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Metallo-supramolecular polymer engineered porous carbon framework encapsulated stable ultra-small nanoparticles: a general approach to construct highly dispersed catalysts

Ai, Yongjian, He, Mengqi, Zhang, Feng, Long, Yang, Li, Yunzheng, Han, Qiang, Ding, Mingyu, Sun, Hong-bin, Liang, Qionglin
Journal of materials chemistry 2018 v.6 no.34 pp. 16680-16689
annealing, carbon, catalysts, chemoselectivity, cobalt, condensation reactions, durability, electrochemistry, energy, environmental protection, hydrogenation, iron, manufacturing, molybdenum, nanocomposites, nanoparticles, nickel, p-nitrophenol, palladium, polymers, rhodium, ruthenium
The development of a general approach for fabricating stable ultra-small heterogeneous nanocatalysts has been intensively pursued. However, issues related to complex synthesis processes and structural stability have restricted their investigation and application. Here we report a facile organometallic conjunction strategy for the large-scale fabrication of porous carbon framework encapsulated highly dispersed sub-3 nm ultra-small nanoparticles (USMNPs@PCF). This methodology is based on the convenient aldol condensation reaction to manufacture a metallo-supramolecular polymer precursor and then consequent annealing to form the target nanocomposite. This technique was successfully applied to the preparation of varieties of USMNPs@PCF, including Fe, Co, Ni, Mo, Ru, Rh, Pd and Pt. As a representative application, the PCF encapsulated sub-3 nm Pd nanoparticles demonstrated remarkable durability and efficiency for chemoselective hydrogenation of nitroarenes to their corresponding anilines under ambient conditions with low catalyst loading. All hydrogenation reactions can complete in 4 min with >99% conversion and >99% chemoselectivity. The turnover frequency (TOF) was up to 11 400 h⁻¹ for p-nitrophenol. This work provides a general, scalable and economical route for the manufacture of sub-3 nm and highly dispersed nanocomposites, which can be used in many other important fields, such as electrochemistry, energy science and environmental protection.