Liu Qing, Yang Ji-Min, Jin Li-Na, Sun Wei-Yin
State Key Laboratory of Coordination Chemistry, Coordination Chemistry Institute, School of Chemistry and Chemical Engineering, Nanjing National Laboratory of Microstructures, Nanjing University, Nanjing 210093 (P.R. China), Fax: (+86) 25-83314502.
Chemistry. 2014 Nov 3;20(45):14783-9. doi: 10.1002/chem.201402923. Epub 2014 Sep 15.
Herein, we report a facile and convenient method for the synthesis of the porous coordination polymer MOF-14 [Cu3 (BTB)2 ] (H3 BTB=4,4',4''-benzene-1,3,5-triyl-tribenzoic acid) as microcrystals with definite shapes and crystal facets controlled by the reaction medium at room temperature. The amount of sodium acetate added to the reaction system plays a crucial role in the shape evolution of MOF-14 from rhombic dodecahedrons to truncated rhombic dodecahedrons and cubes with truncated edges and then to cubes. The addition of a base could accelerate the formation rate of crystal growth and increase the supersaturation of crystal growth, thus resulting in the formation of MOF-14 cube crystals with high-energy crystal facets. The morphological evolution was also observed for HKUST-1 [Cu3 (BTC)2 ] (H3 BTC=1,3,5-benzenetricarbocylic acid) from octahedrons to cubes, thus verifying the probable mechanism of the morphological transformation. The gas-adsorption properties of MOF-14 with different shapes were studied and reveal that the porous coordination-polymer microcrystals display excellent and morphology-dependent sorption properties.
在此，我们报道了一种简便易行的方法，用于在室温下合成多孔配位聚合物MOF-14 [Cu3 (BTB)2 ]（H3 BTB = 4,4',4''-苯-1,3,5-三基-三苯甲酸），该方法可合成具有确定形状和晶面的微晶，其形状受反应介质控制。添加到反应体系中的醋酸钠的量在MOF-14从菱形十二面体到截顶菱形十二面体以及带有截边的立方体再到立方体的形状演变中起着关键作用。碱的添加可以加速晶体生长的形成速率并增加晶体生长的过饱和度，从而导致形成具有高能晶面的MOF-14立方体晶体。还观察到HKUST-1 [Cu3 (BTC)2 ]（H3 BTC = 1,3,5-苯三甲酸）从八面体到立方体的形态演变，从而验证了形态转变的可能机制。研究了不同形状的MOF-14的气体吸附性能，结果表明多孔配位聚合物微晶表现出优异的且与形态相关的吸附性能。
