Synthesis, characterisation and adsorption properties of microporous scandium carboxylates with rigid and flexible frameworks

被引:170
作者
Mowat, John P. S. [1 ]
Miller, Stuart R. [1 ,2 ]
Slawin, Alexandra M. Z. [1 ]
Seymour, Valerie R. [1 ]
Ashbrook, Sharon E. [1 ]
Wright, Paul A. [1 ]
机构
[1] Univ St Andrews, Sch Chem, St Andrews KY16 9ST, Fife, Scotland
[2] Univ Versailles St Quentin Yvelines, Inst Lavoisier, F-78035 Versailles, France
基金
英国工程与自然科学研究理事会;
关键词
Scandium carboxylates; Microporous MOFs; MIL-53; CO2; adsorption; Sc-45 MAS NMR; METAL-ORGANIC-FRAMEWORKS; BUILDING-BLOCKS; CARBON-DIOXIDE; TEREPHTHALATE; MIL-53; TOPOLOGY; SOLIDS; BENZENEDICARBOXYLATE; SC-2(O2CC6H4CO2)(3); DIFFRACTION;
D O I
10.1016/j.micromeso.2010.12.016
中图分类号
O69 [应用化学];
学科分类号
081704 ;
摘要
Conditions for the synthesis of each of the scandium terephthalate frameworks Sc2L3, MIL-53(Sc) (Sc(OH)L) and MIL-88(Sc) (Sc3O(H2O)(2)(OH)L-3) (L = 1.4-benzenedicarboxylate (BDC)) have been established. In addition, the MOFs MIL-100(Sc) (Sc3O(H2O)(2)(OH)L'(2), L' = 1,3,5-benzenetricarboxylate (BTC)) and socMOF (Sc3O(H2O)(3),(NO3-)L ''(1.5), L '' = 3,3',5,5'-azobenzenetetracarboxylate (ABTC)), have been synthesised for the first time with Sc. These materials have been characterised by powder and single crystal X-ray diffraction, H-1, C-13 and Sc-45 MAS NMR, and gas adsorption. MIL-53(Sc) is a highly flexible breathing framework that adopts many different forms, depending on the amount and type of adsorbate included. The structures of the as-prepared solvent-containing form, MIL-53(Sc)-DMF (DMF = dimethylformamide) and of the desolvated, hydrated form, MIL-53(Sc)-H2O, have been determined. The former structure possesses one kind of partially open channel, whereas the latter includes two kinds of channel, closed and slightly open. The hydrated structure's configuration has not previously been observed for MIL-53 materials. 45Sc MAS NMR is a sensitive probe for the Sc environment: distinctive lineshapes are observed for isolated ScO6 octahedra, corner-sharing chains of ScO4(OH)(2) octahedra and Sc3O(O2C-)(6)(OH, H2O)(3) trimers of octahedra. N-2 adsorption at 77 K indicates that the flexible frameworks MIL-88(Sc) and MIL-53(Sc) show no porosity in their desolvated, closed forms, whilst the rigid frameworks Sc2BDC3 (0.26 cm(3) g(-1)), MIL-100(Sc) (0.72 cm(3) g(-1)) and Sc-ABTC (0.57 cm(3) g(-1)) have so far been prepared with appreciable permanent porosity. For CO2 adsorption on desolvated solids, remarkable behaviour is shown by the flexible MIL-53(Sc), which opens in two stages to a maximum capacity of >13 mmol g(-1), while the rigid frameworks show uptakes at 196 K (at p/p(o) = 0.40) of 5.5 mmol g(-1) (Sc2BDC3), 21.3 mmol g(-1) (MIL-100(Sc)) and 13.1 mmol g(-1) (Sc-ABTC). (C) 2010 Elsevier Inc. All rights reserved.
引用
收藏
页码:322 / 333
页数:12
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