Creating Hierarchical Pores by Controlled Linker Thermolysis in Multivariate Metal-Organic Frameworks

Handle URI:
http://hdl.handle.net/10754/626852
Title:
Creating Hierarchical Pores by Controlled Linker Thermolysis in Multivariate Metal-Organic Frameworks
Authors:
Feng, Liang; Yuan, Shuai; Zhang, Liang-Liang; Tan, Kui; Li, Jia-Luo; Kirchon, Angelo; Liu, Ling-Mei; Zhang, Peng; Han, Yu ( 0000-0003-1462-1118 ) ; Chabal, Yves J.; Zhou, Hong-Cai
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. Herein, we report a powerful and general strate-gy, linker thermolysis, to construct ultra-stable 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 decarboxyla-tion 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 ultra-small metal oxide (MO) nanoparticles immobilized in an open framework that exhibits high catalytic activity for Lewis acid catalyzed reactions. Most importantly, this work pro-vides fresh insights into the connection between linker apportionment and vacancy distribution, which may shed light on prob-ing the disordered linker apportionment in multivariate systems, a long-standing challenge in the study of MTV-MOFs.
KAUST Department:
Physical Sciences and Engineering (PSE) Division; Chemical Science Program; Advanced Membranes and Porous Materials Research Center
Citation:
Feng L, Yuan S, Zhang L-L, Tan K, Li J-L, et al. (2018) Creating Hierarchical Pores by Controlled Linker Thermolysis in Multivariate Metal-Organic Frameworks. Journal of the American Chemical Society. Available: http://dx.doi.org/10.1021/jacs.7b12916.
Publisher:
American Chemical Society (ACS)
Journal:
Journal of the American Chemical Society
Issue Date:
18-Jan-2018
DOI:
10.1021/jacs.7b12916
PubMed ID:
29345141
Type:
Article
ISSN:
0002-7863; 1520-5126
Sponsors:
The gas adsorption-desorption studies of this research were supported as part of the Center for Gas Separations Relevant to Clean Energy Technologies, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award Number DE-SC0001015. The PXRD, TGA-MS and TEM characterization and analysis were funded by the Robert A. Welch Foundation through a Welch Endowed Chair to HJZ (A-0030). The spectroscopic characterization and analysis (IR and XPS) were supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-FG02-08ER46491. The catalysis work was funded by the Qatar National Research Fund under Award Number NPRP9-377-1-080. The authors also acknowledge the financial supports of U.S. Department of Energy Office of Fossil Energy, National Energy Technology Laboratory (DE-FE0026472).
Additional Links:
http://pubs.acs.org/doi/10.1021/jacs.7b12916
Appears in Collections:
Articles; Advanced Membranes and Porous Materials Research Center; Physical Sciences and Engineering (PSE) Division; Chemical Science Program

Full metadata record

DC FieldValue Language
dc.contributor.authorFeng, Liangen
dc.contributor.authorYuan, Shuaien
dc.contributor.authorZhang, Liang-Liangen
dc.contributor.authorTan, Kuien
dc.contributor.authorLi, Jia-Luoen
dc.contributor.authorKirchon, Angeloen
dc.contributor.authorLiu, Ling-Meien
dc.contributor.authorZhang, Pengen
dc.contributor.authorHan, Yuen
dc.contributor.authorChabal, Yves J.en
dc.contributor.authorZhou, Hong-Caien
dc.date.accessioned2018-01-28T07:01:36Z-
dc.date.available2018-01-28T07:01:36Z-
dc.date.issued2018-01-18en
dc.identifier.citationFeng L, Yuan S, Zhang L-L, Tan K, Li J-L, et al. (2018) Creating Hierarchical Pores by Controlled Linker Thermolysis in Multivariate Metal-Organic Frameworks. Journal of the American Chemical Society. Available: http://dx.doi.org/10.1021/jacs.7b12916.en
dc.identifier.issn0002-7863en
dc.identifier.issn1520-5126en
dc.identifier.pmid29345141-
dc.identifier.doi10.1021/jacs.7b12916en
dc.identifier.urihttp://hdl.handle.net/10754/626852-
dc.description.abstractSufficient pore size, appropriate stability and hierarchical porosity are three prerequisites for open frameworks designed for drug delivery, enzyme immobilization and catalysis involving large molecules. Herein, we report a powerful and general strate-gy, linker thermolysis, to construct ultra-stable 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 decarboxyla-tion 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 ultra-small metal oxide (MO) nanoparticles immobilized in an open framework that exhibits high catalytic activity for Lewis acid catalyzed reactions. Most importantly, this work pro-vides fresh insights into the connection between linker apportionment and vacancy distribution, which may shed light on prob-ing the disordered linker apportionment in multivariate systems, a long-standing challenge in the study of MTV-MOFs.en
dc.description.sponsorshipThe gas adsorption-desorption studies of this research were supported as part of the Center for Gas Separations Relevant to Clean Energy Technologies, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award Number DE-SC0001015. The PXRD, TGA-MS and TEM characterization and analysis were funded by the Robert A. Welch Foundation through a Welch Endowed Chair to HJZ (A-0030). The spectroscopic characterization and analysis (IR and XPS) were supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-FG02-08ER46491. The catalysis work was funded by the Qatar National Research Fund under Award Number NPRP9-377-1-080. The authors also acknowledge the financial supports of U.S. Department of Energy Office of Fossil Energy, National Energy Technology Laboratory (DE-FE0026472).en
dc.publisherAmerican Chemical Society (ACS)en
dc.relation.urlhttp://pubs.acs.org/doi/10.1021/jacs.7b12916en
dc.rightsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/10.1021/jacs.7b12916.en
dc.titleCreating Hierarchical Pores by Controlled Linker Thermolysis in Multivariate Metal-Organic Frameworksen
dc.typeArticleen
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentChemical Science Programen
dc.contributor.departmentAdvanced Membranes and Porous Materials Research Centeren
dc.identifier.journalJournal of the American Chemical Societyen
dc.eprint.versionPost-printen
dc.contributor.institutionDepartment of Chemistry, Texas A&M University, College Station, Texas 77843-3255, United Statesen
dc.contributor.institutionDepartment of Materials Science and Engineering, University of Texas at Dallas, Richardson, Texas 75080, United Statesen
dc.contributor.institutionDepartment of Materials Science and Engineering, Texas A&M University, College Station, Texas 77843-3003, United Statesen
kaust.authorLiu, Ling-Meien
kaust.authorHan, Yuen

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