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學生 : 張朝欽 指導老師 : 于淑君 博士 中正大學化學暨生物化學所

Synthesis of Pd Nanoparticles Supported Pd(II) Complexes and Catalytic Olefin Hydrogenation and Isomerization Reactions. 學生 : 張朝欽 指導老師 : 于淑君 博士 中正大學化學暨生物化學所. Types of Catalysts. +. Homogeneous Catalyst. Cat. S. S. P. Heterogeneous Catalyst. C. S. S. +. P. Cat. S. S. P. +.

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學生 : 張朝欽 指導老師 : 于淑君 博士 中正大學化學暨生物化學所

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  1. Synthesis of Pd Nanoparticles Supported Pd(II) Complexes and Catalytic Olefin Hydrogenation and Isomerization Reactions 學生 : 張朝欽 指導老師 : 于淑君 博士 中正大學化學暨生物化學所

  2. Types of Catalysts

  3. + Homogeneous Catalyst Cat. S S P

  4. Heterogeneous Catalyst C S S + P

  5. Cat. S S P + Hybrid Catalyst Solid support

  6. c a t a l y s t s Metal oxide Organicpolymer Silica gel Soluble metal complex f u n c t i o n a l g r o u p s c o o r d i n a t i o n l i g a n d s spacer linker The Componemts of Hybrid Catalyst

  7. : polystyrene Phosphines Attached to Polymer-Supported Peptides Leadbeater, N. E.; Marco, M. Chem. Rev. 2002, 102, 3217-3274

  8. Solid/Liquid Separations of Catalysts on Polymers Bergbreiter, D. E. Chem. Rev. 2002, 102, 3345-3384.

  9. The Limitation of Phosphine Ligand a. Oxidation b. Metal Leaching Kinzel, E. J. Chem. Soc. Chem. Commun.1986 1098

  10. Catalyst Design c a t a l y s t s Nanoparticles with controllable solubility Soluble metal complex f u n c t i o n a l g r o u p s c o o r d i n a t i o n l i g a n d s spacer linker

  11. Gold NPs-Supported and SiO2-Supported Catalysts SiO2-L-Pd Au-HS(CH2)11N(H)(O)P(2-py)2PdCl2 (Au-L-Pd) aPd/S(CH2)7CH3 = 1:1.4 (mole ratio)

  12. Catalytic [2+2+2] Alkyne Cyclotrimerization Reactions aReaction conditions: alkyne (0.075 mmol) in CDCl3 (1 mL), catalyst loading = 4 mol%.balkyne (0.56 mmol) in CDCl3 (3 mL), catalyst loading = 4 mol%.. cConversions were determined by 1H-NMR spectroscop dProducts were purified and isolated by flash chromatography on SiO2 with hexane/ethyl acetate. eIsomers ratios were determined by GC.

  13. Motivation and Design catalyst Alternative supporting materials

  14. Palladium(II) Catalyst immobilized on Pd NPs d6-DMSO py * -HNCH2- NH Pd-Ligand-PdCl2 Pd-Ligand-PdCl2 * py -CH3 NH -HNCH2-

  15. Synthesis of Spacer Linker spacer linker L

  16. Bi-phase Synthesis of Octanethiol Protected Pd NPs 40% Particle size distribution = 4.52± 1.32 nm

  17. Synthesis of Pd-Immobilized Pd NPs

  18. CDCl3 * Single-phase Synthesis of Octanethiol Protected Pd-SR NPs (6) 85% Pd-SR (6) Particle size distribution = 2.60 ± 0.5nm Langmuir2002, 18, 1413-1418

  19. Surface Functionalization of Pd-SR NPs -CH3 Pd-L (7) py CDCl3 -HNCH2- * Particle size distribution = 2.72 ± 0.5nm ref. : Phys. Chem. Chem. Phys.2001, 3, 3377-3381

  20. Immobilization of Soluble Pd(II) Complexes d6-DMSO Pd-L-PdCl2 (8) * py -CH3 NH -HNCH2- Particle size distribution = 2.41 ± 0.5nm

  21. 4-iodoanisole 2 H 2 H 3 H Pd(II)-L :1.821×10-5 mol = 10.56 mg thiol:1.214×10-5 mol = 1.77 mg Pd NPs: 15.4-10.56-1.77= 3.07 mg d6-DMSO Pd-L-PdCl2: 15.4 mg 4-iodoanisole: 2.1 mg

  22. Particle size distribution = 2.41 ± 0.5nm Calculation of Surface Pd NPs 單顆奈米原子團表面積： 代入 r = r0 × n1/3 1.2 = 0.169 × n1/3 → n = 362 atom S = 4π r02 n2/3 = 4π (169 × 10-12)2 ×3622/3 =1.82 × 10-17 (m2) 單顆奈米原子團表面原子數： ns = S / π r02 = 1.82 × 10-17 / π (169 × 10-12)2 = 203 atom 表面原子數佔總原子數百分比 = 236 / 455 = 51.86 %

  23. ※經1H-NMR定量得知在15.4 mg的Pd-L-PdCl2 (8) 含有辛硫醇 1.77 mg。 含有Pd(II)錯化合物10.56mg 鈀奈米粒子重 = 3.07 mg 總鈀奈米粒子數 = 3.07 mg ÷ 106420 mg / mol × 6.02 × 1023 atom/mol ÷ 455 atom/particle = 7.96 ×1015particles 辛硫醇分子總數 = 1.77 mg ÷ 146000 mg / mol × 6.02 × 1023 atom/mol = 7.29 × 1018 atom Pd(II)錯化合物總數 = 10.56 mg ÷ 580000 mg / mol × 6.02 × 1023 atom/mol = 1.09 × 1019 atom 單顆鈀奈米粒子表面含： 表面鈀原子數 = 203 atom 每一顆Pd NPs含有: Pd(II)錯化合物:1.09 × 1019 atom÷(7.96×1015 particles)= 1369 atom/particle 辛硫醇= 7.29 × 1018 atom÷(7.96×1015 particles)= 915 atom/particle

  24. Analytical data of Pd Nanoparticles (6), (7) & (8)

  25. Solution 1H NMR Spectra of Pd NPs (6) & (7) • HS(CH2)(CH2)(CH2)6CH3 (n-octanethiol, HSR) CDCl3 * α H β H -CH3 (b) Pd-S(CH2)7CH3 (Pd-SR NPs) (6) β H -CH3 * (c) HS(CH2)11N(H)(O)P(2-py)2 (L) (4)) -HNCH2- py α H β H * (d) RS-Pd-S(CH2)11N(H)(O)P(2-py)2 (Pd-L NPs) (7) py -HNCH2- -CH3 *

  26. IR Spectra of n-Octanethiol & Pd-SR NPs (6)

  27. IR Spectra of Ligand (4), Pd NPs (7) & (8)

  28. IR Spectra of Ligand (4), Pd NPs (7) & (8) 1575(py) 1585 (py)

  29. Hydrogenation Mechanism

  30. Catalytic Hydrogenation Reactions in Hexane In Hexane a Cat. = 0.3 mg, b Cat. = 3.0 mg, c Cat. = 1.0 mg substrate = 3 mmol

  31. Isomerization Mechanism

  32. Hydrogenation Reactions in Various Solvent Systems In Hexane (homo.) In Ethanol (hetero.)

  33. PdCl2(CH3CN)2 vs Pd-L-PdCl2  in Hydrogenation

  34. a Cat. = 1.0 mg, solvent system: ethanol substrate = 3 mmol

  35. Hydrogenation and Isomerization Reactions isomerization Pd-SR(6) 48 66 44 Pd-L-PdCl2 (8) 62 a Cat. = 1.0 mg,solvent system: ethanol

  36. Conclusions • We have developed a method to successfully immobilize molecular Pd(II) complexes catalysts on the surfaces of Pd NPs. • Since the Pd NPs-Pd(II) hybrid catalysts are highly soluble in organic solvents, their structures and reactions could be easily studied by simple solution NMR technique. • The Pd NPs-Pd(II) complexes were proven to be catalysts for a series of hydrogenation and isomerization reactions.

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