Unusual and highly tunable missing-linker defects in zirconium metal-organic framework UiO-66 and their important effects on gas adsorption

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[1] [1,Wu, Hui
[2] 1,Chua, Yong Shen
[3] 1,Krungleviciute, Vaiva
[4] 1,Tyagi, Madhusudan
[5] Chen, Ping
[6] 1,Yildirim, Taner
[7] 1,Zhou, Wei
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Zhou, W. (wzhou@nist.gov) | 1600年 / American Chemical Society卷 / 135期
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UiO-66 is a highly important prototypical zirconium metal-organic framework (MOF) compound because of its excellent stabilities not typically found in common porous MOFs. In its perfect crystal structure; each Zr metal center is fully coordinated by 12 organic linkers to form a highly connected framework. Using high-resolution neutron power diffraction technique; we found the first direct structural evidence showing that real UiO-66 material contains significant amount of missing-linker defects; an unusual phenomenon for MOFs. The concentration of the missing-linker defects is surprisingly high; ∼10% in our sample; effectively reducing the framework connection from 12 to ∼11. We show that by varying the concentration of the acetic acid modulator and the synthesis time; the linker vacancies can be tuned systematically; leading to dramatically enhanced porosity. We obtained samples with pore volumes ranging from 0.44 to 1.0 cm3/g and Brunauer-Emmett-Teller surface areas ranging from 1000 to 1600 m2/g; the largest values of which are ∼150% and ∼60% higher than the theoretical values of defect-free UiO-66 crystal; respectively. The linker vacancies also have profound effects on the gas adsorption behaviors of UiO-66; in particular CO2. Finally; comparing the gas adsorption of hydroxylated and dehydroxylated UiO-66; we found that the former performs systematically better than the latter (particularly for CO2) suggesting the beneficial effect of the -OH groups. This finding is of great importance because hydroxylated UiO-66 is the practically more relevant; non-air-sensitive form of this MOF. The preferred gas adsorption on the metal center was confirmed by neutron diffraction measurements; and the gas binding strength enhancement by the -OH group was further supported by our first-principles calculations. © 2013 American Chemical Society;
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