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Designing Synergistic Nanocatalysts for Multiple Substrate Activation: Interlattice Ag–Fe3O4 Hybrid Materials for CO2‑Inserted Lactones
journal contribution
posted on 2020-02-24, 12:36 authored by U. Chinna Rajesh, Yaroslav Losovyj, Chun-Hsing Chen, Jeffrey M. ZaleskiMultimetallic architectures
that combine chemically diverse materials
to affect tandem reactions within a single scaffold drive future nanocatalyst
development. Here, we show the unique, interlattice growth of the
small molecule activating Ag0 guest within the Lewis acidic/basic
Fe3O4 octahedral host (Fe3O4@Ag-40, 10, 6, 2 at %) via a polyol-hydrothermal procedure. Microscopic
(scanning electron microscopy and energy-dispersive X-ray spectroscopy
) and structural characterization (powder X-ray diffraction and X-ray
photoelectron spectroscopy) of the Fe3O4@Ag
hybrid materials reveal doping of Ag0 in Oh Fe2+ substitutional vacancies
of the Fe3O4 host and Ag0 nanoparticle
growth on and embedded deep within (>400 nm, Ar+ sputtering)
the octahedra. These hybrid materials activate CO2 and
perform C(sp)–H and C(sp3)–Cl bond scission
of alkyne substrates to selectively produce lactone heterocycles in
up to 85% yield. Control reactions delineate two distinct pathways
for the mechanism involving the complementarity of interfacial sites
where alkyne activation occurs at Fe–O sites and CO2 incorporation is predominately managed by Ag0. The recyclability
of the Fe3O4@Ag-40B hybrid catalyst is demonstrated
over five cycles and it shows the structural integrity of the octahedra,
but a gradual drop in yield of the product from 85 to 45% due to slow
depletion of surface Ag NPs is observed. Together, these results illustrate
a rare understanding of the cooperative synergy and mechanism of multimetallic
nanocatalyst interfaces for multiple substrate reactivity.
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energy-dispersive X-ray spectroscopyscaffold drive future nanocatalyst developmentAg 0 guestAg 0Fe 3 O 4 hostAg 0 nanoparticle growthpowder X-ray diffractionCO 2 incorporationscanning electron microscopyMultiple Substrate ActivationFe 3 O 4multimetallic nanocatalyst interfacessurface Ag NPsDesigning Synergistic NanocatalystsX-ray photoelectron spectroscopy-40B
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