CIESC Journal ›› 2020, Vol. 71 ›› Issue (10): 4800-4807.doi: 10.11949/0438-1157.20200680

• Material science and engineering, nanotechnology • Previous Articles     Next Articles

Synthesis of ruthenium-embedded nitrogen-doped graphene for carbon dioxide hydrogenation

Lu LI1,2(),Linghui LIU1,3(),Jinming XU1(),Yanqiang HUANG1,Tao ZHANG1   

  1. 1.Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
    2.College of Chemistry and Chemical Engineering, Yantai University, Yantai 264005, Shandong, China
    3.School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044, China
  • Received:2020-06-02 Revised:2020-07-20 Online:2020-10-05 Published:2020-08-15
  • Contact: Jinming XU E-mail:1562607571@qq.com;lhliu@dicp.ac.cn;xujm@dicp.ac.cn

Abstract:

Two-dimensional (2D) layered materials have attracted great interest in the energy storage and catalysis field due to their graphene-like structure and excellent performance. Ruthenium-embedded nitrogen-doped graphene (Ru-NG) have been obtained by a novel method, using montmorillonite as hard template and Ru-phenanthroline chelate as precursor. After calcination in N2 atmosphere at 800℃, Ru-NG were obtained and further characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and nitrogen sorption. Ru-NG have 2D layered structure just like the montmorillonite template, and C, N, O and Ru are homogeneously distributed on them. The average sizes of Ru nanoparticles do not change much with the increasing of Ru content, and they keep at about 1.2 to 1.4 nm. The XPS results indicate that phenanthroline has been successfully transformed to nitrogen-doped carbon during pyrolysis, and the peaks at 398.5, 400.1 and 401.5 eV suggest the presence of pyridine-like, pyrrole-like and quaternary nitrogen atoms, respectively. Compared with the Ru catalyst supported on activated carbon prepared by the traditional impregnation-reduction method, Ru-NG exhibits excellent catalytic activity in the reaction of hydrogenation of carbon dioxide to formic acid.

Key words: catalyst, carbon dioxide, hydrogenation, hard template method, composites, graphene

CLC Number: 

  • TQ 032.4

Table 1

Synthesis conditions of Ru-NG catalysts with different Ruthenium loadings"

PMIM 质量/ g9.5%氯化钌溶液质量/gRu 含量/%(mass)
3.60.2151.4
3.60.4302.1
3.60.6452.4
3.60.8603.5

Fig.1

XRD patterns and SEM images of Ru-NG catalysts"

Fig.2

Raman spectra of Ru-NG catalysts"

Table 2

Raman spectral parameters of Ru-NG catalysts"

样品D峰G峰R=ID/IG
峰位置/cm-1半峰宽峰位置/cm-1半峰宽
1.4% Ru-NG1378301.71589103.83.01
2.1% Ru-NG1372351.6159186.43.53
2.4% Ru-NG13752931591100.23.01
3.5% Ru-NG13813051585100.62.99

Fig.3

STEM and EDX maps of Ru-NG catlysts"

Fig.4

XPS survey spectra (a) and XPS spectra of N1s peaks (b) of Ru-NG catalysts"

Table 3

Specific surface area and pore volume of Ru-NG catalysts"

样品BET比表面积/(m2/g)孔容/ (cm3/g)
1.4%Ru-NG416.90.26
2.1%Ru-NG397.30.25
2.4%Ru-NG365.00.22

Table 4

Hydrogenation of carbon dioxide to formate with Ru-NG catalysts"

催化剂AAR转换数(TON)
1.4% Ru-NG0.192587
2.4% Ru-NG0.352374
3.5% Ru-NG0.331738
2.5% Ru/AC0.015124

Fig.5

Effects of temperature and pressure on the TON of CO2 over 2.4%Ru-NG"

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