TY - JOUR
T1 - Enhanced Separation of Butane Isomers via Defect Control in a Fumarate/Zirconium-Based Metal Organic Framework
AU - Chen, Zhijie
AU - Feng, Liang
AU - Liu, Lingmei
AU - Bhatt, Prashant
AU - Adil, Karim
AU - Emwas, Abdul-Hamid M.
AU - Assen, Ayalew Hussen Assen
AU - Belmabkhout, Youssef
AU - Han, Yu
AU - Eddaoudi, Mohamed
N1 - KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: The research reported in this publication was supported by funding from King Abdullah University of Science and Technology (KAUST) and CRG Research Grant URF/1/2222-01.
PY - 2018/11/7
Y1 - 2018/11/7
N2 - The discovery of appropriate synthetic reaction conditions for fabricating a stable zirconium-based molecular sieve (Zr-fum-fcu-MOF) with minimal defects and its utilization in the challenging separation of linear paraffins from branched paraffins is reported. The crystallinity and structural defects were modulated and adjusted at the molecular level by controlling the synthetic reaction conditions (i.e., amounts of modulators and ligands). The impact of molecular defects on the separation of n-butane from iso-butane was studied through the preparation, fine characterization, and performance evaluation of Zr-fum-fcu-MOFs with varying degrees of defects. Defect-rich Zr-fum-fcu-MOFs were found to have poor n-butane/iso-butane separation, mainly driven by thermodynamics, while Zr-fum-fcu-MOFs with fewer or minimal defects showed efficient separation, driven mainly by kinetics and full molecular exclusion mechanisms. The impact of intrinsic defects (i.e., missing organic or inorganic blocks) on the associated mechanisms involved in the separation of n-butane/iso-butane was evidenced through single-gas adsorption, mixed-gas column breakthrough experiments, and calorimetric studies. This investigation demonstrates, for the first time, the importance of controlling intrinsic defects to maintain the selective exclusion behavior of hydrocarbon isomers when using molecular sieves.
AB - The discovery of appropriate synthetic reaction conditions for fabricating a stable zirconium-based molecular sieve (Zr-fum-fcu-MOF) with minimal defects and its utilization in the challenging separation of linear paraffins from branched paraffins is reported. The crystallinity and structural defects were modulated and adjusted at the molecular level by controlling the synthetic reaction conditions (i.e., amounts of modulators and ligands). The impact of molecular defects on the separation of n-butane from iso-butane was studied through the preparation, fine characterization, and performance evaluation of Zr-fum-fcu-MOFs with varying degrees of defects. Defect-rich Zr-fum-fcu-MOFs were found to have poor n-butane/iso-butane separation, mainly driven by thermodynamics, while Zr-fum-fcu-MOFs with fewer or minimal defects showed efficient separation, driven mainly by kinetics and full molecular exclusion mechanisms. The impact of intrinsic defects (i.e., missing organic or inorganic blocks) on the associated mechanisms involved in the separation of n-butane/iso-butane was evidenced through single-gas adsorption, mixed-gas column breakthrough experiments, and calorimetric studies. This investigation demonstrates, for the first time, the importance of controlling intrinsic defects to maintain the selective exclusion behavior of hydrocarbon isomers when using molecular sieves.
UR - http://hdl.handle.net/10754/630700
UR - https://pubs.acs.org/doi/10.1021/acs.langmuir.8b03085
UR - http://www.scopus.com/inward/record.url?scp=85057531262&partnerID=8YFLogxK
U2 - 10.1021/acs.langmuir.8b03085
DO - 10.1021/acs.langmuir.8b03085
M3 - Article
SN - 0743-7463
VL - 34
SP - 14546
EP - 14551
JO - Langmuir
JF - Langmuir
IS - 48
ER -