Luo Wei, Chen Yanqiu, Liu Junhua, Yang Yue, Wang Fang, Zhou Zhou
College of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, China.
College of Chemistry and Molecular Engineering, Nanjing Tech University, Nanjing 211816, China.
ACS Appl Mater Interfaces. 2021 Jan 13;13(1):341-349. doi: 10.1021/acsami.0c15776. Epub 2020 Dec 28.
Monoacetin was synthesized using a novel green method in which acetonitrile was hydrolyzed and then esterified with glycerol over Cu-Cr phosphates under the CO atmosphere. Monoacetin was synthesized with high yield (87.6% glycerol conversion and 86.3% monoacetin selectivity) through this one-pot cascade method. In this process, acetonitrile can react with water to form acetamide and further undergo esterification with glycerol. There are two main reasons for obtaining monoacetin in high yield: (1) the interaction of CO with high-temperature liquid water enhances the acid strength of the reaction system and then promotes the activation of acetonitrile; and (2) the introduction of Cr species causes a synergistic effect between Cu and Cr species to adjust the acidity and basicity of the catalyst. The introduction of Cr species converts eight-coordinated Cu into four-coordinated Cu to improve the acidity of the catalyst. The introduction of Cr species also causes the surface oxygen to be transformed into lattice oxygen to enhance the basicity of the catalyst. These bimetallic phosphate materials may provide a new pathway for the application of acid-base bifunctional catalytic reactions.
采用一种新型绿色方法合成了甘油单乙酸酯,该方法是在CO气氛下,使乙腈水解,然后与甘油在磷酸铜 - 铬上进行酯化反应。通过这种一锅法串联反应,甘油单乙酸酯的合成产率较高(甘油转化率为87.6%,甘油单乙酸酯选择性为86.3%)。在此过程中,乙腈可与水反应生成乙酰胺,并进一步与甘油发生酯化反应。高产率获得甘油单乙酸酯有两个主要原因:(1)CO与高温液态水的相互作用增强了反应体系的酸强度,进而促进了乙腈的活化;(2)Cr物种的引入导致Cu和Cr物种之间产生协同效应,从而调节催化剂的酸度和碱度。Cr物种的引入将八配位的Cu转化为四配位的Cu,以提高催化剂的酸度。Cr物种的引入还使表面氧转化为晶格氧,以增强催化剂的碱度。这些双金属磷酸盐材料可能为酸碱双功能催化反应的应用提供一条新途径。