Dataset Information

Heterogeneous Epoxide Carbonylation by Cooperative Ion-Pair Catalysis in Co(CO)₄^--Incorporated Cr-MIL-101.

ABSTRACT: Despite the commercial desirability of epoxide carbonylation to ?-lactones, the reliance of this process on homogeneous catalysts makes its industrial application challenging. Here we report the preparation and use of a Co(CO)₄^--incorporated Cr-MIL-101 (Co(CO)₄?Cr-MIL-101, Cr-MIL-101 = Cr₃O(BDC)₃F, H₂BDC = 1,4-benzenedicarboxylic acid) heterogeneous catalyst for the ring-expansion carbonylation of epoxides, whose activity, selectivity, and substrate scope are on par with those of the reported homogeneous catalysts. We ascribe the observed performance to the unique cooperativity between the postsynthetically introduced Co(CO)₄^- and the site-isolated Lewis acidic Cr(III) centers in the metal-organic framework (MOF). The heterogeneous nature of Co(CO)₄?Cr-MIL-101 allows the first demonstration of gas-phase continuous-flow production of ?-lactones from epoxides, attesting to the potential applicability of the heterogeneous epoxide carbonylation strategy.

SUBMITTER: Park HD

PROVIDER: S-EPMC5445536 | biostudies-literature | 2017 May

REPOSITORIES: biostudies-literature

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Heterogeneous Epoxide Carbonylation by Cooperative Ion-Pair Catalysis in Co(CO)4--Incorporated Cr-MIL-101.

Park Hoyoung D HD Dincă Mircea M Román-Leshkov Yuriy Y

ACS central science 20170321 5

Despite the commercial desirability of epoxide carbonylation to β-lactones, the reliance of this process on homogeneous catalysts makes its industrial application challenging. Here we report the preparation and use of a Co(CO)4--incorporated Cr-MIL-101 (Co(CO)4⊂Cr-MIL-101, Cr-MIL-101 = Cr3O(BDC)3F, H2BDC = 1,4-benzenedicarboxylic acid) heterogeneous catalyst for the ring-expansion carbonylation of epoxides, whose activity, selecti ...[more]

PMID: 28573206

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Project description:In this study, hybrids of nanoporous MIL-101(Cr) and MIL-53(Al) were synthesized using a hydrothermal method for various time periods, ranging from 8 to 40 h. The prepared materials were characterized by powder X-ray diffraction (PXRD) and elemental analysis, and their specific surface areas were measured by N2 sorption at 77 K using the Brunauer-Emmett-Teller (BET) method. To investigate the practical application of these materials, the pure carbon dioxide and methane adsorption capacities of the samples were determined using the volumetric method. The Langmuir model was used to fit the CO2 and CH4 isotherms. Extended Langmuir (EL) equations and the ideal adsorbed solution theory (IAST) models were used to obtain the CO2/CH4 selectivity. The sample with the highest BET specific surface area was selected as a candidate for further investigations. The thermal stability of the selected sample was investigated by thermogravimetric analysis (TGA). Scanning electron microscopy (SEM) was used to characterize the sample morphology. XRD results showed that the sample synthesized over the shortest time corresponded to MIL-101(Cr), while the sample synthesized over the longest time was in agreement with MIL-53(Al). Samples synthesized for time periods between these two limits were assumed to be composites of both MIL-53(Al) and MIL-101(Cr). TGA results indicated that the hybrid materials were thermally stable at temperatures about 100 °C higher than for pure MIL-101(Cr). The BET specific surface area (1746 m2 g-1) and CO2 adsorption capacity (16 mmol g-1) of the selected hybrid sample were about 50% and 35% higher, respectively, compared with those of pure MIL-53(Al), but 30% and 20% lower, respectively, compared with those of pure MIL-101(Cr). Binary adsorption modeling showed the high selectivity of the MIL-101(Cr) and MIL-53(Al) hybrid material for CO2 with a minimum separation factor of about 60 at 298 K. This value was much higher than those reported previously and those observed in this work for the original MIL-101(Cr) or MIL-53(Al). These results demonstrated that the hybrid of MIL-101(Cr) and MIL-53(Al) was a promising material for selective CO2 capture from natural and biogas.

Dataset Information

Heterogeneous Epoxide Carbonylation by Cooperative Ion-Pair Catalysis in Co(CO)₄^--Incorporated Cr-MIL-101.

Publications

Heterogeneous Epoxide Carbonylation by Cooperative Ion-Pair Catalysis in Co(CO)<sub>4</sub><sup>-</sup>-Incorporated Cr-MIL-101.

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