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Cu/La2O3 的表面性质及其在甘油和二氧化碳合成碳酸甘油酯和单醋酸甘油酯中的催化性能。

Surface properties of Cu/La2O3 and its catalytic performance in the synthesis of glycerol carbonate and monoacetin from glycerol and carbon dioxide.

机构信息

Innovative Catalysis Program, Key Lab of Organic Optoelectronics & Molecular Engineering of Ministry of Education, Department of Chemistry, Tsinghua University, Beijing 100084, China.

Innovative Catalysis Program, Key Lab of Organic Optoelectronics & Molecular Engineering of Ministry of Education, Department of Chemistry, Tsinghua University, Beijing 100084, China.

出版信息

J Colloid Interface Sci. 2014 Apr 1;419:31-8. doi: 10.1016/j.jcis.2013.12.049. Epub 2013 Dec 27.

Abstract

Cu/La2O3 catalysts with different Cu loadings were prepared by impregnation method and employed in the synthesis of glycerol carbonate and monoacetin from glycerol and CO2 in the presence of CH3CN. The interface between Cu and La2O3 and the structure of catalysts were characterized by XRD, TEM, H2-TPR, CO2-TPD, N2O chemisorptions, UV-vis DSR and XPS. Cu/La2O3 exhibited high catalytic activity for the conversion of glycerol to glycerol carbonate and monoacetin under mild reaction conditions. The effect of reaction parameters on the carbonylation of glycerol was also studied. CH3CN can break the thermodynamic limit of the reaction of glycerol with CO2 to glycerol carbonate through its hydrolysis. Over 2.3%Cu/La2O3 catalyst, the conversion of glycerol and the selectivity to glycerol carbonate and monoacetin were 33.4%, 45.4% and 52.9%, respectively (150°C, 7.0 MPa, 12 h). The size effect of Cu nanoparticles and the basic property of the supports were also examined. The characterization results suggested that the Cu sizes and basic sites on Cu/La2O3 had significant effect on the conversion and selectivity in the carbonylation of glycerol.

摘要

采用浸渍法制备了不同铜负载量的 Cu/La2O3 催化剂,并将其用于在 CH3CN 存在下由甘油和 CO2 合成碳酸甘油酯和单醋酸甘油酯。通过 XRD、TEM、H2-TPR、CO2-TPD、N2O 化学吸附、UV-vis DSR 和 XPS 对 Cu/La2O3 催化剂中 Cu 与 La2O3 的界面和结构进行了表征。在温和的反应条件下,Cu/La2O3 对甘油转化为碳酸甘油酯和单醋酸甘油酯表现出很高的催化活性。还研究了反应参数对甘油羰基化反应的影响。CH3CN 可以通过水解打破甘油与 CO2 反应生成碳酸甘油酯的热力学限制。在 2.3%以上的 Cu/La2O3 催化剂上,甘油的转化率和碳酸甘油酯及单醋酸甘油酯的选择性分别为 33.4%、45.4%和 52.9%(150°C、7.0 MPa、12 h)。还考察了 Cu 纳米粒子的尺寸效应和载体的碱性性质。表征结果表明,Cu/La2O3 上 Cu 纳米粒子的尺寸和碱性位对甘油羰基化反应的转化率和选择性有显著影响。

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