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Title: One-Step Synthesis of Hybrid Core-Shell Metal-Organic Frameworks

Abstract

Epitaxial growth of MOF-on-MOF composite is an evolving research topic in the quest for multifunctional materials. During prior approaches, the core–shell MOFs were synthesized via a stepwise strategy that involved growing the shell-MOFs on top of the preformed core-MOFs with matched lattice parameters. Yet, the inconvenient stepwise synthesis and the strict lattice-matching requirement have limited the preparation of core–shell MOFs. Herein, we demonstrate that hybrid core–shell MOFs with mismatching lattices can be synthesized under the guidance of nucleation kinetic analysis. A series of MOF composites with mesoporous core and microporous shell were constructed and characterized by optical microscopy, powder X-ray diffraction, gas sorption measurement, and scanning electron microscopy. Isoreticular expansion of microporous shells and orthogonal modification of the core was realized to produce multifunctional MOF composites, which acted as size selective catalysts for olefin epoxidation with high activity and selectivity.

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [2]; ORCiD logo [1]
  1. Texas A & M Univ., College Station, TX (United States)
  2. King Saud Univ., Riyadh (Saudi Arabia)
Publication Date:
Research Org.:
Univ. of California, Berkeley (United States). Energy Frontier Research Center (EFRC) (United States) Center for Gas Separations Relevant to Clean Energy Technologies (CGS)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Fuel Cell Technologies Office (EE-3F); USDOE Office of Fossil Energy (FE)
OSTI Identifier:
1470334
Alternate Identifier(s):
OSTI ID: 1432067
Grant/Contract Number:  
SC0001015; EE0007049; FE0026472
Resource Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 57; Journal Issue: 15; Related Information: CGS partners with University of California, Berkeley; University of California, Davis; Lawrence Berkeley National Laboratory; University of Minnesota; National Energy Technology Laboratory; Texas A&M University; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; core–shell MOFs; nucleation kinetics; olefin epoxidation; size-selective catalyst

Citation Formats

Yang, Xinyu, Yuan, Shuai, Zou, Lanfang, Drake, Hannah, Zhang, Yingmu, Qin, Junsheng, Alsalme, Ali, and Zhou, Hong-Cai. One-Step Synthesis of Hybrid Core-Shell Metal-Organic Frameworks. United States: N. p., 2018. Web. doi:10.1002/anie.201710019.
Yang, Xinyu, Yuan, Shuai, Zou, Lanfang, Drake, Hannah, Zhang, Yingmu, Qin, Junsheng, Alsalme, Ali, & Zhou, Hong-Cai. One-Step Synthesis of Hybrid Core-Shell Metal-Organic Frameworks. United States. doi:10.1002/anie.201710019.
Yang, Xinyu, Yuan, Shuai, Zou, Lanfang, Drake, Hannah, Zhang, Yingmu, Qin, Junsheng, Alsalme, Ali, and Zhou, Hong-Cai. Fri . "One-Step Synthesis of Hybrid Core-Shell Metal-Organic Frameworks". United States. doi:10.1002/anie.201710019. https://www.osti.gov/servlets/purl/1470334.
@article{osti_1470334,
title = {One-Step Synthesis of Hybrid Core-Shell Metal-Organic Frameworks},
author = {Yang, Xinyu and Yuan, Shuai and Zou, Lanfang and Drake, Hannah and Zhang, Yingmu and Qin, Junsheng and Alsalme, Ali and Zhou, Hong-Cai},
abstractNote = {Epitaxial growth of MOF-on-MOF composite is an evolving research topic in the quest for multifunctional materials. During prior approaches, the core–shell MOFs were synthesized via a stepwise strategy that involved growing the shell-MOFs on top of the preformed core-MOFs with matched lattice parameters. Yet, the inconvenient stepwise synthesis and the strict lattice-matching requirement have limited the preparation of core–shell MOFs. Herein, we demonstrate that hybrid core–shell MOFs with mismatching lattices can be synthesized under the guidance of nucleation kinetic analysis. A series of MOF composites with mesoporous core and microporous shell were constructed and characterized by optical microscopy, powder X-ray diffraction, gas sorption measurement, and scanning electron microscopy. Isoreticular expansion of microporous shells and orthogonal modification of the core was realized to produce multifunctional MOF composites, which acted as size selective catalysts for olefin epoxidation with high activity and selectivity.},
doi = {10.1002/anie.201710019},
journal = {Angewandte Chemie (International Edition)},
number = 15,
volume = 57,
place = {United States},
year = {2018},
month = {2}
}

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Cited by: 11 works
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Works referenced in this record:

MOF@MOF: microporous core–shell architectures
journal, January 2009

  • Koh, Kyoungmoo; Wong-Foy, Antek G.; Matzger, Adam J.
  • Chemical Communications, Issue 41
  • DOI: 10.1039/b904526k

A Porous Metal–Organic Framework with Dynamic Pyrimidine Groups Exhibiting Record High Methane Storage Working Capacity
journal, April 2014

  • Li, Bin; Wen, Hui-Min; Wang, Hailong
  • Journal of the American Chemical Society, Vol. 136, Issue 17
  • DOI: 10.1021/ja501810r

A dual functional MOF as a luminescent sensor for quantitatively detecting the concentration of nitrobenzene and temperature
journal, January 2013

  • Ma, Dingxuan; Li, Baiyan; Zhou, Xiaojing
  • Chemical Communications, Vol. 49, Issue 79
  • DOI: 10.1039/c3cc44546a

Isotropic and Anisotropic Growth of Metal–Organic Framework (MOF) on MOF: Logical Inference on MOF Structure Based on Growth Behavior and Morphological Feature
journal, October 2016

  • Choi, Sora; Kim, Taeho; Ji, Hoyeon
  • Journal of the American Chemical Society, Vol. 138, Issue 43
  • DOI: 10.1021/jacs.6b08821

Gas storage in porous metal–organic frameworks for clean energy applications
journal, January 2010

  • Ma, Shengqian; Zhou, Hong-Cai
  • Chem. Commun., Vol. 46, Issue 1
  • DOI: 10.1039/B916295J

A High-Performance Gas-Separation Membrane Containing Submicrometer-Sized Metal-Organic Framework Crystals
journal, November 2010

  • Bae, Tae-Hyun; Lee, Jong Suk; Qiu, Wulin
  • Angewandte Chemie International Edition, Vol. 49, Issue 51, p. 9863-9866
  • DOI: 10.1002/anie.201006141

Molecular Encapsulation beyond the Aperture Size Limit through Dissociative Linker Exchange in Metal–Organic Framework Crystals
journal, August 2014

  • Morabito, Joseph V.; Chou, Lien-Yang; Li, Zhehui
  • Journal of the American Chemical Society, Vol. 136, Issue 36
  • DOI: 10.1021/ja5054779

Linker Installation: Engineering Pore Environment with Precisely Placed Functionalities in Zirconium MOFs
journal, July 2016

  • Yuan, Shuai; Chen, Ying-Pin; Qin, Jun-Sheng
  • Journal of the American Chemical Society, Vol. 138, Issue 28
  • DOI: 10.1021/jacs.6b04501

Dynamically controlled one-pot synthesis of heterogeneous core–shell MOF single crystals using guest molecules
journal, January 2014

  • Wang, Lei; Yang, Weiting; Li, Yangxue
  • Chem. Commun., Vol. 50, Issue 79
  • DOI: 10.1039/C4CC03588G

Porous metal–organic-framework nanoscale carriers as a potential platform for drug delivery and imaging
journal, December 2009

  • Horcajada, Patricia; Chalati, Tamim; Serre, Christian
  • Nature Materials, Vol. 9, Issue 2
  • DOI: 10.1038/nmat2608

Targeted functionalisation of a hierarchically-structured porous coordination polymer crystal enhances its entire function
journal, January 2012

  • Hirai, Kenji; Furukawa, Shuhei; Kondo, Mio
  • Chemical Communications, Vol. 48, Issue 52
  • DOI: 10.1039/c2cc31421e

A robust near infrared luminescent ytterbium metal–organic framework for sensing of small molecules
journal, January 2011

  • Guo, Zhiyong; Xu, Hui; Su, Shengqun
  • Chemical Communications, Vol. 47, Issue 19
  • DOI: 10.1039/c1cc10897b

Flexible Zirconium Metal-Organic Frameworks as Bioinspired Switchable Catalysts
journal, June 2016


Tunable Rare-Earth fcu-MOFs: A Platform for Systematic Enhancement of CO2 Adsorption Energetics and Uptake
journal, May 2013

  • Xue, Dong-Xu; Cairns, Amy J.; Belmabkhout, Youssef
  • Journal of the American Chemical Society, Vol. 135, Issue 20, p. 7660-7667
  • DOI: 10.1021/ja401429x

Porous Zirconium Metal–Organic Framework Constructed from 2D → 3D Interpenetration Based on a 3,6-Connected kgd Net
journal, June 2014

  • Wang, Rongming; Wang, Zhiying; Xu, Yuwen
  • Inorganic Chemistry, Vol. 53, Issue 14
  • DOI: 10.1021/ic5012764

A Homochiral Porous Metal−Organic Framework for Highly Enantioselective Heterogeneous Asymmetric Catalysis
journal, June 2005

  • Wu, Chuan-De; Hu, Aiguo; Zhang, Lin
  • Journal of the American Chemical Society, Vol. 127, Issue 25
  • DOI: 10.1021/ja052431t

Metal–organic framework (MOF): lanthanide(iii)-doped approach for luminescence modulation and luminescent sensing
journal, January 2010

  • Luo, Feng; Batten, Stuart R.
  • Dalton Transactions, Vol. 39, Issue 19
  • DOI: 10.1039/c002822n

Flexible Porous Metal-Organic Frameworks for a Controlled Drug Delivery
journal, May 2008

  • Horcajada, Patricia; Serre, Christian; Maurin, Guillaume
  • Journal of the American Chemical Society, Vol. 130, Issue 21
  • DOI: 10.1021/ja710973k

Metal–organic framework (MOF): a novel sensing platform for biomolecules
journal, January 2013

  • Zhu, Xi; Zheng, Hanye; Wei, Xiaofeng
  • Chemical Communications, Vol. 49, Issue 13
  • DOI: 10.1039/c2cc36661d

Fabrication of ZIF-8@SiO 2 Core-Shell Microspheres as the Stationary Phase for High-Performance Liquid Chromatography
journal, August 2013

  • Fu, Yan-Yan; Yang, Cheng-Xiong; Yan, Xiu-Ping
  • Chemistry - A European Journal, Vol. 19, Issue 40
  • DOI: 10.1002/chem.201301461

Highly efficient separation of carbon dioxide by a metal-organic framework replete with open metal sites
journal, November 2009

  • Britt, D.; Furukawa, H.; Wang, B.
  • Proceedings of the National Academy of Sciences, Vol. 106, Issue 49, p. 20637-20640
  • DOI: 10.1073/pnas.0909718106

Luminescent Functional Metal–Organic Frameworks
journal, June 2011

  • Cui, Yuanjing; Yue, Yanfeng; Qian, Guodong
  • Chemical Reviews, Vol. 112, Issue 2
  • DOI: 10.1021/cr200101d

A luminescent nanoscale metal–organic framework for sensing of nitroaromatic explosives
journal, January 2011

  • Xu, Hui; Liu, Fu; Cui, Yuanjing
  • Chemical Communications, Vol. 47, Issue 11
  • DOI: 10.1039/c0cc05166g

Postsynthetic Covalent Modification of a Neutral Metal−Organic Framework
journal, October 2007

  • Wang, Zhenqiang; Cohen, Seth M.
  • Journal of the American Chemical Society, Vol. 129, Issue 41, p. 12368-12369
  • DOI: 10.1021/ja074366o

Flexible Zirconium Metal-Organic Frameworks as Bioinspired Switchable Catalysts
journal, June 2016

  • Yuan, Shuai; Zou, Lanfang; Li, Haixia
  • Angewandte Chemie International Edition, Vol. 55, Issue 36
  • DOI: 10.1002/anie.201604313

Heterogeneously Hybridized Porous Coordination Polymer Crystals: Fabrication of Heterometallic Core-Shell Single Crystals with an In-Plane Rotational Epitaxial Relationship
journal, February 2009

  • Furukawa, Shuhei; Hirai, Kenji; Nakagawa, Keiji
  • Angewandte Chemie International Edition, Vol. 48, Issue 10, p. 1766-1770
  • DOI: 10.1002/anie.200804836

A High-Performance Gas-Separation Membrane Containing Submicrometer-Sized Metal-Organic Framework Crystals
journal, November 2010


Introduction to Metal–Organic Frameworks
journal, September 2011

  • Zhou, Hong-Cai; Long, Jeffrey R.; Yaghi, Omar M.
  • Chemical Reviews, Vol. 112, Issue 2, p. 673-674
  • DOI: 10.1021/cr300014x

Core–Shell Structures Arise Naturally During Ligand Exchange in Metal–Organic Frameworks
journal, October 2017

  • Boissonnault, Jake A.; Wong-Foy, Antek G.; Matzger, Adam J.
  • Journal of the American Chemical Society, Vol. 139, Issue 42
  • DOI: 10.1021/jacs.7b08349

Nanoscale Metal–Organic Frameworks for Biomedical Imaging and Drug Delivery
journal, October 2011

  • Della Rocca, Joseph; Liu, Demin; Lin, Wenbin
  • Accounts of Chemical Research, Vol. 44, Issue 10, p. 957-968
  • DOI: 10.1021/ar200028a

Metal–organic frameworks as selectivity regulators for hydrogenation reactions
journal, October 2016


Single-Crystal-to-Single-Crystal Metalation of a Metal–Organic Framework: A Route toward Structurally Well-Defined Catalysts
journal, February 2015


Interconversion between Molecular Polyhedra and Metal−Organic Frameworks
journal, May 2009

  • Li, Jian-Rong; Timmons, Daren J.; Zhou, Hong-Cai
  • Journal of the American Chemical Society, Vol. 131, Issue 18
  • DOI: 10.1021/ja901731z

Thermodynamically Guided Synthesis of Mixed-Linker Zr-MOFs with Enhanced Tunability
journal, May 2016

  • Yuan, Shuai; Qin, Jun-Sheng; Zou, Lanfang
  • Journal of the American Chemical Society, Vol. 138, Issue 20
  • DOI: 10.1021/jacs.6b03263

Bipyridine- and Phenanthroline-Based Metal–Organic Frameworks for Highly Efficient and Tandem Catalytic Organic Transformations via Directed C–H Activation
journal, February 2015

  • Manna, Kuntal; Zhang, Teng; Greene, Francis X.
  • Journal of the American Chemical Society, Vol. 137, Issue 7
  • DOI: 10.1021/ja512478y

Design and synthesis of squaramide-based MOFs as efficient MOF-supported hydrogen-bonding organocatalysts
journal, January 2016

  • Zhang, Xiaoping; Zhang, Zhenjie; Boissonnault, Jake
  • Chemical Communications, Vol. 52, Issue 55
  • DOI: 10.1039/C6CC03190K

Multiple Functional Groups of Varying Ratios in Metal-Organic Frameworks
journal, February 2010


Deciphering the Spatial Arrangement of Metals and Correlation to Reactivity in Multivariate Metal–Organic Frameworks
journal, October 2016

  • Liu, Qi; Cong, Hengjiang; Deng, Hexiang
  • Journal of the American Chemical Society, Vol. 138, Issue 42
  • DOI: 10.1021/jacs.6b08724

Size-Controlled Synthesis of Porphyrinic Metal–Organic Framework and Functionalization for Targeted Photodynamic Therapy
journal, March 2016

  • Park, Jihye; Jiang, Qin; Feng, Dawei
  • Journal of the American Chemical Society, Vol. 138, Issue 10
  • DOI: 10.1021/jacs.6b00007

Electrocatalytically Active Graphene–Porphyrin MOF Composite for Oxygen Reduction Reaction
journal, April 2012

  • Jahan, Maryam; Bao, Qiaoliang; Loh, Kian Ping
  • Journal of the American Chemical Society, Vol. 134, Issue 15
  • DOI: 10.1021/ja211433h

Funktionale poröse Koordinationspolymere
journal, April 2004

  • Kitagawa, Susumu; Kitaura, Ryo; Noro, Shin-ichiro
  • Angewandte Chemie, Vol. 116, Issue 18
  • DOI: 10.1002/ange.200300610

Core–Shell Catalysts of Metal Nanoparticle Core and Metal–Organic Framework Shell
journal, November 2014

  • Hu, Pan; Morabito, Joseph V.; Tsung, Chia-Kuang
  • ACS Catalysis, Vol. 4, Issue 12
  • DOI: 10.1021/cs5012662

Proton Conduction with Metal-Organic Frameworks
journal, July 2013


Luminescent Open Metal Sites within a Metal–Organic Framework for Sensing Small Molecules
journal, July 2007


Postsynthetic modification of metal–organic frameworks
journal, January 2009

  • Wang, Zhenqiang; Cohen, Seth M.
  • Chemical Society Reviews, Vol. 38, Issue 5
  • DOI: 10.1039/b802258p

Hybrid porous solids past, present, future
journal, January 2008

  • Férey, Gérard
  • Chem. Soc. Rev., Vol. 37, Issue 1, p. 191-214
  • DOI: 10.1039/B618320B

The pervasive chemistry of metal–organic frameworks
journal, January 2009

  • Long, Jeffrey R.; Yaghi, Omar M.
  • Chemical Society Reviews, Vol. 38, Issue 5, p. 1213-1214
  • DOI: 10.1039/b903811f

De novo synthesis of a metal–organic framework material featuring ultrahigh surface area and gas storage capacities
journal, September 2010

  • Farha, Omar K.; Özgür Yazaydın, A.; Eryazici, Ibrahim
  • Nature Chemistry, Vol. 2, Issue 11, p. 944-948
  • DOI: 10.1038/nchem.834

Zirconium-Metalloporphyrin PCN-222: Mesoporous Metal-Organic Frameworks with Ultrahigh Stability as Biomimetic Catalysts
journal, August 2012

  • Feng, Dawei; Gu, Zhi-Yuan; Li, Jian-Rong
  • Angewandte Chemie, Vol. 124, Issue 41, p. 10453-10456
  • DOI: 10.1002/ange.201204475

Metal–organic framework nanosheets in polymer composite materials for gas separation
journal, November 2014

  • Rodenas, Tania; Luz, Ignacio; Prieto, Gonzalo
  • Nature Materials, Vol. 14, Issue 1
  • DOI: 10.1038/nmat4113

Imparting functionality to a metal–organic framework material by controlled nanoparticle encapsulation
journal, February 2012

  • Lu, Guang; Li, Shaozhou; Guo, Zhen
  • Nature Chemistry, Vol. 4, Issue 4, p. 310-316
  • DOI: 10.1038/nchem.1272

Homochiral Metal–Organic Frameworks for Asymmetric Heterogeneous Catalysis
journal, September 2011

  • Yoon, Minyoung; Srirambalaji, Renganathan; Kim, Kimoon
  • Chemical Reviews, Vol. 112, Issue 2, p. 1196-1231
  • DOI: 10.1021/cr2003147

N-rich zeolite-like metal–organic framework with sodalite topology: high CO2 uptake, selective gas adsorption and efficient drug delivery
journal, January 2012

  • Qin, Jun-Sheng; Du, Dong-Ying; Li, Wen-Liang
  • Chemical Science, Vol. 3, Issue 6
  • DOI: 10.1039/c2sc00017b

Functional Porous Coordination Polymers
journal, April 2004

  • Kitagawa, Susumu; Kitaura, Ryo; Noro, Shin-ichiro
  • Angewandte Chemie International Edition, Vol. 43, Issue 18, p. 2334-2375
  • DOI: 10.1002/anie.200300610

Design and synthesis of an exceptionally stable and highly porous metal-organic framework
journal, November 1999

  • Li, Hailian; Eddaoudi, Mohamed; M., O'Keeffe
  • Nature, Vol. 402, Issue 6759, p. 276-279
  • DOI: 10.1038/46248

Synthesis of Metal-Organic Frameworks (MOFs): Routes to Various MOF Topologies, Morphologies, and Composites
journal, September 2011

  • Stock, Norbert; Biswas, Shyam
  • Chemical Reviews, Vol. 112, Issue 2
  • DOI: 10.1021/cr200304e

Asymmetric olefin epoxidation with sodium hypochlorite catalyzed by easily prepared chiral manganese(III) salen complexes
journal, March 1991

  • Zhang, Wei; Jacobsen, Eric N.
  • The Journal of Organic Chemistry, Vol. 56, Issue 7
  • DOI: 10.1021/jo00007a012

Impact of Preparation and Handling on the Hydrogen Storage Properties of Zn4O(1,4-benzenedicarboxylate)3 (MOF-5)
journal, November 2007

  • Kaye, Steven S.; Dailly, Anne; Yaghi, Omar M.
  • Journal of the American Chemical Society, Vol. 129, Issue 46, p. 14176-14177
  • DOI: 10.1021/ja076877g

Design and Preparation of a Core–Shell Metal–Organic Framework for Selective CO 2 Capture
journal, June 2013

  • Li, Tao; Sullivan, Jeanne E.; Rosi, Nathaniel L.
  • Journal of the American Chemical Society, Vol. 135, Issue 27
  • DOI: 10.1021/ja403008j

Zirconium-Metalloporphyrin PCN-222: Mesoporous Metal-Organic Frameworks with Ultrahigh Stability as Biomimetic Catalysts
journal, August 2012

  • Feng, Dawei; Gu, Zhi-Yuan; Li, Jian-Rong
  • Angewandte Chemie International Edition, Vol. 51, Issue 41
  • DOI: 10.1002/anie.201204475

Anhydrous proton conduction at 150 °C in a crystalline metal–organic framework
journal, October 2009

  • Hurd, Jeff A.; Vaidhyanathan, Ramanathan; Thangadurai, Venkataraman
  • Nature Chemistry, Vol. 1, Issue 9
  • DOI: 10.1038/nchem.402

Metal–organic framework composites
journal, January 2014


UTSA-74: A MOF-74 Isomer with Two Accessible Binding Sites per Metal Center for Highly Selective Gas Separation
journal, April 2016

  • Luo, Feng; Yan, Changsheng; Dang, Lilong
  • Journal of the American Chemical Society, Vol. 138, Issue 17
  • DOI: 10.1021/jacs.6b02030

Stepwise Synthesis of Robust Metal–Organic Frameworks via Postsynthetic Metathesis and Oxidation of Metal Nodes in a Single-Crystal to Single-Crystal Transformation
journal, May 2014

  • Liu, Tian-Fu; Zou, Lanfang; Feng, Dawei
  • Journal of the American Chemical Society, Vol. 136, Issue 22
  • DOI: 10.1021/ja5023283

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