Ru@Al<italic style="font-style: italic"><sub>x</sub></italic>-mSiO<sub>2</sub>中空介孔核壳型催化剂苯酚加氢脱氧制苯性能研究

钟梦宇; 于洪波; 周永柱; 尹宏峰

doi:10.12434/j.issn.2097-2547.20240119

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Ru@Al_x-mSiO₂中空介孔核壳型催化剂苯酚加氢脱氧制苯性能研究

低碳分子转化合成

- Ru@Al_x-mSiO₂中空介孔核壳型催化剂苯酚加氢脱氧制苯性能研究
- Study on performances of Ru@Al_x-mSiO₂ hollow mesoporous core-shell catalysts for phenol hydrodeoxygenation to benzene
- 低碳化学与化工 2024, 49(11): 43-49.
- 作者机构：
  
  1.天津城建大学理学院，天津 300384
  2.中国科学院宁波材料技术与工程研究所，浙江宁波 315201
  3.宁波工程学院材料与化学工程学院，浙江宁波 315211
- 作者简介：
  
  钟梦宇（1998—），硕士研究生，研究方向为纳米催化，E-mail：Zhongmengyu@nimte.ac.cn。
  于洪波（1984—），博士，副研究员，研究方向为纳米催化，E-mail：hongboyu@nbut.edu.cn；
  周永柱（1983—），博士，高级实验师，研究方向为有机化工，E-mail：yzzhou2011@163.com；
  尹宏峰（1977—），博士，研究员，研究方向为工业催化，E-mail：yinhf@nimte.ac.cn。
- 基金信息：
  
  国家自然科学基金(22072171);天津市教委科研计划项目(2017KJ064)
- DOI：10.12434/j.issn.2097-2547.20240119
  中图分类号： TQ426
- 纸质出版日期：2024-11-25，
  
  收稿日期：2024-03-23，
  
  修回日期：2024-04-20，
- 稿件说明：
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钟梦宇,于洪波,周永柱等.Ru@Al_x-mSiO₂中空介孔核壳型催化剂苯酚加氢脱氧制苯性能研究[J].低碳化学与化工,2024,49(11):43-49.

ZHONG Mengyu,YU Hongbo,ZHOU Yongzhu,et al.Study on performances of Ru@Al_x-mSiO₂ hollow mesoporous core-shell catalysts for phenol hydrodeoxygenation to benzene[J].Low-carbon Chemistry and Chemical Engineering,2024,49(11):43-49.
钟梦宇,于洪波,周永柱等.Ru@Al_x-mSiO₂中空介孔核壳型催化剂苯酚加氢脱氧制苯性能研究[J].低碳化学与化工,2024,49(11):43-49. DOI： 10.12434/j.issn.2097-2547.20240119.

ZHONG Mengyu,YU Hongbo,ZHOU Yongzhu,et al.Study on performances of Ru@Al_x-mSiO₂ hollow mesoporous core-shell catalysts for phenol hydrodeoxygenation to benzene[J].Low-carbon Chemistry and Chemical Engineering,2024,49(11):43-49. DOI： 10.12434/j.issn.2097-2547.20240119.

摘要

为解决负载型Ru催化剂在酚类化合物加氢脱氧反应中稳定性差的问题，以含Ru的二氧化硅微球（Ru@SiO

）为前驱体、偏铝酸钠（NaAlO

）为铝源，在碱性条件下通过选择性蚀刻制备了一系列不同Al负载量（质量分数）的中空介孔核壳型催化剂Ru@Al

-mSiO

（

= 0.5、1.0、1.5或2.0）。采用TEM、HAADF-STEM、XRD、N

吸/脱附、NH

-TPD和H

-TPD等对催化剂的微观结构和理化性质进行了表征。以苯酚加氢脱氧制备苯为模型反应，考察了Ru@Al

-mSiO

催化剂的催化性能。结果表明，在60 ℃、2.0 MPa的反应条件下，向Ru@mSiO

中引入Al能显著提高苯选择性，这是因为Al的负载提供了丰富的酸性位点，其不仅可以辅助金属Ru解离H

增加苯酚加氢活性，还能够增强苯酚的脱氧性能进而提高苯选择性。在所有催化剂中，Ru@Al

1.0

-mSiO

展现出了最高的苯酚转化率（80.5%）和苯选择性（96.5%），这归因于金属Ru与硅铝酸盐壳层间的协同效应。此外，由于中空介孔硅铝酸盐壳层的限域保护作用，Ru@Al

1.0

-mSiO

催化剂在多次催化循环加氢脱氧实验后，仍展现出了优异的稳定性。

Abstract

In order to address the issue of poor stability of loaded Ru catalysts in the hydrodeoxygenation reaction of phenolic compounds

a series of hollow mesoporous core-shell catalysts

Ru@Al

-mSiO

(

= 0.5

1.0

1.5 or 2.0)

with varying Al loadings (mass fractions) were prepared by selective etching under alkaline conditions with Ru-containing silica microspheres (Ru@SiO

) as the precursor and sodium meta-aluminate (NaAlO

) as the aluminum source. The microstructures and physicochemical properties of the catalysts were characterized by TEM

HAADF-STEM

XRD

adsorption/desorption

-TPD and H

-TPD. The catalytic performances of Ru@Al

-mSiO

catalysts were investigated using phenol hydrodeoxygenation to prepare benzene as a model reaction. The results show that the incorporation of Al into Ru@mSiO

under the reaction conditions of 60 ℃ and 2.0 MPa can significantly improve the selectivity of benzene. This is attributed to the fact that the Al loading provideds abundant acidic si

tes

which can not only assist the dissociation of H

from the metal Ru to increase the phenol hydrogenation activity

but also enhance the deoxygenation of phenol and thus improve the benzene selectivity. Among all the catalysts

Ru@Al

1.0

-mSiO

exhibits the highest phenol conversion (80.5%) and benzene selectivity (96.5%)

which is attributed to the synergistic effect between the Ru metal and the silicoaluminate shell layer. Furthermore

the hollow mesoporous silica-aluminate shell layer exhibites a domain-limiting protective effect

and Ru@Al

1.0

-mSiO

still exhibits excellent stability in multiple catalytic cycle hydrodeoxygenation experiments.

关键词

酚类化合物Ru基核壳型催化剂苯酚加氢脱氧苯

Keywords

phenolic compoundRu-based core-shell catalystsphenolhydrodeoxygenationbenzene

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Ru@Alx-mSiO2中空介孔核壳型催化剂苯酚加氢脱氧制苯性能研究

Study on performances of Ru@Alx-mSiO2 hollow mesoporous core-shell catalysts for phenol hydrodeoxygenation to benzene

DOI：10.12434/j.issn.2097-2547.20240119

摘要

Abstract

关键词

Keywords

references

Ru@Al_x-mSiO₂中空介孔核壳型催化剂苯酚加氢脱氧制苯性能研究

Study on performances of Ru@Al_x-mSiO₂ hollow mesoporous core-shell catalysts for phenol hydrodeoxygenation to benzene