Role of Modulators in Controlling the Colloidal Stability and Polydispersity of the UiO-66 Metal–Organic Framework

Morris, William; Wang, Shunzhi; Cho, David; Auyeung, Evelyn; Li, Peng; Farha, Omar K.; Mirkin, Chad A.

doi:10.1021/acsami.7b01040

Title: Role of Modulators in Controlling the Colloidal Stability and Polydispersity of the UiO-66 Metal–Organic Framework

Journal Article · Tue May 16 00:00:00 EDT 2017 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.7b01040· OSTI ID:1418044

Morris, William ^[1]; Wang, Shunzhi ^[1]; Cho, David ^[1]; Auyeung, Evelyn ^[1];

^[1];

^[2];

^[1]

Northwestern Univ., Evanston, IL (United States)
Northwestern Univ., Evanston, IL (United States); King Abdulaziz Univ., Jeddah (Saudi Arabia)

We report nanoscale UiO-66 Zr₆(OH)₄O₄(C₈O₄H₄)₆ has been synthesized with a series of carboxylic acid modulators, R-COOH (where R = H, CH₃, CF₃, and CHCl₂). The phase purity and size of each MOF was confirmed by powder X-ray diffraction, BET surface area analysis, and scanning transmission electron microscopy (STEM). Size control of UiO-66 crystals from 20 nm to over 1 μm was achieved, and confirmed by STEM. The colloidal stability of each MOF was evaluated by dynamic light scattering and was found to be highly dependent on the modulator conditions utilized in the synthesis, with both lower pKa and higher acid concentration resulting in more stable structures. Furthermore, STEM was carried out on both colloidally stable samples and those that exhibited a large degree of aggregation, which allowed for visualization of the different degrees of dispersion of the samples. The use of modulators at higher concentrations and with lower pKas leads to the formation of more defects, as a consequence of terephthalic acid ligands being replaced by modulator molecules, thereby enhancing the colloidal stability of the UiO-66 nanoparticles. These findings could have a significant impact on nanoscale MOF material syntheses and applications, especially in the areas of catalysis and drug delivery.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: US Air Force Office of Scientific Research (AFOSR); US Army Research Office (ARO); US Department of the Navy, Office of Naval Research (ONR); Defense Threat Reduction Agency (DTRA); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FA9550-14-1-0274; W911NF-15-1-0151; N00014-15-1-0043; AC02-06CH11357

OSTI ID:: 1418044

Journal Information:: ACS Applied Materials and Interfaces, Vol. 9, Issue 39; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: ENGLISH

Citation Metrics:

Cited by: 151 works

Citation information provided by
Web of Science

References (41)

The Chemistry and Applications of Metal-Organic Frameworks Furukawa, H.; Cordova, K. E.; O'Keeffe, M. Science, Vol. 341, Issue 6149, p. 1230444-1230444 https://doi.org/10.1126/science.1230444	journal	August 2013
Infinite coordination polymer nano- and microparticle structures Spokoyny, Alexander M.; Kim, Dongwoo; Sumrein, Abdelqader Chemical Society Reviews, Vol. 38, Issue 5 https://doi.org/10.1039/b807085g	journal	January 2009
Chemically tailorable colloidal particles from infinite coordination polymers Oh, Moonhyun; Mirkin, Chad A. Nature, Vol. 438, Issue 7068 https://doi.org/10.1038/nature04191	journal	December 2005
Design and synthesis of an exceptionally stable and highly porous metal-organic framework Li, Hailian; Eddaoudi, Mohamed; M., O'Keeffe Nature, Vol. 402, Issue 6759, p. 276-279 https://doi.org/10.1038/46248	journal	November 1999
Nanoscale metal–organic materials Carné, Arnau; Carbonell, Carlos; Imaz, Inhar Chem. Soc. Rev., Vol. 40, Issue 1 https://doi.org/10.1039/C0CS00042F	journal	January 2011
Synthesis of Metal-Organic Frameworks (MOFs): Routes to Various MOF Topologies, Morphologies, and Composites Stock, Norbert; Biswas, Shyam Chemical Reviews, Vol. 112, Issue 2 https://doi.org/10.1021/cr200304e	journal	September 2011
Synthesis of a Metal-Organic Framework Material, Iron Terephthalate, by Ultrasound, Microwave, and Conventional Electric Heating: A Kinetic Study Haque, Enamul; Khan, Nazmul Abedin; Park, Jung Hwa Chemistry - A European Journal, Vol. 16, Issue 3 https://doi.org/10.1002/chem.200902382	journal	December 2009
Trapping Metal-Organic Framework Nanocrystals: An in-Situ Time-Resolved Light Scattering Study on the Crystal Growth of MOF-5 in Solution Hermes, Stephan; Witte, Thomas; Hikov, Todor Journal of the American Chemical Society, Vol. 129, Issue 17 https://doi.org/10.1021/ja068835i	journal	May 2007
Room-Temperature Synthesis of UiO-66 and Thermal Modulation of Densities of Defect Sites DeStefano, Matthew R.; Islamoglu, Timur; Garibay, Sergio J. Chemistry of Materials, Vol. 29, Issue 3 https://doi.org/10.1021/acs.chemmater.6b05115	journal	January 2017
Dependence of crystal size on the catalytic performance of a porous coordination polymer Kiyonaga, Tomokazu; Higuchi, Masakazu; Kajiwara, Takashi Chemical Communications, Vol. 51, Issue 13 https://doi.org/10.1039/C4CC07562E	journal	January 2015
Porous Coordination Polymer Hybrid Device with Quartz Oscillator: Effect of Crystal Size on Sorption Kinetics Uehara, Hiromitsu; Diring, Stéphane; Furukawa, Shuhei Journal of the American Chemical Society, Vol. 133, Issue 31 https://doi.org/10.1021/ja205082p	journal	August 2011
Ion Exchange as a Way of Controlling the Chemical Compositions of Nano- and Microparticles Made from Infinite Coordination Polymers Oh, Moonhyun; Mirkin, Chad A. Angewandte Chemie International Edition, Vol. 45, Issue 33 https://doi.org/10.1002/anie.200601918	journal	August 2006
Modulated Synthesis of Zr-Based Metal-Organic Frameworks: From Nano to Single Crystals Schaate, Andreas; Roy, Pascal; Godt, Adelheid Chemistry - A European Journal, Vol. 17, Issue 24 https://doi.org/10.1002/chem.201003211	journal	May 2011
Controlled Multiscale Synthesis of Porous Coordination Polymer in Nano/Micro Regimes Diring, Stéphane; Furukawa, Shuhei; Takashima, Yohei Chemistry of Materials, Vol. 22, Issue 16 https://doi.org/10.1021/cm101778g	journal	August 2010
Detailed Structure Analysis of Atomic Positions and Defects in Zirconium Metal–Organic Frameworks Øien, Sigurd; Wragg, David; Reinsch, Helge Crystal Growth & Design, Vol. 14, Issue 11 https://doi.org/10.1021/cg501386j	journal	October 2014
Unusual and Highly Tunable Missing-Linker Defects in Zirconium Metal–Organic Framework UiO-66 and Their Important Effects on Gas Adsorption Wu, Hui; Chua, Yong Shen; Krungleviciute, Vaiva Journal of the American Chemical Society, Vol. 135, Issue 28 https://doi.org/10.1021/ja404514r	journal	May 2013
Defect-dependent colossal negative thermal expansion in UiO-66(Hf) metal–organic framework Cliffe, Matthew J.; Hill, Joshua A.; Murray, Claire A. Physical Chemistry Chemical Physics, Vol. 17, Issue 17 https://doi.org/10.1039/C5CP01307K	journal	January 2015
Tuned to Perfection: Ironing Out the Defects in Metal–Organic Framework UiO-66 Shearer, Greig C.; Chavan, Sachin; Ethiraj, Jayashree Chemistry of Materials, Vol. 26, Issue 14 https://doi.org/10.1021/cm501859p	journal	July 2014
Disclosing the Complex Structure of UiO-66 Metal Organic Framework: A Synergic Combination of Experiment and Theory Valenzano, Loredana; Civalleri, Bartolomeo; Chavan, Sachin Chemistry of Materials, Vol. 23, Issue 7, p. 1700-1718 https://doi.org/10.1021/cm1022882	journal	April 2011
Synthesis Modulation as a Tool To Increase the Catalytic Activity of Metal–Organic Frameworks: The Unique Case of UiO-66(Zr) Vermoortele, Frederik; Bueken, Bart; Le Bars, Gaëlle Journal of the American Chemical Society, Vol. 135, Issue 31 https://doi.org/10.1021/ja405078u	journal	July 2013
A New Zirconium Inorganic Building Brick Forming Metal Organic Frameworks with Exceptional Stability Cavka, Jasmina Hafizovic; Jakobsen, Søren; Olsbye, Unni Journal of the American Chemical Society, Vol. 130, Issue 42, p. 13850-13851 https://doi.org/10.1021/ja8057953	journal	October 2008
Facile synthesis of morphology and size-controlled zirconium metal–organic framework UiO-66: the role of hydrofluoric acid in crystallization Han, Yitong; Liu, Min; Li, Keyan CrystEngComm, Vol. 17, Issue 33 https://doi.org/10.1039/C5CE00729A	journal	January 2015
Metal–Organic Framework (MOF) Defects under Control: Insights into the Missing Linker Sites and Their Implication in the Reactivity of Zirconium-Based Frameworks Gutov, Oleksii V.; Hevia, Miguel González; Escudero-Adán, Eduardo C. Inorganic Chemistry, Vol. 54, Issue 17 https://doi.org/10.1021/acs.inorgchem.5b01053	journal	August 2015
Defect-Engineered Metal-Organic Frameworks Fang, Zhenlan; Bueken, Bart; De Vos, Dirk E. Angewandte Chemie International Edition, Vol. 54, Issue 25 https://doi.org/10.1002/anie.201411540	journal	June 2015
Amino acids as highly efficient modulators for single crystals of zirconium and hafnium metal–organic frameworks Marshall, Ross J.; Hobday, Claire L.; Murphie, Colin F. Journal of Materials Chemistry A, Vol. 4, Issue 18 https://doi.org/10.1039/C5TA10401G	journal	January 2016
Defect Engineering: Tuning the Porosity and Composition of the Metal–Organic Framework UiO-66 via Modulated Synthesis Shearer, Greig C.; Chavan, Sachin; Bordiga, Silvia Chemistry of Materials, Vol. 28, Issue 11 https://doi.org/10.1021/acs.chemmater.6b00602	journal	May 2016
The surface chemistry of metal–organic frameworks McGuire, Christina V.; Forgan, Ross S. Chemical Communications, Vol. 51, Issue 25 https://doi.org/10.1039/C4CC04458D	journal	January 2015
Rational Tuning of Water Vapor and CO ₂ Adsorption in Highly Stable Zr-Based MOFs Jasuja, Himanshu; Zang, Ji; Sholl, David S. The Journal of Physical Chemistry C, Vol. 116, Issue 44 https://doi.org/10.1021/jp308657x	journal	October 2012
Water Adsorption in Porous Metal–Organic Frameworks and Related Materials Furukawa, Hiroyasu; Gándara, Felipe; Zhang, Yue-Biao Journal of the American Chemical Society, Vol. 136, Issue 11, p. 4369-4381 https://doi.org/10.1021/ja500330a	journal	March 2014
Water Stable Zr-Benzenedicarboxylate Metal-Organic Frameworks as Photocatalysts for Hydrogen Generation Gomes Silva, Cláudia; Luz, Ignacio; Llabrés i. Xamena, Francesc X. Chemistry - A European Journal, Vol. 16, Issue 36 https://doi.org/10.1002/chem.200903526	journal	August 2010
Surface-Specific Functionalization of Nanoscale Metal-Organic Frameworks Wang, Shunzhi; Morris, William; Liu, Yangyang Angewandte Chemie International Edition, Vol. 54, Issue 49 https://doi.org/10.1002/anie.201506888	journal	October 2015
Shape Control of Colloidal Metal Nanocrystals Tao, Andrea R.; Habas, Susan; Yang, Peidong Small, Vol. 4, Issue 3 https://doi.org/10.1002/smll.200701295	journal	March 2008
Templated Techniques for the Synthesis and Assembly of Plasmonic Nanostructures Jones, Matthew R.; Osberg, Kyle D.; Macfarlane, Robert J. Chemical Reviews, Vol. 111, Issue 6 https://doi.org/10.1021/cr1004452	journal	June 2011
Gold Nanoparticles: Assembly, Supramolecular Chemistry, Quantum-Size-Related Properties, and Applications toward Biology, Catalysis, and Nanotechnology Daniel, Marie-Christine; Astruc, Didier Chemical Reviews, Vol. 104, Issue 1 https://doi.org/10.1021/cr030698+	journal	December 2003
Quantum Dot Solar Cells. Semiconductor Nanocrystals as Light Harvesters Kamat, Prashant V. The Journal of Physical Chemistry C, Vol. 112, Issue 48 https://doi.org/10.1021/jp806791s	journal	October 2008
Magnetic Iron Oxide Nanoparticles: Synthesis, Stabilization, Vectorization, Physicochemical Characterizations, and Biological Applications Laurent, Sophie; Forge, Delphine; Port, Marc Chemical Reviews, Vol. 108, Issue 6, p. 2064-2110 https://doi.org/10.1021/cr068445e	journal	June 2008
Nucleic Acid–Metal Organic Framework (MOF) Nanoparticle Conjugates Morris, William; Briley, William E.; Auyeung, Evelyn Journal of the American Chemical Society, Vol. 136, Issue 20 https://doi.org/10.1021/ja503215w	journal	May 2014
Nanoscale Metal–Organic Frameworks for the Co-Delivery of Cisplatin and Pooled siRNAs to Enhance Therapeutic Efficacy in Drug-Resistant Ovarian Cancer Cells He, Chunbai; Lu, Kuangda; Liu, Demin Journal of the American Chemical Society, Vol. 136, Issue 14 https://doi.org/10.1021/ja4098862	journal	February 2014
Nanoscale Metal–Organic Frameworks for Real-Time Intracellular pH Sensing in Live Cells He, Chunbai; Lu, Kuangda; Lin, Wenbin Journal of the American Chemical Society, Vol. 136, Issue 35 https://doi.org/10.1021/ja507333c	journal	August 2014
Nanomedicine Applications of Hybrid Nanomaterials Built from Metal–Ligand Coordination Bonds: Nanoscale Metal–Organic Frameworks and Nanoscale Coordination Polymers He, Chunbai; Liu, Demin; Lin, Wenbin Chemical Reviews, Vol. 115, Issue 19 https://doi.org/10.1021/acs.chemrev.5b00125	journal	April 2015
Surface Modification and Functionalization of Nanoscale Metal-Organic Frameworks for Controlled Release and Luminescence Sensing Rieter, William J.; Taylor, Kathryn M. L.; Lin, Wenbin Journal of the American Chemical Society, Vol. 129, Issue 32 https://doi.org/10.1021/ja073506r	journal	August 2007

Cited By (20)

Get the light out: nanoscaling MOFs for luminescence sensing and optical applications Wang, Timothy C.; Doty, F. Patrick; Benin, Annabelle I. Chemical Communications, Vol. 55, Issue 32 https://doi.org/10.1039/c9cc01673b	journal	January 2019
Enhancing anticancer cytotoxicity through bimodal drug delivery from ultrasmall Zr MOF nanoparticles Abánades Lázaro, Isabel; Abánades Lázaro, Sandra; Forgan, Ross S. Chemical Communications, Vol. 54, Issue 22 https://doi.org/10.1039/c7cc09739e	journal	January 2018
Controlled Nucleation and Controlled Growth for Size Predicable Synthesis of Nanoscale Metal-Organic Frameworks (MOFs): A General and Scalable Approach Wang, Xiao-Gang; Cheng, Qian; Yu, Yun Angewandte Chemie, Vol. 130, Issue 26 https://doi.org/10.1002/ange.201803766	journal	May 2018
Multivariate Modulation of the Zr MOF UiO‐66 for Defect‐Controlled Combination Anticancer Drug Delivery Abánades Lázaro, Isabel; Wells, Connor J. R.; Forgan, Ross S. Angewandte Chemie, Vol. 132, Issue 13 https://doi.org/10.1002/ange.201915848	journal	February 2020
Metal-Organic Framework Nanoparticles Wang, Shunzhi; McGuirk, C. Michael; d'Aquino, Andrea Advanced Materials, Vol. 30, Issue 37 https://doi.org/10.1002/adma.201800202	journal	June 2018
Selective Separation of Isomeric Dicarboxylic Acid by the Preferable Crystallization of Metal-Organic Frameworks Yang, Pengfei; Gong, Ming; Ye, Yunxi Chemistry - An Asian Journal, Vol. 14, Issue 1 https://doi.org/10.1002/asia.201801582	journal	December 2018
The impact of crystal size and temperature on the adsorption-induced flexibility of the Zr-based metal–organic framework DUT-98 Krause, Simon; Bon, Volodymyr; Du, Hongchu Beilstein Journal of Nanotechnology, Vol. 10 https://doi.org/10.3762/bjnano.10.169	journal	January 2019
Photodynamic Therapy Based on Nanoscale Metal-Organic Frameworks: From Material Design to Cancer Nanotherapeutics Guan, Qun; Li, Yan-An; Li, Wen-Yan Chemistry - An Asian Journal, Vol. 13, Issue 21 https://doi.org/10.1002/asia.201801221	journal	October 2018
Multivariate Modulation of the Zr MOF UiO‐66 for Defect‐Controlled Combination Anticancer Drug Delivery Abánades Lázaro, Isabel; Wells, Connor J. R.; Forgan, Ross S. Angewandte Chemie International Edition, Vol. 59, Issue 13 https://doi.org/10.1002/anie.201915848	journal	March 2020
Nanoscale Zr-Based MOFs with Tailorable Size and Introduced Mesopore for Protein Delivery Wang, Zhe; Hu, Shuanggang; Yang, Jian Advanced Functional Materials, Vol. 28, Issue 16 https://doi.org/10.1002/adfm.201707356	journal	February 2018
Nanoparticles of Metal-Organic Frameworks: On the Road to In Vivo Efficacy in Biomedicine Simon-Yarza, Teresa; Mielcarek, Angelika; Couvreur, Patrick Advanced Materials, Vol. 30, Issue 37 https://doi.org/10.1002/adma.201707365	journal	June 2018
The Chemistry of Reticular Framework Nanoparticles: MOF, ZIF, and COF Materials Ploetz, Evelyn; Engelke, Hanna; Lächelt, Ulrich Advanced Functional Materials, Vol. 30, Issue 41 https://doi.org/10.1002/adfm.201909062	journal	February 2020
Metal–organic framework tethering pH- and thermo-responsive polymer for ON–OFF controlled release of guest molecules Nagata, Shunjiro; Kokado, Kenta; Sada, Kazuki CrystEngComm, Vol. 22, Issue 6 https://doi.org/10.1039/c9ce01731c	journal	January 2020
Synthesis of novel mesoporous sulfated zirconia nanosheets derived from Zr-based metal–organic frameworks Lu, Ningyue; Zhang, Xuelian; Yan, Xiaoliang CrystEngComm, Vol. 22, Issue 1 https://doi.org/10.1039/c9ce01456j	journal	January 2020
Green separation of rare earth elements by valence-selective crystallization of MOFs Yang, Pengfei; Zhuang, Qixin; Li, Yongsheng Chemical Communications, Vol. 55, Issue 99 https://doi.org/10.1039/c9cc07849e	journal	January 2019
Controlling interpenetration through linker conformation in the modulated synthesis of Sc metal-organic frameworks Marshall, Rj; Lennon, Ct; Tao, A. Apollo - University of Cambridge Repository https://doi.org/10.17863/cam.20975	text	January 2018
The impact of crystal size and temperature on the adsorption-induced flexibility of the Zr-based metal-organic framework DUT-98 Krause, Simon; Bon, Volodymyr; Du, Hongchu RWTH Aachen University https://doi.org/10.18154/rwth-2020-02800	text	January 2019
Controlled Nucleation and Controlled Growth for Size Predicable Synthesis of Nanoscale Metal-Organic Frameworks (MOFs): A General and Scalable Approach Wang, Xiao-Gang; Cheng, Qian; Yu, Yun Angewandte Chemie International Edition, Vol. 57, Issue 26 https://doi.org/10.1002/anie.201803766	journal	May 2018
Chemical Control over Nucleation and Anisotropic Growth of Two-Dimensional Covalent Organic Frameworks Castano, Ioannina; Evans, Austin M.; Li, Haoyuan ACS Central Science, Vol. 5, Issue 11 https://doi.org/10.1021/acscentsci.9b00944	journal	September 2019
Engineering a Highly Defective Stable UiO-66 with Tunable Lewis- Brønsted Acidity: The Role of the Hemilabile Linker Feng, Xiao; Hajek, Julianna; Jena, Himanshu Sekhar Journal of the American Chemical Society, Vol. 142, Issue 6 https://doi.org/10.1021/jacs.9b13070	journal	January 2020

Figures / Tables (6)

Similar Records

Polyacids as Modulators for the Synthesis of UiO-66

Journal Article · Tue Jan 01 00:00:00 EST 2019 · Australian Journal of Chemistry · OSTI ID:1418044

Bentz, Kyle C.; Ayala, Sergio; Kalaj, Mark; +1 more

Polyacids as Modulators for the Synthesis of UiO-66

Journal Article · Thu Sep 05 00:00:00 EDT 2019 · Australian Journal of Chemistry · OSTI ID:1418044

Bentz, Kyle C.; Ayala, Jr., Sergio; Kalaj, Mark; +1 more

Heat-Treatment of Defective UiO-66 from Modulated Synthesis: Adsorption and Stability Studies

Journal Article · Sun Oct 15 00:00:00 EDT 2017 · Journal of Physical Chemistry. C · OSTI ID:1418044

Jiao, Yang; Liu, Yang; Zhu, Guanghui; +5 more

Related Subjects

36 MATERIALS SCIENCE
metal−organic frameworks
coordination modulation
nanoparticle
size control
colloidal stability