石墨烯负载镍催化CO2加氢甲烷化

doi:10.7503/cjcu20170348

摘要/Abstract

摘要：

采用改进的Hummers法制备了氧化石墨烯(GO), 经水合肼还原得到石墨烯(RGO), 通过浸渍法制备了石墨烯负载的镍基催化剂(Ni/RGO); 对其催化二氧化碳甲烷化反应的性能进行了研究, 并与以碳纳米管(CNTs)和活性炭(AC)为载体负载的Ni基催化剂进行了比较. 由于催化剂的载体分别为RGO, CNTs和AC, 所以Ni将会表现出不同的形态. 利用红外光谱(FTIR)、比表面积(BET)测试、程序升温还原(H₂-TPR)、 X射线衍射(XRD)分析和透射电子显微镜(TEM)等表征手段对其结构及物理性质进行了表征. 结果表明, Ni/RGO具有相对较大的比表面积(316 m²/g), Ni在Ni/RGO上的颗粒尺寸(5.3 nm)小于其在Ni/CNTs(8.9 nm)和Ni/AC(11.6 nm)上的颗粒尺寸; 该催化剂在二氧化碳甲烷化反应中具有更高的催化活性和选择性, 而且具有良好的使用寿命.

关键词: 石墨烯, 碳纳米管, 活性炭, CO2加氢, 镍催化剂

Abstract:

Graphene oxide(GO) was prepared from purified natural graphite via the modified Hummers method, and hydrazine hydrate reduced graphene oxide supported nickel catalysts were prepared via impregnation method. The influence of different supports of Ni-based catalysts for the carbon dioxide methanation reaction was investigated. Using reduced graphene oxide(RGO), carbon nanotubes(CNTs) and activated carbon(AC) as supports, nickel catalysts with different morphologies were formed. The prepared samples were characterized by FTIR, BET, H₂-TPR, XRD and TEM techniques and applied in carbon dioxide methanation. The results reveal that Ni/RGO has a relative large specific surface area(316 m²/g). The particle size of nickel on Ni/RGO(5.3 nm) is smaller than that on Ni/CNTs(8.9 nm) and Ni/AC(11.6 nm). Ni/RGO shows better catalytic activity and selectivity of carbon dioxide methanation reaction than that on Ni/CNTs and Ni/AC. Ni/RGO catalyst has a remarkable stability.

Key words: Graphene, Carbon nanotubes, Activated carbon, CO2 methanation, Ni catalyst

中图分类号:

O643.3

TrendMD:

张荣斌, 仝塞, 杨金美, 唐纤秾, 黄传庆, 王学文, 冯刚, 蔡建信. 石墨烯负载镍催化CO₂加氢甲烷化. 高等学校化学学报, 2017, 38(12): 2255.

ZHANG Rongbin, TONG Sai, YANG Jinmei, TANG Xiannong, HUANG Chuanqing, WANG Xuewen, FENG Gang, CAI Jianxin. Graphene Supported Nickel Catalyst for Methanation of Carbon Dioxide^†. Chem. J. Chinese Universities, 2017, 38(12): 2255.

图/表 9

Fig.1 FTIR spectra of the supports a. GO; b. CNTs; c. AC; d. RGO.

Fig.2 N2 adsorption-desorption isotherms of the CNTs (A), RGO (B) and AC (C)

Table 1 Specific surface area, interlayer distance and NiO crystallite size of the samples

Sample	S_BET/(m²·g^-1)	2θ/(°)	Interlayer distance^a/nm	Crystallite size/nm
Sample	S_BET/(m²·g^-1)	2θ/(°)	Interlayer distance^a/nm	NiO^b	Ni^c
GO	60	11	0.81
RGO	463	24	0.37
Ni/RGO	316	24.9	0.35	4.1	5.3
CNTs	334	26
Ni/CNTs	149	26		4.0	8.9
AC	868.6	23.7
Ni/AC	739	24.8		6.1	11.6

Fig.3 XRD patterns of pure supports(A), fresh catalysts(B) and after reduction catalysts(C)

Fig.4 TEM images of RGO(A), Ni/RGO(B), Ni/CNTs(C) and Ni/AC(D), the SEM image of RGO(E) and the particle diameter distribution of Ni/RGO(F), Ni/CNTs(G) and Ni/AC(H)

Fig.5 H2-TPR profiles of Ni/AC(a), Ni/CNTs(b) and Ni/RGO(c)

Fig.6 Effects of reaction temperature on CO2 conversion(A), CH4 selectivity(B),CH4 yield(C) over Ni/AC(a), Ni/CNTs(b) and Ni/RGO(c)

Table 2 Comparison of catalytic performance of Ni/AC, Ni/CNTs and Ni/RGO in methanation reaction

Sample	$X C O 2$ (%)	Ni particle size^a/nm	TO $F C O 2 b$ /s^-1	Ni dispersion^c(%)
Ni/RGO	23.7	5.3	0.0659	18.9
Ni/CNTs	13.5	8.9	0.0630	11.2
Ni/AC	7.8	11.6	0.0474	8.6

Table 2 Comparison of catalytic performance of Ni/AC, Ni/CNTs and Ni/RGO in methanation reaction

Sample	$X C O 2$ (%)	Ni particle size^a/nm	TO $F C O 2 b$ /s^-1	Ni dispersion^c(%)
Ni/RGO	23.7	5.3	0.0659	18.9
Ni/CNTs	13.5	8.9	0.0630	11.2
Ni/AC	7.8	11.6	0.0474	8.6

Fig.7 Stable testing of Ni/AC(a), Ni/CNTs(b)and Ni/RGO(c)Reaction conditions: 50 mg catalyst, 400 ℃, 30 mL/min.

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石墨烯负载镍催化CO₂加氢甲烷化

Graphene Supported Nickel Catalyst for Methanation of Carbon Dioxide^†

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