Metal-Free Graphene Quantum Dots Catalyzed Reduction of Aromatic Nitro Compounds in the Presence of LED Light

Document Type : Research Article

Authors

Department of Chemistry, Institute for Advanced Studies in Basic Sciences (IASBS), P.O. Box 45137-6731 Zanjan, I.R. IRAN

Abstract

In this study, for the first time, Graphene Quantum Dots (QGD) was used as a green catalyst for the reduction of aromatic nitro compounds under the Light-Emitting Diode (LED) and metal-free conditions. Prepared graphene quantum dots were characterized using different techniques such as Transmission Electron Microscopy (TEM), X-ray Photoelectron Spectroscopy (XPS), and absorption and emission spectroscopy. Using graphene quantum dots, structurally different aromatic nitro compounds were reduced to corresponding amines at room temperature and gave corresponding amines at high to excellent yields. Finally, the kinetic reduction reaction of different substitutions nitrobenzene (ortho, meta, and para) and the effect of substitution on rate were studied.

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[1] Bacon M., Bradley S.J., Nann, T., Graphene quantum dots. Particle & Particle Systems Characterization,Part. Part. Syst. Charact., 31(4): 415-428 (2014).
[2] Shen J., Zhu Y., Yang X., Li, C., Graphene quantum dots: emergent nanolights for bioimaging, sensors, catalysis and photovoltaic devices, Chem. Commun., 48(31): 3686-3699 (2012).
[3] Li L., Wu G., Yang, G., Peng, J., Zhao, J., Zhu, J.J., Focusing on luminescent graphene quantum dots: current status and future perspectives, Nanoscale, 5(10): 4015-4039 (2013).
[4] Gholinejad M., Ahmadi J., Nájera C., Seyedhamzeh M., Zareh F.,Kompany‐Zareh, M., Graphene Quantum Dot Modified Fe3O4 Nanoparticles Stabilize PdCu Nanoparticles for Enhanced Catalytic Activity in the Sonogashira Reaction. Chem. Cat. Chem., 9(8): 1442-1449 (2017).
[5] Kadam H.K., Tilve, S.G., Advancement in methodologies for reduction of nitroarenes. RSC Adv., 5(101): 83391-83407 (2015).
[7] Zeynizadeh B.,Zabihzadeh, M., Rapid and green reduction of aromatic/aliphatic nitro compounds to amines with NaBH4 and additive Ni2B in H2O. J. Iran. Chem. Soc., 12(7): 1221-1226 (2015).
[8] Corma A., Serna P., Preparation of substituted anilines from nitro compounds by using supported gold catalysts. Nat. Protoc., 1(6): 2590-2595 (2006).
[9] Wang J., Yuan Z., Nie R., Hou Z., Zheng  X., Hydrogenation of nitrobenzene to aniline over silica gel supported nickel catalysts. Ind. Eng. Chem. Res., 49(10): 4664-4669 (2010).
[10] Kantam M.L., Chakravarti R., Pal U., Sreedhar B.,  Bhargava, S., Nanocrystalline Magnesium Oxide‐Stabilized Palladium (0): An Efficient and Reusable Catalyst for Selective Reduction of Nitro Compounds. Adv. Synth. Catal. , 350(6): 822-827 (2008).
[11] Zeynizadeh B., Zabihzadeh M., Shokri Z., Cu nanoparticles: a highly efficient non-noble metal catalyst for rapid reduction of nitro compounds to amines with NaBH4 in water. J. Iran. Chem. Soc., 13(8): 1487-1492 (2016).
[12] Orlandi M., Tosi F., Bonsignore M., Benaglia, M., Metal-Free Reduction of Aromatic and Aliphatic Nitro Compounds to Amines: A HSiCl3-Mediated Reaction of Wide General Applicability. Org. Lett., 17(16): 3941-3943 (2015).
[14] Maki Y., Sugiyama H., KikuchiK., Seto, S., THIOL-ACTIVATED SODIUM BOROHYDRIDE REDUCTION OF NITRO COMPOUNDS. Chem. Lett., 4(10): 1093-1094 (1975).
[16] Park, K.K., Oh, C.H. and Sim, W.J., 1995. Chemoselective reduction of nitroarenes and nitroalkanes by sodium dithionite using octylviologen as an electron transfer catalyst. J. Org. Chem., 60(19): 6202-6204 (1995).
[17] Ma C.B., Zhu Z.T., Wang H.X., Huang X., Zhang X., Qi X., Zhang H.L., Zhu Y., Deng X., Peng Y., Han, Y., A general solid-state synthesis of chemically-doped fluorescent graphene quantum dots for bioimaging and optoelectronic applications. Nanoscale, 7(22): 10162-10169 (2015).
[18] Shchukarev, A.,Korolkov, D., XPS study of group IA carbonates. Open Chem., 2(2):347-362 (2004).
[20] Zolfigol, M. A., Amani K., Ghorbani-Choghamarani A., Hajjami M., Ayazi-Nasrabadi R., Jafari S. Chemo and homoselective catalytic oxidation of sulfides to sulfoxides with supported nitric acid on silica gel and poly vinyl pyrrolidone (PVP) catalyzed by KBr and/or NaBr. Catal. Commun. 9(8) :1739-1744 (2008)
[21] Hasaninejad A., Chehardoli G., Zolfigol M. A.,  Abdoli A. Uronium Hydrogen Sulfate/Urea- Hydrogen Peroxide as a Green and Metal- Free Catalytic System for the Efficient, Chemo-, and Homoselective Oxidation of Sulfides to Sulfoxides. Phosphorus, Sulfur, and Silicon, 186 (2): 271–280, (2011).
[22] Amani K., Zolfigol M. A.,  Ghorbani-Choghamarani A., Hajjami M. Ferric nitrate in the presence of catalytic amounts of KBr or NaBr: an efficient and homoselective catalytic media for the selective oxidation of sulfides to sulfoxides. Monatsh. Chem., 140(1): 65–68(2009).
[23] Mondal P., Ghosal K., Bhattacharyya S.K., Das M., Bera A., Ganguly D., Kumar P., Dwivedi J., Gupta R.K., Martí A.A., Gupta B.K., Formation of a gold–carbon dot nanocomposite with superior catalytic ability for the reduction of aromatic nitro groups in water. RSC Adv., 4(49): 25863-25866 (2014).
[25] 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