Abstract
Glycerol can be converted to valuable products such as epichlorohydrin which is an important intermediate applied in various industries. For example, dioxane derivatives, which are important pharmaceuticals, can be obtained from epichlorohydrin. In the present study, ZIF-8, ZIF-67, MIL-100, and UiO-66 were applied for the direct cyclodimerization of epichlorohydrin. These MOFs were selected because they were already applied asactive catalysts in ring opening of epoxides. Among them, ZIF-8 showed the highest activity and selectivity in the absence of any solvent or co-catalyst. Using ZIF-8asa catalyst, the cyclodimer product (1,4-dioxane 2,5-bis-chloromethyl) was obtained in a yield of about 70% which was significantly superior to previous homo or heterogeneous catalysts for this reaction. Due to ZIF-8 structure and the proposed mechanism, the cyclodimerization reaction catalyzed either by the defects in the structure and/or on the surface. Furthermore, acidic-basic characteristics were also in play. The NH 3 and CO 2 temperature-programed desorption technique were utilized to identify the active sites and thereby reaction mechanism. Moreover, because of similar properties of ZIF-8 to zeolites, the activity of commercial ZSM-5 for the same reaction was also investigated in this work.
| Original language | English |
|---|---|
| Journal | Arabian Journal of Chemistry |
| DOIs | |
| Publication status | Accepted/In press - 1 Jan 2017 |
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Keywords
- Cyclodimerization
- Epichlorohydrin
- MOFs
- Oligomerization
- Temperature program desorption (TPD)
- ZIF
ASJC Scopus subject areas
- Chemistry(all)
- Chemical Engineering(all)
Cite this
Selective cyclodimerization of epichlorohydrin to dioxane derivatives over MOFs. / Mousavi, Bibimaryam; Chaemchuen, Somboon; Phatanasri, Suphot; Chen, Cheng; Zeng, Cheng; Ganguly, Rakesh; Zhuiykov, Serge; Verpoort, Francis.
In: Arabian Journal of Chemistry, 01.01.2017.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Selective cyclodimerization of epichlorohydrin to dioxane derivatives over MOFs
AU - Mousavi, Bibimaryam
AU - Chaemchuen, Somboon
AU - Phatanasri, Suphot
AU - Chen, Cheng
AU - Zeng, Cheng
AU - Ganguly, Rakesh
AU - Zhuiykov, Serge
AU - Verpoort, Francis
PY - 2017/1/1
Y1 - 2017/1/1
N2 - Glycerol can be converted to valuable products such as epichlorohydrin which is an important intermediate applied in various industries. For example, dioxane derivatives, which are important pharmaceuticals, can be obtained from epichlorohydrin. In the present study, ZIF-8, ZIF-67, MIL-100, and UiO-66 were applied for the direct cyclodimerization of epichlorohydrin. These MOFs were selected because they were already applied asactive catalysts in ring opening of epoxides. Among them, ZIF-8 showed the highest activity and selectivity in the absence of any solvent or co-catalyst. Using ZIF-8asa catalyst, the cyclodimer product (1,4-dioxane 2,5-bis-chloromethyl) was obtained in a yield of about 70% which was significantly superior to previous homo or heterogeneous catalysts for this reaction. Due to ZIF-8 structure and the proposed mechanism, the cyclodimerization reaction catalyzed either by the defects in the structure and/or on the surface. Furthermore, acidic-basic characteristics were also in play. The NH 3 and CO 2 temperature-programed desorption technique were utilized to identify the active sites and thereby reaction mechanism. Moreover, because of similar properties of ZIF-8 to zeolites, the activity of commercial ZSM-5 for the same reaction was also investigated in this work.
AB - Glycerol can be converted to valuable products such as epichlorohydrin which is an important intermediate applied in various industries. For example, dioxane derivatives, which are important pharmaceuticals, can be obtained from epichlorohydrin. In the present study, ZIF-8, ZIF-67, MIL-100, and UiO-66 were applied for the direct cyclodimerization of epichlorohydrin. These MOFs were selected because they were already applied asactive catalysts in ring opening of epoxides. Among them, ZIF-8 showed the highest activity and selectivity in the absence of any solvent or co-catalyst. Using ZIF-8asa catalyst, the cyclodimer product (1,4-dioxane 2,5-bis-chloromethyl) was obtained in a yield of about 70% which was significantly superior to previous homo or heterogeneous catalysts for this reaction. Due to ZIF-8 structure and the proposed mechanism, the cyclodimerization reaction catalyzed either by the defects in the structure and/or on the surface. Furthermore, acidic-basic characteristics were also in play. The NH 3 and CO 2 temperature-programed desorption technique were utilized to identify the active sites and thereby reaction mechanism. Moreover, because of similar properties of ZIF-8 to zeolites, the activity of commercial ZSM-5 for the same reaction was also investigated in this work.
KW - Cyclodimerization
KW - Epichlorohydrin
KW - MOFs
KW - Oligomerization
KW - Temperature program desorption (TPD)
KW - ZIF
UR - http://www.scopus.com/inward/record.url?scp=85030635652&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85030635652&partnerID=8YFLogxK
U2 - 10.1016/j.arabjc.2017.09.011
DO - 10.1016/j.arabjc.2017.09.011
M3 - Article
JO - Arabian Journal of Chemistry
JF - Arabian Journal of Chemistry
SN - 1878-5352
ER -