醇在固体催化剂上的绿色催化氧化.pptVIP

Seminar II * Green, Catalytic Oxidations of Alcohols on Solid Catalysts * Contents Introduction 1 Intrinsically Solid Catalysts 2 Heterogenized Metal Complexes 3 Conclusion 4 * Selective oxidation of alcohols to the corresponding carbonyl compounds is one of the most important functional-group transformations in modern organic synthesis. The word-wide annual production of carbonyl compounds is over 107 tonnes and many of them are produced from the oxidation of alcohols. Introduction Oxidation of alcohol * Introduction 2 Stoichiometric expensive oxidants (e.g. TPAP, TEMPO) Toxic heavy metal reagents (e.g. Cr, Mn) 1 3 Green oxidants (e.g. O2, air ) The only by-product * Intrinsically Solid Catalysts Supported Pd catalysts 1 Supported Ru catalysts 2 Mechanism 3 * Pd catalysts Pd/Al2O3 Catalysts Pd/Al2O3 catalyst (Pd, 0.32 wt %), solvent-free, small Pd nanoparticles (ca. 5 nm), Y. Wang. et.al. Adv. Synth. Catal. 347 (2005) 1356-1360 C. Mondelli, A. Baiker. J. Catal. et.al. 252 (2007) 77-87 Recently, A. Baiker studied the effect of Bi on 0.75 wt% Bi–5 wt% Pd/Al2O3 catalyst. ATR-IR and XAS indicated that Bi-promoted Pd/Al2O3 catalyst was more resistant against over-oxidation. * Pd catalysts Pd-HAP Catalysts K. Kaneda. et. al. J. Am. Chem. Soc. 126 (2004) 10657-10666 * 0.25% Au-0.25% Pd/TiO2上催化氧化醇的活性 Pd catalysts 0.25%Au-0.25%Pd/TiO2 gives high TOF and high selectivity. the Au-Pd nanocrystals were made of a Au-rich core with a Pd-rich shell. Au as an electronic promoter for Pd D. I. Enache, G. J. Hutching. et. al. Science. 311 (2006) 362-365 L. Prati. et. al. J. Catal. 244 (2006) 113-121 G. J. Hutching. et. al. Catal. Today. 122 (2007) 407-411 Au-Pd catalysts 0.73%Au–0.27%Pd/AC and 0.6%Au–0.4%Pt/AC Sol method ----------a single alloyed phase Au/Pd catalyst showed a positive synergistic effect; Au/Pt, a negative one. * Ru/Al2O3 Ru catalysts overoxidation of unactivated primary alcohols to the carboxylic acids overcome by the addition of a sma