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제108회 대한화학회 학술발표회, 총회 및 기기전시회 안내 Chemical Hydrogen Material for Hydrogen Fuel Cell Applications: Palladium Catalysts for Dehydrogenation of Ammonia Borane

2011년 7월 30일 18시 18분 22초
Ⅰ-IND.P-16 이곳을 클릭하시면 발표코드에 대한 설명을 보실 수 있습니다.
목 <발표Ⅰ>
저자 및
김성관, 강상욱
고려대학교 소재화학과, Korea
The efficient catalytic dehydrocoupling of a range of amine-borane adducts, R1R2NH?BH2R3 (R1, R2, and R3= Alkyl or Aryl) by a series of Pd(II) precatalysts has been demonstrated. Cationic Pd(II) complexes were found to promote the transformation of R1R2NH?BH2R3 to BR3NR1R2H2 in a homogeneous catalytic process. The corresponding ammonia borane spent fuel was completely recovered from the tetraglyme solution in the form of BNHx, and the catalyst debris was transformed into the nanoparticles (NPs). The PdNPs catalyzed methanolysis, selectively converted the spent fuel to B(OMe)3 and [Me(OH)N]2CH2. After the second catalysis, the PdNPs were completely recovered from the methanol solution. The reaction mechanism of the dehydrocoupling was investigated by DFT calculations. On the basis of the computational study, we propose that the catalytic dehydrogenation reactions proceed via an intramolecular pathway. It can clearly be seen that inclusion of four acetonitrille ligands in the model leads to the significant stabilization of all the intermediates and the transition states, as compared to the models containing less number of NCMe species. Considering the kinetics, one might notice the two rate determining steps with the relatively low activation barriers Such relatively low values of E# as compared to the energy of isolated reactants are in line with the fast kinetics of the palladium catalyst.