title: Systematic and Dramatic Tuning on Gas Sorption Performance in Heterometallic Metal-Organic Frameworks.
abstract: Despite their having much greater potential for compositional and structural diversity, heterometallic metal-organic frameworks (MOFs) reported so far have lagged far behind their homometallic counterparts in terms of CO2 uptake performance. Now the power of heterometallic MOFs is in full display, as shown by a series of new materials (denoted CPM-200s) with superior CO2 uptake capacity (up to 207.6 cm(3)/g at 273 K and 1 bar), close to the all-time record set by MOF-74-Mg. The isosteric heat of adsorption can also be tuned from -16.4 kJ/mol for CPM-200-Sc/Mg to -79.6 kJ/mol for CPM-200-V/Mg. The latter value is the highest reported for MOFs with Lewis acid sites. Some members of the CPM-200s family consist of combinations of metal ions (e.g., Mg/Ga, Mg/Fe, Mg/V, Mg/Sc) that have never been shown to coexist in any known crystalline porous materials. Such previously unseen combinations become reality through a cooperative crystallization process, which leads to the most intimate form of integration between even highly dissimilar metals, such as Mg(2+) and V(3+). The synergistic effects of heterometals bestow CPM-200s with the highest CO2 uptake capacity among known heterometallic MOFs and place them in striking distance of the all-time CO2 uptake record.
authors.affiliation: Department of Chemistry, University of California , Riverside, California 92521, United States.
authors.forename: Quan-Guo
authors.initials: QG
authors.lastname: Zhai
authors.affiliation: Department of Chemistry and Biochemistry, California State University , Long Beach, California 90840, United States.
authors.forename: Xianhui
authors.initials: X
authors.lastname: Bu
authors.affiliation: Department of Chemistry, University of California , Riverside, California 92521, United States.
authors.forename: Chengyu
authors.initials: C
authors.lastname: Mao
authors.affiliation: Department of Chemistry, University of California , Riverside, California 92521, United States.
authors.forename: Xiang
authors.initials: X
authors.lastname: Zhao
authors.affiliation: Department of Chemistry, University of California , Riverside, California 92521, United States.
authors.forename: Pingyun
authors.initials: P
authors.lastname: Feng