Creating Hierarchical Pores by Controlled Linker Thermolysis in Multivariate Metal-Organic Frameworks
Chabal, Yves J.
KAUST DepartmentPhysical Sciences and Engineering (PSE) Division
Chemical Science Program
Advanced Membranes and Porous Materials Research Center
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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.
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.
SponsorsThe 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).
PublisherAmerican Chemical Society (ACS)
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