Catalytic properties of pristine and defect-engineered Zr-MOF-808 metal organic frameworks†,Catalysis Science & Technology

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Catalytic properties of pristine and defect-engineered Zr-MOF-808 metal organic frameworks†
Catalysis Science & Technology ( IF 4.4 ) Pub Date : 2018-06-22 00:00:00 , DOI: 10.1039/c8cy00742j
H.-H. Mautschke _{1,

2,

3,

4,

5} , F. Drache _{6,

7,

8,

9} , I. Senkovska _{6,

7,

8,

9} , S. Kaskel _{6,

7,

8,

9} , F. X. Llabrés i Xamena _{1,

2,

3,

4,

5}

Affiliation

Various defect-engineered Zr-trimesate MOF-808 compounds (DE-MOF-808) have been prepared by mixing the tricarboxylate ligands with dicarboxylate ligands; viz. isophthalate, pyridine-3,5-dicarboxylate, 5-hydroxy-isophthalate, or 5-amino-isophthalate. The resulting mixed-ligand compounds, MOF-808-X (X = IP, Pydc, OH or NH₂) were all found to be highly crystalline and isostructural to the unmodified MOF-808. Pristine MOF-808 showed better catalytic performance than a UiO-66 reference compound for the Meerwein–Ponndorf–Verley (MPV) reduction of carbonyl compounds. This was attributed to a higher availability of coordinatively unsaturated Zr⁴⁺ sites (cus) in MOF-808 upon removal of formate ions. Meanwhile, cus in UiO-66 are only located at defect sites and are thus much less abundant. Further improvement of the catalytic activity of defect-engineered MOF-808-IP and MOF-808-Pydc was observed, which may be related with the occurrence of less crowded Zr⁴⁺ sites in DE-MOF-808. The wider pore structure of MOF-808 with respect to UiO-66 compounds translates into a sharp improvement of the activity for the MPV reduction of bulky substrates, as shown for estrone reduction to estradiol. Interestingly, MOF-808 produces a notable diastereoselectivity towards the elusive 17-α-hydroxy estradiol.

中文翻译：

原始和缺陷设计的Zr-MOF-808金属有机骨架的催化性能†

通过将三羧酸酯配体与二羧酸酯配体混合，已经制备了多种缺陷工程化的Zr-三酸酯MOF-808化合物（DE-MOF-808）。即间苯二甲酸，3,5-二羧酸吡啶，5-羟基间苯二甲酸或5-氨基间苯二甲酸。发现所得的混合配体化合物MOF-808-X（X ＝ IP，Pydc，OH或NH ₂）对于未修饰的MOF-808都是高度结晶的并且是同构的。原始的MOF-808在Meerwein-Ponndorf-Verley（MPV）还原羰基化合物方面显示出比UiO-66参考化合物更好的催化性能。这归因于去除甲酸根离子后，MOF-808中较高的配位不饱和Zr ⁴⁺位点（cus）具有较高的利用率。同时，cusUiO-66中的“痕迹”仅位于缺陷部位，因此数量少得多。观察到缺陷工程MOF-808-IP和MOF-808-Pydc的催化活性进一步提高，这可能与DE-MOF-808中较少拥挤的Zr ⁴⁺位点的发生有关。相对于UiO-66化合物，MOF-808较宽的孔结构转化为大体积底物的MPV还原活性的急剧改善，如雌酮还原为雌二醇所示。有趣的是，MOF-808对难以捉摸的17-α-羟基雌二醇产生显着的非对映选择性。

更新日期：2018-06-22

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