淡江大學機構典藏:Item 987654321/25403
English  |  正體中文  |  简体中文  |  全文筆數/總筆數 : 62797/95867 (66%)
造訪人次 : 3734983      線上人數 : 401
RC Version 7.0 © Powered By DSPACE, MIT. Enhanced by NTU Library & TKU Library IR team.
搜尋範圍 查詢小技巧:
  • 您可在西文檢索詞彙前後加上"雙引號",以獲取較精準的檢索結果
  • 若欲以作者姓名搜尋,建議至進階搜尋限定作者欄位,可獲得較完整資料
  • 進階搜尋
    請使用永久網址來引用或連結此文件: https://tkuir.lib.tku.edu.tw/dspace/handle/987654321/25403


    題名: Theoretical Study on the Reaction Mechanism of Nickel Atoms with Carbon Dioxide
    作者: 黃德彥;Hwang, Der-yan;Mebel, Alexander M.
    貢獻者: 淡江大學化學學系
    日期: 2000-11-16
    上傳時間: 2009-12-01
    出版者: American Chemical Society (ACS)
    摘要: Ab initio and density functional calculations of the potential energy surfaces for the Ni + CO2 → NiO + CO reaction in the lowest triplet and singlet electronic states have been carried out at the B3LYP/6-31G*, B3LYP/6-311G*, B3LYP/6-311+G(3df), CCSD(T)/6-311G*, and CCSD(T)/6-311+G(3df) theoretical levels. The reaction is calculated to preferentially occur in the triplet state and to proceed by the formation of a cyclic four-member ring C2v-symmetric NiOCO intermediate (t-cyc) that lies ∼19 kcal/mol above the reactants. The barrier for the initial reaction step is about 23 kcal/mol. From t-cyc the reaction continues via transition state t-TS2 toward the linear t-CONiO complex. The latter is stabilized by ∼10 kcal/mol with respect to the products, NiO (3Σ-) + CO, and can dissociate producing them without exit barrier. The highest barrier at the reaction pathway, about 53 kcal/mol, occurs at t-TS2. The reverse NiO (3Σ-) + CO reaction yielding Ni atoms and CO2 with exothermicity of 36 kcal/mol is shown to have a barrier of 15 kcal/mol relative to the reactants occurring at the second reaction step. On this basis, nickel oxide is expected to be less efficient for oxidizing CO to CO2 than the oxides of alkaline earth metals. Reduction of CO2 to CO can be significantly enhanced in the presence of Ni atoms due to much lower endothermicity (36−37 kcal/mol) and activation barrier (∼53 kca/mol) for the t-Ni + CO2 → NiO (3Σ-) + CO reaction as compared to those for the unimolecular decomposition of carbon dioxide. The accuracies of different theoretical methods for calculations of the reaction energies have been compared.
    關聯: Journal of physical chemistry A 104(49), pp.11622-11627
    DOI: 10.1021/jp002402z
    顯示於類別:[化學學系暨研究所] 期刊論文

    文件中的檔案:

    檔案 描述 大小格式瀏覽次數
    0KbUnknown253檢視/開啟
    Theoretical Study on the Reaction Mechanism of Nickel Atoms with Carbon Dioxide.pdf78KbAdobe PDF3檢視/開啟

    在機構典藏中所有的資料項目都受到原著作權保護.

    TAIR相關文章

    DSpace Software Copyright © 2002-2004  MIT &  Hewlett-Packard  /   Enhanced by   NTU Library & TKU Library IR teams. Copyright ©   - 回饋