文献类型：期刊文献

英文题名：Tuning the Adsorption-Induced Phase Change in the Flexible Metal Organic Framework Co(bdp)

作者：Taylor, Mercedes K.[1,3];Runcevski, Tomce[1,3];Oktawiec, Julia[1];Gonzalez, Miguel I.[1];Siegelman, Rebecca L.[1];Mason, Jarad A.[1,3];Ye, Jinxing[4];Brown, Craig M.[5,6];Long, Jeffrey R.[1,2,3]

机构：[1]Univ Calif Berkeley, Dept Chem, Berkeley, CA 94720 USA;[2]Univ Calif Berkeley, Dept Chem & Biomol Engn, Berkeley, CA 94720 USA;[3]Lawrence Berkeley Natl Lab, Div Mat Sci, Berkeley, CA 94720 USA;[4]East China Univ Sci & Technol, Sch Pharm, Minist Educ, Engn Res Ctr Pharmaceut Proc Chem, 130 Meilong Rd, Shanghai 200237, Peoples R China;[5]NIST, NIST Ctr Neutron Res, Gaithersburg, MD 20899 USA;[6]Univ Delaware, Dept Chem & Biomol Engn, Newark, DE 19716 USA

年份：2016

卷号：138

期号：45

起止页码：15019

外文期刊名：JOURNAL OF THE AMERICAN CHEMICAL SOCIETY

收录：;EI(收录号：20164803058877);WOS:【SCI-EXPANDED(收录号:WOS:000388428200033)】；

基金：Early stages of the synthetic chemistry, including the synthesis of H2(F-bdp) and Co(F-bdp), were supported by the U.S. Department of Energy, Advanced Research Projects Agency-Energy (ARPA-e). The remainder of the synthetic chemistry was funded by the Department of Energy, Office of Energy Efficiency and Renewable Energy, Fuel Cell Technologies Office under Grant DE-AC02-05CH11231. Methane adsorption measurements and structural studies were supported by the Center for Gas Separations Relevant to Clean Energy Technologies, an Energy Frontier Research Center supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Award DE-SC0001015. Single-crystal diffraction data were collected on the 11.3.1 Beamline at the Advanced Light Source User Facility at Lawrence Berkeley National Laboratory, which is supported by the Director, Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy. Powder X-ray diffraction data were collected on the 17-BM Beamline at the Advanced Photon Source, a U.S. Department of Energy Office of Science User Facility operated by Argonne National Laboratory. We thank Douglas Reed, Matthew Kapelewski, Dr. Brian Wiers, and Prof. Jiwoong Lee for helpful discussions and for experimental assistance, and Dr. Katie R Meihaus for editorial assistance. We also thank the National Science Foundation for providing graduate fellowship support for M.K.T., J.O., and J.A.M.

语种：英文

外文关键词：Deformation - Metals - Ligands - Phase change materials - Organometallics - High pressure engineering - X ray diffraction - Deuterium - Gas adsorption - Porosity - Alkylation

摘要：Metal-organic frameworks that flex to undergo structural phase changes upon gas adsorption are promising materials for gas storage and separations, and achieving synthetic control over the pressure at which these changes occur is crucial to the design of such materials for specific applications. To this end, a new family of materials based on the flexible metal organic framework Co(bdp) (bdp(2-) = 1,4-benzenedipyrazolate) has been prepared via the introduction of fluorine, deuterium, and methyl functional groups on the bdp(2-) ligand, namely, Co(F-bdp), Co(p-F-2-bdp), Co(o-F-2-bdp), Co(D-4-bdp), and Co(p-Me-2-bdp). These frameworks are isoreticular to the parent framework and exhibit similar structural flexibility, transitioning from a low-porosity, collapsed phase to high-porosity, expanded phases with increasing gas pressure. Powder X-ray diffraction studies reveal that fluorination of the aryl ring disrupts edge-to-face pi-pi interactions, which work to stabilize the collapsed phase at low gas pressures, while deuteration preserves these interactions and methylation strengthens them. In agreement with these observations, high-pressure CH4 adsorption isotherms show that the pressure of the CH4-induced framework expansion can be systematically controlled by ligand functionalization, as materials without edge-to-face interactions in the collapsed phase expand at lower CH4 pressures, while frameworks with strengthened edge-to-face interactions expand at higher pressures. Importantly, this work puts forth a general design strategy relevant to many other families of flexible metal-organic frameworks, which will be a powerful tool in optimizing these phase-change materials for industrial applications.