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Title: Creating Hierarchical Pores by Controlled Linker Thermolysis in Multivariate Metal–Organic Frameworks

Abstract

Sufficient pore size, appropriate stability, and hierarchical porosity are three prerequisites for open frameworks designed for drug delivery, enzyme immobilization, and catalysis involving large molecules. In this work, we report a powerful and general strategy, linker thermolysis, to construct ultrastable hierarchically porous metal–organic frameworks (HP-MOFs) with tunable pore size distribution. Linker instability, usually an undesirable trait of MOFs, was exploited to create mesopores by generating crystal defects throughout a microporous MOF crystal via thermolysis. The crystallinity and stability of HP-MOFs remain after thermolabile linkers are selectively removed from multivariate metal–organic frameworks (MTV-MOFs) through a decarboxylation process. A domain-based linker spatial distribution was found to be critical for creating hierarchical pores inside MTV-MOFs. Furthermore, linker thermolysis promotes the formation of ultrasmall metal oxide nanoparticles immobilized in an open framework that exhibits high catalytic activity for Lewis acid-catalyzed reactions. Lastly and most importantly, this work provides fresh insights into the connection between linker apportionment and vacancy distribution, which may shed light on probing the disordered linker apportionment in multivariate systems, a long-standing challenge in the study of MTV-MOFs.

Authors:
ORCiD logo [1];  [1];  [1]; ORCiD logo [2];  [1];  [1];  [3];  [1]; ORCiD logo [3]; ORCiD logo [2]; ORCiD logo [1]
  1. Texas A & M Univ., College Station, TX (United States)
  2. Univ. of Texas at Dallas, Richardson, TX (United States)
  3. King Abdullah Univ. of Science and Technology, Thuwal (Saudi Arabia)
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 Fossil Energy (FE); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1470336
Grant/Contract Number:  
SC0001015; FG02-08ER46491; FE0026472
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 140; Journal Issue: 6; 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:
36 MATERIALS SCIENCE; 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

Feng, Liang, Yuan, Shuai, Zhang, Liang-Liang, Tan, Kui, Li, Jia-Luo, Kirchon, Angelo, Liu, Ling-Mei, Zhang, Peng, Han, Yu, Chabal, Yves J., and Zhou, Hong-Cai. Creating Hierarchical Pores by Controlled Linker Thermolysis in Multivariate Metal–Organic Frameworks. United States: N. p., 2018. Web. doi:10.1021/jacs.7b12916.
Feng, Liang, Yuan, Shuai, Zhang, Liang-Liang, Tan, Kui, Li, Jia-Luo, Kirchon, Angelo, Liu, Ling-Mei, Zhang, Peng, Han, Yu, Chabal, Yves J., & Zhou, Hong-Cai. Creating Hierarchical Pores by Controlled Linker Thermolysis in Multivariate Metal–Organic Frameworks. United States. doi:10.1021/jacs.7b12916.
Feng, Liang, Yuan, Shuai, Zhang, Liang-Liang, Tan, Kui, Li, Jia-Luo, Kirchon, Angelo, Liu, Ling-Mei, Zhang, Peng, Han, Yu, Chabal, Yves J., and Zhou, Hong-Cai. Thu . "Creating Hierarchical Pores by Controlled Linker Thermolysis in Multivariate Metal–Organic Frameworks". United States. doi:10.1021/jacs.7b12916. https://www.osti.gov/servlets/purl/1470336.
@article{osti_1470336,
title = {Creating Hierarchical Pores by Controlled Linker Thermolysis in Multivariate Metal–Organic Frameworks},
author = {Feng, Liang and Yuan, Shuai and Zhang, Liang-Liang and Tan, Kui and Li, Jia-Luo and Kirchon, Angelo and Liu, Ling-Mei and Zhang, Peng and Han, Yu and Chabal, Yves J. and Zhou, Hong-Cai},
abstractNote = {Sufficient pore size, appropriate stability, and hierarchical porosity are three prerequisites for open frameworks designed for drug delivery, enzyme immobilization, and catalysis involving large molecules. In this work, we report a powerful and general strategy, linker thermolysis, to construct ultrastable hierarchically porous metal–organic frameworks (HP-MOFs) with tunable pore size distribution. Linker instability, usually an undesirable trait of MOFs, was exploited to create mesopores by generating crystal defects throughout a microporous MOF crystal via thermolysis. The crystallinity and stability of HP-MOFs remain after thermolabile linkers are selectively removed from multivariate metal–organic frameworks (MTV-MOFs) through a decarboxylation process. A domain-based linker spatial distribution was found to be critical for creating hierarchical pores inside MTV-MOFs. Furthermore, linker thermolysis promotes the formation of ultrasmall metal oxide nanoparticles immobilized in an open framework that exhibits high catalytic activity for Lewis acid-catalyzed reactions. Lastly and most importantly, this work provides fresh insights into the connection between linker apportionment and vacancy distribution, which may shed light on probing the disordered linker apportionment in multivariate systems, a long-standing challenge in the study of MTV-MOFs.},
doi = {10.1021/jacs.7b12916},
journal = {Journal of the American Chemical Society},
issn = {0002-7863},
number = 6,
volume = 140,
place = {United States},
year = {2018},
month = {1}
}

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Works referencing / citing this record:

Generation of Hierarchical Porosity in Metal-Organic Frameworks by the Modulation of Cation Valence
journal, June 2019

  • Qi, Shi-Chao; Qian, Xin-Yu; He, Qiu-Xia
  • Angewandte Chemie International Edition, Vol. 58, Issue 30
  • DOI: 10.1002/anie.201903323

Direct water-based synthesis and characterization of new Zr/Hf-MOFs with dodecanuclear clusters as IBUs
journal, January 2018

  • Waitschat, Steve; Reinsch, Helge; Arpacioglu, Merve
  • CrystEngComm, Vol. 20, Issue 35
  • DOI: 10.1039/c8ce00949j

High temperature expulsion of thermolabile groups for pore-space expansion in metal–organic frameworks
journal, January 2019

  • Bryant, Macguire R.; Ablott, Timothy A.; Telfer, Shane G.
  • CrystEngComm, Vol. 21, Issue 1
  • DOI: 10.1039/c8ce01740a

Constructing new metal–organic frameworks with complicated ligands from “One-Pot” in situ reactions
journal, January 2019

  • Kong, Xiang-Jing; He, Tao; Zhang, Yong-Zheng
  • Chemical Science, Vol. 10, Issue 14
  • DOI: 10.1039/c9sc00178f

Generation of Hierarchical Porosity in Metal-Organic Frameworks by the Modulation of Cation Valence
journal, June 2019

  • Qi, Shi-Chao; Qian, Xin-Yu; He, Qiu-Xia
  • Angewandte Chemie International Edition, Vol. 58, Issue 30
  • DOI: 10.1002/anie.201903323

Direct water-based synthesis and characterization of new Zr/Hf-MOFs with dodecanuclear clusters as IBUs
journal, January 2018

  • Waitschat, Steve; Reinsch, Helge; Arpacioglu, Merve
  • CrystEngComm, Vol. 20, Issue 35
  • DOI: 10.1039/c8ce00949j

High temperature expulsion of thermolabile groups for pore-space expansion in metal–organic frameworks
journal, January 2019

  • Bryant, Macguire R.; Ablott, Timothy A.; Telfer, Shane G.
  • CrystEngComm, Vol. 21, Issue 1
  • DOI: 10.1039/c8ce01740a

Constructing new metal–organic frameworks with complicated ligands from “One-Pot” in situ reactions
journal, January 2019

  • Kong, Xiang-Jing; He, Tao; Zhang, Yong-Zheng
  • Chemical Science, Vol. 10, Issue 14
  • DOI: 10.1039/c9sc00178f