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Experimental-theoretical study of the epoxide structures effect on the CO2 conversion to cyclic carbonates catalyzed by hybrid titanate nanostructures
Journal of CO2 Utilization ( IF 7.7 ) Pub Date : 2019-11-30 , DOI: 10.1016/j.jcou.2019.11.024
Wesley F. Monteiro , Michele O. Vieira , Eduardo F. Laschuk , Paolo R. Livotto , Sandra M.O. Einloft , Michèle O. de Souza , Rosane A. Ligabue

Hybrid nanostructures were produced from several ionic liquids (ILs) anchored on titanate nanotubes (TNT). Ionic liquids ILs composed by the 1-methyl-3-(3-trimethoxysilylpropyl)imidazolium cation associated with the [Cl], [BF4], [PF6] or [Tf2N] anions were studied. The highest anchored amounts of IL were obtained with the [Cl] and [Tf2N] anions, respectively, of 31.5 and 43.5 % w/w. These hybrid nanostructures were used in the direct conversion of CO2 to cyclic carbonates through the coupling reaction with various epoxides (epichlorohydrin, styrene oxide, glycidyl isopropyl ether, and propylene oxide). With styrene oxide, the best results were obtained using the [Cl] and [BF4] IL, showing TON values of 35.6 and 18.4, and TOF values of 17.2 and 9.2 h−1, respectively. The TNT-[IL][Cl] was also used with different epoxides (i.e. epichlorohydrin, styrene oxide, glycidyl isopropyl ether and propylene oxide) being more reactive in the reactions with epichlorohydrin (TON = 86.3, TOF =21.6 h−1) and styrene oxide (TON = 47.0 TOF =11.7 h−1). Theoretical studies showed that the high reactivity of styrene oxide can be associated with their lower HOMO-LUMO energy gap, while epichlorohydrin presented high electron withdrawing effect by chlorine, generating the higher electronegativity. Besides that, by NBO analysis, both molecules presented lower donor – acceptor interact energy which may favor the opening of the ring.



中文翻译:

混合钛酸酯纳米结构催化环氧化物结构对CO 2转化成环状碳酸酯的实验理论研究

杂化纳米结构是由锚定在钛酸酯纳米管(TNT)上的几种离子液体(IL)产生的。通过与[氯相关联的1-甲基-3-(3-三甲氧基甲硅烷)咪唑鎓阳离子组成的离子液体离子液体-,[BF] 4 - ],[PF 6 - ]或[TF 2 Ñ - ]进行了研究阴离子。与获得IL的最高量锚[氯- ]和[TF 2 Ñ - ]阴离子分别为31.5和43.5%重量/瓦特 这些杂化纳米结构用于直接转化CO 2通过与各种环氧化物(环氧氯丙烷,氧化苯乙烯,缩水甘油基异丙基醚和环氧丙烷)的偶联反应生成环状碳酸酯。与氧化苯乙烯,使用得到了最好的结果[氯- ]和[BF 4 - ] IL,表示和35.6和18.4 TON值,和17.2 TOF值9.2ħ -1分别。TNT- [IL] [Cl]还与不同的环氧化物(环氧氯丙烷,氧化苯乙烯,缩水甘油基异丙基醚和环氧丙烷)一起使用,在与环氧氯丙烷的反应中具有更高的反应性(TON = 86.3,TOF = 21.6 h -1),氧化苯乙烯(TON = 47.0 TOF = 11.7 h -1)。理论研究表明,环氧乙烷的高反应性与其较低的HOMO-LUMO能隙有关,而环氧氯丙烷则表现出较高的氯电子吸电子作用,产生较高的电负性。除此之外,通过NBO分析,两个分子都呈现出较低的供体-受体相互作用能,这可能有利于环的打开。

更新日期:2019-11-30
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