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Current Catalysis

Editor-in-Chief

ISSN (Print): 2211-5447
ISSN (Online): 2211-5455

Research Article

Synthesis of Cost-effective Trimetallic Oxide Nanocatalysts for the Reduction of Nitroarenes in Presence of NaBH4 in an Aqueous Medium

Author(s): Arnab Mukherjee, Mrinal K. Adak, Anirban Chowdhury and Debasis Dhak*

Volume 8, Issue 1, 2019

Page: [41 - 55] Pages: 15

DOI: 10.2174/2211544708666181129100631

Price: $65

Abstract

Background: To prevent the environmental pollution, the release of the carcinogenic reagents like nitroarenes, especially nitrobenzene must be reduced or to find a way to convert these hazardous materials into less harmful material. For the reduction of nitroarenes, various types of catalysts such as metal nanoparticles (mainly coinage and group VIII) and platinum group metals were used. The chemo/homo selectivity of the reduction of nitroarenes was tested mainly in an organic solvent medium.

Method: Trimetallic oxide nanocatalysts were prepared chemically and characterized via Thermogravimetric analysis (TGA), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Scanning electron microscope (SEM) and solid UV studies. A series of nitroarenes were subjected to get their amine analogues using the NaBH4 in an aqueous medium using the synthesized catalysts. The completion of the reduction process was confirmed by the spectroscopic analysis.

Results: The average crystallite of the trimetallic oxide nanocatalysts was found to be 14-32nm. The reductions were selective (homo/chemo) and kinetics followed the Lindemann-Hinshelwood pseudofirst order kinetics with the rate constant in the order of 10-3 s-1. Hydroxylamine intermediate was found to be formed in the reduction procedure.

Conclusion: The catalysts showed promising for the selectivity (homo/chemo). The reduction processes were less time consuming e.g. nitrobenzene took 10 mins and a series of nitroanilines required 35-40 s for the reduction. In short, the trimetallic nano-oxide catalysts possess fast reaction process, cost-effective, easy to handle, reusable and hence could be promising for industrial waste treatment.

Keywords: Nano-catalyst, heterogeneous catalysis, nitro compounds, homo/chemoselectivity, reaction mechanism, hydroxyl amine.

Graphical Abstract
[1]
Fountoulaki, S.; Daikopoulou, V.; Gkizis, P.L.; Tamiolakis, I.; Armatas, G.S.; Lykakis, I.N. Mechanistic studies of the reduction of nitroarenes by NaBH4 or hydrosilanes catalyzed by supported gold nanoparticles. ACS Catal., 2014, 4, 3504-3511.
[2]
Mu, Y.; Yu, H.Q.; Zheng, J.C.; Zhang, S.J.; Sheng, G.P. Reductive degradation of nitrobenzene in aqueous solution by zero-valent iron. Chemosphere, 2004, 54, 789-794.
[3]
van der Zee, F.P.; Lettinga, G.; Field, J.A. Azo dye decolourisation by anaerobic granular sludge. Chemosphere, 2001, 44, 1169-1176.
[4]
Nielsen, P.H.; Christensen, T.H. Variability of biological degradation of phenolic hydrocarbons in an aerobic aquifer determined by laboratory batch experiments. J. Contam. Hydrol., 1994, 17, 55-67.
[5]
Zolfigol, M.A.; Amani, K.; Ghorbani-Choghamarani, A.; Hajjami, M.; Ayazi-Nasrabadi, R.; Jafari, S. Catal. Commun., 2008, 9, 1739-1744.
[6]
Shi, F.; Tse, M.K.; Marga-Matina Pohl, A.; Brűckner, S.; Zhang, M. Beller. Tuning catalytic activity between homogeneous and heterogeneous catalysis: improved activity and selectivity of free nano-Fe2O3 in selective oxidations. Angew. Chem. Int. Ed., 2007, 46, 8866-8868.
[7]
Patil, R. D.; Sassona, Y. Chemoselective reduction of nitroarenes to aromatic amines with commercial metallic iron powder in water under mild reaction conditions. Org. Chem. Curr. Res. 2015.
[http://dx.doi.org/10.4172/2161-0401.1000154]
[8]
Feng, H.; Li, Y.; Lin, S.; Van der Eycken, E.V.; Song, G. Nano Cu-catalyzed efficient and selective reduction of nitroarenes under combined microwave and ultrasound irradiation. Sustain. Chem. Process, 2014, 2, 14.
[9]
Pradhan, N.; Pal, A.; Pal, T. Catalytic reduction of aromatic nitro compounds by coinage metal nanoparticles. Langmuir, 2001, 17, 1800-1802.
[10]
Saha, A.; Ranu, B.C. Highly chemoselective reduction of aromatic nitro compounds by copper nanoparticles/ammonium formate. J. Org. Chem., 2008, 73, 6867-6870.
[11]
Chen, W.; Zhang, Z.; Li, X.; Wu, D.; Xue, Y.; Li, L. Reducing DBPs formation in chlorination of Br-containing Diclofenac via Fe-Cu-MCM-41/O3 peroxidation: Efficiency, characterization DBPs precursors and mechanism. J. Taiwan Inst. Chem. Eng., 2018, 84, 101-109.
[12]
Rahaim, R.J.; Maleczka, R.E. Pd-Catalyzed silicon hydride reductions of aromatic and aliphatic nitro groups. Org. Lett., 2005, 7, 5087-5090.
[13]
Shil, A.K.; Das, P. Solid supported platinum (0) nanoparticles catalyzed chemo-selective reduction of nitroarenes to N-arylhydroxylamines. Green Chem., 2013, 15, 3421-3428.
[14]
Schabel, T.; Belger, C.; Plietker, B. A mild chemoselective ru-catalyzed reduction of alkynes, ketones, and nitro compounds. Org. Lett., 2013, 15, 2858-2861.
[15]
Shokouhimehr, M.; Kim, T.; Jun, S.W.; Shin, K.; Jang, Y.; Kim, B.H.; Kim, J.; Hyeon, T. Magnetically separable carbon nanocomposite catalysts for efficient nitroarene reduction and Suzuki reactions. Appl. Catal. A, 2014, 476, 133-139.
[16]
Shokouhimehr, M. Magnetically separable and sustainable nanostructured catalysts for heterogeneous reduction of nitroaromatics. Catalysts, 2015, 5, 534-560.
[17]
Dey, R.; Mukherjee, N.; Ahammed, S.; Ranu, B.C. Highly selective reduction of nitroarenes by iron(0) nanoparticles in water. Chem. Commun. , 2012, 48, 7982-7984.
[18]
de Noronha, R.G.; Romão, C.C.; Fernandes, A.C. Highly chemo- and regioselective reduction of aromatic nitro compounds using the system silane/oxo-rhenium complexes. J. Org. Chem., 2009, 74, 6960-6964.
[19]
Peng, Q.; Zhang, Y.; Shi, F.; Deng, Y. Fe2O3-supported nano-gold catalyzed one-pot synthesis of N-alkylated anilines from nitroarenesand alcohols. Chem. Commun. , 2011, 47, 6476-6478.
[20]
Liawa, B.J.; Chen, Y.Z. Catalysis of ultrafine Cu-B catalyst for hydrogenation of olefinic and carbonyl groups. Appl. Catal. A Gen., 2000, 196, 199-207.
[21]
Jung, K.; Joo, O. Preparation of Cu/ZnO/M2O3 (M = Al, Cr) catalyst to stabilize Cu/ZnO catalyst in methanol dehydrogenation. Catal. Lett., 2002, 84, 21-25.
[22]
Venugopal, A.; Palgunadi, J.; Jung, K.D.; Joo, O.S.; Shin, C. Cu–Zn–Cr2O3 catalysts for dimethyl ether synthesis: Structure and activity relationship. Catal. Lett., 2008, 123, 142.
[23]
Li, J.; Liu, C.; Liu, Y. Mater. J. Au/graphene hydrogel: Synthesis, characterization and its use for catalytic reduction of 4-nitrophenol. J. Mater. Chem., 2012, 22, 8426.
[24]
Goyal, A.; Bansal, S.; Singhal, S. Facile reduction of nitrophenols: Comparative catalytic efficiency of MFe2O4 (M = Ni, Cu, Zn) nano ferrites. Int. J. Hydrogen Energy, 2014, 39, 4895-4908.
[25]
Hosseini, S.A.; Niaei, A.; Salari, D.; Nabavi, S.R. Nanocrystalline AMn2O4 (A=Co, Ni, Cu) spinels for remediation of volatile organic compounds-synthesis, characterization and catalytic performance. Ceram. Int., 2012, 38, 1655-1661.
[26]
Dhak, D.; Pramanik, P. Particle size comparison of soft‐chemically prepared transition metal (Co, Ni, Cu, Zn) aluminate spinels. J. Am. Ceram. Soc., 2006, 89, 1014-1102.
[27]
Cho, C.M.; Noh, J.H.; Cho, I.; An, J.; Hong, K.S. Low‐temperature hydrothermal synthesis of pure BiFeO3 nanopowders using triethanolamine and their applications as visible‐light photocatalysts. J. Am. Ceram. Soc., 2008, 91, 3753-3755.
[28]
Tauc, J.; Grigorovici, R.; Vancu, A. Optical properties and electronic structure of amorphous germanium. Phys. Status Solidi, B , 1996, 15, 627-637.
[29]
Tsuchiya, H.; Fujimoto, S.; Chihara, O.; Shibata, T. Semiconductive behavior of passive films formed on pure Cr and Fe–Cr alloys in sulfuric acid solution. Electrochim. Acta, 2002, 47, 4357-4366.
[30]
Nassar, M.Y.; Ahmed, I.S.; Samir, I. A novel synthetic route for magnesium aluminate (MgAl2O4) nanoparticles using sol–gel auto combustion method and their photocatalytic properties. Spectrochim. Acta, 2014, 131, 329-334.
[31]
Onfroy, T.; Clet, G.; Houalla, M. Correlations between acidity, surface structure, and catalytic activity of niobium oxide supported on zirconia. J. Phys. Chem. B, 2005, 109, 14588-14594.
[32]
Gao, X.; Wachs, I.E.; Wong, M.S.Y.; Ying, J.Y. Structural and reactivity properties of Nb–MCM-41: Comparison with that of highly dispersed Nb2O5/SiO2 catalysts. J. Catal., 2001, 203, 18-24.
[33]
Olhero, S.M.; Ganesh, I.; Torres, P.M.C.; Ferreira, J.M.F. Surface passivation of MgAl2O4 spinel powder by chemisorbing H3PO4 for easy aqueous processing. Langmuir, 2008, 24, 9525-9530.
[34]
Puriwat, J.; Chaitree, W.; Suriye, K.; Dokjampa, S.; Praserthdam, P.; Panpranot, J. Elucidation of the basicity dependence of 1-butene isomerization on MgO/Mg(OH)2 catalysts. Catal. Commun., 2010, 12, 80-85.
[35]
Acharyya, S.S.; Ghosh, S.; Bal, R. Fabrication of three-dimensional (3D) raspberry-like copper chromite spinel catalyst in a facile hydrothermal route and its activity in selective hydroxylation of benzene to phenol. ACS Appl. Mater. Interfaces, 2014, 6, 14451-14459.
[36]
Bajaj, R.; Sharma, M.; Bahadur, D. Visible light-driven novel nanocomposite (BiVO4/CuCr2O4) for efficient degradation of organic dye. Dalton Trans., 2013, 42, 6736-6744.
[37]
Usoltseva, N.V.; Korobochkin, V.V.; Balmashnov, M.A.; Dolinina, A.S. Solution transformation of the products of AC electrochemical metal oxidation. Procedia Chem., 2015, 15, 84-89.
[38]
Ying, J.Y.; Benziger, J.B.; Gleiter, H. Photoacoustic infrared spectroscopy of nanoclusters Al2O3clusters and cluster-assembled solids. Phys. Rev. B , 1993, 48, 1830-1836.
[39]
Kannan, S.; Ferreira, J.M.F. Synthesis and thermal stability of hydroxyapatite−β-tricalcium phosphate composites with cosubstituted sodium, magnesium, and fluorine. Chem. Mater., 2006, 18, 198-203.
[40]
Dotzauer, D.M.; Bhattacharjee, S.; Wen, Y.; Bruening, M.L. Nanoparticle-containing membranes for the catalytic reduction of nitroaromatic compounds. Langmuir, 2009, 25, 1865-1871.
[41]
Shin, H. Huh, S. Au/Au@Polythiophene core/shell nanospheres for heterogeneous catalysis of nitroarenes. ACS Appl. Mater. Interfaces, 2012, 4, 6324-6331.
[42]
Zhang, F.; Liu, N.; Zhao, P.; Sun, J.; Wang, P.; Ding, W.; Liu, J.; Jin, J.; Ma, J. Gold on amine-functionalized magnetic nanoparticles: A novel and efficient catalyst for hydrogenation reactions. Appl. Surf. Sci., 2012, 263, 471-475.
[43]
Kozuch, S.; Martin, J.M.L. What makes for a bad catalytic cycle? A theoretical study on the suzuki−miyaura reaction within the energetic span model. ACS Catal., 2011, 1, 246-253.
[44]
Ye, W.; Yu, J.; Zhou, Y.; Gao, D.; Wang, D.; Wang, D.; Xue, D. Green synthesis of Pt–Au dendrimer-like nanoparticles supported on polydopamine-functionalized graphene and their high performance toward 4-nitrophenol reduction. Appl. Catal. B. Environ.,, 2016, 181, 371-378.
[45]
Ghosh, S.K.; Mandal, M.; Kundu, S.; Nath, S.; Pal, T. Bimetallic Pt–Ni nanoparticles can catalyze reduction of aromatic nitro compounds by sodium borohydride in aqueous solution. Appl. Catal. A, 2004, 268, 61-66.
[46]
Karaoğlu, E. özel, U.; Caner, C.; Baykal, A.; Summak, M.M.; Sözeri, H. Synthesis and characterization of NiFe2O4–Pd magnetically recyclable catalyst for hydrogenation reaction. Mater. Res. Bull., 2012, 47, 4316-4321.
[47]
Zhang, Y.; Yuan, X.; Wang, Y.; Chen, Y. One-pot photochemical synthesis of graphene composites uniformly deposited with silver nanoparticles and their high catalytic activity towards the reduction of 2-nitroaniline. J. Mater. Chem., 2012, 22, 7245-7251.
[49]
Feng, J.; Su, L.; Ma, Y.; Ren, C.; Guo, Q.; Chen, X. CuFe2O4 magnetic nanoparticles: A simple and efficient catalyst for the reduction of nitrophenol. Chem. Eng. J., 2013, 221, 16-24.
[50]
Kemp, W. Organic Spectroscopy, 3rd ed; , 1991, pp. 58-72.
[51]
Mukherjee, K.S.; Mukhopadhyay, B. Organic Spectroscopy through Solved Problems., New Central Book Agancy (P) Ltd,. 2015, 23-25.
[52]
Lan, H.; Wang, A.; Liu, R.; Liu, H.; Qu, J. Heterogeneous photo-Fenton degradation of acid red B over Fe2O3 supported on activated carbon fiber. J. Hazard. Mater., 2015, 285, 167-172.
[53]
Liang, H.; Chen, W.; Jiang, X.; Xu, X.; Xu, B.; Wang, Z. Synthesis of 2D hollow hematite microplatelets with tuneable porosity and their comparative photocatalytic activities. J. Mater. Chem. A ., 2014, 2, 4340-4346.
[54]
Corma, A.; Concepci, P.; Serna, P. A different reaction pathway for the reduction of aromatic nitro compounds on gold catalysts. Angew. Chem., 2007, 119, 7404-7407.

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