CAJ | 학술논문

基于密度泛函理论方法,采用广义梯度近似方法结合周期平板模型,对甲醇氧化羰基化反应中CuCl (111)表面上CO和CH3 O的吸附、共吸附及CH3 OCO的吸附进行了系统研究,探讨了CO和CH3 O反应生成CH3OCO以及CH3OCO和CH3O反应生成碳酸二甲酯(DMC)的动力学特性.计算结果表明,在CuCl(111)表面的共吸附体系中, CO和CH3 O之间的相互作用力比自由态的CO和CH3 O之间的作用力大； CO和CH3 O反应生成CH3 OCO为整个甲醇氧化羰基化反应的速控步骤,活化能为113.19 kJ/mol,计算结果与实验结果一致.
기우밀도범함이론방법,채용엄의제도근사방법결합주기평판모형,대갑순양화탄기화반응중CuCl (111)표면상CO화CH3 O적흡부、공흡부급CH3 OCO적흡부진행료계통연구,탐토료CO화CH3 O반응생성CH3OCO이급CH3OCO화CH3O반응생성탄산이갑지(DMC)적동역학특성.계산결과표명,재CuCl(111)표면적공흡부체계중, CO화CH3 O지간적상호작용력비자유태적CO화CH3 O지간적작용력대； CO화CH3 O반응생성CH3 OCO위정개갑순양화탄기화반응적속공보취,활화능위113.19 kJ/mol,계산결과여실험결과일치.
Based on density functional theory method in the generalized gradient approximation, together with the periodic slab model, the single adsorption of CO and CH3 O, as well as the co-adsorption of CO and CH3 O on CuCl(111) surface involving in methanol oxidative carbonylation to dimethyl carbonate( DMC) were sys-tematically investigated. The reaction mechanisms of CO interaction with CH3 O leading to CH3 OCO and CH3OCO interaction with CH3O to DMC on CuCl(111) surface were discussed. The calculated results indi-cate that the interaction between CO and CH3 O in the co-adsorption system is stronger than that between free CO and CH3 O in gas phase, CO insertion into adsorbed CH3 O on CuCl(111) surface to CH3 OCO species are the rate-limiting step for the oxidative carbonylation of methanol to DMC, and the corresponding activation bar-rier is 113. 19 kJ/mol, the calculated results are in accordance with the reported experimental facts.