.
You, B.; Jiang, N.; Sheng, M. L.; Drisdell, W. S.; Yano, J.; Sun, Y. J. Bimetal-organic framework self-adjusted synthesis of support-free nonprecious electrocatalysts for efficient oxygen reduction. ACS Catal. 2015, 5, 7068-7076.
Xu, Y. T.; Xiao, X. F.; Ye, Z. M.; Zhao, S. L.; Shen, R. G.; He, C. T.; Zhang, J. P.; Li, Y. D.; Chen, X. M. Cage- confinement pyrolysis route to ultrasmall tungsten carbide nanoparticles for efficient electrocatalytic hydrogen evolution. J. Am. Chem. Soc. 2017, 139, 5285-5288.
Pei, Y. C.; Qi, Z. Y.; Li, X. L.; Maligal-Ganesh, R. V.; Goh, T. W.; Xiao, C. X.; Wang, T. Y.; Huang, W. Y. Morphology inherence from hollow MOFs to hollow carbon polyhedrons in preparing carbon-based electrocatalysts. J. Mater. Chem. A 2017, 5, 6186-6192.
Li, X. L.; Zhang, B. Y.; Fang, Y. H.; Sun, W. J.; Qi, Z. Y.; Pei, Y. C.; Qi, S. Y.; Yuan, P. Y.; Luan, X. C.; Goh, T. W. et al. Metal-organic-framework-derived carbons: Applications as solid-base catalyst and support for Pd nanoparticles in tandem catalysis. Chem. -Eur. J. 2017, 23, 4266-4270.
Yang, Q. H.; Xu, Q.; Jiang, H. L. Metal-organic frameworks meet metal nanoparticles: Synergistic effect for enhanced catalysis. Chem. Soc. Rev. 2017, 46, 4774-4808.
Ji, S. F.; Chen, Y. J.; Fu, Q.; Chen, Y. F.; Dong, J. C.; Chen, W. X.; Li, Z.; Wang, Y.; Gu, L.; He, W. et al. Confined pyrolysis within metal-organic frameworks to form uniform Ru3 clusters for efficient oxidation of alcohols. J. Am. Chem. Soc. 2017, 139, 9795-9798.
Chen, Y. J.; Ji, S. F.; Wang, Y. G.; Dong, J. C.; Chen, W. X.; Li, Z.; Shen, R. A.; Zheng, L. R.; Zhuang, Z. B.; Wang, D. S. et al. Isolated single iron atoms anchored on N-doped porous carbon as an efficient electrocatalyst for the oxygen reduction reaction. Angew. Chem., Int. Ed. 2017, 56, 6937-6941.
Chen, Y. Z.; Wang, C. M.; Wu, Z. Y.; Xiong, Y. J.; Xu, Q.; Yu, S. H.; Jiang, H. L. From bimetallic metal-organic framework to porous carbon: High surface area and multicomponent active dopants for excellent electrocatalysis. Adv. Mater. 2015, 27, 5010-5016.
Xia, W.; Mahmood, A.; Zou, R. Q.; Xu, Q. Metal-organic frameworks and their derived nanostructures for electrochemical energy storage and conversion. Energ. Environ. Sci. 2015, 8, 1837-1866.
Zhang, W.; Wu, Z. Y.; Jiang, H. L.; Yu, S. H. Nanowire- directed templating synthesis of metal-organic framework nanofibers and their derived porous doped carbon nanofibers for enhanced electrocatalysis. J. Am. Chem. Soc. 2014, 136, 14385-14388.
Teranishi, T.; Hosoe, M.; Tanaka, T.; Miyake, M. Size control of monodispersed Pt nanoparticles and their 2D organization by electrophoretic deposition. J. Phys. Chem. B 1999, 103, 3818-3827.
Song, H.; Rioux, R. M.; Hoefelmeyer, J. D.; Komor, R.; Niesz, K.; Grass, M.; Yang, P. D.; Somorjai, G. A. Hydrothermal growth of mesoporous SBA-15 silica in the presence of PVP-stabilized Pt nanoparticles: Synthesis, characterization, and catalytic properties. J. Am. Chem. Soc. 2006, 128, 3027-3037.
Pei, Y. C.; Xiao, C. X.; Goh, T. W.; Zhang, Q. H.; Goes, S. N.; Sun, W. J.; Huang, W. Y. Tuning surface properties of amino-functionalized silica for metal nanoparticle loading: The vital role of an annealing process. Surf. Sci. 2016, 648, 299-306.
Jana, N. R.; Gearheart, L.; Murphy, C. J. Seeding growth for size control of 5-40 nm diameter gold nanoparticles. Langmuir 2001, 17, 6782-6786.
Li, Y.; Boone, E.; El-Sayed, M. A. Size effects of PVP-Pd nanoparticles on the catalytic Suzuki reactions in aqueous solution. Langmuir 2002, 18, 4921-4925.
Massalski, T. B.; Okamoto, H.; Subramanian, P. R.; Kacprzak, L. Binary Alloy Phase Diagrams, 2nd ed.; ASM International: Ohio, 1990.
Rösler, C.; Fischer, R. A. Metal-organic frameworks as hosts for nanoparticles. Crystengcomm 2015, 17, 199-217.
Stephenson, C. J.; Hupp, J. T.; Farha, O. K. Pt@ZIF-8 composite for the regioselective hydrogenation of terminal unsaturations in 1, 3-dienes and alkynes. Inorg. Chem. Front. 2015, 2, 448-452.
Park, K. S.; Ni, Z.; Côté, A. P.; Choi, J. Y.; Huang, R. D.; Uribe-Romo, F. J.; Chae, H. K.; O'Keeffe, M.; Yaghi, O. M. Exceptional chemical and thermal stability of zeolitic imidazolate frameworks. Proc. Natl. Acad. Sci. USA 2006, 103, 10186-10191.
Jiang, H. L.; Liu, B.; Akita, T.; Haruta, M.; Sakurai, H.; Xu, Q. Au@ZIF-8: Co oxidation over gold nanoparticles deposited to metal-organic framework. J. Am. Chem. Soc. 2009, 131, 11302-11303.
Zhou, H. R.; Yang, X. F.; Li, L.; Liu, X. Y.; Huang, Y. Q.; Pan, X. L.; Wang, A. Q.; Li, J.; Zhang, T. PdZn intermetallic nanostructure with Pt-Zn-Pd ensembles for highly active and chemoselective semi-hydrogenation of acetylene. ACS Catal. 2016, 6, 1054-1061.
Iihama, S.; Furukawa, S.; Komatsu, T. Efficient catalytic system for chemoselective hydrogenation of halonitrobenzene to haloaniline using PtZn intermetallic compound. ACS Catal. 2016, 6, 742-746.
Furukawa, S.; Yoshida, Y.; Komatsu, T. Chemoselective hydrogenation of nitrostyrene to aminostyrene over Pd- and Rh-based intermetallic compounds. ACS Catal. 2014, 4, 1441-1450.
Du, X. X.; He, Y.; Wang, X. X.; Wang, J. N. Fine-grained and fully ordered intermetallic PtFe catalysts with largely enhanced catalytic activity and durability. Energy Environ. Sci. 2016, 9, 2623-2632.
Cui, Z. M.; Chen, H.; Zhou, W. D.; Zhao, M. T.; DiSalvo, F. J. Structurally ordered Pt3Cr as oxygen reduction electrocatalyst: Ordering control and origin of enhanced stability. Chem. Mater. 2015, 27, 7538-7545.
Shim, J.; Lee, J.; Ye, Y.; Hwang, J.; Kim, S. K.; Lim, T. H.; Wiesner, U.; Lee, J. One-pot synthesis of intermetallic electrocatalysts in ordered, large-pore mesoporous carbon/silica toward formic acid oxidation. ACS Nano 2012, 6, 6870-6881.
Chung, D. Y.; Jun, S. W.; Yoon, G.; Kwon, S. G.; Shin, D. Y.; Seo, P.; Yoo, J. M.; Shin, H.; Chung, Y. H.; Kim, H. et al. Highly durable and active PtFe nanocatalyst for electrochemical oxygen reduction reaction. J. Am. Chem. Soc. 2015, 137, 15478-15485.
Magno, L. M.; Sigle, W.; van Aken, P. A.; Angelescu, D.; Stubenrauch, C. Size control of PtPb intermetallic nanoparticles prepared via microemulsions. Phys. Chem. Chem. Phys. 2011, 13, 9134-9136.