Abstract
The aerobic oxidation of cyclohexene was done using the heterometallic metal organic frameworks (MOFs) {[La2Cu3(μ-H2O)(ODA)6(H2O)3]⋅3H2O}n (LaCuODA)) (1) and {[La2Co3(ODA)6(H2O)6]∙12H2O}n (LaCoODA) (2) as catalysts, in solvent free conditions (ODA, oxydiacetic acid). After 24 h of reaction, the catalytic system showed that LaCoODA had a better catalytic performance than that of LaCuODA (conversion 85% and 67%). The structures of both catalysts were very similar, showing channels running along the c axis. The physicochemical properties of both MOFs were determined to understand the catalytic performance. The Langmuir surface area of LaCoODA was shown to be greater than that of LaCuODA, while the acid strength and acid sites were greater for LaCuODA. On the other hand, the redox potential of the active sites was related to CoII/CoIII in LaCoODA and CuII/CuI in LaCuODA. Therefore, it is concluded that the Langmuir surface area and the redox potentials were more important than the acid strength and acid sites of the studied MOFs, in terms of the referred catalytic performance. Finally, the reaction conditions were also shown to play an important role in the catalytic performance of the studied systems. Especially, the type of oxidant and the way to supply it to the reaction medium influenced the catalytic results.
Highlights
The oxidation of cyclic olefins is a reaction that has become of interest for many industries, such as the agrochemical, pharmaceutical, and perfumery industries, as well as the manufacture of adhesives [1,2,3,4], because the products of this reaction such as epoxides, alcohol, ketones, and aldehydes are used in commodities
X-ray structural analyses of LaCuODA (1) and LaCoODA (2) reveal reveal that both belong to the hexagonal crystal with system, with space group for 1 and that both belong to the hexagonal crystal system, space group
The CO2 absorption measurements complement the crystallographic results, showing that the BET and Langmuir surface areas are bigger for LaCoODA as compared with LaCuODA
Summary
The oxidation of cyclic olefins is a reaction that has become of interest for many industries, such as the agrochemical, pharmaceutical, and perfumery industries, as well as the manufacture of adhesives [1,2,3,4], because the products of this reaction such as epoxides, alcohol, ketones, and aldehydes are used in commodities. Catalysts 2020, 10, 589 for these compounds, in order to decrease the carbon footprint and the generation of environmentally harmful sub-products [5]. Catalysis is an important tool in many industrial processes when it comes to reducing the energy cost, as well as the reaction time and the sub-product generation, enhancing the selectivity. In this sense, homogeneous and supported catalysts are classically used in the oxidation of cycloalkenes [6,7]. Heterogeneous catalysts, inorganic polymers, present a good alternative, as these are insoluble and stable under the usual cycloalkene oxidation conditions. The corresponding catalytic activity of inorganic polymers can be found in the literature in several reviews [8,9,10,11,12,13,14]
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have