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

doi:10.7503/cjcu20170844

Abstract

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

CLC Number:

O643.3

TrendMD:

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

Figures/Tables 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

References 41

[1]	Blaser H.U., Science, 2006, 313(5785), 312—313
[2]	Meng X.C., Cheng H. Y., Akiyama Y., Hao Y. F., Qiao W. B., Yu Y. C., Zhao F. Y., Fujita S. I., Arai M., J. Catal., 2009, 264(1), 1—10
[3]	Li C.H., Yu Z. X., Yao K. F., Ji S. F., Liang J., J. Mol. Catal. A, 2005, 226(1), 101—105
[4]	Nie R.F., Wang J. H., Wang L. N., Qin Y., Chen P., Hou Z. Y., Carbon, 2012, 50(2), 586—596
[5]	Gelder E.A., Jackson S. D., Lok C. M, Catal. Lett., 2002, 84(3/4), 205—208
[6]	Chary K.V. R., Srikanth C. S., Catal. Lett., 2008, 128(1/2), 164—170
[7]	Corma A., Concepcion P., Serna P., Angew. Chem. Int.Ed., 2007, 46(38), 7266—7269
[8]	Burge H.D., Collins D. J., Davis B. H, Ind. Eng. Chem. Prod. Res. Dev., 1980, 19(3), 389—391
[9]	Li H.X., Zhao Q. F., Wan Y., Dai W. L., Qiao M. H., J. Catal., 2006, 244(2), 251—254
[10]	Wang J.H., Yuan Z. L., Nie R. F., Hou Z. Y., Zheng X. M, Ind. Eng. Chem. Res., 2010, 49(10), 4664—4669
[11]	Jagadeesh R.V., Wienhoefer G., Westerhaus F. A., Surkus A. E., Pohl M. M., Junge H., Junge K., Beller M, Chem. Commun., 2011, 47(39), 10972—10974
[12]	Schlogl R., Angew. Chem. Int.Ed., 2003, 42(18), 2004—2008
[13]	Kandemir T., Schuster M.E., Senyshyn A., Behrens M., Schloegl R, Angew. Chem. Int. Ed., 2013, 52(48), 12723—12726
[14]	Vojvodic A., Medford A.J., Studt F., Abild-Pedersen F., Khan T. S., Bligaard T., Norskov J. K, Chem. Phys. Lett., 2014, 598, 108—112
[15]	Galvis H.M. T., Bitter J. H., Khare C. B., Ruitenbeek M., Dugulan A. I., de Jong K. P., Science, 2012, 335(6070), 835—838
[16]	Koeken A.C. J., Galvis H. M. T., Davidian T., Ruitenbeek M., de Jong K. P, Angew. Chem. Int. Ed., 2012, 51(29), 7190—7193
[17]	Schulz H., Catal. Today, 2013, 214, 140—151
[18]	Jacobs G., Ma W.P., Gao P., Todic B., Bhatelia T., Bukur D. B., Davis B. H., Catal. Today, 2013, 214, 100—139
[19]	Qi G.S., Yang R. T., Appl. Catal. B, 2003, 44(3), 217—225
[20]	Guo X.G., Fang G. Z., Li G., Ma H., Fan H. J., Yu L., Ma C., Wu X., Deng D. H., Wei M. M., Tan D. L., Si R., Zhang S., Li J. Q., Sun L. T., Tang Z. C., Pan X. L., Bao X. H., Science, 2014, 344(6184), 616—619
[21]	Lefevre M., Proietti E., Jaouen F., Dodelet J.P., Science, 2009, 324(5923), 71—74
[22]	Jagadeesh R.V., Surkus A. E., Junge H., Pohl M. M., Radnik J., Rabeah J., Huan H., Schunemann V., Bruckner A., Beller M., Science, 2013, 342(6162), 1073—1076
[23]	Shi J.J., Wang Y. Y., Du W. C., Hou Z. Y., Carbon, 2016, 99, 330—337
[24]	Du W.C., Xia S. X., Nie R. F., Hou Z. Y, Ind. Eng. Chem. Res., 2014, 53(12), 4589—4594
[25]	Nie R.F., Shi J. J., Du W. C., Ning W. S., Hou Z. Y., Xiao F. S., J. Mater. Chem. A, 2013, 1(32), 9037—9045
[26]	Zeng X.Y., You C. H., Leng L. M., Dang D., Qiao X. C., Li X. H., Li Y. W., Liao S. J., Adzic R. R., J. Mater. Chem. A, 2015, 3(21), 11224—11231
[27]	Chen J.L., Yan X. P., J. Mater. Chem., 2010, 20(21), 4328—4332
[28]	Shi J.J., Zhao M. S., Wang Y. Y., Fu J., Lu X. Y., Hou Z. Y., J. Mater. Chem. A, 2016, 4(16), 5842—5848
[29]	Stankovich S., Dikin D.A., Piner R. D., Kohlhaas K. A., Kleinhammes A., Jia Y. Y., Wu Y., Nguyen S. T., Ruoff R. S., Carbon, 2007, 45(7), 1558—1565
[30]	Liu S., Wang J.Q., Zeng J., Ou J. F., Li Z. P., Liu X. H., Yang S. R., J. Power Sources, 2010, 195(15), 4628—4633
[31]	Liang Y.Y., Li Y. G., Wang H. L., Zhou J. G., Wang J., Regier T., Dai H. J., Nat. Mater., 2011, 10(10), 780—786
[32]	Gao Y.J., Hu G., Zhong J., Shi Z. J., Zhu Y. S., Su D. S., Wang J. G., Bao X. H., Ma D, Angew. Chem. Int. Ed., 2013, 52(7), 2109—2113
[33]	Wu Z.S., Winter A., Chen L., Sun Y., Turchanin A., Feng X. L., Müllen K, Adv. Mater., 2012, 24(37), 5130—5135
[34]	Chen P., Xiao T.Y., Qian Y. H., Li S. S., Yu S. H, Adv. Mater., 2013, 25(23), 3192—3196
[35]	Xiao M.L., Zhu J. B., Feng L. G., Liu C. P., Xing W, Adv. Mater., 2015, 27(15), 2521—2527
[36]	Hu Y., Jensen J.O., Zhang W., Martin S., Chenitz R., Pan C., Xing W., Bjerrum N. J., Li Q. F., J. Mater. Chem. A, 2015, 3(4), 1752—1760
[37]	Guo D.H., Shibuya R., Akiba C., Saji S., Kondo T., Nakamura J., Science, 2016, 351(6271), 361—365
[38]	Zhao Y., Watanabe K., Hashimoto K., J. Mater. Chem. A, 2013, 1(4), 1450—1456
[39]	Nie R., Miao M., Du W.C., Shi J. J., Liu Y. C., Hou Z. Y., Appl. Catal. B, 2016, 180, 607—613
[40]	Groves M.N., Chan A. S. W., Malardier-Jugroot C., Jugroot M, Chem. Phys. Lett., 2009, 481(4—6), 214—219
[41]	Kim H., Robertson A.W., Kim S. O., Kim J. M., Warner J. H., ACS Nano, 2015, 9(6), 5947—5957

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

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 16

References 41

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	WANG Ruina, SUN Ruifen, ZHONG Tianhua, CHI Yuwu. Fabrication of a Dispersible Large-sized Graphene Quantum Dot Assemblies from Graphene Oxide and Its Electrogenerated Chemiluminescence Behaviors [J]. Chem. J. Chinese Universities, 2022, 43(8): 20220161.
[2]	ZHANG Xinxin, XU Di, WANG Yanqiu, HONG Xinlin, LIU Guoliang, YANG Hengquan. Effect of Mn Promoter on CuFe-based Catalysts for CO₂ Hydrogenation to Higher Alcohols [J]. Chem. J. Chinese Universities, 2022, 43(7): 20220187.
[3]	ZHOU Zixuan, YANG Haiyan, SUN Yuhan, GAO Peng. Recent Progress in Heterogeneous Catalysts for the Hydrogenation of Carbon Dioxide to Methanol [J]. Chem. J. Chinese Universities, 2022, 43(7): 20220235.
[4]	DING Yang, WANG Wanhui, BAO Ming. Recent Progress in Porous Framework-immobilized Molecular Catalysts for CO₂Hydrogenation to Formic Acid [J]. Chem. J. Chinese Universities, 2022, 43(7): 20220309.
[5]	HUANG Xiaoshun, MA Haiying, LIU Shujuan, WANG Bin, WANG Hongli, QIAN Bo, CUI Xinjiang, SHI Feng. Recent Advances on Indirect Conversion of Carbon Dioxide to Chemicals [J]. Chem. J. Chinese Universities, 2022, 43(7): 20220222.
[6]	ZHOU Leilei, CHENG Haiyang, ZHAO Fengyu. Research Progress of CO₂ Hydrogenation over Pd-based Heterogeneous Catalysts [J]. Chem. J. Chinese Universities, 2022, 43(7): 20220279.
[7]	SONG Youwei, AN Jiangwei, WANG Zheng, WANG Xuhui, QUAN Yanhong, REN Jun, ZHAO Jinxian. Effects of Ag，Zn，Pd-doping on Catalytic Performance of Copper Catalyst for Selective Hydrogenation of Dimethyl Oxalate [J]. Chem. J. Chinese Universities, 2022, 43(6): 20210842.
[8]	YAN Jiasen, HAN Xianying, DANG Zhaohan, LI Jiangang, HE Xiangming. Preparation and Performance of Paraffin/Expanded Graphite/Graphene Composite Phase Change Heat Storage Material [J]. Chem. J. Chinese Universities, 2022, 43(6): 20220054.
[9]	CAO Lei, CHEN Meijun, YUAN Gang, CHANG Gang, ZHANG Xiuhua, WANG Shengfu, HE Hanping. Solution-gated Graphene Field Effect Transistor Sensor Based on Crown Ether Functionalization for the Detection of Mercury Ion [J]. Chem. J. Chinese Universities, 2022, 43(4): 20210688.
[10]	HU Huimin, CUI Jing, LIU Dandan, SONG Jiaxin, ZHANG Ning, FAN Xiaoqiang, ZHAO Zhen, KONG Lian, XIAO Xia, XIE Zean. Influence of Different Transition Metal Decoration on the Propane Dehydrogenation Performance over Pt/M-DMSN Catalysts [J]. Chem. J. Chinese Universities, 2022, 43(4): 20210815.
[11]	ZHENG Xuelian, YANG Cuicui, TIAN Weiquan. The Second Order Nonlinear Optical Properties of Azulene-defect Graphene Nanosheets with Full Armchair Edge [J]. Chem. J. Chinese Universities, 2022, 43(3): 20210806.
[12]	MENG Xiangyu, ZHAN Qi, WU Yanan, MA Xiaoshuang, JIANG Jingyi, SUN Yueming, DAI Yunqian. Photothermal Enhanced Photocatalytic Hydrogenation Performance of Au/RGO/Na₂Ti₃O₇ [J]. Chem. J. Chinese Universities, 2022, 43(3): 20210655.
[13]	YU Bin, CHEN Xiaoyan, ZHAO Yue, CHEN Weichang, XIAO Xinyan, LIU Haiyang. Graphene Oxide-based Cobalt Porphyrin Composites for Electrocatalytic Hydrogen Evolution Reaction [J]. Chem. J. Chinese Universities, 2022, 43(2): 20210549.
[14]	WANG Xueli, SONG Xiangwei, XIE Yanning, DU Niyang, WANG Zhenxin. Preparation， Characterization of Partially Reduced Graphene Oxide and Its Killing Effect on Human Cervical Cancer Cells [J]. Chem. J. Chinese Universities, 2022, 43(2): 20210595.
[15]	HU Bo, ZHU Haochen. Dielectric Constant of Confined Water in a Bilayer Graphene Oxide Nanosystem [J]. Chem. J. Chinese Universities, 2022, 43(2): 20210614.