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Martinez, Abraham; Shikhaliyev, Kanan; Li, Xuemin; Han, Jinyi; Chaudhuri, Kaustav; Hwang, Son-Jong; Urban-Klaehn, Jagoda M; Kuperman, Alexander; Gaffney, Anne; Lauterbach, Jochen; et al (, Reaction Chemistry & Engineering)Multi-scale upcycling of PPG polymer synthesizes propionaldehyde in 95% selectivity & 86% yield.more » « less
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Needham, Brittany D.; Funabashi, Masanori; Adame, Mark D.; Wang, Zhuo; Boktor, Joseph C.; Haney, Jillian; Wu, Wei-Li; Rabut, Claire; Ladinsky, Mark S.; Hwang, Son-Jong; et al (, Nature)
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Okrut, Alexander; Aigner, Martina; Schöttle, Christian; Grosso-Giordano, Nicolás A.; Hwang, Son-Jong; Ouyang, Xiaoying; Zones, Stacey; Katz, Alexander (, Dalton Transactions)We report a scalable delamination procedure for a SSZ-70-framework layered-zeolite precursor, which for the first time does not involve either sonication or long-chain surfactants. Our approach instead relies on the mild heating of layered zeolite precursor B-SSZ-70(P) in an aqueous solution containing Zn(NO 3 ) 2 and tetrabutylammonium fluoride. Powder X-ray diffraction data are consistent with a loss of long-range order along the z -direction, while 29 Si MAS NMR spectroscopy demonstrates preservation of the zeolite framework crystallinity during delamination. The resulting delaminated material, DZ-2, possesses 1.4-fold higher external surface area relative to the nondelaminated three-dimensional zeolite B-SSZ-70, based on N 2 physisorption data at 77 K. DZ-2 was functionalized with cationic Ti heteroatoms to synthesize Ti-DZ-2 via exchange with framework B. Ti-DZ-2 contains isolated titanium centers in its crystalline framework, as shown by UV-Vis spectroscopy. The generality of the synthetic delamination approach and catalyst synthesis is demonstrated with the synthesis of delaminated material DZ-3, which is derived from layered zeolite precursor ERB-1(P) with MWW framework topology. Upon catalytic testing for the epoxidation of 1-octene with ethylbenzene hydroperoxide as oxidant, under harsh tail-end conditions that deactivate amorphous Ti-silica-based catalysts, Ti-DZ-2 exhibits the highest per-Ti-site activity, selectivity, and stability for 1-octene epoxidation of all catalysts investigated. This testing includes the prior benchmark delaminated zeolite catalyst in this area, Ti-UCB-4, which possesses similar external surface area to Ti-DZ-2 but requires sonication and long-chain surfactants for its synthesis. The synthesis of DZ-2 is the first example of an economical delamination of layered zeolite precursor SSZ-70(P) and opens up new doors to the development of delaminated zeolites as commercial catalysts.more » « less
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