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结构修饰剂对 Zr 掺杂 SBA-15 硅合成的影响及其作为催化剂在糠醛加氢制备高附加值产物的 Meerwein-Ponndorf-Verley 还原反应中的应用。

Influence of Structure-modifying Agents in the Synthesis of Zr-doped SBA-15 Silica and Their Use as Catalysts in the Furfural Hydrogenation to Obtain High Value-added Products through the Meerwein-Ponndorf-Verley Reduction.

机构信息

Departamento de Química Inorgánica, Cristalografía y Mineralogía, Facultad de Ciencias, Campus de Teatinos, Universidad de Málaga, 29071 Málaga, Spain.

出版信息

Int J Mol Sci. 2019 Feb 14;20(4):828. doi: 10.3390/ijms20040828.

Abstract

Zr-doped mesoporous silicas with different textural parameters have been synthesized in the presence of structure-modifying agents, and then characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), N₂ adsorption-desorption at -196 °C, NH₃ thermoprogrammed desorption (NH₃⁻TPD), CO₂ thermoprogrammed desorption (CO₂⁻TPD), and X-ray photoelectron spectroscopy (XPS). These porous materials were evaluated in the furfural hydrogenation through the Meerwein-Ponndorf-Verley (MPV) reaction. The catalytic results indicate that the catalyst synthesized under hydrothermal conditions and adding a pore expander agent is more active and selective to furfuryl alcohol. However, the Zr-doped porous silica catalysts that were synthesized at room temperature, which possess narrow pore sizes, tend to form -propyl furfuryl and difurfuryl ethers, coming from etherification between furfuryl alcohol (FOL) and isopropanol molecules (used as H-donor) by a S2 mechanism.

摘要

具有不同结构参数的 Zr 掺杂介孔硅在结构改性剂的存在下被合成,然后通过 X 射线衍射(XRD)、透射电子显微镜(TEM)、N₂在-196°C 下吸附-解吸、NH₃程序升温脱附(NH₃⁻TPD)、CO₂程序升温脱附(CO₂⁻TPD)和 X 射线光电子能谱(XPS)进行表征。这些多孔材料在通过 Meerwein-Ponndorf-Verley(MPV)反应进行糠醛加氢反应中进行了评价。催化结果表明,在水热条件下合成并添加扩孔剂的催化剂对糠醇具有更高的活性和选择性。然而,在室温下合成的、具有较窄孔径的 Zr 掺杂多孔硅催化剂则倾向于形成-丙基糠基醚和二糠基醚,这是通过 S2 机制由糠醇(FOL)和异丙醇分子(用作 H 供体)之间的醚化反应形成的。

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