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

Title: Thermodynamically Guided Synthesis of Mixed-Linker Zr-MOFs with Enhanced Tunability

Abstract

Guided by thermodynamics, we have synthesized two mixed-linker zirconium-based metal–organic frameworks (Zr-MOFs), namely, PCN-133 and PCN-134. Both of them possess a layer-pillar structure, in which the connection between Zr6 clusters and primary BTB linkers form a (3,6)-connected kdg layer that is further extended into 3D frameworks by auxiliary DCDPS/TCPP linkers (BTB = benzene tribenzoate, DCDPS = 4,4'-dicarboxydiphenyl sulfone, TCPP = tetrakis(4-carboxyphenyl)porphyrin). PCN-134 demonstrates high porosity (N2 uptake of 717 cm3·g–1 and BET surface area of 1946 cm2·g–1) and excellent chemical stability in aqueous solutions with pH values ranging from 0 to 13. More importantly, PCN-134 tolerates the partial absence of auxiliary linkers leading to structural defects during the assembly process while preserving its framework integrity. Furthermore, the defect density can be systematically controlled by tuning the occupancy of the auxiliary linker, which in turn affects the MOF properties. For instance, the dichromate uptake of PCN-134 is tuned by adjusting the BTB/TCPP ratios, which gives rise to an efficient dichromate absorbent when the TCPP molar ratio in linkers is set as 22%. Additionally, the photocatalytic reduction of Cr(VI) in aqueous solution was also performed by PCN-134–22%TCPP which exhibits excellent catalytic activity. This work not only opens up a new synthetic routemore » toward mixed-linker MOFs, but also provides tunable control of MOF defects and, in turn, the properties.« less

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [1]
  1. Texas A & M Univ., College Station, TX (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Gas Separations Relevant to Clean Energy Technologies (CGS)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); ConocoPhillips
OSTI Identifier:
1470340
Grant/Contract Number:  
SC0001015; EE0007049
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 138; Journal Issue: 20; 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 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
membrane; carbon capture; materials and chemistry by design; synthesis (novel materials); synthesis (self-assembly); synthesis (scalable processing); layers; metal organic frameworks; defects; cluster chemistry; stability

Citation Formats

Yuan, Shuai, Qin, Jun-Sheng, Zou, Lanfang, Chen, Ying-Pin, Wang, Xuan, Zhang, Qiang, and Zhou, Hong-Cai. Thermodynamically Guided Synthesis of Mixed-Linker Zr-MOFs with Enhanced Tunability. United States: N. p., 2016. Web. doi:10.1021/jacs.6b03263.
Yuan, Shuai, Qin, Jun-Sheng, Zou, Lanfang, Chen, Ying-Pin, Wang, Xuan, Zhang, Qiang, & Zhou, Hong-Cai. Thermodynamically Guided Synthesis of Mixed-Linker Zr-MOFs with Enhanced Tunability. United States. doi:10.1021/jacs.6b03263.
Yuan, Shuai, Qin, Jun-Sheng, Zou, Lanfang, Chen, Ying-Pin, Wang, Xuan, Zhang, Qiang, and Zhou, Hong-Cai. Fri . "Thermodynamically Guided Synthesis of Mixed-Linker Zr-MOFs with Enhanced Tunability". United States. doi:10.1021/jacs.6b03263. https://www.osti.gov/servlets/purl/1470340.
@article{osti_1470340,
title = {Thermodynamically Guided Synthesis of Mixed-Linker Zr-MOFs with Enhanced Tunability},
author = {Yuan, Shuai and Qin, Jun-Sheng and Zou, Lanfang and Chen, Ying-Pin and Wang, Xuan and Zhang, Qiang and Zhou, Hong-Cai},
abstractNote = {Guided by thermodynamics, we have synthesized two mixed-linker zirconium-based metal–organic frameworks (Zr-MOFs), namely, PCN-133 and PCN-134. Both of them possess a layer-pillar structure, in which the connection between Zr6 clusters and primary BTB linkers form a (3,6)-connected kdg layer that is further extended into 3D frameworks by auxiliary DCDPS/TCPP linkers (BTB = benzene tribenzoate, DCDPS = 4,4'-dicarboxydiphenyl sulfone, TCPP = tetrakis(4-carboxyphenyl)porphyrin). PCN-134 demonstrates high porosity (N2 uptake of 717 cm3·g–1 and BET surface area of 1946 cm2·g–1) and excellent chemical stability in aqueous solutions with pH values ranging from 0 to 13. More importantly, PCN-134 tolerates the partial absence of auxiliary linkers leading to structural defects during the assembly process while preserving its framework integrity. Furthermore, the defect density can be systematically controlled by tuning the occupancy of the auxiliary linker, which in turn affects the MOF properties. For instance, the dichromate uptake of PCN-134 is tuned by adjusting the BTB/TCPP ratios, which gives rise to an efficient dichromate absorbent when the TCPP molar ratio in linkers is set as 22%. Additionally, the photocatalytic reduction of Cr(VI) in aqueous solution was also performed by PCN-134–22%TCPP which exhibits excellent catalytic activity. This work not only opens up a new synthetic route toward mixed-linker MOFs, but also provides tunable control of MOF defects and, in turn, the properties.},
doi = {10.1021/jacs.6b03263},
journal = {Journal of the American Chemical Society},
number = 20,
volume = 138,
place = {United States},
year = {2016},
month = {5}
}

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

Citation Metrics:
Cited by: 105 works
Citation information provided by
Web of Science

Save / Share:

Works referencing / citing this record:

Stable Metal-Organic Frameworks: Design, Synthesis, and Applications
journal, February 2018


A Stimuli-Responsive Zirconium Metal-Organic Framework Based on Supermolecular Design
journal, July 2017

  • Krause, Simon; Bon, Volodymyr; Stoeck, Ulrich
  • Angewandte Chemie, Vol. 129, Issue 36
  • DOI: 10.1002/ange.201702357

Pore-Environment Engineering with Multiple Metal Sites in Rare-Earth Porphyrinic Metal-Organic Frameworks
journal, March 2018

  • Zhang, Liangliang; Yuan, Shuai; Feng, Liang
  • Angewandte Chemie International Edition, Vol. 57, Issue 18
  • DOI: 10.1002/anie.201802661

Construction of hierarchically porous metal–organic frameworks through linker labilization
journal, May 2017

  • Yuan, Shuai; Zou, Lanfang; Qin, Jun-Sheng
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms15356

Overcoming the crystallization and designability issues in the ultrastable zirconium phosphonate framework system
journal, May 2017

  • Zheng, Tao; Yang, Zaixing; Gui, Daxiang
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms15369

Retrosynthesis of multi-component metal−organic frameworks
journal, February 2018


A highly stable amino-coordinated MOF for unprecedented block off N 2 adsorption and extraordinary CO 2 /N 2 separation
journal, January 2016

  • Zhang, Ling; Jiang, Ke; Jiang, Mengdie
  • Chemical Communications, Vol. 52, Issue 93
  • DOI: 10.1039/c6cc07858c

A new transformation of coumarins via direct C–H bond activation utilizing an iron–organic framework as a recyclable catalyst
journal, January 2018

  • Pham, Phuc H.; Doan, Son H.; Tran, Hang T. T.
  • Catalysis Science & Technology, Vol. 8, Issue 5
  • DOI: 10.1039/c7cy02139a

Supramolecular frameworks based on 5,10,15,20-tetra(4-carboxyphenyl)porphyrins
journal, January 2018

  • Morshedi, Mahbod; Ward, Jas S.; Kruger, Paul E.
  • Dalton Transactions, Vol. 47, Issue 3
  • DOI: 10.1039/c7dt04162d

Construction of unprecedented pillar-layered metal organic frameworks via a dual-ligand strategy for dye degradation
journal, January 2018

  • Tang, Yu-Huan; Wang, Fei; Zhang, Jian
  • Dalton Transactions, Vol. 47, Issue 12
  • DOI: 10.1039/c7dt04484d

Structures and single crystal to single crystal transformations of cadmium frameworks using a flexible tripodal ligand
journal, January 2018

  • Zhang, Zongyao; Xu, Lijin; Cao, Rui
  • New Journal of Chemistry, Vol. 42, Issue 7
  • DOI: 10.1039/c7nj05125e

A flexible thioether-based MOF as a crystalline sponge for structural characterization of liquid organic molecules
journal, January 2017

  • Yang, Xin-Yu; Yuan, Shuai; Qin, Jun-Sheng
  • Materials Chemistry Frontiers, Vol. 1, Issue 9
  • DOI: 10.1039/c7qm00152e

Incorporation of an intact dimeric Zr 12 oxo cluster from a molecular precursor in a new zirconium metal–organic framework
journal, January 2018

  • Bezrukov, Andrey A.; Törnroos, Karl W.; Le Roux, Erwan
  • Chemical Communications, Vol. 54, Issue 22
  • DOI: 10.1039/c8cc00507a

Tunability of fluorescent metal–organic frameworks through dynamic spacer installation with multivariate fluorophores
journal, January 2018

  • Chen, Cheng-Xia; Qiu, Qian-Feng; Pan, Mei
  • Chemical Communications, Vol. 54, Issue 97
  • DOI: 10.1039/c8cc07441k

An ultrastable Zr-MOF for fast capture and highly luminescence detection of Cr 2 O 7 2− simultaneously in an aqueous phase
journal, January 2018

  • Sun, Xiaodong; Yao, Shuo; Yu, Chengyang
  • Journal of Materials Chemistry A, Vol. 6, Issue 15
  • DOI: 10.1039/c8ta01060a

A Zn( ii ) metal–organic framework constructed by a mixed-ligand strategy for CO 2 capture and gas separation
journal, January 2019

  • Zou, Lifei; Yuan, Jiaqi; Yuan, Yang
  • CrystEngComm, Vol. 21, Issue 21
  • DOI: 10.1039/c9ce00343f

A highly augmented, (12,3)-connected Zr-MOF containing hydrated coordination sites for the catalytic transformation of gaseous CO 2 to cyclic carbonates
journal, January 2019

  • Jin, Guanghua; Sensharma, Debobroto; Zhu, Nianyong
  • Dalton Transactions, Vol. 48, Issue 41
  • DOI: 10.1039/c9dt02117e

A multifunctional Zr( iv )-based metal–organic framework for highly efficient elimination of Cr( vi ) from the aqueous phase
journal, January 2019

  • Liu, Junmin; Ye, Yu; Sun, Xiaodong
  • Journal of Materials Chemistry A, Vol. 7, Issue 28
  • DOI: 10.1039/c9ta04026a

The stepwise substitution in the hierarchical building of {Co 11 Cd 6 } cluster-based MOFs from {Co 14 } precursor
journal, January 2020

  • Chen, Yun-Kai; Tao, Ye; Qin, Huang-Fei
  • Inorganic Chemistry Frontiers
  • DOI: 10.1039/d0qi00537a

Framework disorder and its effect on selective hysteretic sorption of a T-shaped azole-based metal–organic framework
journal, January 2019


Pore-Environment Engineering with Multiple Metal Sites in Rare-Earth Porphyrinic Metal-Organic Frameworks
journal, March 2018

  • Zhang, Liangliang; Yuan, Shuai; Feng, Liang
  • Angewandte Chemie, Vol. 130, Issue 18
  • DOI: 10.1002/ange.201802661