Green Preparation of Multiwalled Carbon Nanotubes Supported Pd and Cu Nanoparticles with Novel Vic-dioxime Metal Complexes

Abstract

The preparation of multi-walled carbon nanotubes (MW-CNTs) supported Cu and Pd nanoparticles on utilizing a supercritical carbon dioxide deposition method were investigated. Novel vic-dioxime complexes of Cu(II) and Pd(II) were used as metallic precursors. The ligand used in these precursors were 4-(trifluoromethyl)aniline-vic-dioxide. Ligand and metal complexes were synthesized and identified with various analyses method including ¹H and ¹⁹F NMR, FT-IR, UV-Vis, elemental analysis and magnetic susceptibility. MW-CNTs supported Pd and Cu nanoparticles were characterized by high-resolution transmission electron microscopy (HR_TEM), X-ray diffraction (XRD) and scanning electron microscopy with EDX (SEM_EDX). SEM_EDX and HR_TEM micrographs showed a homogenous distribution of reasonably well-dispersed Cu and Pd nanoparticles on the support. The nature and crystallinity of the nano metal particles were confirmed using XRD. Crystallite sizes ranged from 7-20 nm for palladium and 20-30 nm for copper. This study demonstrated that these oxime complexes are suitable precursors for the preparation of supported nanoparticles using a supercritical carbon dioxide deposition method. 

Keywords

• vic-dioxime,metal complex,precursor,green chemistry,supercritical deposition

References

1. 1. Ulusal F, Darendeli B, Erünal E, Eğitmen A, Güzel B. Supercritical carbon dioxide deposition of γ-Alumina supported Pd nanocatalysts with new precursors and using on Suzuki-Miyaura coupling reactions. The Journal of Supercritical Fluids. 2017;127:111–120.
2. 2. Cangul B, Zhang LC, Aindow M, Erkey C. Preparation of carbon black supported Pd, Pt and Pd–Pt nanoparticles using supercritical CO2 deposition. The Journal of Supercritical Fluids. 2009; 50: 82–90.
3. 3. Zhang Y, Erkey C. Preparation of supported metallic nanoparticles using supercritical fluids: A review. The Journal of Supercritical Fluids. 2006;38:252–267.
4. 4. Daoush WM, Lim BK, Mo CB, Nam DH, Hong SH. Electrical and mechanical properties of carbon nanotube reinforced copper nanocomposites fabricated by electroless deposition process. Materials Science and Engineering: A. 2009;513–514:247–253.
5. 5. Park PW, Ledford JS. The influence of surface structure on the catalytic activity of alumina supported copper oxide catalysts. Oxidation of carbon monoxide and methane. Applied Catalysis B: Environmental. 1998;15:221–231.
6. 6. Rather S, Zacharia R, Hwang SW, Naik M, Nahm KS. Hydrogen uptake of palladium-embedded MW-CNTs produced by impregnation and condensed phase reduction method. Chemical Physics Letters. 2007;441:261–267.
7. 7. Lam F, Hu X. A new system design for the preparation of copper/activated carbon catalyst by metal-organic chemical vapor deposition method. Chemical Engineering Science. 2003;58:687 – 695.
8. 8. Ulusal H, Fındıkkıran G, Demirkol O, Akbaşlar D, Giray ES. Supercritical diethylether: A novel solvent for the synthesis of aryl-3,4,5,6,7,9-hexahydroxanthene-1,8-diones. The Journal of Supercritical Fluids. 2015;105:146–150.

9. 9. Zhang Y, Erkey C. Preparation of supported metallic nanoparticles using supercritical fluids: A review. The Journal of Supercritical Fluids. 2006;38:252–267.
10. 10. Dobrovolna Z, Kacer P, Cerveny L. Competitive hydrogenation in alkene–alkyne–diene systems with palladium and platinum catalysts. Journal of Molecular Catalysis A: Chemical. 1998;130:279-284.
11. 11. Ye XR, Lin Y, Whang C, Engelhard MH, Wang Y, Wai CM. Supercritical fluid synthesis and characterization of catalytic metal nanoparticles on carbon nanotubes. Journal of Materials Chemistry. 2004;14:908-913.
12. 12. Kim J, Kelly MJ, Lamb HH, Roberts GW, Kiserow D. Characterization of palladium (Pd) on alumina catalysts prepared using liquid carbon dioxide. The Journal of Physical Chemistry C. 2008; 112: 10446–10452.
13. 13. Erünal E, Ulusal F, Aslan MY, Güzel B, Üner D. Enhancement of hydrogen storage capacity of multi-walled carbon nanotubes with palladium doping prepared through supercritical CO2 deposition method. International Journal of Hydrogen Energy. 2018; 43: 10755-1076
14. 14. Yildirim B, Özcan E, Deveci P. New glyoxime derivatives and their transition metal complexes. Russian Journal of Coordination Chemistry. 2007;33:417–421.
15. 15. Teoh WH, Mammucari R, Foster NR. Solubility of organometallic complexes in supercritical carbon dioxide: A review. Journal of Organometallic Chemistry. 2013;724:102-116.
16. 16. Aschenbrenner O, Kemper S, Dahmena N, Schaber K, Dinjus E. Solubility of β-diketonates, cyclopentadienyls, and cyclooctadiene complexes with various metals in supercritical carbon dioxide. Journal of Supercritical Fluids. 2007; 41: 179–186.
17. 17. Guzel B, Avşar G, Çınkır H. Supercritical carbon dioxide-soluble fluorus vic-dioxime ligands and their Ni(II) complexes: synthesis, characterization and solubility properties. Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry. 2007;37:801-804.
18. 18. Ulusal F, Güzel B. Deposition of palladium by the hydrogen assisted on SBA-15 with a new precursor using supercritical carbon dioxide. The Journal of Supercritical Fluids. 2018; 133: 233–238.
19. 19. Cabanas A, Blackburn J, Watkins J. Deposition of Cu films from supercritical fluids using Cu(I) β-diketonate precursors. Microelectronic Engineering. 2002;64:53-61.
20. 20. Ulusal F. Güzel B. Synthesis and Characterization of Novel Pd and Cu vic-dioxime Precursors for Their Supercritical Deposition on Multiwalled Carbon Nanotubes. Journal of the Turkish Chemical Society, Section A: Chemistry. 2018; 5(2): 635-52.