Abstract
Ultra-fine gold (<2 nm), silver (5 ± 2 nm), and palladium (<1–2 nm) nanoparticles stabilized in polyvinylpyrrolidone shell were synthesized in N,N-dimethylformamide, using molecular oxygen dissolved in the electrolyte as mediator, by the reduction of the metals’ ions and complexes at the controlled potential of the oxygen reduction to its radical-anion. Pd-nanoparticles showed high catalytic activity in the reactions of p-nitrophenol reduction and Suzuki cross-coupling. Long-term ageing of spherical Ag-nanoparticles for 60 days in the post- electrolysis solution resulted in their consolidation (up to 17 ± 5 nm; the average size of crystallites 7.5 (3) nm). Upon similar exposure of Au-nanoparticles for 15 days, V-shaped nanoparticles were formed (length 112 ± 53 nm, width 58 ± 22 nm, crystallites 20(2)–31(1) nm); upon the isolation, dispersing into ethanol, and exposure for 48 h, hexagonal nanoparticles (105 ± 29 nm) and polygons (56 ± 25 nm, crystallites 24(2)–51(1) nm; upon dispersing into water and exposure for 8 h, spherical nanoparticles (13 ± 8 nm, crystallites 7(1)–13.4(5) nm). Thus obtained nanoparticles are characterized by methods of cyclic voltammetry, dynamic light scattering, scanning and high resolution transmission electron microscopy, and X-ray powder diffraction.
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Pomogailo, A.D., Rozenberg, A.S., and Uflyand, I.E., Nanochastitsy metallov v polimerakh (Metal Nanoparticles in Solutions), Moscow: himiya, 2000.
Roldughin, V.I., Quantum-size colloid metal systems, Russ. Chem. Rev., 2000, vol. 69, p. 821.
Daniel, M.C. and Astruc, D., Gold nanoparticles: assembly, supramolecular chemistry, quantum-sizerelated properties, and applications toward biology, catalysis, and nanotechnology, Chem. Rev., 2004, vol. 104, p. 293.
Suzdalev, I.P., Nanotekhnologiya: fiziko-khimiya nanoklasterov, nanostruktur i nanomaterialov (Nanotechnology: Physical Chemistry of Nanoclusters, Nanostructures, and Nanomaterials), 2nd ed., Librokom, 2009.
Volkov, V.V., Kravchenko, T.A., and Roldughin, V.I., Metal nanoparticles in catalytic polymer membranes and ion-exchange systems for advanced purification of water from molecular oxygen, Russ. Chem. Rev., 2013, vol. 82, p. 465.
Dykman, L.A., Bogatyrev, V.A., Shchegolev, S.Yu., and Khlebtsov, N.G., Zolotye nanochastitsy. Sintez, svoistva, biomeditsinskoe primenenie (Gold Nanoparticles. Synthesis, Properties, Biomedical Applications), Moscow: Nauka, 2008.
Kharisov, B.I., Kharissova, O.V., and Ortiz-Méndez, U., Handbook of Less-common Nanostructures. CRC Press, Taylor and Francis Group, 2012.
Spravochnik po elektrokhimii (A Handbook of Electrochemistry), Sukhotin, A.M., Ed., Leningrad: Khimiya, 1981.
Petrii, O.A., Electrosynthesis of nanostructures and nanomaterials, Russ. Chem. Rev., 2015, vol. 84, p. 159.
Saez, V. and Mason, T.J., Sonoelectrochemical synthesis of nanoparticles, Molecules, 2009, vol. 14, p. 4284.
Zhu, J., Liu, S., Palchik, O., Koltypin, Y., and Gedanken, A., Shape-controlled synthesis of silver nanoparticles by pulse sonoelectrochemical methods, Langmuir, 2000, vol. 16, p. 6396.
Reisse, J., Caulier, T., Deckerkheer, C., Fabre, O., Vandercammen, J., Delplancke, J.L., and Winand, R., Quantitative sonochemistry, Ultrasonics Sonochemistry, 1996, vol. 3, p. 147.
Reetz, M.T. and Helbig, W., Size-selective synthesis of nanostructured transition metal clusters, J. Amer. Chem. Soc., 1994, vol. 116, p. 7401.
Becker, J.A., Schäfer, R., Festag, R., Ruland, W., Wendorff, J.H., Pebler, J., Quaiser, S.A., Helbig, W., and Reetz, M.T., Electrochemical growth of superparamagnetic cobalt clusters, J. Chem. Phys., 1995, vol. 103, p. 2520.
Reetz, M.T., Quaiser, S.A., and Merk, C., Electrochemical preparation of nanostructured titanium clusters: characterization and use in McMurry-type coupling reactions, Chem. Ber., 1996, vol. 129, p. 741.
Reetz, M T., Helbig, W., Quaiser, S.A., Stimming, U., Breuer, N., and Vogel, R., Visualization of surfactants on nanostructured palladium clusters by a combination of STM and high-resolution TEM, Science, 1995, vol. 267, p. 367.
Reetz, M.T., Winter, M., Breinbauer, R., Thurn-Albrecht, T., and Vogel, W., Size-selective electrochemical preparation of surfactant-stabilized Pd-, Niand Pt/Pd colloids, Chem. Eur. J., 2001, vol. 7, p. 1084.
Yanilkin, V.V., Nasybullina, G.R., Ziganshina, A.Yu., Nizamiev, I.R., Kadirov, M.K., Korshin, D.E., and Konovalov, A.I., Tetraviologen calix[4]resorcine as a mediator of the electrochemical reduction of [PdCl4]2− for the production of Pd0 nanoparticles, Mendeleev Commun., 2014, vol. 24, p. 108.
Yanilkin, V.V., Nasybullina, G.R., Sultanova, E.D., Ziganshina, A.Yu., and Konovalov, A.I., Methyl viologen and tetraviologen calix[4]resorcinol as mediators of the electrochemical reduction of [PdCl4]2− with formation of finely dispersed Pd0, Russ. Chem. Bull., Int. Ed., 2014, vol. 63, p. 1409.
Yanilkin, V.V., Nastapova, N.V., Nasretdinova, G.R., Mukhitova, R.K., Ziganshina, A.Yu., Nizameev, I.R., and Kadirov, M.K., Mediated electrochemical synthesis of Pd0 nanoparticles in solution, Russ. J. Electrochem., 2015, vol. 51, p. 951.
Fedorenko, S., Jilkin, M., Nastapova, N., Yanilkin, V., Bochkova, O., Buriliov, V., Nizameev, I., Nasretdinova, G., Kadirov, M., Mustafina, A., and Budnikova, Y., Surface decoration of silica nanoparticles by Pd(0) deposition for catalytic application in aqueous solutions, Colloids and Surfaces A: Physicochem. Eng. Aspects., 2015, vol. 486, p. 185.
Yanilkin, V.V., Nastapova, N.V., Sultanova, E.D., Nasretdinova, G.R., Mukhitova, R.K., Ziganshina, A.Yu., Nizameev, I.R., and Kadirov, M.K., Electrochemical synthesis of nanocomposite of palladium nanoparticles with polymer viologen-containing nanocapsule, Russ. Chem. Bull., Int. Ed., 2016, vol. 65, p. 125.
Nasretdinova, G.R., Osin, Y.N., Gubaidullin, A.T., and Yanilkin, V.V., Methylviologen mediated electrosynthesis of palladium nanoparticles stabilized with CTAC, J. Electrochem. Soc., 2016, vol. 163, p. G99.
Nasretdinova, G.R., Fazleeva, R.R., Mukhitova, R.K., Nizameev, I.R., Kadirov, M.K., Ziganshina, A.Yu., and Yanilkin, V.V., Electrochemical synthesis of silver nanoparticles in solution, Electrochem. Commun., 2015, vol. 50, p. 69.
Nasretdinova, G.R., Fazleeva, R.R., Mukhitova, R.K., Nizameev, I.R., Kadirov, M.K., Ziganshina, A.Yu., and Yanilkin, V.V., Electrochemical mediated synthesis of silver nanoparticles in solution, Russ. J. Electrochem., 2015, vol. 51, p. 1029.
Yanilkin, V.V., Nastapova, N.V., Nasretdinova, G.R., Fazleeva, R.R., Toropchina, A.V., and Osin, Y.N., Methylviologen mediated electrochemical reduction of AgCl—a new route to produce a silica core/Ag shell nanocomposite material in solution, Electrochem. Commun., 2015, vol. 59, p. 60.
Nasretdinova, G.R., Fazleeva, R.R., Osin, Y.N., Gubaidullin, A.T., and Yanilkin, V.V., Methylviologen mediated electrochemical synthesis of silver nanoparticles by reduction of AgCl nanospheres stabilized with cetyltrimethylammonium chloride, Russ. J. Electrochem., 2017, vol. 53, p. 31.
Yanilkin, V.V., Nasretdinova, G.R., Osin, Y.N., and Salnikov, V.V., Anthracene-mediated electrochemical synthesis of metallic cobalt nanoparticles in solution, Electrochim. Acta, 2015, vol. 168, p. 82.
Yanilkin, V.V., Nastapova, N.V., Nasretdinova, G.R., Fedorenko, S.V., Jilkin, M.E., Mustafina, A.R., Gubaidullin, A.T., and Osin, Y.N., Methylviologen mediated electrosynthesis of gold nanoparticles in the solution bulk, RSC Advances, 2016, vol. 6, p. 1851.
Yanilkin, V.V., Nastapova, N.V., Nasretdinova, G.R., Osin, Yu.N., and Gubaidullin, A.T., Fullerene mediated electrosynthesis of Au/C60 nanocomposite, ECS J. Solid State Sci. Technol., 2017, vol. 6, p. M19.
Yanilkin, V.V., Nastapova, N.V., Nasretdinova, G.R., Fazleeva, R.R., Fedorenko, S.V., Mustafina, A.R., and Osin, Y.N., Methylviologen-mediated electrochemical synthesis of platinum nanoparticles in solution bulk, Russ. J. Electrochem., 2017, vol. 53, p. 509.
Yanilkin, V.V., Nastapova, N.V., Nasretdinova, G.R., Fazleeva, R.R., and Osin, Y.N., Molecular oxygen as a mediator in the electrosynthesis of gold nanoparticles in DMF, Electrochem. Commun., 2016, vol. 69, p. 36.
Solubility Data Series. Oxygen and Ozone. Battino, R., Ed., Oxford: Pergamon, 1981, vol. 7.
DIFFRAC Plus Evaluation package EVA, Version 11, User’s Manual, Bruker AXS, Karlsruhe, Germany, 2005.
TOPAS V3: General profile and structure analysis software for powder diffraction data. (2005). Technical Reference. Bruker AXS. Karlsruhe, Germany.
Tan, H., Santbergen, R., Smets, A.H.M., and Zeman, M., Plasmonic light trapping in thin-film silicon solar cells with improved self-assembled silver nanoparticles, Nano Lett., 2012, vol. 12, p. 4070.
Yakhvarov, D.G., Kagirov, R.M., Rizvanov, I.Kh., Morozov, V.I., and Sinyashin, O.G., New aspects of the electroreduction of palladium dichloride complex with 1,2-bis(diphenylphosphino)ethane, Mendeleev Commun., 2009, vol. 19, p. 190.
Plieth, W.J., Electrochemical properties of small clusters of metal atoms and their role in the surface enhanced Raman scattering, J. Phys. Chem., 1982, vol. 86, p. 3166.
Sultanova, E.D., Salnikov, V.V., Mukhitova, R.K., Zuev, Yu.F., Osin, Yu.N., Zakharova, L.Ya., Ziganshina, A.Y., and Konovalov, A.I., High catalytic activity of palladium nanoparticle clusters supported on a spherical polymer network, Chem. Commun., 2015, vol. 51, p. 13317.
Hervés, P., Pérez-Lorenzo, M., Liz-Marzán, L.M., Dzubiella, J., Lu, Y., and Ballauff, M., Catalysis by metallic nanoparticles in aqueous solution: model reactions, Chem. Soc. Rev., 2012, vol. 41, p. 5577.
Zhou, X., Xu, W., Liu, G., Panda, D., and Chen, P., Size-Dependent Catalytic Activity and Dynamics of Gold Nanoparticles at the Single-Molecule Level, J. Amer. Chem. Soc., 2010, vol. 132, p. 138.
Gu, S., Wunder, S., Lu, Y., Ballauff, M., Rademann, K., Fenger, R., Jaquet, B., and Zaccone, A., Kinetic Analysis of the Catalytic Reduction of 4-Nitrophenol by Metallic Nanoparticles, J. Phys. Chem. C, 2014, vol. 118, p. 18618.
He, R., Wang, Y-Ch., Wang, X., Wang, Zh., Liu, G., Zhou, W., Wen, L., Li, Q., Wang, X., Chen, X., Zeng, J., and Hou, J.G., Facile synthesis of pentacle gold–copper alloy nanocrystals and their plasmonic and catalytic properties, Nature Commun., 2014, vol. 5, p. 4327.
Zeng, J., Zhang, Q., Chen, J., and Xia, Y., A Comparison Study of the Catalytic Properties of Au-Based Nanocages, Nanoboxes, and Nanoparticles, Nano Lett., 2010, vol. 10, p. 30.
Ma, T., Yang, W., Liu, S., Zhang, H., and Liang, F., A Comparison Reduction of 4-Nitrophenol by Gold Nanospheres and Gold Nanostars, Catalysts, 2017, vol. 7, p. 38.
Seo, Y.S., Ahn, E-Y., Park, J., Kim, T.Y., Hong, J.E., Kim, K., and Park, Y., Catalytic reduction of 4-nitrophenol with gold nanoparticles synthesized by caffeic acid, Nanoscale Res. Lett., 2017, vol. 12, p. 7.
Nanotechnology for Water and Wastewater Treatment, Lens, P., Virkutyte, J., Jegatheesan, V., and Al-Abed, S., Eds., London, New York: IWA Publishing, 2013.
Mejías, N., Pleixats, R., Shafir, A., Medio-Simón, M., and Asensio, G., Water-soluble palladium nanoparticles: click synthesis and applications as a recyclable catalyst in suzuki cross-couplings in aqueous media, Eur. J. Org. Chem., 2010, vol. 26, p. 5090.
Nanoparticles and Catalysis, Astruc, D., Ed., Weinheim: Wiley-VCH, 2008.
Magdesieva, T.V., Nikitin, O.M., Levitsky, O.A., Zinovyeva, V.A., Bezverkhyy, I., Zolotukhina, E.V., and Vorotyntsev, M.A., Polypyrrole–palladium nanoparticles composite as efficient catalyst for Suzuki–Miyaura coupling, J. Mol. Catal. A: Chem., 2012, vol. 353–354, p. 50.
Chatterjee, A. and Ward, T.R., Recent Advances in the Palladium Catalyzed Suzuki–Miyaura Cross-Coupling Reaction in Water, Catal. Lett., 2016, vol. 146, p. 820.
Han, F.-Sh., Transition-metal-catalyzed Suzuki–Miyaura cross-coupling reactions: a remarkable advance from palladium to nickel catalysts, Chem. Soc. Rev., 2013, vol. 42, p. 5270.
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Original Russian Text © V.V. Yanilkin, N.V. Nastapova, R.R. Fazleeva, G.R. Nasretdinova, E.D. Sultanova, A.Yu. Ziganshina, A.T. Gubaidullin, A.I. Samigullina, V.G. Evtyugin, V.V. Vorob’ev, Yu.N. Osin, 2018, published in Elektrokhimiya, 2018, Vol. 54, No. 3, pp. 307–326.
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Yanilkin, V.V., Nastapova, N.V., Fazleeva, R.R. et al. Molecular Oxygen as Mediator in the Metal Nanoparticles’ Electrosynthesis in N,N-Dimethylformamide. Russ J Electrochem 54, 265–282 (2018). https://doi.org/10.1134/S1023193518030102
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DOI: https://doi.org/10.1134/S1023193518030102