MIL-101(Cr)-NH2负载Pd低温催化糠醛高选择性加氢生成四氢糠醇

doi:10.1016/S1872-2067(18)63009-8

催化学报 ›› 2018, Vol. 39 ›› Issue (2): 319-326.DOI: 10.1016/S1872-2067(18)63009-8

MIL-101(Cr)-NH₂负载Pd低温催化糠醛高选择性加氢生成四氢糠醇

殷冬冬^a, 任航星^b, 李闯^a, 刘进轩^c, 梁长海^a

a 大连理工大学先进材料与催化工程实验室, 辽宁大连 116024;
b 邯郸净化设备研究所, 河北邯郸 056027;
c 大连理工大学精细化工国家重点实验室, 人工光合作用研究所, 辽宁大连 116024

收稿日期:2017-11-10 修回日期:2017-12-26 出版日期:2018-02-18 发布日期:2018-02-10
通讯作者: 梁长海, 刘进轩
基金资助:
国家自然科学基金（21573031，21673032）；大连市高层次人才创新支持计划项目（2016RD09）；中央高校基本科研业务费资助（DUT17LK21）；厦门大学固体表面物理化学国家重点实验室开放课题（201507）.

Highly selective hydrogenation of furfural to tetrahydrofurfuryl alcohol over MIL-101(Cr)-NH₂ supported Pd catalyst at low temperature

Dongdong Yin^a, Hangxing Ren^b, Chuang Li^a, Jinxuan Liu^c, Changhai Liang^a

a Laboratory of Advanced Materials and Catalytic Engineering, Dalian University of Technology, Dalian 116024, Liaoning, China;
b Purification Equipment Research Institute of CSIC, Handan 056027, Hebei, China;
c State Key Laboratory of Fine Chemicals, Institute of Artificial Photosynthesis, Dalian University of Technology, Dalian 116024, Liaoning, China

Received:2017-11-10 Revised:2017-12-26 Online:2018-02-18 Published:2018-02-10
Contact: 10.1016/S1872-2067(18)63009-8
Supported by:
This work was supported by the National Natural Science Foundation of China (21573031, 21673032), Program for Excellent Talents in Dalian City (2016RD09), the Fundamental Research Funds for the Central Universities (DUT17LK21), the State Key Laboratory of Physical Chemistry of Solid Surfaces, Xiamen University (201507).

摘要/Abstract

摘要：

随着资源枯竭和环境污染严重问题的凸显，生物质转化的研究越来越多，特别是生物质催化裂解制备生物燃料及高附加值的化学品.糠醛是一种半纤维素酸解的产物，也是生产糠醇、四氢糠醇、2-甲基呋喃、环戊酮等的重要原料.其中四氢糠醇既可以用于生产其他高附加值化学品，也可以用作生物燃料或者燃料添加剂.虽然Pd/MFI，Ni/SiO₂，Pd-Ir/SiO₂等催化剂均可用于糠醛选择加氢制备四氢糠醇，但是反应通常在高温高压条件下进行.为此我们希望找到一种在温和条件下使用的高效催化剂.MOF多孔材料具有丰富的孔道结构、极高的比表面积、表面可修饰的特点，还可与其他客体发生相互作用，进而影响催化性能.因此本课题组合成了一种含有氨基的MOF材料MIL-101（Cr）-NH₂，进一步利用表面氨基吸附Pd的氯酸盐前体，经还原直接制得负载型催化剂Pd@MIL-101（Cr）-NH₂，并用于糠醛选择加氢反应.
本文采用X射线粉末衍射（PXRD）、热重分析（TG）、N₂物理吸附-脱附、透射电镜（TEM）等手段表征了所制的MOFs和催化剂.通过将MIL-101（Cr）-NH₂和不同Pd@MIL-101（Cr）-NH₂的XRD谱与标准谱图对比，发现MIL-101（Cr）-NH₂已成功合成，并在催化剂制备过程中和反应之后仍然保持稳定.TG结果表明，所制备MIL-101（Cr）-NH₂在低于350℃时结构不会被破环.MIL-101（Cr）-NH₂的比表面积可达到1669 m² g^-1，孔容达1.35 cm³ g^-1，从而为Pd纳米粒子均匀分散在载体上提供了可能性.各Pd@MIL-101（Cr）-NH₂样品的TEM照片我们看出，Pd纳米粒子可均匀分散在MIL-101（Cr）-NH₂上，粒径为3-4 nm.对比实验表明，氨基与金属的相互作用有利于Pd纳米粒子分散均匀.
将Pd@MIL-101（Cr）-NH₂用于糠醛选择加氢反应时，在40℃，2 MPa H₂的温和条件下，反应6 h后糠醛完全转化为四氢糠醇其选择性接近100%.表现出比文献报导的更加优异的催化性能.这得益于高度均匀分散的Pd纳米粒子，以及催化剂载体与Pd纳米粒子的配位作用和π-π相互作用.结果还表明当高于80℃反应时，即有副产物生成，进一步提高反应温度会促进环戊酮的生成.可见，Pd@MIL-101（Cr）-NH₂所表现的低温高加氢活性对提高四氢糠醇选择性至关重要.

关键词: 金属有机框架材料, 氨基功能化, 钯纳米粒子, 生物质, 选择加氢

Abstract:

An efficient heterogeneous catalyst, Pd@MIL-101(Cr)-NH₂, is prepared through a direct pathway of anionic exchange followed by hydrogen reduction with amino-containing MIL-101 as the host matrix. The composite is thermally stable up to 350℃ and the Pd nanoparticles uniformly disperse on the matal organic framework (MOF) support, which are attributed to the presence of the amino groups in the frameworks of MIL-101(Cr)-NH₂. The selective hydrogenation of biomass-based furfural to tetrahydrofurfuryl alcohol is investigated by using this multifunctional catalyst Pd@MIL-101(Cr)-NH₂ in water media. A complete hydrogenation of furfural is achieved at a low temperature of 40℃ with the selectivity of tetrahydrofurfuryl alcohol close to 100%. The amine-functionalized MOF improves the hydrogen bonding interactions between the intermediate furfuryl alcohol and the support, which is conducive for the further hydrogenation of furfuryl alcohol to tetrahydrofurfuryl alcohol in good coor-dination with the metal sites.

Key words: Metal-organic frameworks, Amino functionalization, Pd nanoparticle, Biomass, Selective hydrogenation

殷冬冬, 任航星, 李闯, 刘进轩, 梁长海. MIL-101(Cr)-NH₂负载Pd低温催化糠醛高选择性加氢生成四氢糠醇[J]. 催化学报, 2018, 39(2): 319-326.

Dongdong Yin, Hangxing Ren, Chuang Li, Jinxuan Liu, Changhai Liang. Highly selective hydrogenation of furfural to tetrahydrofurfuryl alcohol over MIL-101(Cr)-NH₂ supported Pd catalyst at low temperature[J]. Chinese Journal of Catalysis, 2018, 39(2): 319-326.

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MIL-101(Cr)-NH₂负载Pd低温催化糠醛高选择性加氢生成四氢糠醇

Highly selective hydrogenation of furfural to tetrahydrofurfuryl alcohol over MIL-101(Cr)-NH₂ supported Pd catalyst at low temperature

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