负载钌的氮掺杂石墨烯催化剂的制备及应用

doi:10.11949/0438-1157.20200680

摘要/Abstract

摘要：

利用人工合成的蒙脱石做硬模板，以插层的邻菲罗啉-钌络合物为前体，在惰性气氛下热解后用氢氟酸和盐酸刻蚀除去蒙脱石模板制备出负载钌纳米粒子的氮掺杂石墨烯催化剂（Ru-NG）。Ru-NG具有与模板蒙脱石类似的层状石墨烯结构，C、N、O及Ru元素在其上分布均匀。Ru-NG中钌的含量随钌前体的加入量的增加而增加，但受蒙脱石片层的物理限域作用及与含氮物种的配位作用，钌纳米粒子的粒径却无显著变化，且粒径均一，平均粒径在1.2~1.4 nm范围内。与传统浸渍-还原法制备的活性炭负载的Ru催化剂相比，Ru-NG在二氧化碳加氢生成甲酸反应中表现出优异的催化活性。

关键词: 催化剂, 二氧化碳, 加氢, 硬模板法, 复合材料, 石墨烯

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

中图分类号:

TQ 032.4

李路, 刘灵惠, 徐金铭, 黄延强, 张涛. 负载钌的氮掺杂石墨烯催化剂的制备及应用[J]. 化工学报, 2020, 71(10): 4800-4807.

Lu LI, Linghui LIU, Jinming XU, Yanqiang HUANG, Tao ZHANG. Synthesis of ruthenium-embedded nitrogen-doped graphene for carbon dioxide hydrogenation[J]. CIESC Journal, 2020, 71(10): 4800-4807.

图/表 9

表1 不同钌负载量催化剂的制备参数

Table 1 Synthesis conditions of Ru-NG catalysts with different Ruthenium loadings

PMIM 质量/ g	9.5%氯化钌溶液质量/g	Ru 含量/%(mass)
3.6	0.215	1.4
3.6	0.430	2.1
3.6	0.645	2.4
3.6	0.860	3.5

图1 催化剂的XRD谱图与SEM图

Fig.1 XRD patterns and SEM images of Ru-NG catalysts

图2 Ru-NG 催化剂的拉曼图谱

Fig.2 Raman spectra of Ru-NG catalysts

表2 Ru-NG 催化剂的拉曼特征峰参数

Table 2 Raman spectral parameters of Ru-NG catalysts

样品	D峰		G峰		R=I_D/I_G
样品	峰位置/cm^-1	半峰宽	峰位置/cm^-1	半峰宽	R=I_D/I_G
1.4% Ru-NG	1378	301.7	1589	103.8	3.01
2.1% Ru-NG	1372	351.6	1591	86.4	3.53
2.4% Ru-NG	1375	293	1591	100.2	3.01
3.5% Ru-NG	1381	305	1585	100.6	2.99

图3 Ru-NG催化剂的扫描透射电镜与元素分布图

Fig.3 STEM and EDX maps of Ru-NG catlysts

图4 Ru-NG催化剂的XPS全谱和N1s拟合谱图

Fig.4 XPS survey spectra (a) and XPS spectra of N1s peaks (b) of Ru-NG catalysts

表3 Ru-NG催化剂的比表面积和孔容

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-NG	416.9	0.26
2.1%Ru-NG	397.3	0.25
2.4%Ru-NG	365.0	0.22

表4 Ru-NG催化剂的二氧化碳加氢制甲酸反应活性

Table 4 Hydrogenation of carbon dioxide to formate with Ru-NG catalysts

催化剂	AAR^①	转换数（TON）^②
1.4% Ru-NG	0.19	2587
2.4% Ru-NG	0.35	2374
3.5% Ru-NG	0.33	1738
2.5% Ru/AC	0.015	124

图5 温度与压力对CO2转换数（TON）的影响

Fig.5 Effects of temperature and pressure on the TON of CO2 over 2.4%Ru-NG

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