铜基MOF的CO氧化机理

利用第一原理密度泛函理论，研究了CO在铜基MOF ( CuBTC )上氧化的反应机理。研究显示CO和O2 弱吸附在轮形Cu2构筑单元铜的顶位上，并且电子从O2和CO转移到Cu，通过两个机理(Eley-Rideal 机理和 Langmuir-Hinshelwood机理)的研究，揭示了CO在CuBTC的氧化是准Langmuir-Hinshelwood机理，先在铜上吸附的CO和氧气先越过1.8eV的能垒形成OOCO的中间体，然后分解成CO2，同时有活性氧吸附在Cu位，活性氧与第二个CO反应生成CO2。总的来说，研究有助于理解CO在铜基 MOFs的氧化。

The mechanism of CO Oxidation on Cu-based MOFs

The reaction mechanisms of CO oxidation on the Cu(II)-based metal-organic framework ( CuBTC ) were investigated by means of the first-principle density functional theory calculations. Our studies reveal that both O2 and CO weakly adsorb on the atop of Cu in the paddle-wheel Cu2 building blocks, due to the fact that the electrons transfer from O2 or CO to Cu. Via the investigation of two different mechanisms (Eley-Rideal mechanism and Langmuir-Hinshelwood mechanism), we think that CO is oxidated on CuBTC by Quasi-Langmuir-Hinshelwood mechanism, which can be summarized as: (1) The adsorbed CO reacts with O2 to form OOCO intermediate by energy barrier of 1.80 eV, and further decomposes to form CO2; (2) The residual activated O-CuBTC further reacts readily with another CO molecule and generates another CO2 . Generally, our studies may provide a help for understanding CO oxidation on Cu-based MOFs.