skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Solvent-Induced Self-Assembly Strategy to Synthesize Well-Defined Hierarchically Porous Polymers

Abstract

Porous polymers with well-orchestrated nanomorphologies are useful in many fields, but high surface area, hierarchical structure, and ordered pores are difficult to be satisfied in one polymer simultaneously. A solvent-induced self-assembly strategy to synthesize hierarchical porous polymers with tunable morphology, mesoporous structure, and microporous pore wall is reported. The poly(ethylene oxide)-b-polystyrene (PEO-b-PS) diblock copolymer micelles are cross-linked via Friedel–Crafts reaction, which is a new way to anchor micelles into porous polymers with well-defined structure. Varying the polarity of the solvent has a dramatic effect upon the oleophobic/oleophylic interaction, and the self-assembly structure of PEO-b-PS can be tailored from aggregated nanoparticles to hollow spheres even mesoporous bulk. A morphological phase diagram is accomplished to systematically evaluate the influence of the composition of PEO-b-PS and the mixed solvent component on the pore structure and morphology of products. The hypercrosslinked hollow polymer spheres provide a confined microenvironment for the in situ reduction of K2PdCl4 to ultrasmall Pd nanoparticles, which exhibit excellent catalytic performance in solvent-free catalytic oxidation of hydrocarbons and alcohols.

Authors:
 [1];  [1];  [1];  [1];  [1]; ORCiD logo [1];  [2]
  1. Jilin Univ., Changchun (China). State Key Lab. of Inorganic Synthesis and Preparative Chemistry
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Jilin Univ., Changchun (China)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); Young Thousand Talented Program (China); National Natural Science Foundation of China (NNSFC); “111” Project of the Ministry of Education of China
OSTI Identifier:
1511925
Grant/Contract Number:  
AC05-00OR22725; 21671073; 21621001; 21671074; B17020
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Materials
Additional Journal Information:
Journal Volume: 31; Journal Issue: 11; Journal ID: ISSN 0935-9648
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; hierarchical porous polymer; hypercrosslinked polymer; porous material; solvent-free catalysis; solvent-induced self-assembly

Citation Formats

Gao, Tu‐Nan, Wang, Tao, Wu, Wei, Liu, Yali, Huo, Qisheng, Qiao, Zhen‐An, and Dai, Sheng. Solvent-Induced Self-Assembly Strategy to Synthesize Well-Defined Hierarchically Porous Polymers. United States: N. p., 2019. Web. doi:10.1002/adma.201806254.
Gao, Tu‐Nan, Wang, Tao, Wu, Wei, Liu, Yali, Huo, Qisheng, Qiao, Zhen‐An, & Dai, Sheng. Solvent-Induced Self-Assembly Strategy to Synthesize Well-Defined Hierarchically Porous Polymers. United States. doi:10.1002/adma.201806254.
Gao, Tu‐Nan, Wang, Tao, Wu, Wei, Liu, Yali, Huo, Qisheng, Qiao, Zhen‐An, and Dai, Sheng. Fri . "Solvent-Induced Self-Assembly Strategy to Synthesize Well-Defined Hierarchically Porous Polymers". United States. doi:10.1002/adma.201806254. https://www.osti.gov/servlets/purl/1511925.
@article{osti_1511925,
title = {Solvent-Induced Self-Assembly Strategy to Synthesize Well-Defined Hierarchically Porous Polymers},
author = {Gao, Tu‐Nan and Wang, Tao and Wu, Wei and Liu, Yali and Huo, Qisheng and Qiao, Zhen‐An and Dai, Sheng},
abstractNote = {Porous polymers with well-orchestrated nanomorphologies are useful in many fields, but high surface area, hierarchical structure, and ordered pores are difficult to be satisfied in one polymer simultaneously. A solvent-induced self-assembly strategy to synthesize hierarchical porous polymers with tunable morphology, mesoporous structure, and microporous pore wall is reported. The poly(ethylene oxide)-b-polystyrene (PEO-b-PS) diblock copolymer micelles are cross-linked via Friedel–Crafts reaction, which is a new way to anchor micelles into porous polymers with well-defined structure. Varying the polarity of the solvent has a dramatic effect upon the oleophobic/oleophylic interaction, and the self-assembly structure of PEO-b-PS can be tailored from aggregated nanoparticles to hollow spheres even mesoporous bulk. A morphological phase diagram is accomplished to systematically evaluate the influence of the composition of PEO-b-PS and the mixed solvent component on the pore structure and morphology of products. The hypercrosslinked hollow polymer spheres provide a confined microenvironment for the in situ reduction of K2PdCl4 to ultrasmall Pd nanoparticles, which exhibit excellent catalytic performance in solvent-free catalytic oxidation of hydrocarbons and alcohols.},
doi = {10.1002/adma.201806254},
journal = {Advanced Materials},
number = 11,
volume = 31,
place = {United States},
year = {2019},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 8 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

A Chemically Functionalizable Nanoporous Material [Cu3(TMA)2(H2O)3]n
journal, February 1999


Introduction of π-Complexation into Porous Aromatic Framework for Highly Selective Adsorption of Ethylene over Ethane
journal, June 2014

  • Li, Baiyan; Zhang, Yiming; Krishna, Rajamani
  • Journal of the American Chemical Society, Vol. 136, Issue 24
  • DOI: 10.1021/ja502119z

Design and Preparation of Porous Polymers
journal, April 2012

  • Wu, Dingcai; Xu, Fei; Sun, Bin
  • Chemical Reviews, Vol. 112, Issue 7
  • DOI: 10.1021/cr200440z

Two-Dimensional Mesoscale-Ordered Conducting Polymers
journal, September 2016

  • Liu, Shaohua; Zhang, Jian; Dong, Renhao
  • Angewandte Chemie International Edition, Vol. 55, Issue 40
  • DOI: 10.1002/anie.201606988

A hypercrosslinking-induced self-assembly strategy for preparation of advanced hierarchical porous polymers with customizable functional components
journal, January 2017

  • Xu, Hongji; Wu, Jinlun; Zheng, Bingna
  • Chemical Communications, Vol. 53, Issue 38
  • DOI: 10.1039/C7CC01417A

Hollow Microporous Organic Capsules Loaded with Highly Dispersed Pt Nanoparticles for Catalytic Applications
journal, May 2014

  • Yang, Xinjia; Song, Kunpeng; Tan, Liangxiao
  • Macromolecular Chemistry and Physics, Vol. 215, Issue 12
  • DOI: 10.1002/macp.201400107

Fabrication of novel polymeric and carbonaceous nanoscale networks by the union of self-assembly and hypercrosslinking
journal, January 2014

  • Li, Zhenghui; Wu, Dingcai; Huang, Xin
  • Energy & Environmental Science, Vol. 7, Issue 9
  • DOI: 10.1039/C4EE00941J

Hierarchical assembly of micro-/nano-building blocks: bio-inspired rigid structural functional materials
journal, January 2011

  • Yao, Hong-Bin; Fang, Hai-Yu; Wang, Xiao-Han
  • Chemical Society Reviews, Vol. 40, Issue 7
  • DOI: 10.1039/c0cs00121j

Block Copolymer Micelles with Inverted Morphologies
journal, July 2017

  • Gröschel, André H.; Walther, Andreas
  • Angewandte Chemie International Edition, Vol. 56, Issue 37
  • DOI: 10.1002/anie.201703765

Solvent-free aerobic oxidation of hydrocarbons and alcohols with Pd@N-doped carbon from glucose
journal, March 2013

  • Zhang, Pengfei; Gong, Yutong; Li, Haoran
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms2586

Directed self-assembly of block copolymers: a tutorial review of strategies for enabling nanotechnology with soft matter
journal, January 2014

  • Hu, Hanqiong; Gopinadhan, Manesh; Osuji, Chinedum O.
  • Soft Matter, Vol. 10, Issue 22
  • DOI: 10.1039/c3sm52607k

Tunable Self-Assembly of Diblock Copolymers into Colloidal Particles with Triply Periodic Minimal Surfaces
journal, May 2017

  • Lin, Zhixing; Liu, Shaohua; Mao, Wenting
  • Angewandte Chemie International Edition, Vol. 56, Issue 25
  • DOI: 10.1002/anie.201702591

A New Strategy to Microporous Polymers: Knitting Rigid Aromatic Building Blocks by External Cross-Linker
journal, April 2011

  • Li, Buyi; Gong, Ruini; Wang, Wei
  • Macromolecules, Vol. 44, Issue 8
  • DOI: 10.1021/ma200630s

Intricate Hollow Structures: Controlled Synthesis and Applications in Energy Storage and Conversion
journal, February 2017


Water-Dispersible, Responsive, and Carbonizable Hairy Microporous Polymeric Nanospheres
journal, October 2015

  • Mai, Weicong; Sun, Bin; Chen, Luyi
  • Journal of the American Chemical Society, Vol. 137, Issue 41
  • DOI: 10.1021/jacs.5b08978

Self-assembly of block copolymers
journal, January 2012

  • Mai, Yiyong; Eisenberg, Adi
  • Chemical Society Reviews, Vol. 41, Issue 18
  • DOI: 10.1039/c2cs35115c

Hyper-Cross-Linking Mediated Self-Assembly Strategy To Synthesize Hollow Microporous Organic Nanospheres
journal, September 2017

  • He, Zidong; Zhou, Minghong; Wang, Tianqi
  • ACS Applied Materials & Interfaces, Vol. 9, Issue 40
  • DOI: 10.1021/acsami.7b08657

Product Selectivity Controlled by Zeolite Crystals in Biomass Hydrogenation over a Palladium Catalyst
journal, June 2016

  • Wang, Chengtao; Wang, Liang; Zhang, Jian
  • Journal of the American Chemical Society, Vol. 138, Issue 25
  • DOI: 10.1021/jacs.6b04951

Polymer Vesicles
journal, August 2002


Hollow Microporous Organic Capsules
journal, July 2013

  • Li, Buyi; Yang, Xinjia; Xia, Lingling
  • Scientific Reports, Vol. 3, Issue 1
  • DOI: 10.1038/srep02128

Porous polymer catalysts with hierarchical structures
journal, January 2015

  • Sun, Qi; Dai, Zhifeng; Meng, Xiangju
  • Chemical Society Reviews, Vol. 44, Issue 17
  • DOI: 10.1039/C5CS00198F

Self-assembly concepts for multicompartment nanostructures
journal, January 2015

  • Gröschel, André H.; Müller, Axel H. E.
  • Nanoscale, Vol. 7, Issue 28
  • DOI: 10.1039/C5NR02448J

New Polymer Colloidal and Carbon Nanospheres: Stabilizing Ultrasmall Metal Nanoparticles for Solvent-Free Catalysis
journal, April 2017


Porous, Crystalline, Covalent Organic Frameworks
journal, November 2005

  • Côté, Adrien P.; Benin, Annabelle I.; Ockwig, Nathan W.
  • Science, Vol. 310, Issue 5751, p. 1166-1170
  • DOI: 10.1126/science.1120411

Functionalized TiO 2 Nanoparticles for Use for in Situ Anion Immobilization
journal, September 2005

  • Mattigod, Shas V.; Fryxell, Glen E.; Alford, Kentin
  • Environmental Science & Technology, Vol. 39, Issue 18
  • DOI: 10.1021/es048982l

Hypercrosslinked porous polymer materials: design, synthesis, and applications
journal, January 2017

  • Tan, Liangxiao; Tan, Bien
  • Chemical Society Reviews, Vol. 46, Issue 11
  • DOI: 10.1039/C6CS00851H

Polymers of intrinsic microporosity (PIMs): organic materials for membrane separations, heterogeneous catalysis and hydrogen storage
journal, January 2006

  • McKeown, Neil B.; Budd, Peter M.
  • Chemical Society Reviews, Vol. 35, Issue 8, p. 675-683
  • DOI: 10.1039/b600349d

Hierarchically Porous Polymers from Hyper-cross-linked Block Polymer Precursors
journal, January 2015

  • Seo, Myungeun; Kim, Soobin; Oh, Jaehoon
  • Journal of the American Chemical Society, Vol. 137, Issue 2
  • DOI: 10.1021/ja511581w

Hydrogen Storage in Microporous Hypercrosslinked Organic Polymer Networks
journal, April 2007

  • Wood, Colin D.; Tan, Bien; Trewin, Abbie
  • Chemistry of Materials, Vol. 19, Issue 8
  • DOI: 10.1021/cm070356a

Lab-in-a-Shell: Encapsulating Metal Clusters for Size Sieving Catalysis
journal, August 2014

  • Qiao, Zhen-An; Zhang, Pengfei; Chai, Song-Hai
  • Journal of the American Chemical Society, Vol. 136, Issue 32
  • DOI: 10.1021/ja505903r

Fabrication of Hollow Microporous Carbon Spheres from Hyper-Crosslinked Microporous Polymers
journal, May 2016


Porous Organic Materials: Strategic Design and Structure–Function Correlation
journal, December 2016


Stepwise Crosslinking: A Facile Yet Versatile Conceptual Strategy to Nanomorphology-Persistent Porous Organic Polymers
journal, May 2017


Polymeric molecular sieve membranes via in situ cross-linking of non-porous polymer membrane templates
journal, April 2014

  • Qiao, Zhen-An; Chai, Song-Hai; Nelson, Kimberly
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms4705

Thermodynamics versus Kinetics in Nanosynthesis
journal, December 2014

  • Wang, Yawen; He, Jiating; Liu, Cuicui
  • Angewandte Chemie International Edition, Vol. 54, Issue 7
  • DOI: 10.1002/anie.201402986

Ordered Mesoporous Silicas and Carbons with Large Accessible Pores Templated from Amphiphilic Diblock Copolymer Poly(ethylene oxide)- b -polystyrene
journal, February 2007

  • Deng, Yonghui; Yu, Ting; Wan, Ying
  • Journal of the American Chemical Society, Vol. 129, Issue 6
  • DOI: 10.1021/ja067379v

Storage of Hydrogen, Methane, and Carbon Dioxide in Highly Porous Covalent Organic Frameworks for Clean Energy Applications
journal, July 2009

  • Furukawa, Hiroyasu; Yaghi, Omar M.
  • Journal of the American Chemical Society, Vol. 131, Issue 25, p. 8875-8883
  • DOI: 10.1021/ja9015765

A Micelle Fusion–Aggregation Assembly Approach to Mesoporous Carbon Materials with Rich Active Sites for Ultrasensitive Ammonia Sensing
journal, September 2016

  • Luo, Wei; Zhao, Tao; Li, Yuhui
  • Journal of the American Chemical Society, Vol. 138, Issue 38
  • DOI: 10.1021/jacs.6b07355

Layered microporous polymers by solvent knitting method
journal, March 2017


Inspiration and application in the evolution of biomaterials
journal, November 2009


Conjugated Microporous Poly(aryleneethynylene) Networks
journal, September 2007

  • Jiang, Jia-Xing; Su, Fabing; Trewin, Abbie
  • Angewandte Chemie International Edition, Vol. 46, Issue 45
  • DOI: 10.1002/anie.200701595

Hypercrosslinked Phenolic Polymers with Well-Developed Mesoporous Frameworks
journal, February 2015

  • Zhang, Jinshui; Qiao, Zhen-An; Mahurin, Shannon M.
  • Angewandte Chemie International Edition, Vol. 54, Issue 15
  • DOI: 10.1002/anie.201500305

Dual-Template Synthesis of 2D Mesoporous Polypyrrole Nanosheets with Controlled Pore Size
journal, August 2016


Pore Space Partition by Symmetry-Matching Regulated Ligand Insertion and Dramatic Tuning on Carbon Dioxide Uptake
journal, January 2015

  • Zhao, Xiang; Bu, Xianhui; Zhai, Quan-Guo
  • Journal of the American Chemical Society, Vol. 137, Issue 4
  • DOI: 10.1021/ja512137t

Polymeric Photocatalysts Based on Graphitic Carbon Nitride
journal, February 2015


Solvent-Free Oxidation of Primary Alcohols to Aldehydes Using Au-Pd/TiO 2 Catalysts
journal, January 2006


New Insight into the Synthesis of Large-Pore Ordered Mesoporous Materials
journal, January 2017

  • Wei, Jing; Sun, Zhenkun; Luo, Wei
  • Journal of the American Chemical Society, Vol. 139, Issue 5
  • DOI: 10.1021/jacs.6b11411