4.7 Article

Comparative study of manganese oxides with different oxidation states for catalytic carbonylation of n-butylamine by CO2

Journal

JOURNAL OF CO2 UTILIZATION
Volume 68, Issue -, Pages -

Publisher

ELSEVIER SCI LTD
DOI: 10.1016/j.jcou.2022.102382

Keywords

Manganese oxides; CO2 capture and utilization; N; N?-dibutylurea; Oxygen vacancy

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Four manganese oxides (MnO, MnO2, Mn2O3, Mn3O4) were synthesized with different oxidation states and investigated for their catalytic performances in the carbonylation of n-butylamine by CO2. MnO2 showed the highest catalytic activity with a yield of 91.60% for N,N'-dibutylurea using PEG 400 as solvent under the reaction conditions of 160 degrees C, 4 h, and 5.0 MPa. Characterization results indicated that the oxygen vacancy content on the surface of manganese oxides played a key role in the catalytic performances of the carbonylation reaction.
The four manganese oxides with different oxidation states (MnO, MnO2, Mn2O3, Mn3O4) was synthesized using the hydrothermal method through adjusting process parameters and feedstock ratio, and their catalytic per-formances for the carbonylation of n-butylamine by CO2 were also investigated. The results showed that the catalytic activities of manganese oxides with different oxidation states in the catalytic carbonylation of n-butylamine by CO2 follow the order of MnO2 > Mn3O4 > Mn2O3 > MnO, in which MnO2 with the Mn4+ ion exhibited as high as 91.60% yield of N,N'-dibutylurea using polyethylene glycol 400 (PEG 400) as solvent under the reaction conditions of 160 degrees C, 4 h, and 5.0 MPa. And then a series of characterization including XRD, XPS, H2- TPR, and CO2/NH3-TPD were performed on the as-synthesized manganese oxides with different oxidation states, indicating that the content of oxygen vacancy on the surface of the manganese oxides with different oxidation states plays a key role in catalytic performances of the carbonylation of n-butylamine with CO2.

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