Cu(II)-Schiff base covalently anchored to MIL-125(Ti)-NH2 as heterogeneous catalyst for oxidation reactions
Cu(II)-Schiff base covalently anchored to MIL-125(Ti)-NH2 as heterogeneous catalyst for oxidation reactions
复制标题
DOI：
10.1016/j.jcis.2018.07.140
复制
发表时间：
2018-12-15
影响因子：
9.9
通讯作者：
Garcia, Hermenegildo
中科院分区：
文献类型：
--
作者：
Daliran, Saba;Santiago-Portillo, Andrea;Garcia, Hermenegildo
MIL-125（Ti）-NH 2通过水杨醛与对苯二甲酸酯氨基反应形成水杨醛亚胺作为Cu ~（2+）的配体而被修饰。通过MIL-125（Ti）-NH 2-Sal-Cu的FTIR光谱和通过MIL-125（Ti）-NH 2-Sal-Cu溶解后有机连接体的H-NMR光谱分析来评估合成后改性的成功。与表现出差活性的母体MIL-125（Ti）-NH 2和MIL-125（Ti）-NH 2-Sal-Cu催化剂相比，Cu-Schiff碱络合物在MIL-125（Ti）-NH 2-Sal-Cu催化剂中的存在用于通过叔丁基过氧化氢（TBHP，3eq.）显著提高了催化活性。热过滤试验和可重复使用性实验证实了该过程是非均相的，并且MIL-125（Ti）-NH 2-Sal-Cu在反应条件下是稳定的。使用N-（t）丁基苯基硝酮的淬灭研究和EPR谱表明（BuOO）-Bu-t的产生。和（BuO中心点）-Bu-t。研究了MIL-125（Ti）-NH_2-Sal-Cu催化剂对苯甲醇、脂环醇、脂肪醇和正丁醇的氧化性能。(C)2018爱思唯尔公司All rights reserved.
MIL-125(Ti)-NH2 has been modified by reaction of salicylaldehyde with the terephthalate amino groups to form a salicylideneimine that act as ligand of Cu2+. The success of the postsynthetic modification was assessed by FTIR spectroscopy of the MIL-125(Ti)-NH2-Sal-Cu and by analysis by H-1 NMR spectroscopy of the organic linkers upon dissolution of MIL-125(Ti)-NH2-Sal-Cu. In comparison with parent MIL-125(Ti)-NH2 and MIL-125(Ti)-NH2-Sal, that exhibit a poor activity, the presence of the Cu-Schiff base complex in MIL-125(Ti)-NH2-Sal-Cu catalyst for the oxidation of 1-phenylethanol by tert-butylhydroperoxyde (TBHP, 3 eq.) increases notably the catalytic activity. Hot filtration test and reusability experiments confirm that the process is heterogeneous and that MIL-125(Ti)-NH2-Sal-Cu is stable under the reaction conditions. Quenching studies and EPR spectra using N-(t)butylphenylnitrone indicate the generation of (BuOO)-Bu-t. and (BuO center dot)-Bu-t under the reaction conditions. The scope of MIL-125(Ti)-NH2-Sal-Cu as oxidation catalyst by (BuOOH)-Bu-t was studied for benzyl alcohol as well as alicyclic and aliphatic alcohols and ethylbenzene. (C) 2018 Elsevier Inc. All rights reserved.