Topology-Guided Design and Syntheses of Highly Stable Mesoporous Porphyrinic Zirconium Metal–Organic Frameworks with High Surface Area

Liu, Tian-Fu; Feng, Dawei; Chen, Ying-Pin; Zou, Lanfang; Bosch, Mathieu; Yuan, Shuai; Wei, Zhangwen; Fordham, Stephen; Wang, Kecheng; Zhou, Hong-Cai

doi:10.1021/ja5111317

Title: Topology-Guided Design and Syntheses of Highly Stable Mesoporous Porphyrinic Zirconium Metal–Organic Frameworks with High Surface Area

Journal Article · Fri Dec 12 00:00:00 EST 2014 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/ja5111317· OSTI ID:1245499

Liu, Tian-Fu ^[1]; Feng, Dawei ^[1]; Chen, Ying-Pin ^[2]; Zou, Lanfang ^[1]; Bosch, Mathieu ^[1]; Yuan, Shuai ^[1]; Wei, Zhangwen ^[1]; Fordham, Stephen ^[1]; Wang, Kecheng ^[1]; Zhou, Hong-Cai ^[1]

Department of Chemistry, Texas A&,M University, College Station, Texas 77842-3012, United States
Department of Chemistry, Texas A&,M University, College Station, Texas 77842-3012, United States, Department of Material Science and Engineering, Texas A&,M University, College Station, Texas 77843, United States

Through a topology-guided strategy, a series of Zr₆-containing isoreticular porphyrinic metal–organic frameworks (MOFs), PCN-228, PCN-229, and PCN-230, with ftw-a topology were synthesized using the extended porphyrinic linkers. The bulky porphyrin ring ligand effectively prevents the network interpenetration which often appears in MOFs with increased linker length. The pore apertures of the structures range from 2.5 to 3.8 nm, and PCN-229 demonstrates the highest porosity and BET surface area among the previously reported Zr-MOFs. Additionally, by changing the relative direction of the terminal phenyl rings, this series replaces a Zr₈ cluster with a smaller Zr₆ cluster in a topologically identical framework. The high connectivity of the Zr₆ cluster yields frameworks with enhanced stability despite high porosity and ultralarge linker. As a representative example, PCN-230, constructed with the most extended porphyrinic linker, shows excellent stability in aqueous solutions with pH values ranging from 0 to 12 and demonstrates one of the highest pH tolerances among all porphyrinic MOFs. This work not only presents a successful example of rational design of MOFs with desired topology, but also provides a strategy for construction of stable mesoporous MOFs.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Gas Separations (CGS); Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; USDOE Advanced Research Projects Agency - Energy (ARPA-E)

Grant/Contract Number:: SC0001015; AR0000249; AC02-06CH11357

OSTI ID:: 1245499

Alternate ID(s):: OSTI ID: 1386982

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Vol. 137 Journal Issue: 1; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 304 works

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Title: Topology-Guided Design and Syntheses of Highly Stable Mesoporous Porphyrinic Zirconium Metal–Organic Frameworks with High Surface Area

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