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Title: Chemically Controllable Porous Polymer–Nanocrystal Composites with Hierarchical Arrangement Show Substrate Transport Selectivity

Abstract

Functional organic–inorganic hybrid materials with tunable properties are useful across many application areas, ranging from gas storage to electronics, flame retardants, separations, and catalysis. Combining polymers, with a suite of functional groups and conformational flexibility, and inorganic nanoparticles, with tunable surface chemistry and composition, yields hybrids with novel functional properties. Specifically, in catalysis, control of the electronic environment at a metal interface is paramount in determining the catalytic properties. In this contribution, we describe a modular process to prepare porous polymer–nanocrystal (NC) composites in a hierarchical, multilayered synthesis, in which multiple parameters can be accurately tuned: polymer functional groups and the corresponding pore structure, the polymer layer thickness, and the NC size, shape, and composition. This process provides for a variety of controlled materials with high surface area, tunable chemistry, and thermal and chemical stabilities. Furthermore, we demonstrate their utility for shape- and size-selective catalytic conversions both in oxidation and hydrogenation reactions, where they show increased selectivity by orders of magnitude compared to conventional polymer-supported metal catalysts. In light of the high degree of control in the composite structure, this method allows for the design and realization of catalysts for several reactions and reaction environments and for nanomaterials with othermore » applications.« less

Authors:
ORCiD logo [1];  [1];  [1];  [1];  [1];  [1];  [2]; ORCiD logo [1]
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  1. Stanford Univ., CA (United States). SUNCAT Center for Interface Science and Catalysis
  2. Exxon Mobil Research and Engineering, Annandale, NJ (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1656772
Grant/Contract Number:  
AC02-76SF00515; DGE-1656518
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 32; Journal Issue: 13; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Palladium; Composites; Monomers; Layers; Catalysts

Citation Formats

Riscoe, Andrew R., Wrasman, Cody J., Menon, Aditya, Dinakar, Bhavish, Goodman, Emmett D., Kunz, Larissa Y., Yacob, Sara, and Cargnello, Matteo. Chemically Controllable Porous Polymer–Nanocrystal Composites with Hierarchical Arrangement Show Substrate Transport Selectivity. United States: N. p., 2020. Web. doi:10.1021/acs.chemmater.0c02233.
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Riscoe, Andrew R., Wrasman, Cody J., Menon, Aditya, Dinakar, Bhavish, Goodman, Emmett D., Kunz, Larissa Y., Yacob, Sara, & Cargnello, Matteo. Chemically Controllable Porous Polymer–Nanocrystal Composites with Hierarchical Arrangement Show Substrate Transport Selectivity. United States. https://doi.org/10.1021/acs.chemmater.0c02233
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Riscoe, Andrew R., Wrasman, Cody J., Menon, Aditya, Dinakar, Bhavish, Goodman, Emmett D., Kunz, Larissa Y., Yacob, Sara, and Cargnello, Matteo. Wed . "Chemically Controllable Porous Polymer–Nanocrystal Composites with Hierarchical Arrangement Show Substrate Transport Selectivity". United States. https://doi.org/10.1021/acs.chemmater.0c02233. https://www.osti.gov/servlets/purl/1656772.
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@article{osti_1656772,
title = {Chemically Controllable Porous Polymer–Nanocrystal Composites with Hierarchical Arrangement Show Substrate Transport Selectivity},
author = {Riscoe, Andrew R. and Wrasman, Cody J. and Menon, Aditya and Dinakar, Bhavish and Goodman, Emmett D. and Kunz, Larissa Y. and Yacob, Sara and Cargnello, Matteo},
abstractNote = {Functional organic–inorganic hybrid materials with tunable properties are useful across many application areas, ranging from gas storage to electronics, flame retardants, separations, and catalysis. Combining polymers, with a suite of functional groups and conformational flexibility, and inorganic nanoparticles, with tunable surface chemistry and composition, yields hybrids with novel functional properties. Specifically, in catalysis, control of the electronic environment at a metal interface is paramount in determining the catalytic properties. In this contribution, we describe a modular process to prepare porous polymer–nanocrystal (NC) composites in a hierarchical, multilayered synthesis, in which multiple parameters can be accurately tuned: polymer functional groups and the corresponding pore structure, the polymer layer thickness, and the NC size, shape, and composition. This process provides for a variety of controlled materials with high surface area, tunable chemistry, and thermal and chemical stabilities. Furthermore, we demonstrate their utility for shape- and size-selective catalytic conversions both in oxidation and hydrogenation reactions, where they show increased selectivity by orders of magnitude compared to conventional polymer-supported metal catalysts. In light of the high degree of control in the composite structure, this method allows for the design and realization of catalysts for several reactions and reaction environments and for nanomaterials with other applications.},
doi = {10.1021/acs.chemmater.0c02233},
journal = {Chemistry of Materials},
number = 13,
volume = 32,
place = {United States},
year = {Wed Jun 17 00:00:00 EDT 2020},
month = {Wed Jun 17 00:00:00 EDT 2020}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1021/acs.chemmater.0c02233
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