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Mild acid functionalization of metal-organic framework and its catalytic effect on esterification of acetic acid with n-butanol
Molecular Catalysis ( IF 4.6 ) Pub Date : 2019-12-24 , DOI: 10.1016/j.mcat.2019.110635
Xijun Hu , Kai Ma , Aghil Sabbaghi , Xuanming Chen , Amrita Chatterjee , Frank L.Y. Lam

Mild acid functionalization method is used to synthesize sulfonic acid functionalized metal-organic framework (MOF), particularly, S-MIL-101, and is evaluated as a heterogeneous catalyst for esterification of acetic acid with n-butanol. BrÖnsted acidic S-MIL-101 is developed by post-synthetic functionalization of the MOF, NH2-MIL-101(Al). The incorporation of propylsulfonic acid groups was carried out by nucleophilic ring-open reaction between amino groups in NH2-MIL-101 and 1,3- propanesultone. The mild functionalization method successfully introduces BrÖnsted acidity to the NH2-MIL-101(Al), without any significant structural degradation as confirmed by structural characterizations. As a BrÖnsted acidic heterogeneous catalyst, S-MIL-101 exhibits 66% acetic acid conversion at a low esterification temperature of 70 °C and is successfully reused for 3 reaction cycles without any considerable leaching. The performance of S-MIL-101 is comparable to commercial Amberlyst-15 and Nafion NR-50. various structural characterizations and kinetic studies were performed and the excellent performance of S-MIL-101 as a solid acid catalyst is attributed to the high surface area and favorable influence of the BrÖnsted acidic sulfonic groups.



中文翻译:

金属-有机骨架的轻度酸官能化及其对乙酸与正丁醇酯化的催化作用

温和的酸官能化方法用于合成磺酸官能化的金属有机骨架(MOF),尤其是S-MIL-101,并被评估为用于乙酸与正丁醇酯化的非均相催化剂。布朗斯特德酸性S-MIL-101是通过MOF NH 2 -MIL-101(Al)的后合成功能化开发的。通过NH 2 -MIL-101中的氨基与1,3-丙烷磺酸内酯之间的亲核开环反应进行丙基磺酸基团的引入。温和的官能化方法成功地将布朗斯台德酸度引入到NH 2中-MIL-101(Al),没有任何明显的结构降解,如结构表征所证实。作为布朗斯台德酸性多相催化剂,S-MIL-101在70℃的低酯化温度下显示出66%的乙酸转化率,并成功地重复使用了3个反应周期,而没有任何明显的浸出。S-MIL-101的性能可与商用Amberlyst-15和Nafion NR-50媲美。进行了各种结构表征和动力学研究,S-MIL-101作为固体酸催化剂的出色性能归因于高表面积和布朗斯台德酸性磺酸基团的有利影响。

更新日期:2019-12-25
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