Pt在MgAl2O4载体上的分散程度对催化苯甲醛加氢反应影响

doi:10.1016/S1872-2067(17)62815-8

催化学报 ›› 2017, Vol. 38 ›› Issue (9): 1613-1620.DOI: 10.1016/S1872-2067(17)62815-8

Pt在MgAl₂O₄载体上的分散程度对催化苯甲醛加氢反应影响

鄢峰^a,b, 赵才贤^a, 易兰花^a, 张景才^b, 葛炳辉^c, 张涛^b, 李为臻^b

a 湘潭大学化学系环境友好化学与应用教育部重点实验室, 湖南湘潭 411105;
b 中国科学院大连化学物理研究所催化基础国家重点实验室, 辽宁大连 116023;
c 中国科学院物理研究所北京凝聚态物理国家实验室, 北京 100190

收稿日期:2017-02-14 修回日期:2017-03-15 出版日期:2017-09-18 发布日期:2017-09-06
通讯作者: 易兰花, 李为臻
基金资助:
国家自然科学基金（21403213，21673226，21376236，U1462121）；中国科学院"百人计划"；国家重点研发计划（2016YFA0202801）；中国科学院战略性先导科技专项（XDB17020100）；辽宁省科技厅（2015020086-101）；湖南省自然科学基金（2016JJ2128）.

Effect of the degree of dispersion of Pt over MgAl₂O₄ on the catalytic hydrogenation of benzaldehyde

Feng Yan^a,b, Caixian Zhao^a, Lanhua Yi^a, Jingcai Zhang^b, Binghui Ge^c, Tao Zhang^b, Weizhen Li^b

a Key Laboratory of Environmentally Friendly Chemistry and Applications of Ministry of Education, School of Chemistry, Xiangtan University, Xiangtan 411105, Hunan, China;
b State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China;
c Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China

Received:2017-02-14 Revised:2017-03-15 Online:2017-09-18 Published:2017-09-06
Contact: 10.1016/S1872-2067(17)62815-8
Supported by:
This work was supported by the National Natural Science Foundation of China (21403213, 21673226, 21376236, U1462121), the "Hundred Talents Programme" of the Chinese Academy of Sciences, and National Key R&D Program of China (2016YFA0202801), and the "Strategic Priority Research Program" of the Chinese Academy of Sciences (XDB17020100), Department of Science and Technology of Liaoning province under contract of 2015020086-101, and the Natural Science Foundation of Hunan Province (2016JJ2128).

摘要/Abstract

摘要：

构建催化剂特别是在亚纳米尺度下分散的贵金属催化剂的构效关系是多相催化研究领域中的主要任务之一.我们采用与金属Pt具有强相互作用的MgAl₂O₄尖晶石作为载体，通过简单浸渍法制备了在纳米、亚纳米和单原子尺度上分散的Pt催化剂.首先利用X射线衍射和原子分辨的球差校正电镜，确定了Pt在MgAl₂O₄尖晶石载体表面上随负载量增大逐渐形成孤立的和相邻的单原子Pt，然后逐渐形成无定形Pt聚集体和小晶粒；然后利用电感耦合等离子体光谱和CO化学吸附测定了催化剂中Pt的含量和分散度；进一步通过测定CO在Pt表面吸附的红外光谱，区分了载体表面单原子和金属颗粒表面原子的CO吸附特征结构，并据此对不同结构的Pt原子进行了半定量估算.考察了具有不同Pt分散结构的Pt/MgAl₂O₄催化剂的催化苯甲醛选择性加氢能力，发现以载体表面Pt单原子物种为主的催化剂，可在较宽的温度区间内保持较高的部分加氢产物苯甲醇的选择性（60-150 ℃，苯甲醇选择性99.4-97.9%，甲苯选择性~0.4%），而以Pt纳米颗粒为主的催化剂上苯甲醇选择性降低显著，同时生成较多深度加氢产物甲苯（60-150 ℃，苯甲醇选择性99.0-93.1%，甲苯选择性0.7-5.0%）.此外，我们测定了各催化剂在不同转化率（~20-90%）时催化剂加氢反应的质量比活性和转化频率（TOF），并在较低苯甲醛转化率（~20%）时，估算了不同结构Pt物种对苯甲醛加氢反应的本征活性，发现Pt纳米颗粒表面原子比MgAl₂O₄载体表面Pt单原子本征活性更高（4807 h^-1 versus 3277 h^-1）.综上，Pt单原子催化剂具有贵金属原子利用率高，本征活性和加氢选择性高等优点；Pt纳米催化剂表面原子深度加氢能力强，加氢选择性较差，虽本征活性更高，但不足以补偿贵金属原子利用率降低带来的活性损失，Pt质量比活性显著低于单原子催化剂.此外，MgAl₂O₄尖晶石负载的单原子Pt催化剂也具有良好的催化反应循环稳定性，是一种较为理想的催化苯甲醛选择性加氢制苯甲醇催化剂.

关键词: 铂, 镁铝尖晶石, 单原子催化剂, 选择加氢, 苯甲醛, 苯甲醇

Abstract:

One of the central tasks in the field of heterogeneous catalysis is to establish structure-function relationships for these catalysts, especially for precious metals dispersed on the sub-nanometer scale. Here, we report the preparation of MgAl₂O₄-supported Pt nanoparticles, amorphous aggre-gates and single atoms, and evaluate their ability to catalyze the hydrogenation of benzaldehyde. The Pt species were characterized by N₂ adsorption, X-ray diffraction (XRD), aberration-corrected transmission electron microscopy (ACTEM), CO chemisorption and in situ Fourier transform infra-red spectroscopy of the chemisorbed CO, as well as by inductively coupled plasma atomic emission spectroscopy. They existed as isolated or neighboring single atoms on the MgAl₂O₄ support, and formed amorphous Pt aggregates and then nanocrystallites with increased Pt loading. On the MgAl₂O₄ support, single Pt atoms were highly active in the selective catalytic hydrogenation of ben-zaldehyde to benzyl alcohol. The terrace atoms of the Pt particles were more active but less selec-tive; this was presumably due to their ability to form bridged carbonyl adsorbates. The MgAl₂O₄-supported single-atom Pt catalyst is a novel catalyst with a high precious atom efficiency and excellent catalytic hydrogenation ability and selectivity.

Key words: Platinum, MgAl₂O₄ spinel, Single-atom catalyst, Selective hydrogenation, Benzaldehyde, Benzyl alcohol

鄢峰, 赵才贤, 易兰花, 张景才, 葛炳辉, 张涛, 李为臻. Pt在MgAl₂O₄载体上的分散程度对催化苯甲醛加氢反应影响[J]. 催化学报, 2017, 38(9): 1613-1620.

Feng Yan, Caixian Zhao, Lanhua Yi, Jingcai Zhang, Binghui Ge, Tao Zhang, Weizhen Li. Effect of the degree of dispersion of Pt over MgAl₂O₄ on the catalytic hydrogenation of benzaldehyde[J]. Chinese Journal of Catalysis, 2017, 38(9): 1613-1620.

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Pt在MgAl₂O₄载体上的分散程度对催化苯甲醛加氢反应影响

Effect of the degree of dispersion of Pt over MgAl₂O₄ on the catalytic hydrogenation of benzaldehyde

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