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A regulatable oxidative valorization of furfural with aliphatic alcohols catalyzed by functionalized metal-organic frameworks-supported Au nanoparticles
Journal of Catalysis ( IF 6.5 ) Pub Date : 2018-05-26 , DOI: 10.1016/j.jcat.2018.04.030
Liangmin Ning , Shengyun Liao , Xuguang Liu , Pengfei Guo , Zhenya Zhang , Haigang Zhang , Xinli Tong

The oxidative upgrading of furfural (FUR) and aliphatic alcohols is an important way to produce desirable precursor of jet fuel or value-added furanic compound. Therein, developing a highly active catalytic system with switchable product selectivity still remains a challenge. In this work, we report a novel strategy on regulating the oxidative condensation and oxidative esterification of FUR with aliphatic alcohol in the presence of molecular oxygen. Firstly, [email protected] is prepared using different methods and employed as the catalyst for the oxidative valorization of FUR with methanol. It is found that the impregnation-reduction-H2 (I-H) method is the best where a 100% selectivity of methyl-2-furoate with a complete conversion was obtained using [email protected] as catalyst. Then, a series of metal-organic frameworks (MOFs) supported Au nanoparticles ([email protected]) such as [email protected], [email protected]2, [email protected]2, [email protected] and [email protected]3Cl have been prepared with I-H method and employed for oxidative valorization of furfural with ethanol. Experimental results showed that, in “FUR-ethanol-O2” system, the [email protected] can efficiently regulate the oxidative condensation and oxidative esterification as two competitive reaction pathways. With [email protected] as the catalyst, the oxidative condensation process is dominant in which 84.1% selectivity of furan-2-acrolein is attained; Meanwhile, the [email protected] is beneficial to the occurrence of oxidative esterification and generation of ethyl-2-furoate. At last, based on the catalyst characterization and the numerous control experiments, a possible catalytic reaction mechanism for conversion of FUR is proposed.



中文翻译:

官能化的金属有机骨架负载的金纳米粒子催化脂肪族醇对糠醛的可调节氧化价

糠醛(FUR)和脂肪族醇的氧化提质是生产航空燃料或增值呋喃化合物的理想前体的重要方法。其中,开发具有可切换的产物选择性的高活性催化体系仍然是一个挑战。在这项工作中,我们报告了在分子氧存在下用脂肪醇调节FUR的氧化缩合和氧化酯化的新策略。首先,使用不同的方法制备[电子邮件保护的],并将其用作FUR与甲醇的氧化增值的催化剂。发现浸渍-还原-H 2IH)方法是最好的方法,其中使用[电子邮件保护]作为催化剂可获得100%选择性的完全转化的2-糠酸甲酯。然后,一系列金属有机框架(MOF)支持了Au纳米颗粒([受电子邮件保护]),例如[受电子邮件保护],[受电子邮件保护] 2,[受电子邮件保护] 2,[受电子邮件保护]和[受电子邮件保护] 3 Cl已经通过IH方法制备,并用于糠醛与乙醇的氧化增值。实验结果表明,在“ FUR-乙醇-O 2系统中,[电子邮件保护]可以有效地调节氧化缩合和氧化酯化作为两个竞争性反应途径。以[电子邮件保护的]为催化剂,氧化缩合过程占主导地位,其中呋喃-2-丙烯醛的选择性达到了84.1%。同时,[电子邮件保护的]有利于发生氧化酯化和生成2-糠酸乙酯。最后,基于催化剂的表征和大量的控制实验,提出了一种可能的催化反应机理,以转化为FUR。

更新日期:2018-05-26
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