甲醇氧化羰基合成碳酸二甲酯反应机理的DFT研究
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摘要
作为一种优秀的绿色化学品，碳酸二甲酯（DMC）具有优良的化学反应性能和广泛的应用前景。目前应用于甲醇氧化羰基合成DMC体系中的催化剂主要包括两种：负载型含氯催化剂和交换型分子筛类催化剂。其中，相比分子筛催化剂，负载型含氯催化剂拥有更好的活性；但含氯型催化剂组成复杂，单独制备单一晶型较为困难，故而很难明确其活性组分及不同组分间的活性差异。本文采用量子化学手段，分别对六种负载型含氯催化剂（γ-Cu2(OH)3Cl，-Cu2(OH)3Cl，Cu(OH)Cl，CuCl2，Pd/CuCl2，2Pd/CuCl2）模型上甲醇氧化羰基合成DMC的反应机理进行考察，从而明确不同催化剂活性组分，以及催化剂活性组分的各个组成部分或组成元素在催化反应中所起的作用，从而为实验上改进催化剂或研发新型催化剂提供了理论依据和理论指导。
在含Cl型催化剂表面上，反应机理可分为甲醇氧化反应，CO插入反应，DMC生成反应和表面重构反应四个步骤。甲醇吸附位为催化剂顶层Cl原子顶端，甲醇通过羟基H与Cl原子间的相互作用吸附于催化剂表面，吸附过程中部分电子从甲醇转移到催化剂表面，同时甲醇羟基得到活化，使得氧化反应更容易进行。但是，在不同的含氯催化剂表面，甲醇氧化过程并不完全相同。在γ-Cu2(OH)3Cl(021)和-Cu2(OH)3Cl(011)催化剂表面上，甲醇氧化过程为Cl首先脱离催化剂表面，与甲醇羟基H原子作用，生成CH3O H Cl中间体结构；进而该中间体分解为甲氧基和HCl，而CH3O H Cl中间体的分解过程也是整个甲醇氧化羰基合成DMC反应的速率控制步骤。而在Cu(OH)Cl(001)和CuCl2(001)，Pd/CuCl2(001)，2Pd/CuCl2(001)催化剂表面上，甲醇氧化过程则为Cl直接与甲醇反应，生成甲氧基和HCl，不存在其他中间体，该步骤亦为这三种催化剂表面上甲醇氧化羰基合成DMC反应的速率控制步骤。
在三种碱式氯化铜表面（γ-Cu2(OH)3Cl(021)，-Cu2(OH)3Cl(011)和Cu(OH)Cl）上，CO为物理吸附。CO插入反应的产物CH3OCO的吸附稳定性对下一步反应，DMC生成的活化能影响较大，CH3OCO的吸附能越低，则生成DMC所需活化能越低。而在CuCl2(001)和Pd掺杂的CuCl2(001)（包括Pd/CuCl2(001)，2Pd/CuCl2(001)两种）表面上，CO为化学吸附态，此时，CO的吸附位对CO插入反应活化能影响较小。且在Pd掺杂的CuCl2(001)表面上，反应产物CH3OCO的吸附位置和吸附构型则对DMC生成反应有较大影响，当CH3O和CH3OCO分别与Pd原子和Cu原子同时存在相互作用时，生成DMC较为容易。而当DMC脱离催化剂表面后，失去Cl的催化剂表面均可自发与体系中的O2和HCl反应，并释放大量的热。
As an important green chemical intermediate, dimethyl carbonate (DMC) is anenvironmentally benign compound with versatile chemical reactivity and excellentprospects of application. Two series of catalyst, supported chlorine containingcatalysts and exchanged zeolite catalysts, are known to be activated and investigatedmost in gas-phase oxidative carbonylation of methanol to form DMC. Comparingwith the zeolite catalysts, the chlorine containing catalysts show higher activity.However, the complicated composition of the supported chlorine containing catalystslimits the deeper investigation of the catalysts and the reaction details. The force ofthis dissertation is to investigate the reaction mechanism of the gas-phaseoxycarbonylation of methanol on different chlorine containing catalysts (includingγ-Cu2(OH)3Cl,-Cu2(OH)3Cl, Cu(OH)Cl, CuCl2, Pd/CuCl2,2Pd/CuCl2), thus toclarify the role of the catalyst components in the reaction and provide someinformation for catalyst improvements.
On the surfaces of chlorine containing catalysts, the reaction mechanism can beseparated into four main steps: methanol oxidation, CO insertion, DMC formation andsurface reconstruction. During the reaction, the methanol molecularly adsorbed at thetop site of the Cl atom on the top slayer of the surface through the hydroxyl H atom,and the electron transfer between the CH3OH and the surface activated the CH3OH.However, the oxidation process is slightly different on different surfaces. On theγ-Cu2(OH)3Cl(021) and-Cu2(OH)3Cl(011) surfaces, the Cl atom escaped from thesurface and bonded with the methanol first (formed CH3O H Cl) then reacted withthe methanol to form adsorbed methoxyl and HCl; and the calculated results indicatethe decomposition of the CH3O H Cl is the rate-limit step of the whole methanoloxycarbonylation reaction. But on the surfaces of Cu(OH)Cl(001), CuCl2(001) andPd/CuCl2(001), the Cl atom reacted with the methanol directly to form the methoxyland HCl, and the methanol oxidation is also the rate-limit step of the mechanism onthese three surfaces.
The CO species physically adsorbed on the surfaces of γ-Cu2(OH)3Cl(021),
-Cu2(OH)3Cl(011) and Cu(OH)Cl(001). And the stability of the CH3OCO adsorptionwould further affect the DMC formation process, the lowest energy barrier for DMCformation step appears when the adsorption of CH3OCO is weakest. Comparatively, the CO species chemically adsorbed on CuCl2(001) and Pd/CuCl2(001) surfaces. Andthe adsorption site of CO has slight effect on the energy barrier of CO insertion.Meanwhile, the adsorption site of CH3OCO and CH3O will strongly affect the DMCformation process. The lowest energy barrier for DMC formation step appears whenCH3OCO and CH3O adsorbed on both Cu and Pd atoms. Furthermore, the surfacereconstruction process on all chlorine containing catalyst is spontaneous andexothermic, which needs the HCl and O2at the same time.
在含Cl型催化剂表面上，反应机理可分为甲醇氧化反应，CO插入反应，DMC生成反应和表面重构反应四个步骤。甲醇吸附位为催化剂顶层Cl原子顶端，甲醇通过羟基H与Cl原子间的相互作用吸附于催化剂表面，吸附过程中部分电子从甲醇转移到催化剂表面，同时甲醇羟基得到活化，使得氧化反应更容易进行。但是，在不同的含氯催化剂表面，甲醇氧化过程并不完全相同。在γ-Cu2(OH)3Cl(021)和-Cu2(OH)3Cl(011)催化剂表面上，甲醇氧化过程为Cl首先脱离催化剂表面，与甲醇羟基H原子作用，生成CH3O H Cl中间体结构；进而该中间体分解为甲氧基和HCl，而CH3O H Cl中间体的分解过程也是整个甲醇氧化羰基合成DMC反应的速率控制步骤。而在Cu(OH)Cl(001)和CuCl2(001)，Pd/CuCl2(001)，2Pd/CuCl2(001)催化剂表面上，甲醇氧化过程则为Cl直接与甲醇反应，生成甲氧基和HCl，不存在其他中间体，该步骤亦为这三种催化剂表面上甲醇氧化羰基合成DMC反应的速率控制步骤。
在三种碱式氯化铜表面（γ-Cu2(OH)3Cl(021)，-Cu2(OH)3Cl(011)和Cu(OH)Cl）上，CO为物理吸附。CO插入反应的产物CH3OCO的吸附稳定性对下一步反应，DMC生成的活化能影响较大，CH3OCO的吸附能越低，则生成DMC所需活化能越低。而在CuCl2(001)和Pd掺杂的CuCl2(001)（包括Pd/CuCl2(001)，2Pd/CuCl2(001)两种）表面上，CO为化学吸附态，此时，CO的吸附位对CO插入反应活化能影响较小。且在Pd掺杂的CuCl2(001)表面上，反应产物CH3OCO的吸附位置和吸附构型则对DMC生成反应有较大影响，当CH3O和CH3OCO分别与Pd原子和Cu原子同时存在相互作用时，生成DMC较为容易。而当DMC脱离催化剂表面后，失去Cl的催化剂表面均可自发与体系中的O2和HCl反应，并释放大量的热。
As an important green chemical intermediate, dimethyl carbonate (DMC) is anenvironmentally benign compound with versatile chemical reactivity and excellentprospects of application. Two series of catalyst, supported chlorine containingcatalysts and exchanged zeolite catalysts, are known to be activated and investigatedmost in gas-phase oxidative carbonylation of methanol to form DMC. Comparingwith the zeolite catalysts, the chlorine containing catalysts show higher activity.However, the complicated composition of the supported chlorine containing catalystslimits the deeper investigation of the catalysts and the reaction details. The force ofthis dissertation is to investigate the reaction mechanism of the gas-phaseoxycarbonylation of methanol on different chlorine containing catalysts (includingγ-Cu2(OH)3Cl,-Cu2(OH)3Cl, Cu(OH)Cl, CuCl2, Pd/CuCl2,2Pd/CuCl2), thus toclarify the role of the catalyst components in the reaction and provide someinformation for catalyst improvements.
On the surfaces of chlorine containing catalysts, the reaction mechanism can beseparated into four main steps: methanol oxidation, CO insertion, DMC formation andsurface reconstruction. During the reaction, the methanol molecularly adsorbed at thetop site of the Cl atom on the top slayer of the surface through the hydroxyl H atom,and the electron transfer between the CH3OH and the surface activated the CH3OH.However, the oxidation process is slightly different on different surfaces. On theγ-Cu2(OH)3Cl(021) and-Cu2(OH)3Cl(011) surfaces, the Cl atom escaped from thesurface and bonded with the methanol first (formed CH3O H Cl) then reacted withthe methanol to form adsorbed methoxyl and HCl; and the calculated results indicatethe decomposition of the CH3O H Cl is the rate-limit step of the whole methanoloxycarbonylation reaction. But on the surfaces of Cu(OH)Cl(001), CuCl2(001) andPd/CuCl2(001), the Cl atom reacted with the methanol directly to form the methoxyland HCl, and the methanol oxidation is also the rate-limit step of the mechanism onthese three surfaces.
The CO species physically adsorbed on the surfaces of γ-Cu2(OH)3Cl(021),
-Cu2(OH)3Cl(011) and Cu(OH)Cl(001). And the stability of the CH3OCO adsorptionwould further affect the DMC formation process, the lowest energy barrier for DMCformation step appears when the adsorption of CH3OCO is weakest. Comparatively, the CO species chemically adsorbed on CuCl2(001) and Pd/CuCl2(001) surfaces. Andthe adsorption site of CO has slight effect on the energy barrier of CO insertion.Meanwhile, the adsorption site of CH3OCO and CH3O will strongly affect the DMCformation process. The lowest energy barrier for DMC formation step appears whenCH3OCO and CH3O adsorbed on both Cu and Pd atoms. Furthermore, the surfacereconstruction process on all chlorine containing catalyst is spontaneous andexothermic, which needs the HCl and O2at the same time.
引文
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