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Spatially orthogonal chemical functionalization of a hierarchical pore network for catalytic cascade reactions


The chemical functionality within porous architectures dictates their performance as heterogeneous catalysts1; however, synthetic routes to control the spatial distribution of individual functions within porous solids are limited. Here we report the fabrication of spatially orthogonal bifunctional porous catalysts, through the stepwise template removal and chemical functionalization of an interconnected silica framework. Selective removal of polystyrene nanosphere templates from a lyotropic liquid crystal-templated silica sol–gel matrix, followed by extraction of the liquid crystal template, affords a hierarchical macroporous–mesoporous architecture. Decoupling of the individual template extractions allows independent functionalization of macropore and mesopore networks on the basis of chemical and/or size specificity. Spatial compartmentalization of, and directed molecular transport between, chemical functionalities affords control over the reaction sequence in catalytic cascades2,3; herein illustrated by the Pd/Pt-catalysed oxidation of cinnamyl alcohol to cinnamic acid. We anticipate that our methodology will prompt further design of multifunctional materials4,5,6 comprising spatially compartmentalized functions.

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Figure 1: Synthetic strategy for spatially orthogonal functionalization of hierarchical architectures.
Figure 2: Visualization of spatially orthogonal Pd and Pt NPs.
Figure 3: Reaction dynamics of cinnamyl alcohol oxidation.


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This work was supported by the EPSRC (EP/G007594/4). A.F.L. was supported by an EPSRC Leadership Fellowship, K.W. by a Royal Society Industry Fellowship, and S.K.B. by a Durham University Addison Wheeler Fellowship and The Leverhulme Trust ECF schemes. L.M.B. acknowledges the EPSRC for a studentship. Electron microscopy access was provided through the Leeds EPSRC Nanoscience and Nanotechnology Research Equipment Facility (LENNF) (EP/K023853/1), the University of Birmingham Nanoscale Physics Laboratory, and DU GJ Russell Microscopy Facility.

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A.F.L., C.M.A.P. and K.W. planned the experiments. C.M.A.P. synthesized all porous materials and performed catalytic testing. L.M.B. and S.K.B. synthesized and characterized the Pd colloids. C.M.A.P., M.A.I. and N.S.H. undertook materials characterization. A.F.L. wrote the manuscript.

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Correspondence to Adam F. Lee.

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The authors declare no competing financial interests.

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Parlett, C., Isaacs, M., Beaumont, S. et al. Spatially orthogonal chemical functionalization of a hierarchical pore network for catalytic cascade reactions. Nature Mater 15, 178–182 (2016).

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