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

Title: A versatile synthetic route for the preparation of titanium metal–organic frameworks

Abstract

Exploitation of new titanium metal–organic frameworks (Ti-MOFs) with high crystallinity has been attracting great attention due to their vast application potential in photocatalysis. Herein a versatile synthetic strategy, namely, High Valence Metathesis and Oxidation (HVMO), is developed to synthesize a series of Ti-MOFs with predesigned topologies and structures. The crystallinity of these Ti-MOFs was well maintained throughout, as confirmed by powder X-ray diffraction and gas adsorption measurements. Significantly, there were only a few examples of Ti-MOFs, not to mention a general synthetic strategy for various kinds of Ti-MOFs in the literature. This contribution also illustrates the intriguing potential of Ti-MOF platforms in photocatalysis.

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1]
  1. Texas A&M Univ., College Station, TX (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Energy Frontier Research Centers (EFRC) (United States). Center for Gas Separations Relevant to Clean Energy Technologies (CGS)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Fuel Cell Technologies Office (EE-3F); USDOE Advanced Research Projects Agency - Energy (ARPA-E); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1236869
Alternate Identifier(s):
OSTI ID: 1386963
Grant/Contract Number:  
SC0001015
Resource Type:
Accepted Manuscript
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 7; Journal Issue: 2; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; membrane, carbon capture, materials and chemistry by design, synthesis (novel materials), synthesis (self-assembly), synthesis (scalable processing)

Citation Formats

Zou, Lanfang, Feng, Dawei, Liu, Tian-Fu, Chen, Ying-Pin, Yuan, Shuai, Wang, Kecheng, Wang, Xuan, Fordham, Stephen, and Zhou, Hong-Cai. A versatile synthetic route for the preparation of titanium metal–organic frameworks. United States: N. p., 2015. Web. doi:10.1039/C5SC03620H.
Zou, Lanfang, Feng, Dawei, Liu, Tian-Fu, Chen, Ying-Pin, Yuan, Shuai, Wang, Kecheng, Wang, Xuan, Fordham, Stephen, & Zhou, Hong-Cai. A versatile synthetic route for the preparation of titanium metal–organic frameworks. United States. doi:10.1039/C5SC03620H.
Zou, Lanfang, Feng, Dawei, Liu, Tian-Fu, Chen, Ying-Pin, Yuan, Shuai, Wang, Kecheng, Wang, Xuan, Fordham, Stephen, and Zhou, Hong-Cai. Mon . "A versatile synthetic route for the preparation of titanium metal–organic frameworks". United States. doi:10.1039/C5SC03620H. https://www.osti.gov/servlets/purl/1236869.
@article{osti_1236869,
title = {A versatile synthetic route for the preparation of titanium metal–organic frameworks},
author = {Zou, Lanfang and Feng, Dawei and Liu, Tian-Fu and Chen, Ying-Pin and Yuan, Shuai and Wang, Kecheng and Wang, Xuan and Fordham, Stephen and Zhou, Hong-Cai},
abstractNote = {Exploitation of new titanium metal–organic frameworks (Ti-MOFs) with high crystallinity has been attracting great attention due to their vast application potential in photocatalysis. Herein a versatile synthetic strategy, namely, High Valence Metathesis and Oxidation (HVMO), is developed to synthesize a series of Ti-MOFs with predesigned topologies and structures. The crystallinity of these Ti-MOFs was well maintained throughout, as confirmed by powder X-ray diffraction and gas adsorption measurements. Significantly, there were only a few examples of Ti-MOFs, not to mention a general synthetic strategy for various kinds of Ti-MOFs in the literature. This contribution also illustrates the intriguing potential of Ti-MOF platforms in photocatalysis.},
doi = {10.1039/C5SC03620H},
journal = {Chemical Science},
number = 2,
volume = 7,
place = {United States},
year = {2015},
month = {11}
}

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

Citation Metrics:
Cited by: 46 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Dynamic DMF Binding in MOF-5 Enables the Formation of Metastable Cobalt-Substituted MOF-5 Analogues
journal, July 2015


A homochiral metal–organic porous material for enantioselective separation and catalysis
journal, April 2000

  • Seo, Jung Soo; Whang, Dongmok; Lee, Hyoyoung
  • Nature, Vol. 404, Issue 6781, p. 982-986
  • DOI: 10.1038/35010088

Postsynthetic Ligand and Cation Exchange in Robust Metal–Organic Frameworks
journal, October 2012

  • Kim, Min; Cahill, John F.; Fei, Honghan
  • Journal of the American Chemical Society, Vol. 134, Issue 43
  • DOI: 10.1021/ja3079219

Synthesis, Structure, and Metalation of Two New Highly Porous Zirconium Metal–Organic Frameworks
journal, June 2012

  • Morris, William; Volosskiy, Boris; Demir, Selcuk
  • Inorganic Chemistry, Vol. 51, Issue 12, p. 6443-6445
  • DOI: 10.1021/ic300825s

Synthesis and O 2 Reactivity of a Titanium(III) Metal–Organic Framework
journal, October 2015


Hydrocarbon Separations in a Metal-Organic Framework with Open Iron(II) Coordination Sites
journal, March 2012


Computational Design of Metal–Organic Frameworks Based on Stable Zirconium Building Units for Storage and Delivery of Methane
journal, September 2014

  • Gomez-Gualdron, Diego A.; Gutov, Oleksii V.; Krungleviciute, Vaiva
  • Chemistry of Materials, Vol. 26, Issue 19
  • DOI: 10.1021/cm502304e

Postsynthetic modification of metal–organic frameworks—a progress report
journal, January 2011

  • Tanabe, Kristine K.; Cohen, Seth M.
  • Chem. Soc. Rev., Vol. 40, Issue 2
  • DOI: 10.1039/C0CS00031K

Remarkable Lewis acid catalytic performance of the scandium trimesate metal organic framework MIL-100(Sc) for C–C and CN bond-forming reactions
journal, January 2013

  • Mitchell, Laura; Gonzalez-Santiago, Berenice; Mowat, John P. S.
  • Catal. Sci. Technol., Vol. 3, Issue 3
  • DOI: 10.1039/C2CY20577G

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

A Reversible Crystallinity-Preserving Phase Transition in Metal–Organic Frameworks: Discovery, Mechanistic Studies, and Potential Applications
journal, June 2015

  • Liu, Dahuan; Liu, Tian-Fu; Chen, Ying-Pin
  • Journal of the American Chemical Society, Vol. 137, Issue 24
  • DOI: 10.1021/jacs.5b02999

Construction of Ultrastable Porphyrin Zr Metal–Organic Frameworks through Linker Elimination
journal, October 2013

  • Feng, Dawei; Chung, Wan-Chun; Wei, Zhangwen
  • Journal of the American Chemical Society, Vol. 135, Issue 45
  • DOI: 10.1021/ja408084j

A New Photoactive Crystalline Highly Porous Titanium(IV) Dicarboxylate
journal, July 2009

  • Dan-Hardi, Meenakshi; Serre, Christian; Frot, Théo
  • Journal of the American Chemical Society, Vol. 131, Issue 31, p. 10857-10859
  • DOI: 10.1021/ja903726m

Iron(III)-Based Metal–Organic Frameworks As Visible Light Photocatalysts
journal, September 2013

  • Laurier, Katrien G. M.; Vermoortele, Frederik; Ameloot, Rob
  • Journal of the American Chemical Society, Vol. 135, Issue 39
  • DOI: 10.1021/ja405086e

Photocatalytic CO 2 reduction by a mixed metal (Zr/Ti), mixed ligand metal–organic framework under visible light irradiation
journal, January 2015

  • Lee, Yeob; Kim, Sangjun; Kang, Jeung Ku
  • Chemical Communications, Vol. 51, Issue 26
  • DOI: 10.1039/C5CC00686D

Reticular synthesis and the design of new materials
journal, June 2003

  • Yaghi, Omar M.; O'Keeffe, Michael; Ockwig, Nathan W.
  • Nature, Vol. 423, Issue 6941, p. 705-714
  • DOI: 10.1038/nature01650

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

Separation of Hexane Isomers in a Metal-Organic Framework with Triangular Channels
journal, May 2013


Titanium oxo-clusters: precursors for a Lego-like construction of nanostructured hybrid materials
journal, January 2011

  • Rozes, Laurence; Sanchez, Clément
  • Chemical Society Reviews, Vol. 40, Issue 2
  • DOI: 10.1039/c0cs00137f

Efficient hydrogen production and photocatalytic reduction of nitrobenzene over a visible-light-responsive metal–organic framework photocatalyst
journal, January 2013

  • Toyao, Takashi; Saito, Masakazu; Horiuchi, Yu
  • Catalysis Science & Technology, Vol. 3, Issue 8
  • DOI: 10.1039/c3cy00211j

Selective gas adsorption and separation in metal–organic frameworks
journal, January 2009

  • Li, Jian-Rong; Kuppler, Ryan J.; Zhou, Hong-Cai
  • Chemical Society Reviews, Vol. 38, Issue 5, p. 1477-1504
  • DOI: 10.1039/b802426j

A robust amino-functionalized titanium(iv) based MOF for improved separation of acid gases
journal, January 2013

  • Vaesen, Sébastien; Guillerm, Vincent; Yang, Qingyuan
  • Chemical Communications, Vol. 49, Issue 86
  • DOI: 10.1039/c3cc45828h

Ligand Redox Non-innocence in the Stoichiometric Oxidation of Mn 2 (2,5-dioxidoterephthalate) (Mn-MOF-74)
journal, February 2014

  • Cozzolino, Anthony F.; Brozek, Carl K.; Palmer, Ryan D.
  • Journal of the American Chemical Society, Vol. 136, Issue 9
  • DOI: 10.1021/ja411808r

Selective adsorption of ethylene over ethane and propylene over propane in the metal–organic frameworks M2(dobdc) (M = Mg, Mn, Fe, Co, Ni, Zn)
journal, January 2013

  • Geier, Stephen J.; Mason, Jarad A.; Bloch, Eric D.
  • Chemical Science, Vol. 4, Issue 5
  • DOI: 10.1039/c3sc00032j

A p-type Ti( iv )-based metal–organic framework with visible-light photo-response
journal, January 2014

  • Gao, Junkuo; Miao, Jianwei; Li, Pei-Zhou
  • Chem. Commun., Vol. 50, Issue 29
  • DOI: 10.1039/C3CC49440C

Synthesis, Structure and Properties of Related Microporous N , N ‘-Piperazinebismethylenephosphonates of Aluminum and Titanium
journal, March 2006

  • Serre, Christian; Groves, John A.; Lightfoot, Philip
  • Chemistry of Materials, Vol. 18, Issue 6
  • DOI: 10.1021/cm052149l

Evaluating metal–organic frameworks for natural gas storage
journal, January 2014

  • Mason, Jarad A.; Veenstra, Mike; Long, Jeffrey R.
  • Chemical Science, Vol. 5, Issue 1, p. 32-51
  • DOI: 10.1039/C3SC52633J

Luminescent metal–organic frameworks for chemical sensing and explosive detection
journal, January 2014

  • Hu, Zhichao; Deibert, Benjamin J.; Li, Jing
  • Chem. Soc. Rev., Vol. 43, Issue 16
  • DOI: 10.1039/C4CS00010B

Conformational Locking by Design: Relating Strain Energy with Luminescence and Stability in Rigid Metal–Organic Frameworks
journal, November 2012

  • Shustova, Natalia B.; Cozzolino, Anthony F.; Dincă, Mircea
  • Journal of the American Chemical Society, Vol. 134, Issue 48
  • DOI: 10.1021/ja3103154

Applications of metal–organic frameworks in heterogeneous supramolecular catalysis
journal, January 2014

  • Liu, Jiewei; Chen, Lianfen; Cui, Hao
  • Chemical Society Reviews, Vol. 43, Issue 16, p. 6011-6061
  • DOI: 10.1039/C4CS00094C

Targeted Synthesis of a Porous Aromatic Framework with High Stability and Exceptionally High Surface Area
journal, November 2009

  • Ben, Teng; Ren, Hao; Ma, Shengqian
  • Angewandte Chemie International Edition, Vol. 48, Issue 50, p. 9457-9460
  • DOI: 10.1002/anie.200904637

Topology-Guided Design and Syntheses of Highly Stable Mesoporous Porphyrinic Zirconium Metal–Organic Frameworks with High Surface Area
journal, December 2014

  • Liu, Tian-Fu; Feng, Dawei; Chen, Ying-Pin
  • Journal of the American Chemical Society, Vol. 137, Issue 1
  • DOI: 10.1021/ja5111317

An Amine-Functionalized Titanium Metal-Organic Framework Photocatalyst with Visible-Light-Induced Activity for CO2 Reduction
journal, February 2012

  • Fu, Yanghe; Sun, Dengrong; Chen, Yongjuan
  • Angewandte Chemie International Edition, Vol. 51, Issue 14
  • DOI: 10.1002/anie.201108357

Coordination chemistry strategies for dynamic helicates: time-programmable chirality switching with labile and inert metal helicates
journal, January 2012

  • Miyake, Hiroyuki; Tsukube, Hiroshi
  • Chemical Society Reviews, Vol. 41, Issue 21
  • DOI: 10.1039/c2cs35192g

Postsynthetic Methods for the Functionalization of Metal–Organic Frameworks
journal, September 2011

  • Cohen, Seth M.
  • Chemical Reviews, Vol. 112, Issue 2, p. 970-1000
  • DOI: 10.1021/cr200179u

Hydrothermal Synthesis and Characterization of an Ethylenediamine-Templated Mixed-Valence Titanium Phosphate
journal, February 2000

  • Ekambaram, S.; Serre, Christian; Férey, Gérard
  • Chemistry of Materials, Vol. 12, Issue 2
  • DOI: 10.1021/cm990492i

Crystallized Frameworks with Giant Pores:  Are There Limits to the Possible?
journal, April 2005

  • Férey, Gérard; Mellot-Draznieks, Caroline; Serre, Christian
  • Accounts of Chemical Research, Vol. 38, Issue 4
  • DOI: 10.1021/ar040163i

Ti 3+ -, V 2+/3+ -, Cr 2+/3+ -, Mn 2+ -, and Fe 2+ -Substituted MOF-5 and Redox Reactivity in Cr- and Fe-MOF-5
journal, August 2013

  • Brozek, Carl K.; Dincă, Mircea
  • Journal of the American Chemical Society, Vol. 135, Issue 34
  • DOI: 10.1021/ja4064475

Kinetically tuned dimensional augmentation as a versatile synthetic route towards robust metal–organic frameworks
journal, December 2014

  • Feng, Dawei; Wang, Kecheng; Wei, Zhangwen
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms6723

A Flexible Photoactive Titanium Metal-Organic Framework Based on a [Ti IV 33 -O)(O) 2 (COO) 6 ] Cluster
journal, September 2015

  • Bueken, Bart; Vermoortele, Frederik; Vanpoucke, Danny E. P.
  • Angewandte Chemie International Edition, Vol. 54, Issue 47
  • DOI: 10.1002/anie.201505512

A Chromium Terephthalate-Based Solid with Unusually Large Pore Volumes and Surface Area
journal, September 2005

  • Ferey, G.; Mellot-Draznieks, C.; Serre, C.
  • Science, Vol. 309, Issue 5743, p. 2040-2042
  • DOI: 10.1126/science.1116275

Enhancing optical absorption of metal–organic frameworks for improved visible light photocatalysis
journal, January 2013

  • Nasalevich, Maxim A.; Goesten, Maarten G.; Savenije, Tom J.
  • Chem. Commun., Vol. 49, Issue 90
  • DOI: 10.1039/C3CC46398B

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

Engineering the Optical Response of the Titanium-MIL-125 Metal–Organic Framework through Ligand Functionalization
journal, July 2013

  • Hendon, Christopher H.; Tiana, Davide; Fontecave, Marc
  • Journal of the American Chemical Society, Vol. 135, Issue 30
  • DOI: 10.1021/ja405350u

A New Zirconium Inorganic Building Brick Forming Metal Organic Frameworks with Exceptional Stability
journal, October 2008

  • Cavka, Jasmina Hafizovic; Jakobsen, Søren; Olsbye, Unni
  • Journal of the American Chemical Society, Vol. 130, Issue 42, p. 13850-13851
  • DOI: 10.1021/ja8057953

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

Transmetalations in two metal–organic frameworks with different framework flexibilities: Kinetics and core–shell heterostructure
journal, January 2012

  • Song, Xiaokai; Jeong, Seok; Kim, Dongwook
  • CrystEngComm, Vol. 14, Issue 18
  • DOI: 10.1039/c2ce26115d

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

Cation exchange at the secondary building units of metal–organic frameworks
journal, January 2014


A single crystalline porphyrinic titanium metal–organic framework
journal, January 2015

  • Yuan, Shuai; Liu, Tian-Fu; Feng, Dawei
  • Chemical Science, Vol. 6, Issue 7
  • DOI: 10.1039/C5SC00916B

Gram-scale, high-yield synthesis of a robust metal–organic framework for storing methane and other gases
journal, January 2013

  • Wilmer, Christopher E.; Farha, Omar K.; Yildirim, Taner
  • Energy & Environmental Science, Vol. 6, Issue 4
  • DOI: 10.1039/c3ee24506c

High Methane Storage Capacity in Aluminum Metal–Organic Frameworks
journal, February 2014

  • Gándara, Felipe; Furukawa, Hiroyasu; Lee, Seungkyu
  • Journal of the American Chemical Society, Vol. 136, Issue 14, p. 5271-5274
  • DOI: 10.1021/ja501606h

Large-Pore Apertures in a Series of Metal-Organic Frameworks
journal, May 2012


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

    Works referencing / citing this record:

    Chemical Engineering of Photoactivity in Heterometallic Titanium-Organic Frameworks by Metal Doping
    journal, June 2018

    • Castells-Gil, Javier; Padial, Natalia M.; Almora-Barrios, Neyvis
    • Angewandte Chemie International Edition, Vol. 57, Issue 28
    • DOI: 10.1002/anie.201802089

    Titanium-Carboxylate Metal-Organic Framework Based on an Unprecedented Ti-Oxo Chain Cluster
    journal, October 2018

    • Keum, Yesub; Park, Seonghun; Chen, Ying-Pin
    • Angewandte Chemie International Edition, Vol. 57, Issue 45
    • DOI: 10.1002/anie.201809762

    A Porphyrin-Based Porous rtl Metal-Organic Framework as an Efficient Catalyst for the Cycloaddition of CO 2 to Epoxides
    journal, October 2016

    • Jiang, Wei; Yang, Jin; Liu, Ying-Ying
    • Chemistry - A European Journal, Vol. 22, Issue 47
    • DOI: 10.1002/chem.201603465

    Designed Cluster Assembly of Multidimensional Titanium Coordination Polymers: Syntheses, Crystal Structure and Properties
    journal, February 2018

    • Wang, Chao; Liu, Chao; Tian, Hong-Rui
    • Chemistry - A European Journal, Vol. 24, Issue 12
    • DOI: 10.1002/chem.201705013

    Actinide-Based Porphyrinic MOF as a Dehydrogenation Catalyst
    journal, October 2018

    • Hu, Kong-Qiu; Huang, Zhi-Wei; Zhang, Zhi-Hui
    • Chemistry - A European Journal, Vol. 24, Issue 63
    • DOI: 10.1002/chem.201804284

    A Co II -based metal–organic framework based on [Co 63 -OH) 4 ] units exhibiting selective sorption of C 2 H 2 over CO 2 and CH 4
    journal, January 2016

    • Chen, Di-Ming; Tian, Jia-Yue; Liu, Chun-Sen
    • CrystEngComm, Vol. 18, Issue 21
    • DOI: 10.1039/c6ce00709k

    [Ti 12 In 6 O 18 (OOCC 6 H 5 ) 30 ]: a multifunctional hetero-polyoxotitanate nanocluster with high stability and visible photoactivity
    journal, January 2017

    • Liu, Shengjun; Hu, Wei; Nath, Jayanta Kr.
    • Dalton Transactions, Vol. 46, Issue 3
    • DOI: 10.1039/c6dt04261a

    Systematic variation of the optical bandgap in titanium based isoreticular metal–organic frameworks for photocatalytic reduction of CO 2 under blue light
    journal, January 2017

    • Logan, Matthew W.; Ayad, Suliman; Adamson, Jeremy D.
    • Journal of Materials Chemistry A, Vol. 5, Issue 23
    • DOI: 10.1039/c7ta00437k

    A dual-functional indium–organic framework towards organic pollutant decontamination via physically selective adsorption and chemical photodegradation
    journal, January 2017

    • Li, Qing; Xue, Dong-Xu; Zhang, Yu-Feng
    • Journal of Materials Chemistry A, Vol. 5, Issue 27
    • DOI: 10.1039/c7ta02216f

    An anionic metal–organic framework: metathesis of zinc( ii ) with copper( ii ) for efficient C 3 /C 2 hydrocarbon and organic dye separation
    journal, January 2018

    • Liu, Xiuping; Hao, Chunlian; Li, Jing
    • Inorganic Chemistry Frontiers, Vol. 5, Issue 11
    • DOI: 10.1039/c8qi00773j

    De novo synthesis of mesoporous photoactive titanium( iv )–organic frameworks with MIL-100 topology
    journal, January 2019

    • Castells-Gil, Javier; M. Padial, Natalia; Almora-Barrios, Neyvis
    • Chemical Science, Vol. 10, Issue 15
    • DOI: 10.1039/c8sc05218b