Oda Sıcaklığında Benzen Hidrojenlenmesinde Katalizör Olarak Kullanılan Tungsten(VI) Oksit Destekli Rodyum(0) Nanoparçacıkları

Rodyum(III) iyonları ilk önce sulu çözelti içinde tungsten(VI) oksit (WO3) üzerine tutturulmuş ve WO3 yüzeyi üzerinde rodyum(0) nanoparçacıkları (Rh NPs) oluşturmak için sulu NaBH4 ile indirgenmiştir. Rh NPs/WO3 katalizörü santrifüjleme ile ayrıldıktan sonra gelişmiş analitik tekniklerle tanımlanmıştır. Sonuçlar Rh NPs’nin başarılı bir şekilde WO3 yüzeyinde oluştuğunu göstermektedir. Rh NPs/WO3 katalizörünün 131 h-1 çevrim frekansı değeri ile 25.0±0.1ºC’ de solventsiz benzen hidrojenlenmesinde çok aktif olduğu bulunmuştur

Tungsten(VI) Oxide Supported Rhodium(0) Nanoparticles Used as Catalyst in Hydrogenation of Benzene at Room Temperature

Rhodium(III) ions were first impregnated on the surface of tungsten(VI) oxide (WO3) in aqueous solution and reduced with aqueous NaBH4 to form rhodium(0) nanoparticles (Rh NPs) on the surface of WO3. After the isolation of the Rh NPs/WO3 catalyst by centrifugation, it was characterized by advanced analytical techniques. The results reveal the successful formation of Rh NPs on the surface of WO3. Rh NPs/WO3 catalyst with a turnover frequency value of 131 h-1 was found to be very active in hydrogenation of neat benzene at 25.0±0.1ºC.

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V. Mevellec, A. Nowicki, A. Roucoux, C. Dujardin, P. Granger, E. Payen, K. Philippot, A simple and reproducible method for the synthesis of silicasupported rhodium nanoparticles and their investigation in the hydrogenation of aromatic compounds, New J. Chem., 30 (2006) 1214–1219.
H. Liu, R. Fang, Z. Li, Y. Li, Solventless hydrogenation of benzene to cyclohexane over a heterogeneous Ru– Pt bimetallic catalyst, Chemical Eng. Sci., 122 (2015) 350–359.
C. Vangelis, A. Bouriazos, S. Sotiriou, M. Samorski, B. Gutsche, G. Papadogianakis, Catalytic conversions in green aqueous media: Highly efficient biphasic hydrogenation of benzene to cyclohexane catalyzed by Rh/TPPTS complexes, J. Catal., 274 (2010) 21–28.
M. Zahmakıran, Y. Tonbul, S. Özkar, Ruthenium(0) Nanoclusters Stabilized by a Nanozeolite Framework: Isolable, Reusable, and Green Catalyst for the Hydrogenation of Neat Aromatics under Mild Conditions with the Unprecedented Catalytic Activity and Lifetime, J. Am. Chem. Soc., 132 (2010) 6541– 6549.
H.B. Pan, C.M. Wai, Sonochemical One-Pot Synthesis of Carbon Nanotube-Supported Rhodium Nanoparticles for Room-Temperature Hydrogenation of Arenes, J. Phys. Chem. C., 113 (2009) 19782-88.
H.B. Pan, C.M. Wai, Facile sonochemical synthesis of carbon nanotube-supported bimetallic Pt–Rh nanoparticles for room temperature hydrogenation of arenes, New J. Chem., 35 (2011) 1649–1660.
F. Li, B.C. Gates, Size-Dependent Catalytic Activity of Zeolite-Supported Iridium Clusters, J. Phys. Chem. C, 111 (2007) 262-267.
S. Akbayrak, S. Özkar, Hydrogen Generation from the Hydrolysis of Ammonia Borane Using Transition Metal Nanoparticles as Catalyst, in: Hydrogen Production Technologies, Wiley-VCH, Weinheim, Germany, 2017.
N. Li, Y. Zheng, L. Wei, H. Teng, J. Zhou, Metal nanoparticles supported on WO3 nanosheets for highly selective hydrogenolysis of cellulose to ethylene glycol, Green Chem., 19 (2017) 682–691.
S.J. Kim, S.J. Choi, J.S. Jang, N.H. Kim, M. Hakim, H. L. Tuller, I.D. Kim, Mesoporous WO3 Nanofibers with Protein- Templated Nanoscale Catalysts for Detection of Trace Biomarkers in Exhaled Breath, ACS Nano, 10 (2016) 5891-5899.
M.S. Tsaia, C.J. Lua, P.G. Su, One-pot synthesis of AuNPs/RGO/WO3 nanocomposite for simultaneously sensing hydroquinone and catechol, Mater. Chem. Phys., 215 (2018) 293–298
G.R. Gattorno, A. Galano, E. Torres-Garcia, Surface acid–basic properties of WOx–ZrO2 and catalytic efficiency in oxidative desulfurization, Appl. Catal. B, 92 (2009) 1-8.
C.D. Baertsch, K.T. Komala, Y.H. Chua, E. Iglesia, Genesis of Brønsted Acid Sites during Dehydration of 2-Butanol on Tungsten Oxide Catalysts, J. Catal., 205 (2002) 44-57.
M. Scheithauer, T.K. Cheung, R.E. Jentoft, R.K. Grasselli, B.C. Gates, H. Knözinger, Characterization of WOx/ZrO2 by Vibrational Spectroscopy and n-Pentane Isomerization Catalysis, J. Catal., 180 (1998) 1-13.
P. Wang, J. Feng, Y. Zhao, S. Wang, J. Liu, MOFDerived Tungstated Zirconia as Strong Solid Acids toward High Catalytic Performance for Acetalization. ACS Appl. Mater. Interfaces, 8 (2016) 23755-23762.
K. Miecznikowski, Enhancement of activity of PtRh nanoparticles towards oxidation of ethanol through modification with molybdenum oxide or tungsten oxide. J Solid State Electrochem, 16 (2012) 2723–2731.
I.R. Rutkowska, A. Wadas, P.J. Kulesza, Mixed layered WO3/ZrO2 films (with and without rhodium) as active supports for PtRu nanoparticles: enhancement of oxidation of ethanol, Electrochimica Acta, 210 (2016) 575–587.
P.J. Barczuk, H. Tsuchiya, J.M. Macak, P. Schmuki, D. Szymanska, O. Makowski, K. Miecznikowski, P.J. Kulesza, Enhancement of the Electrocatalytic Oxidation of Methanol at Pt/Ru Nanoparticles Immobilized in Different WO3 Matrices, Electrochem. Solid-State Lett., 9 (2006) E13-E16.
F. Micoud, F. Maillard, A. Bonnefont, N. Job, M. Chatenet, The role of the support in COads monolayer electrooxidation on Pt nanoparticles: Pt/WOx vs. Pt/C, Phys. Chem. Chem. Phys., 12 (2010) 1182-1193.
S. Akbayrak, Y. Tonbul, S. Özkar, Ceria supported rhodium nanoparticles: Superb catalytic activity in hydrogen generation from the hydrolysis of ammonia borane, Appl. Catal. B, 198 (2016) 162–170.
Y. Tonbul, M. Zahmakiran, S. Özkar, Iridium(0) nanoparticles dispersed in zeolite framework: A highly active and long-lived green nanocatalyst for the hydrogenation of neat aromatics at room temperature, Appl. Catal. B, 148-149 (2014) 466–472.
S.M. Baghbanian, M. Farhang, S.M. Vahdat, M. Tajbakhsh, Hydrogenation of arenes, nitroarenes, and alkenes catalyzed by rhodium nanoparticles supported on natural nanozeolite clinoptilolite, J. Mol. Catal. A Chem., 407 (2015) 128-136.
M. Zahmakiran, Y. Roman-Leshkov, Y. Zang, Rhodium(0) Nanoparticles Supported on Nanocrystalline Hyroxyapatite: Highly Effective Catalytic System for the Solvent- Free Hydrogenation of Aromatics at Room Temperature, Langmuir, 28 (2012) 60-64.
I.S. Park, M.S. Kwon, K.Y. Kang, J.S. Lee, J. Parka, Rhodium and Iridium Nanoparticles Entrapped in Aluminum Oxyhydroxide Nanofibers: Catalysts for Hydrogenations of Arenes and Ketones at Room Temperature with Hydrogen Balloon, Adv. Synth. Catal., 349 (2007) 2039–2047.
H.B. Pan, C.M. Wai, Sonochemical one-pot synthesis of carbon nanotube supported rhodium nanoparticles for room-temperature hydrogenation of arenes, J. Phys. Chem. C, 113 (2009) 19782-19788.
B. Yoon, H.B. Pan, C.M. Wai, Relative catalytic activities of carbon nanotube supported metallic nanoparticles for room-temperature hydrogenation of benzene, J. Phys. Chem. C, 113 (2009) 1520-1525.
C. Hubert, E. G. Bile, A. Denicourt-Nowicki, A. Roucoux, Rh(0) colloids supported on TiO2: a highly active and pertinent tandem in neat water for the hydrogenation of aromatics Green Chem., 13 (2011)1766–1771.
D. Marquardt, C. Vollmer, R. Thomann , P. Steurer, R. Mülhaupt, E. Redel, C. Janiak, The use of microwave irradiation for the easy synthesis of graphenesupported transition metal nanoparticles in ionic liquids, Carbon, 49 (2011) 1326-1332.
J. Pellegatta, C. Blandy, V. ColliRre, R. Choukroun, B. Chadret, P. Cheng, K. Philippot, Catalytic investigation of rhodium nanoparticles in hydrogenation of benzene and phenylacetylene, J. Mol. Catal. A ,178 (2002) 55-61.
M.J. Jacinto, P.K. Kiyohara, S.H. Masunaga, R.F. Jardim, L.M. Rossi, Recoverable rhodium nanoparticles: Synthesis, characterization and catalytic performance in hydrogenation reactions Appl. Catal. A, 338 (2008) 52–57.
S. Niembro, S. Donnici, A. Shafir, A. Vallribera, M.L. Buil, M.A. Esteruelas, C. Larramona, Perfluoro-tagged rhodium and ruthenium nanoparticles immobilized on silica gel as highly active catalysts for hydrogenation of arenes under mild conditions, New J. Chem., 37 (2013) 278-282.
M.H. Seeberger, R.A. Jones, Synthesis of Polymersupported Transition Metal Catalysts via Phosphido Linkages:Heterogeneous Catalysts for the Hydrogenation of Aromatic Compounds under Mild Conditions, J. Chem. Soc. Chem. Comm., 6 (1985) 373.
G. S. Fonseca, A.P. Umpierre, P. F. P. Fichtner, S.R. Teixeira, J. Dupont, The Use of Imidazolium Ionic Liquids for the Formation and Stabilization of Ir0 and Rh0 Nanoparticles: Efficient Catalysts for the Hydrogenation of Arenes, Chem. Eur. J., 9 (2003) 3263-3269.
L. Zhu, H. Sun, J. Zheng, C. Yu, N. Zhang, Q. Shu, B. H. Chen, Combining Ru, Ni and Ni(OH)2 active sites for improving catalytic performance in benzene hydrogenation, Mater. Chem. Phys., 192 (2017) 8-16.
Y. Li, G. Lan, H. Wang, H. Tang, X. Yan, H. Liu, Controlled synthesis of highly dispersed semi-embedded ruthenium nanoparticles in porous carbon framework with more exposed active sites, Catal. Commun., 20 (2012) 29-35.
R.M. Esteban, K. Schütte, D. Marquardt, J. Barthel, F. Beckert, R. Mülhaupt, C. Janiak, Synthesis of ruthenium@graphene nanomaterials in propylene carbonate as re-usable catalysts for the solvent-free hydrogenation of benzene, Nano-Structures NanoObjects, 2 (2015) 28-34.
H. Bi, X. Tan, R. Dou, Y. Pei, M. Qiao, B. Sun, B. Zong, Ru-B nanoparticles on metal-organic frameworks as excellent catalysts for hydrogenation of benzene to cyclohexane under mild reaction conditions, Green Chem., 18 (2016) 2216-2221.
Y. Ma, Y. Huang, Y. Cheng, L. Wang, X. Li, Biosynthesized ruthenium nanoparticles supported on carbon nanotubes as efficient catalysts for hydrogenation of benzene to cyclohexane: an eco-friendly and economical bioreduction method, Appl. Catal. A, 484 (2014) 154-160.
F.B. Su, F.Y. Lee, L. Lv, J.J. Liu, X.N. Tian, X.S. Zhao, Sandwiched ruthenium/carbon nanostructures for highly active heterogeneous hydrogenation, Adv. Funct. Mater., 17 (2007) 1926-1931.
X. Kang, J. Zhang, W. Shang, T. Wu, P. Zhang, B. Han, Z. Wu, G. Mo, X. Xing, One-step synthesis of highly efficient nanocatalysts on the supports with hierarchical pores using porous ionic liquid-water gel, J. Am. Chem. Soc., 136 (2014) 3768-3771.
D. Chen, M. Huang, S. He, S. He, L. Ding, Q. Wang, S. Yu, S. Miao, Ru-MOF enwrapped by montmorillonite for catalyzing benzene hydrogenation, Appl. Clay Sci., 119 (2016) 109-115.
R.M. Esteban, K. Schütte, P. Brandt, D. Marquardt, H. Meyer, F. Beckert, R. Mülhaupt, H. Kölling, C. Janiak, Iridium@graphene composite nanomaterials synthesized in ionic liquid as re-usable catalysts for solvent-free hydrogenation of benzene and cyclohexene, Nano-Structures & Nano-Objects 2 (2015) 11–18.
C.W. Scheeren, G. Machado, J. Dupont, P.F.P. Fichtner, S.R. Texeira, Nanoscale Pt(0) Particles Prepared in Imidazolium Room Temperature Ionic Liquids: Synthesis from an Organometallic Precursor, Characterization, and Catalytic Properties in Hydrogenation Reactions, Inorg. Chem., 42 (2003) 4738–4742.