Solvent-Free Synthetic Route for Cerium(IV) Metal-Organic Frameworks with UiO-66 Architecture and Their Photocatalytic Applications
Solvent-Free Synthetic Route for Cerium(IV) Metal-Organic Frameworks with UiO-66 Architecture and Their Photocatalytic Applications
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DOI：
10.1021/acsami.9b13730
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发表时间：
2019-12-04
影响因子：
9.5
通讯作者：
Costantino, Ferdinando
中科院分区：
文献类型：
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作者：
Campanelli, Matteo;Del Giacco, Tiziana;Costantino, Ferdinando
提出了一种近无溶剂合成Ce-UiO-66金属有机骨架（MOFs）的方法。通过在研钵中强力研磨试剂硝酸铈铵（CAN）和羧基连接体几分钟，并加入少量乙酸（AcOH）作为调节剂（8.75当量，0.5mL）来获得MOF。然后将浆液转移到2 mL小瓶中并在120 ° C下加热1天。MOFs的组成，结晶度和孔隙率进行了表征，并作为非均相催化剂的光氧化反应的取代苄醇苯甲醛在近紫外光照射下。的催化性能，如选择性，转化率和动力学，超过那些类似的系统，通过化学氧化研究使用类似的Ce-MOFs作为催化剂。此外，发现MOF可重复使用多达三个循环而不损失活性。密度泛函理论（DFT）计算被用来充分描述的电子结构的最佳性能的MOFs和实验观察到的催化活性提供有用的信息。
A near solvent-free synthetic route for Ce-UiO-66 metal-organic frameworks (MOFs) is presented. The MOFs are obtained by energetically grinding the reagents, cerium ammonium nitrate (CAN) and the carboxylic linkers, in a mortar for a few minutes with the addition of a small amount of acetic acid (AcOH) as a modulator (8.75 equiv, 0.5 mL). The slurry is then transferred into a 2 mL vial and heated at 120 degrees C for 1 day. The MOFs have been characterized for their composition, crystallinity, and porosity and employed as heterogeneous catalysts for the photo-oxidation reaction of substituted benzylic alcohols to benzaldaldehydes under near-ultraviolet light irradiation. The catalytic performances, such as selectivity, conversion, and kinetics, exceed those of similar systems studied by chemical oxidation using similar Ce-MOFs as a catalyst. Moreover, the MOFs were found to be reusable up to three cycles without loss of activity. Density functional theory (DFT) calculations were used to fully describe the electronic structure of the best performing MOFs and to provide useful information on the catalytic activity experimentally observed.