Universität zu Köln

Marandi, Afsaneh ORCID: 0000-0001-7599-7771, Bahadori, Mehrnaz, Tangestaninejad, Shahram ORCID: 0000-0001-5263-9795, Moghadam, Majid, Mirkhani, Valiollah, Mohammadpoor-Baltork, Iraj, Frohnhoven, Robert, Mathur, Sanjay, Sandleben, Aaron ORCID: 0000-0002-4141-7406 and Klein, Axel ORCID: 0000-0003-0093-9619 (2019). Cycloaddition of CO2 with epoxides and esterification reactions using the porous redox catalyst Co-POM@MIL-101(Cr). New J. Chem., 43 (39). S. 15585 - 15596. CAMBRIDGE: ROYAL SOC CHEMISTRY. ISSN 1369-9261

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Abstract

The catalytic activity of the recently reported Co-POM@MIL-101(Cr) composite, synthesized from K-5[CoW12O40] (Co-POM) and chromium(iii) terephthalate (MIL-101), was studied in the solvent-free cycloaddition of CO2 with epoxides and esterification of acetic acid with various alcohols. The materials containing varying amounts of Co-POM were synthesized using a one-pot HF-free method in a bottle around ship strategy. The material was thoroughly characterized using several methods such as powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and electron paramagnetic resonance spectroscopy (EPR). Temperature programmed desorption (TPD) of NH3 and CO2, and the CO2 adsorption capacity (adsorption isotherms) were used to study the acid-base properties of the materials. The combination of the electron-transfer character of Co(iii)-POM and ordered mesopores in MIL-101(Cr) creates an efficient catalytic system with mild conditions (90 degrees C and 20 bar CO2 pressure) for solvent-free cycloaddition of CO2 to various epoxides. Esterification of acetic acid with alcohols was also carried out using the Co-POM@MIL-101 catalysts and high yields were achieved for different alcohols. The catalysis experiments also clearly show that the active site in this heterogeneous catalyst is the Co(iii) center in the Keggin anion structure. It presumably conducts both the cycloaddition of CO2 to epoxides and the esterification reaction via an outer-sphere electron transfer mechanism using the Co(iii)/Co(ii) redox pair. The heterogeneous Co-POM@MIL-101 catalysts were separated by simple filtration and reused five times in the cycloaddition of CO2 with styrene epoxide and seven times for the esterification of acetic acid with benzyl alcohol with negligible leaching of Co-POM and no considerable loss of activity.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Marandi, Afsaneh UNSPECIFIED orcid.org/0000-0001-7599-7771 UNSPECIFIED Bahadori, Mehrnaz UNSPECIFIED UNSPECIFIED UNSPECIFIED Tangestaninejad, Shahram UNSPECIFIED orcid.org/0000-0001-5263-9795 UNSPECIFIED Moghadam, Majid UNSPECIFIED UNSPECIFIED UNSPECIFIED Mirkhani, Valiollah UNSPECIFIED UNSPECIFIED UNSPECIFIED Mohammadpoor-Baltork, Iraj UNSPECIFIED UNSPECIFIED UNSPECIFIED Frohnhoven, Robert UNSPECIFIED UNSPECIFIED UNSPECIFIED Mathur, Sanjay UNSPECIFIED UNSPECIFIED UNSPECIFIED Sandleben, Aaron UNSPECIFIED orcid.org/0000-0002-4141-7406 UNSPECIFIED Klein, Axel UNSPECIFIED orcid.org/0000-0003-0093-9619 UNSPECIFIED
URN:	urn:nbn:de:hbz:38-130612
DOI:	10.1039/c9nj02607j
Journal or Publication Title:	New J. Chem.
Volume:	43
Number:	39
Page Range:	S. 15585 - 15596
Date:	2019
Publisher:	ROYAL SOC CHEMISTRY
Place of Publication:	CAMBRIDGE
ISSN:	1369-9261
Language:	English
Faculty:	Faculty of Mathematics and Natural Sciences
Divisions:	Faculty of Mathematics and Natural Sciences > Department of Chemistry > Institute of Inorganic Chemistry
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language METAL-ORGANIC FRAMEWORK; CYCLIC CARBONATES SYNTHESIS; HETEROGENEOUS CATALYST; HIGHLY EFFICIENT; SELECTIVE CAPTURE; POLYOXOMETALATE; OXIDATION; ALCOHOLS; MIL-101; TRANSITION Multiple languages Chemistry, Multidisciplinary Multiple languages
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/13061