DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Fabrication of Au25(SG)18–ZIF-8 Nanocomposites: A Facile Strategy to Position Au25(SG)18 Nanoclusters Inside and Outside ZIF-8

Abstract

Multifunctional composite materials are currently highly desired for sustainable energy applications. A general strategy to integrate atomically precise Au25(SG)18 with ZIF-8 (Zn(MeIm)2, MeIm = 2-methylimidazole), is developed in this paper via the typical Zn-carboxylate type of linkage. Au25(SG)18 are uniformly encapsulated into a ZIF-8 framework (Au25(SG)18@ZIF-8) by coordination-assisted self-assembly. In contrast, Au25(SG)18 integrated by simple impregnation is oriented along the outer surface of ZIF-8 (Au25(SG)18/ZIF-8). The porous structure and thermal stability of these nanocomposites are characterized by N2 adsorption–desorption isothermal analysis and thermal gravimetric analysis. The distribution of Au25(SG)18 in the two nanocomposites is confirmed by electron microscopy, and the accessibility of Au25(SG)18 is evaluated by the 4-nitrophenol reduction reaction. The as-prepared nanocomposites retain the high porosity and thermal stability of the ZIF-8 matrix, while also exhibiting the desired catalytic and optical properties derived from the integrated Au25(SG)18 nanoclusters (NCs). Au25(SG)18@ZIF-8 with isolated Au25 sites is a promising heterogenous catalyst with size selectivity imparted by the ZIF-8 matrix. Finally, the structural distinction between Au25(SG)18@ZIF-8 and Au25(SG)18/ZIF-8 determines their different emission features, and provides a new strategy to adjust the optical behavior of Au25(SG)18 for applications in bioimaging and biotherapy.

Authors:
 [1];  [1];  [1];  [2];  [3];  [4]; ORCiD logo [1];  [1]
  1. Sun Yat-Sen Univ., Guangzhou (China). School of Chemistry. Key Lab. of Environment and Energy Chemistry of Guangdong Higher Education Inst.
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences. Chemical Science Division
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences. Materials Science and Technology Division
  4. Sun Yat-Sen Univ., Guangzhou (China). Instrumental Analysis and Research Centre
Publication Date:
Research Org.:
Sun Yat-Sen Univ., Guangzhou (China); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC); National Natural Science Foundation of China (NSFC); 973 Program (China); Natural Science Foundation (NSF) of Guangdong Province (China); Fundamental Research Funds for the Central Universities (China)
OSTI Identifier:
1422599
Grant/Contract Number:  
AC05-00OR22725; 2014CB845600; 21643017; 21720102007; 2016A030313268; S2013030013474; 201504010031; 17lgzd18
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Materials
Additional Journal Information:
Journal Volume: 30; Journal Issue: 6; 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; 4-NP reduction; Au25(SG)18 nanocluster; fluorescence; nanocomposites; ZIF-8

Citation Formats

Luo, Yucheng, Fan, Shiyan, Yu, Wenqian, Wu, Zili, Cullen, David A., Liang, Chaolun, Shi, Jianying, and Su, Chengyong. Fabrication of Au25(SG)18–ZIF-8 Nanocomposites: A Facile Strategy to Position Au25(SG)18 Nanoclusters Inside and Outside ZIF-8. United States: N. p., 2017. Web. doi:10.1002/adma.201704576.
Luo, Yucheng, Fan, Shiyan, Yu, Wenqian, Wu, Zili, Cullen, David A., Liang, Chaolun, Shi, Jianying, & Su, Chengyong. Fabrication of Au25(SG)18–ZIF-8 Nanocomposites: A Facile Strategy to Position Au25(SG)18 Nanoclusters Inside and Outside ZIF-8. United States. https://doi.org/10.1002/adma.201704576
Luo, Yucheng, Fan, Shiyan, Yu, Wenqian, Wu, Zili, Cullen, David A., Liang, Chaolun, Shi, Jianying, and Su, Chengyong. Fri . "Fabrication of Au25(SG)18–ZIF-8 Nanocomposites: A Facile Strategy to Position Au25(SG)18 Nanoclusters Inside and Outside ZIF-8". United States. https://doi.org/10.1002/adma.201704576. https://www.osti.gov/servlets/purl/1422599.
@article{osti_1422599,
title = {Fabrication of Au25(SG)18–ZIF-8 Nanocomposites: A Facile Strategy to Position Au25(SG)18 Nanoclusters Inside and Outside ZIF-8},
author = {Luo, Yucheng and Fan, Shiyan and Yu, Wenqian and Wu, Zili and Cullen, David A. and Liang, Chaolun and Shi, Jianying and Su, Chengyong},
abstractNote = {Multifunctional composite materials are currently highly desired for sustainable energy applications. A general strategy to integrate atomically precise Au25(SG)18 with ZIF-8 (Zn(MeIm)2, MeIm = 2-methylimidazole), is developed in this paper via the typical Zn-carboxylate type of linkage. Au25(SG)18 are uniformly encapsulated into a ZIF-8 framework (Au25(SG)18@ZIF-8) by coordination-assisted self-assembly. In contrast, Au25(SG)18 integrated by simple impregnation is oriented along the outer surface of ZIF-8 (Au25(SG)18/ZIF-8). The porous structure and thermal stability of these nanocomposites are characterized by N2 adsorption–desorption isothermal analysis and thermal gravimetric analysis. The distribution of Au25(SG)18 in the two nanocomposites is confirmed by electron microscopy, and the accessibility of Au25(SG)18 is evaluated by the 4-nitrophenol reduction reaction. The as-prepared nanocomposites retain the high porosity and thermal stability of the ZIF-8 matrix, while also exhibiting the desired catalytic and optical properties derived from the integrated Au25(SG)18 nanoclusters (NCs). Au25(SG)18@ZIF-8 with isolated Au25 sites is a promising heterogenous catalyst with size selectivity imparted by the ZIF-8 matrix. Finally, the structural distinction between Au25(SG)18@ZIF-8 and Au25(SG)18/ZIF-8 determines their different emission features, and provides a new strategy to adjust the optical behavior of Au25(SG)18 for applications in bioimaging and biotherapy.},
doi = {10.1002/adma.201704576},
journal = {Advanced Materials},
number = 6,
volume = 30,
place = {United States},
year = {Fri Dec 22 00:00:00 EST 2017},
month = {Fri Dec 22 00:00:00 EST 2017}
}

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

Citation Metrics:
Cited by: 92 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Ultrafine Gold Clusters Incorporated into a Metal-Organic Framework
journal, December 2010

  • Jiang, Hai-Long; Lin, Qi-Pu; Akita, Tomoki
  • Chemistry - A European Journal, Vol. 17, Issue 1
  • DOI: 10.1002/chem.201002088

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

Recent advances in the synthesis and catalytic applications of ligand-protected, atomically precise metal nanoclusters
journal, September 2016


Quantum Sized Gold Nanoclusters with Atomic Precision
journal, June 2012

  • Qian, Huifeng; Zhu, Manzhou; Wu, Zhikun
  • Accounts of Chemical Research, Vol. 45, Issue 9
  • DOI: 10.1021/ar200331z

Extremely High Stability of Glutathionate-Protected Au25 Clusters Against Core Etching
journal, May 2007


A unified view of ligand-protected gold clusters as superatom complexes
journal, July 2008

  • Walter, M.; Akola, J.; Lopez-Acevedo, O.
  • Proceedings of the National Academy of Sciences, Vol. 105, Issue 27
  • DOI: 10.1073/pnas.0801001105

Glutathione-Protected Gold Clusters Revisited:  Bridging the Gap between Gold(I)−Thiolate Complexes and Thiolate-Protected Gold Nanocrystals
journal, April 2005

  • Negishi, Yuichi; Nobusada, Katsuyuki; Tsukuda, Tatsuya
  • Journal of the American Chemical Society, Vol. 127, Issue 14
  • DOI: 10.1021/ja042218h

Exceptional chemical and thermal stability of zeolitic imidazolate frameworks
journal, June 2006

  • Park, K. S.; Ni, Z.; Cote, A. P.
  • Proceedings of the National Academy of Sciences, Vol. 103, Issue 27, p. 10186-10191
  • DOI: 10.1073/pnas.0602439103

Fluorescence origin and spectral broadening mechanism in atomically precise Au8 nanoclusters
journal, January 2013

  • Wen, Xiaoming; Yu, Pyng; Toh, Yon-Rui
  • Nanoscale, Vol. 5, Issue 21
  • DOI: 10.1039/c3nr03015f

Soft, Oxidative Stripping of Alkyl Thiolate Ligands from Hydroxyapatite-Supported Gold Nanoclusters for Oxidation Reactions
journal, December 2015

  • Zhang, Bin; Fang, Jun; Li, Jingguo
  • Chemistry - An Asian Journal, Vol. 11, Issue 4
  • DOI: 10.1002/asia.201501074

Synthesis of Au@ZIF-8 single- or multi-core–shell structures for photocatalysis
journal, January 2014

  • Chen, Liyong; Peng, Yan; Wang, Hong
  • Chemical Communications, Vol. 50, Issue 63
  • DOI: 10.1039/C4CC02818J

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


Selective Nucleation and Growth of Metal−Organic Open Framework Thin Films on Patterned COOH/CF 3 -Terminated Self-Assembled Monolayers on Au(111)
journal, October 2005

  • Hermes, Stephan; Schröder, Felicitas; Chelmowski, Rolf
  • Journal of the American Chemical Society, Vol. 127, Issue 40
  • DOI: 10.1021/ja053523l

Unique Ultrafast Visible Luminescence in Monolayer-Protected Au 25 Clusters
journal, December 2010

  • Devadas, Mary Sajini; Kim, Junhyung; Sinn, Ekkehard
  • The Journal of Physical Chemistry C, Vol. 114, Issue 51
  • DOI: 10.1021/jp107033n

The Inconsistency in Adsorption Properties and Powder XRD Data of MOF-5 Is Rationalized by Framework Interpenetration and the Presence of Organic and Inorganic Species in the Nanocavities
journal, March 2007

  • Hafizovic, Jasmina; Bjørgen, Morten; Olsbye, Unni
  • Journal of the American Chemical Society, Vol. 129, Issue 12
  • DOI: 10.1021/ja0675447

Surface and Bulk Integrations of Single-Layered Au or Ag Nanoparticles onto Designated Crystal Planes {110} or {100} of ZIF-8
journal, April 2013

  • Li, Zheng; Zeng, Hua Chun
  • Chemistry of Materials, Vol. 25, Issue 9
  • DOI: 10.1021/cm400260g

Controlled Self-Assembly of Metal–Organic Frameworks on Metal Nanoparticles for Efficient Synthesis of Hybrid Nanostructures
journal, September 2011

  • Tsuruoka, Takaaki; Kawasaki, Hiroko; Nawafune, Hidemi
  • ACS Applied Materials & Interfaces, Vol. 3, Issue 10
  • DOI: 10.1021/am200974t

Structure-Correlated Dual Fluorescent Bands in BSA-Protected Au 25 Nanoclusters
journal, May 2012

  • Wen, Xiaoming; Yu, Pyng; Toh, Yon-Rui
  • The Journal of Physical Chemistry C, Vol. 116, Issue 21
  • DOI: 10.1021/jp303530h

Catalysis by metal nanoparticles embedded on metal–organic frameworks
journal, January 2012

  • Dhakshinamoorthy, Amarajothi; Garcia, Hermenegildo
  • Chemical Society Reviews, Vol. 41, Issue 15
  • DOI: 10.1039/c2cs35047e

Rapid synthesis of zeolitic imidazolate framework-8 (ZIF-8) nanocrystals in an aqueous system
journal, January 2011

  • Pan, Yichang; Liu, Yunyang; Zeng, Gaofeng
  • Chemical Communications, Vol. 47, Issue 7
  • DOI: 10.1039/c0cc05002d

Sub-nanometre sized metal clusters: from synthetic challenges to the unique property discoveries
journal, January 2012

  • Lu, Yizhong; Chen, Wei
  • Chemical Society Reviews, Vol. 41, Issue 9
  • DOI: 10.1039/c2cs15325d

Visible to Infrared Luminescence from a 28-Atom Gold Cluster
journal, April 2002

  • Link, Stephan; Beeby, Andrew; FitzGerald, Simon
  • The Journal of Physical Chemistry B, Vol. 106, Issue 13
  • DOI: 10.1021/jp014259v

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

CO Oxidation Catalyzed by Oxide-Supported Au 25 (SR) 18 Nanoclusters and Identification of Perimeter Sites as Active Centers
journal, June 2012

  • Nie, Xiaotao; Qian, Huifeng; Ge, Qingjie
  • ACS Nano, Vol. 6, Issue 7
  • DOI: 10.1021/nn301019f

Atomically Precise Gold Nanoclusters as New Model Catalysts
journal, March 2013

  • Li, Gao; Jin, Rongchao
  • Accounts of Chemical Research, Vol. 46, Issue 8
  • DOI: 10.1021/ar300213z

Step-by-Step Route for the Synthesis of Metal−Organic Frameworks
journal, December 2007

  • Shekhah, Osama; Wang, Hui; Kowarik, Stefan
  • Journal of the American Chemical Society, Vol. 129, Issue 49, p. 15118-15119
  • DOI: 10.1021/ja076210u

High-resolution separation of thiolate-protected gold clusters by reversed-phase high-performance liquid chromatography
journal, January 2016

  • Niihori, Yoshiki; Uchida, Chihiro; Kurashige, Wataru
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 6
  • DOI: 10.1039/C5CP04660B

A new matrix of MALDI-TOF MS for the analysis of thiolate-protected gold clusters
journal, January 2012

  • Kouchi, Haruki; Kawasaki, Hideya; Arakawa, Ryuichi
  • Analytical Methods, Vol. 4, Issue 11
  • DOI: 10.1039/c2ay26013a

Two distinct fluorescent quantum clusters of gold starting from metallic nanoparticles by pH-dependent ligand etching
journal, October 2008

  • Habeeb Muhammed, Madathumpady Abubaker; Ramesh, Subramani; Sinha, Sudarson Sekhar
  • Nano Research, Vol. 1, Issue 4
  • DOI: 10.1007/s12274-008-8035-2

The support effect on the size and catalytic activity of thiolated Au 25 nanoclusters as precatalysts
journal, January 2015


Mechanistic insights from atomically precise gold nanocluster-catalyzed reduction of 4-nitrophenol
journal, October 2016

  • Zhao, Shuo; Das, Anindita; Zhang, Hui
  • Progress in Natural Science: Materials International, Vol. 26, Issue 5
  • DOI: 10.1016/j.pnsc.2016.08.009

Superatomic Orbitals under Spin–Orbit Coupling
journal, September 2014

  • Jiang, De-en; Kühn, Michael; Tang, Qing
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 19
  • DOI: 10.1021/jz501745z

Thiolate Ligands as a Double-Edged Sword for CO Oxidation on CeO 2 Supported Au 25 (SCH 2 CH 2 Ph) 18 Nanoclusters
journal, April 2014

  • Wu, Zili; Jiang, De-en; Mann, Amanda K. P.
  • Journal of the American Chemical Society, Vol. 136, Issue 16
  • DOI: 10.1021/ja5018706

Atomically precise metal nanoclusters: stable sizes and optical properties
journal, January 2015


Metal–organic frameworks as scaffolds for the encapsulation of active species: state of the art and future perspectives
journal, January 2012

  • Juan-Alcañiz, Jana; Gascon, Jorge; Kapteijn, Freek
  • Journal of Materials Chemistry, Vol. 22, Issue 20
  • DOI: 10.1039/c2jm15563j

Catalysis with Metal Nanoparticles Immobilized within the Pores of Metal–Organic Frameworks
journal, March 2014

  • Aijaz, Arshad; Xu, Qiang
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 8, p. 1400-1411
  • DOI: 10.1021/jz5004044

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

Temperature-Dependent Optical Absorption Properties of Monolayer-Protected Au 25 and Au 38 Clusters
journal, October 2011

  • Devadas, Mary Sajini; Bairu, Semere; Qian, Huifeng
  • The Journal of Physical Chemistry Letters, Vol. 2, Issue 21
  • DOI: 10.1021/jz2012897

Geometric and Electronic Structure of Au 25 (SPhX) 18 (X = H, F, Cl, Br, CH 3 , and OCH 3 )
journal, August 2010

  • Aikens, Christine M.
  • The Journal of Physical Chemistry Letters, Vol. 1, Issue 17
  • DOI: 10.1021/jz1009828

Stable and recyclable Au 25 clusters for the reduction of 4-nitrophenol
journal, January 2013

  • Shivhare, Atal; Ambrose, Stephen J.; Zhang, Haixia
  • Chem. Commun., Vol. 49, Issue 3
  • DOI: 10.1039/C2CC37205C

N,N-Dimethylformamide-stabilized gold nanoclusters as a catalyst for the reduction of 4-nitrophenol
journal, January 2012


The excited state dynamics of protein-encapsulated Au nanoclusters
journal, August 2014


Thiolate-Mediated Selectivity Control in Aerobic Alcohol Oxidation by Porous Carbon-Supported Au 25 Clusters
journal, September 2014

  • Yoskamtorn, Tatchamapan; Yamazoe, Seiji; Takahata, Ryo
  • ACS Catalysis, Vol. 4, Issue 10
  • DOI: 10.1021/cs501010x

Investigating the Intrinsic Ethanol/Water Separation Capability of ZIF-8: An Adsorption and Diffusion Study
journal, March 2013

  • Zhang, Ke; Lively, Ryan P.; Zhang, Chen
  • The Journal of Physical Chemistry C, Vol. 117, Issue 14
  • DOI: 10.1021/jp401548b

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, Vol. 118, Issue 10, p. 1587-1589
  • DOI: 10.1002/ange.200503778

Works referencing / citing this record:

Heterostructures of MOFs and Nanorods for Multimodal Imaging
journal, October 2018

  • Zhang, Hongyu; Hao, Changlong; Qu, Aihua
  • Advanced Functional Materials, Vol. 28, Issue 48
  • DOI: 10.1002/adfm.201805320

Miscible‐Solvent‐Assisted Two‐Phase Synthesis of Monolayer‐Ligand‐Protected Metal Nanoclusters with Various Sizes
journal, January 2020


Evaluation of the BET Theory for the Characterization of Meso and Microporous MOFs
journal, August 2018

  • Ambroz, Filip; Macdonald, Thomas J.; Martis, Vladimir
  • Small Methods, Vol. 2, Issue 11
  • DOI: 10.1002/smtd.201800173

Facile Hydrophobication of Glutathione-Protected Gold Nanoclusters and Encapsulation into Poly(lactide-co-glycolide) Nanocarriers
journal, July 2019

  • Alkilany, Alaaldin M.; Alsotari, Shrouq; Alkawareek, Mahmoud Y.
  • Scientific Reports, Vol. 9, Issue 1
  • DOI: 10.1038/s41598-019-47543-4

Au 25 (SR) 18 : the captain of the great nanocluster ship
journal, January 2018

  • Kang, Xi; Chong, Hanbao; Zhu, Manzhou
  • Nanoscale, Vol. 10, Issue 23
  • DOI: 10.1039/c8nr02973c

Rational encapsulation of atomically precise nanoclusters into metal–organic frameworks by electrostatic attraction for CO 2 conversion
journal, January 2018

  • Sun, Lili; Yun, Yapei; Sheng, Hongting
  • Journal of Materials Chemistry A, Vol. 6, Issue 31
  • DOI: 10.1039/c8ta04667k

A dual-zwitterion functionalized ultra-hydrophilic metal–organic framework with ingenious synergy for enhanced enrichment of glycopeptides
journal, January 2019

  • Li, Dapeng; Zhang, Jinghui; Xie, Guangshan
  • Chemical Communications, Vol. 55, Issue 93
  • DOI: 10.1039/c9cc06785j

A liquid metal composite by ZIF-8 encapsulation
journal, January 2020

  • Liu, Yong; Wang, Qian; Deng, Jinqi
  • Chemical Communications, Vol. 56, Issue 12
  • DOI: 10.1039/c9cc09330c

Activation of atom-precise clusters for catalysis
journal, January 2020

  • Sudheeshkumar, V.; Sulaiman, Kazeem O.; Scott, Robert W. J.
  • Nanoscale Advances, Vol. 2, Issue 1
  • DOI: 10.1039/c9na00549h

A Cu-Doped ZIF-8 metal organic framework as a heterogeneous solid catalyst for aerobic oxidation of benzylic hydrocarbons
journal, January 2019

  • Nagarjun, Nagarathinam; Dhakshinamoorthy, Amarajothi
  • New Journal of Chemistry, Vol. 43, Issue 47
  • DOI: 10.1039/c9nj03698a

pH-Responsive metal–organic framework encapsulated gold nanoclusters with modulated release to enhance photodynamic therapy/chemotherapy in breast cancer
journal, January 2020

  • Zhang, Luyun; Gao, Yang; Sun, Sijia
  • Journal of Materials Chemistry B, Vol. 8, Issue 8
  • DOI: 10.1039/c9tb02621e

Facile Hydrophobication of Glutathione-Protected Gold Nanoclusters and Encapsulation into Poly(lactide-co-glycolide) Nanocarriers
journal, July 2019

  • Alkilany, Alaaldin M.; Alsotari, Shrouq; Alkawareek, Mahmoud Y.
  • Scientific Reports, Vol. 9, Issue 1
  • DOI: 10.1038/s41598-019-47543-4