Fe2O3/rGO/N-rGO催化剂的制备及在硝基苯选择性加氢中的应用

doi:10.7503/cjcu20170844

摘要/Abstract

摘要：

以氧化石墨烯、苯胺及醋酸亚铁为原料, 采用可控的聚合-热解工艺制备了一种复合铁基催化剂. 表征结果表明, 高分散的氧化铁纳米颗粒(Fe₂O₃ NPs)被固载于石墨烯/氮杂石墨烯复合膜上; 通过改变热解温度, 可以得到一系列结构和形貌各异的催化剂(Fe₂O₃/rGO/N-rGO). 经过700 ℃热解得到的催化剂(Fe₂O₃/rGO/N-rGO-700)具有较大的比表面积、微孔-介孔复合孔道和高度分散的Fe₂O₃ NPs, 其在硝基苯选择性加氢反应中表现出优异的活性和稳定性.

关键词: 铁催化, 热解, 石墨烯, 氮杂石墨烯, 加氢

Abstract:

Iron-based catalysts exhibited excellent performance for ammonia synthesis, production of olefins(via Fischer-Tropsch synthesis), selective catalytic reduction of NO_x, and so on. It is of great significance to explore new applications and mechanisms of iron catalysis, which has attracted more attention for its abundance, low price, and nontoxicity. Herein, a convenient and stable iron oxide(Fe₂O₃)-based catalyst was prepared via the pyrolysis of graphene oxide, aniline and ferrous acetate at varied temperature(denoted as Fe₂O₃/rGO/N-rGO), in which active Fe₂O₃ nanoparticles(NPs) were supported on composite carbon films composed of reduced graphene oxide and nitrogen-reduced graphene oxide. The resulting Fe₂O₃/rGO/N-rGO composites were applied for the selective hydrogenation of nitrobenzene. It was found that Fe₂O₃/rGO/N-rGO-700 composite was highly active and stable for the direct selective hydrogenation of nitrobenzene to aniline under mild conditions, because of large surface area, micropore-mesopore compound channel and dispersed Fe₂ $O 3$ NPs. At the same time, it was found that the hydrogenation of NB performed mainly in a direct routine, which can depress the formation of those byproducts with high boiling points.

Key words: Iron catalysis, Pyrolysis, Graphene, Nitrogen-doped graphene, Hydrogenation

中图分类号:

O643.3

TrendMD:

王莹钰, 赵怀远, 侯昭胤. Fe₂O₃/rGO/N-rGO催化剂的制备及在硝基苯选择性加氢中的应用. 高等学校化学学报, 2018, 39(8): 1750.

WANG Yingyu, ZHAO Huaiyuan, HOU Zhaoyin. Synthesis of Fe₂O₃/rGO/N-rGO Catalyst and Its Application in Selective Hydrogenation of Nitrobenzene^†. Chem. J. Chinese Universities, 2018, 39(8): 1750.

图/表 16

Scheme 1 Reaction pathways for the hydrogenation of NB[10]

Scheme 2 Synthesis of Fe2O3/rGO/N-rGO composite

Fig.1 N2 adsorption-desorption isotherms(A) and pores size distributions(B, C) of Fe2O3/rGO/N-rGO-500(a), Fe2O3/rGO/N-rGO-600(b), Fe2O3/rGO/N-rGO-700(c) and Fe2O3/rGO/N-rGO-900(d)Profile (C) is the enlarged part of profile (B).

Table 1 Structures of Fe2O3/rGO/N-rGO catalysts

Sample	Pore volume/(cm³·g^-1)		Pore size/nm		S_BET/(m²·g^-1)
Sample	Micropore	Mesopore	Micropore	Mesopore	S_BET/(m²·g^-1)
Fe₂O₃/rGO/N-rGO-500	—	0.171	—	3.66	179.9
Fe₂O₃/rGO/N-rGO-600	—	0.171	—	3.93	199.1
Fe₂O₃/rGO/N-rGO-700	0.119	0.177	0.71	3.92	324.3
Fe₂O₃/rGO/N-rGO-900	0.089	0.081	0.80,1.74	3.93	174.4

Fig.2 Raman spectra of GO(a), Fe2O3/rGO/N-rGO-500(b), Fe2O3/rGO/N-rGO-600(c), Fe2O3/rGO/N-rGO-700(d) and Fe2O3/rGO/N-rGO-900(e)

Table 2 Raman analysis results of different catalysts

No.	Sample	Raman analysis
No.	Sample	I_D/I_G	I_2D/I_G
1	GO	0.92	0.26
2	Fe₂O₃/rGO/N-rGO-500	1.02	0.13
3	Fe₂O₃/rGO/N-rGO-600	0.95	0.19
4	Fe₂O₃/rGO/N-rGO-700	0.95	0.21
5	Fe₂O₃/rGO/N-rGO-900	0.94	0.16

Fig.3 XRD patterns of N-free catalyst(a), Fe-free catalyst(b), Fe2O3/rGO/N-rGO-500(c), Fe2O3/ rGO/N-rGO-600(d), Fe2O3/rGO/N-rGO-700(e) and Fe2O3/rGO/N-rGO-900(f)

Fig.4 SEM(A) and TEM(B, C) images of Fe2O3/rGO/N-rGO-500 catalyst

Fig.6 SEM(A) and TEM(B, C) images of Fe2O3/rGO/N-rGO-900 catalyst

Fig.5 SEM(A) and TEM(B, C) images of Fe2O3/rGO/N-rGO-700 catalyst

Fig.7 XPS spectra of elemental analysis in survey(A) and N1s(B) and percentage of nitrogen species(C) of Fe2O3/rGO/N-rGO-500(a), Fe2O3/rGO/N-rGO-600(b), Fe2O3/rGO/N-rGO-700(c) and Fe2O3/rGO/N-rGO-900(d)

Table 3 Surface composition of Fe2O3/rGO/N-rGO catalysts*

Sample	Relative molar percentage(%)				Relative elemental percentage(%)
Sample	C	O	N	Fe	Pyridinic N	Pyrrolic N	Graphitic N
Fe₂O₃/rGO/N-rGO-500	84.55	7.61	7.83	0.01	32.5	45.8	21.7
Fe₂O₃/rGO/N-rGO-600	84.75	7.34	7.81	0.10	31.1	45.0	23.9
Fe₂O₃/rGO/N-rGO-700	85.53	7.00	7.30	0.17	27.2	40.8	32.0
Fe₂O₃/rGO/N-rGO-900	90.18	6.18	3.52	0.12	23.5	29.4	47.1

Table 4 Hydrogenation of nitrobenzene over different catalystsa

No.	Sample	Conversion(%)	Selectivity(%)
No.	Sample	Conversion(%)	AN	Others^b
1	Fe₂O₃/rGO/N-rGO-500	71.4	82.3	17.7
2	Fe₂O₃/rGO/N-rGO-600	76.7	86.4	13.6
3	Fe₂O₃/rGO/N-rGO-700	86.5	90.2	9.8
4	Fe₂O₃/rGO/N-rGO-900	72.4	82.8	17.2
5	Fe₃O₄@MgO	29.8	75.7	24.3
6	Fe₃O₄@SiO₂	33.9	81.5	18.5
7	Fe₃O₄@Al₂O₃	41.5	85.0	15.0
8	Fe₃O₄@AC	44.0	91.1	9.9
9	N-free catalyst	42.6	88.8	11.2
10	Fe-free catalyst	27.8	86.4	13.6
11	GO	16.4	76.8	23.2

Fig.8 Recycle experiment over Fe2O3/rGO/N-rGO-700 catalystReaction conditions: 0.25 mmol nitrobenzene in 8.0 mL ethanol, initial n(Fe)=10 μmol, 120 ℃, p(H2)=2.0 MPa, 4.0 h.

Fig.9 Time-on-stream of NB hydrogenation over Fe2O3/rGO/N-rGO-700 catalysta. Conversion of NB; b. selectivity to AN; c. selectivity to NSB; d. selectivity to PHA. Reaction conditions: 0.25 mmol nitrobenzene in 8.0 mL ethanol, initial n(Fe)=10 μmol, 120 ℃, p(H2)=2.0 MPa.

Scheme 3 Proposed reaction pathway for the hydrogenation of NB over Fe2O3/rGO/N-rGO-700 catalyst

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Fe₂O₃/rGO/N-rGO催化剂的制备及在硝基苯选择性加氢中的应用

Synthesis of Fe₂O₃/rGO/N-rGO Catalyst and Its Application in Selective Hydrogenation of Nitrobenzene^†

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