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

Title: Regulating the spatial distribution of metal nanoparticles within metal-organic frameworks to enhance catalytic efficiency

Abstract

Composites incorporating metal nanoparticles (MNPs) within metal-organic frameworks (MOFs) have broad applications in many fields. However, the controlled spatial distribution of the MNPs within MOFs remains a challenge for addressing key issues in catalysis, for example, the efficiency of catalysts due to the limitation of molecular diffusion within MOF channels. We report a facile strategy that enables MNPs to be encapsulated into MOFs with controllable spatial localization by using metal oxide both as support to load MNPs and as a sacrificial template to grow MOFs. This strategy is versatile to a variety of MNPs and MOF crystals. By localizing the encapsulated MNPs closer to the surface of MOFs, the resultant MNPs@MOF composites not only exhibit effective selectivity derived from MOF cavities, but also enhanced catalytic activity due to the spatial regulation of MNPs as close as possible to the MOF surface.

Authors:
 [1];  [1];  [1];  [2];  [3];  [1];  [1];  [1];  [4];  [1];  [2]; ORCiD logo [3]
  1. Beijing Univ. of Chemical Technology (China). State Key Lab. of Chemical Resource Engineering
  2. Nanjing Univ. of Technology (China). Key Lab. of Flexible Electronics (KLOFE), Inst. of Advanced Materials (IAM) and Jiangsu National Synergetic Innovation Center for Advanced Materials (SICAM)
  3. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
  4. Argonne National Lab. (ANL), Argonne, IL (United States). X-Ray Science Division
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); National Natural Science Foundation of China (NNSFC); Beijing Nova Program; Fundamental Research Funds for the Central Univ. (China); National Basic Research Program of China; Nanjing Tech Univ. (China); Central Committee of the Communist Party of China (CPC)
OSTI Identifier:
1439872
Grant/Contract Number:  
AC02-06CH11357; 21271019; 21574065; 21504043; 21604038; Z121103002512023; YS1406; IRT1205; 2014CB932104; 2015CB932200; 21625401; BK20140044; BK20160975
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 8; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 77 NANOSCIENCE AND NANOTECHNOLOGY; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Metal–organic frameworks; Nanoparticles; Organic–inorganic nanostructures

Citation Formats

Yang, Qiu, Liu, Wenxian, Wang, Bingqing, Zhang, Weina, Zeng, Xiaoqiao, Zhang, Cong, Qin, Yongji, Sun, Xiaoming, Wu, Tianpin, Liu, Junfeng, Huo, Fengwei, and Lu, Jun. Regulating the spatial distribution of metal nanoparticles within metal-organic frameworks to enhance catalytic efficiency. United States: N. p., 2017. Web. doi:10.1038/ncomms14429.
Yang, Qiu, Liu, Wenxian, Wang, Bingqing, Zhang, Weina, Zeng, Xiaoqiao, Zhang, Cong, Qin, Yongji, Sun, Xiaoming, Wu, Tianpin, Liu, Junfeng, Huo, Fengwei, & Lu, Jun. Regulating the spatial distribution of metal nanoparticles within metal-organic frameworks to enhance catalytic efficiency. United States. doi:10.1038/ncomms14429.
Yang, Qiu, Liu, Wenxian, Wang, Bingqing, Zhang, Weina, Zeng, Xiaoqiao, Zhang, Cong, Qin, Yongji, Sun, Xiaoming, Wu, Tianpin, Liu, Junfeng, Huo, Fengwei, and Lu, Jun. Tue . "Regulating the spatial distribution of metal nanoparticles within metal-organic frameworks to enhance catalytic efficiency". United States. doi:10.1038/ncomms14429. https://www.osti.gov/servlets/purl/1439872.
@article{osti_1439872,
title = {Regulating the spatial distribution of metal nanoparticles within metal-organic frameworks to enhance catalytic efficiency},
author = {Yang, Qiu and Liu, Wenxian and Wang, Bingqing and Zhang, Weina and Zeng, Xiaoqiao and Zhang, Cong and Qin, Yongji and Sun, Xiaoming and Wu, Tianpin and Liu, Junfeng and Huo, Fengwei and Lu, Jun},
abstractNote = {Composites incorporating metal nanoparticles (MNPs) within metal-organic frameworks (MOFs) have broad applications in many fields. However, the controlled spatial distribution of the MNPs within MOFs remains a challenge for addressing key issues in catalysis, for example, the efficiency of catalysts due to the limitation of molecular diffusion within MOF channels. We report a facile strategy that enables MNPs to be encapsulated into MOFs with controllable spatial localization by using metal oxide both as support to load MNPs and as a sacrificial template to grow MOFs. This strategy is versatile to a variety of MNPs and MOF crystals. By localizing the encapsulated MNPs closer to the surface of MOFs, the resultant MNPs@MOF composites not only exhibit effective selectivity derived from MOF cavities, but also enhanced catalytic activity due to the spatial regulation of MNPs as close as possible to the MOF surface.},
doi = {10.1038/ncomms14429},
journal = {Nature Communications},
number = ,
volume = 8,
place = {United States},
year = {2017},
month = {2}
}

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

Citation Metrics:
Cited by: 43 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Ligand-Directed Strategy for Zeolite-Type Metal–Organic Frameworks: Zinc(II) Imidazolates with Unusual Zeolitic Topologies
journal, February 2006

  • Huang, Xiao-Chun; Lin, Yan-Yong; Zhang, Jie-Peng
  • Angewandte Chemie International Edition, Vol. 45, Issue 10, p. 1557-1559
  • DOI: 10.1002/anie.200503778

Metal–Organic Framework-Immobilized Polyhedral Metal Nanocrystals: Reduction at Solid–Gas Interface, Metal Segregation, Core–Shell Structure, and High Catalytic Activity
journal, October 2013

  • Aijaz, Arshad; Akita, Tomoki; Tsumori, Nobuko
  • Journal of the American Chemical Society, Vol. 135, Issue 44
  • DOI: 10.1021/ja4093055

Core-Shell Noble-Metal@Metal-Organic-Framework Nanoparticles with Highly Selective Sensing Property
journal, February 2013

  • He, Liangcan; Liu, Yong; Liu, Jingzhu
  • Angewandte Chemie International Edition, Vol. 52, Issue 13
  • DOI: 10.1002/anie.201209903

Synergistic Catalysis of Au@Ag Core−Shell Nanoparticles Stabilized on Metal−Organic Framework
journal, February 2011

  • Jiang, Hai-Long; Akita, Tomoki; Ishida, Tamao
  • Journal of the American Chemical Society, Vol. 133, Issue 5
  • DOI: 10.1021/ja1099006

Metal–organic framework materials as catalysts
journal, January 2009

  • Lee, JeongYong; Farha, Omar K.; Roberts, John
  • Chemical Society Reviews, Vol. 38, Issue 5, p. 1450-1459
  • DOI: 10.1039/b807080f

Hollow Zn/Co ZIF Particles Derived from Core-Shell ZIF-67@ZIF-8 as Selective Catalyst for the Semi-Hydrogenation of Acetylene
journal, August 2015

  • Yang, Jian; Zhang, Fengjun; Lu, Haiyuan
  • Angewandte Chemie International Edition, Vol. 54, Issue 37
  • DOI: 10.1002/anie.201504242

Hierarchical Zn/Ni-MOF-2 Nanosheet-Assembled Hollow Nanocubes for Multicomponent Catalytic Reactions
journal, July 2014


Immobilizing Highly Catalytically Active Pt Nanoparticles inside the Pores of Metal–Organic Framework: A Double Solvents Approach
journal, August 2012

  • Aijaz, Arshad; Karkamkar, Abhi; Choi, Young Joon
  • Journal of the American Chemical Society, Vol. 134, Issue 34
  • DOI: 10.1021/ja3043905

Metal–Organic Frameworks (MOFs)
journal, January 2014

  • Zhou, Hong-Cai “Joe”; Kitagawa, Susumu
  • Chem. Soc. Rev., Vol. 43, Issue 16
  • DOI: 10.1039/C4CS90059F

Yolk–Shell Nanocrystal@ZIF-8 Nanostructures for Gas-Phase Heterogeneous Catalysis with Selectivity Control
journal, August 2012

  • Kuo, Chun-Hong; Tang, Yang; Chou, Lien-Yang
  • Journal of the American Chemical Society, Vol. 134, Issue 35
  • DOI: 10.1021/ja306869j

Metal Nanocrystals Embedded in Single Nanocrystals of MOFs Give Unusual Selectivity as Heterogeneous Catalysts
journal, September 2014

  • Na, Kyungsu; Choi, Kyung Min; Yaghi, Omar M.
  • Nano Letters, Vol. 14, Issue 10
  • DOI: 10.1021/nl503007h

Potential applications of metal-organic frameworks
journal, December 2009

  • Kuppler, Ryan J.; Timmons, Daren J.; Fang, Qian-Rong
  • Coordination Chemistry Reviews, Vol. 253, Issue 23-24
  • DOI: 10.1016/j.ccr.2009.05.019

A series of isoreticular chiral metal–organic frameworks as a tunable platform for asymmetric catalysis
journal, July 2010

  • Ma, Liqing; Falkowski, Joseph M.; Abney, Carter
  • Nature Chemistry, Vol. 2, Issue 10
  • DOI: 10.1038/nchem.738

Fabrication of metal nanoparticles in metal–organic frameworks
journal, January 2013

  • Moon, Hoi Ri; Lim, Dae-Woon; Suh, Myunghyun Paik
  • Chem. Soc. Rev., Vol. 42, Issue 4
  • DOI: 10.1039/C2CS35320B

Semiconductor@Metal–Organic Framework Core–Shell Heterostructures: A Case of ZnO@ZIF-8 Nanorods with Selective Photoelectrochemical Response
journal, January 2013

  • Zhan, Wen-wen; Kuang, Qin; Zhou, Jian-zhang
  • Journal of the American Chemical Society, Vol. 135, Issue 5
  • DOI: 10.1021/ja311085e

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


Stable metal-organic frameworks containing single-molecule traps for enzyme encapsulation
journal, January 2015

  • Feng, Dawei; Liu, Tian-Fu; Su, Jie
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms6979

Rationally tuned micropores within enantiopure metal-organic frameworks for highly selective separation of acetylene and ethylene
journal, February 2011

  • Xiang, Sheng-Chang; Zhang, Zhangjing; Zhao, Cong-Gui
  • Nature Communications, Vol. 2, Issue 1
  • DOI: 10.1038/ncomms1206

Polyoxometalate-based homochiral metal-organic frameworks for tandem asymmetric transformation of cyclic carbonates from olefins
journal, December 2015

  • Han, Qiuxia; Qi, Bo; Ren, Weimin
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms10007

Hydroformylation of alkenes over rhodium supported on the metal-organic framework ZIF-8
journal, July 2014


Optimized Metal–Organic-Framework Nanospheres for Drug Delivery: Evaluation of Small-Molecule Encapsulation
journal, February 2014

  • Zhuang, Jia; Kuo, Chun-Hong; Chou, Lien-Yang
  • ACS Nano, Vol. 8, Issue 3
  • DOI: 10.1021/nn406590q

Chemiresistive Sensor Arrays from Conductive 2D Metal–Organic Frameworks
journal, October 2015

  • Campbell, Michael G.; Liu, Sophie F.; Swager, Timothy M.
  • Journal of the American Chemical Society, Vol. 137, Issue 43
  • DOI: 10.1021/jacs.5b09600

Mesoscopic architectures of porous coordination polymers fabricated by pseudomorphic replication
journal, June 2012

  • Reboul, Julien; Furukawa, Shuhei; Horike, Nao
  • Nature Materials, Vol. 11, Issue 8
  • DOI: 10.1038/nmat3359

Metal-Organic Frameworks: A Rapidly Growing Class of Versatile Nanoporous Materials
journal, October 2010

  • Meek, Scott T.; Greathouse, Jeffery A.; Allendorf, Mark D.
  • Advanced Materials, Vol. 23, Issue 2
  • DOI: 10.1002/adma.201002854

Platinum–nickel frame within metal-organic framework fabricated in situ for hydrogen enrichment and molecular sieving
journal, September 2015

  • Li, Zhi; Yu, Rong; Huang, Jinglu
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms9248

Core–Shell Palladium Nanoparticle@Metal–Organic Frameworks as Multifunctional Catalysts for Cascade Reactions
journal, January 2014

  • Zhao, Meiting; Deng, Ke; He, Liangcan
  • Journal of the American Chemical Society, Vol. 136, Issue 5
  • DOI: 10.1021/ja411468e

Metals@MOFs - Loading MOFs with Metal Nanoparticles for Hybrid Functions
journal, July 2010

  • Meilikhov, Mikhail; Yusenko, Kirill; Esken, Daniel
  • European Journal of Inorganic Chemistry, Vol. 2010, Issue 24, p. 3701-3714
  • DOI: 10.1002/ejic.201000473

Integration of Porous Coordination Polymers and Gold Nanorods into Core–Shell Mesoscopic Composites toward Light-Induced Molecular Release
journal, May 2013

  • Khaletskaya, Kira; Reboul, Julien; Meilikhov, Mikhail
  • Journal of the American Chemical Society, Vol. 135, Issue 30
  • DOI: 10.1021/ja403108x

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

Mesoporous Metal-Organic Frameworks with Size-, Shape-, and Space-Distribution-Controlled Pore Structure
journal, March 2015


A Family of Metal-Organic Frameworks Exhibiting Size-Selective Catalysis with Encapsulated Noble-Metal Nanoparticles
journal, April 2014


Designable Yolk–Shell Nanoparticle@MOF Petalous Heterostructures
journal, December 2013

  • Liu, Yayuan; Zhang, Weina; Li, Shaozhou
  • Chemistry of Materials, Vol. 26, Issue 2
  • DOI: 10.1021/cm4034319

Exploiting chemically selective weakness in solids as a route to new porous materials
journal, April 2015

  • Morris, Russell E.; Čejka, Jiří
  • Nature Chemistry, Vol. 7, Issue 5
  • DOI: 10.1038/nchem.2222

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

Metal organic framework-mediated synthesis of highly active and stable Fischer-Tropsch catalysts
journal, March 2015

  • Santos, Vera P.; Wezendonk, Tim A.; Jaén, Juan José Delgado
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms7451

Destruction of chemical warfare agents using metal–organic frameworks
journal, March 2015

  • Mondloch, Joseph E.; Katz, Michael J.; Isley III, William C.
  • Nature Materials, Vol. 14, Issue 5
  • DOI: 10.1038/nmat4238

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

Well-Defined Metal-Organic Framework Hollow Nanocages
journal, November 2013


Multifunctional Nanoparticle@MOF Core-Shell Nanostructures
journal, August 2013


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

Metal–Organic Framework Materials as Chemical Sensors
journal, September 2011

  • Kreno, Lauren E.; Leong, Kirsty; Farha, Omar K.
  • Chemical Reviews, Vol. 112, Issue 2, p. 1105-1125
  • DOI: 10.1021/cr200324t

Extra adsorption and adsorbate superlattice formation in metal-organic frameworks
journal, November 2015

  • Sung Cho, Hae; Deng, Hexiang; Miyasaka, Keiichi
  • Nature, Vol. 527, Issue 7579
  • DOI: 10.1038/nature15734

Supramolecular binding and separation of hydrocarbons within a functionalized porous metal–organic framework
journal, December 2014

  • Yang, Sihai; Ramirez-Cuesta, Anibal J.; Newby, Ruth
  • Nature Chemistry, Vol. 7, Issue 2
  • DOI: 10.1038/nchem.2114

The Chemistry and Applications of Metal-Organic Frameworks
journal, August 2013

  • Furukawa, H.; Cordova, K. E.; O'Keeffe, M.
  • Science, Vol. 341, Issue 6149, p. 1230444-1230444
  • DOI: 10.1126/science.1230444

Kinetics of dissolution-precipitation reaction at the surface of small particles: modelling and application
journal, August 2011


Scalable Room-Temperature Conversion of Copper(II) Hydroxide into HKUST-1 (Cu 3 (btc) 2 )
journal, November 2012


Toward Homogenization of Heterogeneous Metal Nanoparticle Catalysts with Enhanced Catalytic Performance: Soluble Porous Organic Cage as a Stabilizer and Homogenizer
journal, June 2015

  • Sun, Jian-Ke; Zhan, Wen-Wen; Akita, Tomoki
  • Journal of the American Chemical Society, Vol. 137, Issue 22
  • DOI: 10.1021/jacs.5b04029

Soft porous crystals
journal, November 2009

  • Horike, Satoshi; Shimomura, Satoru; Kitagawa, Susumu
  • Nature Chemistry, Vol. 1, Issue 9, p. 695-704
  • DOI: 10.1038/nchem.444

Metal–organic framework composites
journal, January 2014


Metal–Organic Frameworks for Separations
journal, September 2011

  • Li, Jian-Rong; Sculley, Julian; Zhou, Hong-Cai
  • Chemical Reviews, Vol. 112, Issue 2, p. 869-932
  • DOI: 10.1021/cr200190s

Efficient and tunable white-light emission of metal–organic frameworks by iridium-complex encapsulation
journal, November 2013

  • Sun, Chun-Yi; Wang, Xin-Long; Zhang, Xiao
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms3717

    Works referencing / citing this record:

    Atomic-layer-deposition-formed sacrificial template for the construction of an MIL-53 shell to increase selectivity of hydrogenation reactions
    journal, January 2019

    • Xu, Tiantian; Sun, Kai; Gao, Daowei
    • Chemical Communications, Vol. 55, Issue 53
    • DOI: 10.1039/c9cc02727k

    Synthesis of glycerol carbonate over a 2D coordination polymer built with Nd 3+ ions and organic ligands
    journal, January 2018

    • Franco, Chris H. J.; Chagas, Poliane; Caldeira, Gabriela S.
    • Dalton Transactions, Vol. 47, Issue 32
    • DOI: 10.1039/c8dt01803k

    Metal-Organic Frameworks Encapsulating Active Nanoparticles as Emerging Composites for Catalysis: Recent Progress and Perspectives
    journal, September 2018


    High stability of ultra-small and isolated gold nanoparticles in metal–organic framework materials
    journal, January 2019

    • Cure, Jérémy; Mattson, Eric; Cocq, Kévin
    • Journal of Materials Chemistry A, Vol. 7, Issue 29
    • DOI: 10.1039/c8ta12334a

    Zeolitic-imidazolate frameworks derived Pt-free counter electrodes for high-performance quantum dot-sensitized solar cells
    journal, May 2018

    • Xu, Wenjiao; Sun, Yuxiu; Ding, Bin
    • Royal Society Open Science, Vol. 5, Issue 5
    • DOI: 10.1098/rsos.180335

    Metal-Organic Frameworks Encapsulating Active Nanoparticles as Emerging Composites for Catalysis: Recent Progress and Perspectives
    journal, September 2018


    Synthesis of glycerol carbonate over a 2D coordination polymer built with Nd 3+ ions and organic ligands
    journal, January 2018

    • Franco, Chris H. J.; Chagas, Poliane; Caldeira, Gabriela S.
    • Dalton Transactions, Vol. 47, Issue 32
    • DOI: 10.1039/c8dt01803k

    High stability of ultra-small and isolated gold nanoparticles in metal–organic framework materials
    journal, January 2019

    • Cure, Jérémy; Mattson, Eric; Cocq, Kévin
    • Journal of Materials Chemistry A, Vol. 7, Issue 29
    • DOI: 10.1039/c8ta12334a

    Atomic-layer-deposition-formed sacrificial template for the construction of an MIL-53 shell to increase selectivity of hydrogenation reactions
    journal, January 2019

    • Xu, Tiantian; Sun, Kai; Gao, Daowei
    • Chemical Communications, Vol. 55, Issue 53
    • DOI: 10.1039/c9cc02727k

    Zeolitic-imidazolate frameworks derived Pt-free counter electrodes for high-performance quantum dot-sensitized solar cells
    journal, May 2018

    • Xu, Wenjiao; Sun, Yuxiu; Ding, Bin
    • Royal Society Open Science, Vol. 5, Issue 5
    • DOI: 10.1098/rsos.180335