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在Rh16/In2O3催化剂上催化二氧化碳加氢合成甲醇的机理:密度泛函理论与微动力学模型的联合研究

王宇宁 龚杰松 周嘉斌 陈志远 田冬 纳薇 高文桂

王宇宁, 龚杰松, 周嘉斌, 陈志远, 田冬, 纳薇, 高文桂. 在Rh16/In2O3催化剂上催化二氧化碳加氢合成甲醇的机理:密度泛函理论与微动力学模型的联合研究[J]. 燃料化学学报(中英文). doi: 10.1016/S1872-5813(24)60460-3
引用本文: 王宇宁, 龚杰松, 周嘉斌, 陈志远, 田冬, 纳薇, 高文桂. 在Rh16/In2O3催化剂上催化二氧化碳加氢合成甲醇的机理:密度泛函理论与微动力学模型的联合研究[J]. 燃料化学学报(中英文). doi: 10.1016/S1872-5813(24)60460-3
WANG Yuning, GONG Jiesong, ZHOU Jiabin, CHEN Zhiyuan, TIAN Dong, NA Wei, GAO Wengui. Mechanism of Methanol Synthesis from CO2 Hydrogenation over Rh16/In2O3 Catalysts: A Combined Study on Density Functional Theory and Microkinetic Modeling[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(24)60460-3
Citation: WANG Yuning, GONG Jiesong, ZHOU Jiabin, CHEN Zhiyuan, TIAN Dong, NA Wei, GAO Wengui. Mechanism of Methanol Synthesis from CO2 Hydrogenation over Rh16/In2O3 Catalysts: A Combined Study on Density Functional Theory and Microkinetic Modeling[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(24)60460-3

在Rh16/In2O3催化剂上催化二氧化碳加氢合成甲醇的机理:密度泛函理论与微动力学模型的联合研究

doi: 10.1016/S1872-5813(24)60460-3
基金项目: 云南省重大科技专项计划(202302AG050005-2)资助
详细信息
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    Tel: 13608865529, E-mail: gaowengui@126.com

  • 中图分类号: TQ032

Mechanism of Methanol Synthesis from CO2 Hydrogenation over Rh16/In2O3 Catalysts: A Combined Study on Density Functional Theory and Microkinetic Modeling

Funds: The project was supported by the Major Science and Technology Special Project of Yunnan Province (202302AG050005-2).
  • 摘要: 本研究采用密度泛函理论 (DFT) 和微动力学模型分析了 Rh16/In2O3 催化剂上二氧化碳 (CO2) 氢化成甲醇 (CH3OH) 的情况;研究了 Rh16/In2O3 界面上 H2 的自发解离和 CO2 的有效吸附,其中, In2O3 中的氧空位提供了有利的效果。此外,Bader 电荷分析显示 Rh16 上带有轻微的正电荷,这对于理解催化剂的电子特性和活性非常重要。证实了RWGS+CO-Hydro 途径是甲醇合成的主要途径,其特点是经过一系列中间转化:CO2*→COOH*→CO*+OH*→HCO*→CH2O*→CH2OH*→ CH3OH*。在不同温度 (373−873K) 和压力 (10−2−103 bar) 下进行的反应速率控制程度分析 (DRC) 揭示了两个关键的动力学现象:在较低温度和较高压力下,转化步骤 CO* + H* → HCO * 显着影响总体反应速率;而在较高温度下,CH2O* + H* → CH3O* 的步骤占主导地位。
  • 图  1  四种Rh金属团簇及其直径

    Figure  1  SeVeral Rh metal clusters and their diameters

    图  2  (a)由20个Rh原子组成的Rh棒状模型,将Rh模型加载到有缺陷的In2O3表面上,In2O3表面上的四个 O 原子与四个 Rh 原子相互作用,导致 Rh 以 Rh16 的形式结合;(b)Rh16/In2O3基底:侧视图(上)、俯视图(下);(c)Rh16/In2O3(110) 模型及Rh16 /In2O3模型中的差分电荷分布图,模型(上),差分电荷分布图(下)

    Figure  2  2(a) Rh rod-shaped model composed of 20 Rh atoms, the Rh model is loaded onto the defective In2O3 surface, the four O atoms on the In2O3 surface interact with the four Rh atoms, resulting in Rh in the form of Rh16 combine; combine (b) Rh16/In2O3 substrate: side view (top), top view (bottom); (c) Differential charge distribution diagram in Rh16/In2O3(110) model and Rh16/In2O3 model, model (top), differential charge distribution diagram (bottom)

    图  3  Rh16/In2O3中反应物质的稳定吸附结构及其吸附位置

    Figure  3  Stable adsorption structure and adsorption position of reactive substances in Rh16/In2O3

    图  4  Rh16附近二氧化碳分子周围的电荷分布

    Figure  4  Charge distribution around carbon dioxide molecules near Rh16

    图  5  CO2到甲醇反应路径,黑色为HCOO路径,绿色代表COOH路径,蓝色代表RWGS路径,其他颜色代表分支反应路径

    Figure  5  Reaction pathways from CO2to methanol Black represents the formate (HCOO) pathway, green represents the carboxyl (COOH) pathway, blue represents the RWGS pathway, and other colors represent branch reaction pathways

    图  6  Rh16/In2O3催化剂上 HCOO 路径合成甲醇的势能曲线

    Figure  6  Potential energy curve of methanol synthesis via HCOO pathway over Rh16/In2O3 catalyst

    图  7  CO2甲醇的加氢作用,HCOO通道主自由基反应的初始、过渡和最终状态的优化结构

    Figure  7  Hydrogenation of CO2methanol, optimized structures of the initial, transition and final states of the main radical reaction of the HCOO channel

    图  8  CO2加氢生成甲醇羧基途径的势能面(PES)

    Figure  8  Potential energy surface (PES) of the CO2 hydrogenation to methanol carboxyl pathway

    图  9  Rh16/In2O3上CO2加氢合成甲醇,对 COOH 通道各个自由基反应的初始、过渡和最终状态进行了优化结构,其余分支反应如图7所示

    Figure  9  Methanol is synthesized from CO2 hydrogenation on Rh16/In2O3. The initial, transition and final states of each free radical reaction in the COOH channel are optimized. The remaining branch reactions are shown in Figure 7

    图  10  在Rh16/In2O3催化剂上,RWGS+CO-二氧化碳加氢成甲醇的势能面(PES)

    Figure  10  Potential energy surface (PES) of RWGS+CO-carbon dioxide hydrogenation to methanol on Rh16/In2O3 catalyst

    图  11  对RWGS + CO-HydrO通道的二氧化碳加氢反应合成甲醇的单个原始反应的初始、过渡和最终状态的优化结构,其余分支反应见图7

    Figure  11  Optimized structures of the initial, transition and final states of a single original reaction for the synthesis of methanol from carbon dioxide hydrogenation of the RWGS + CO-HydrO channel. The remaining branch reactions are shown in Figure 7

    图  12  不同压力和温度下的整体反应速率

    Figure  12  Overall reaction rate at different pressures and temperatures

    图  13  (a)、 (b)、 (c)不同反应步骤的 DRC 动力学曲线作为温度和压力的函数(d) 反应步骤的 DRC 与温度曲线

    Figure  13  (a), (b), (c) DRC kinetic curves for different reaction steps as a function of temperature and pressure(d) DRC vs. temperature curves of reaction steps

    表  1  五种Rh金属团簇的功函数

    Table  1  Work functions of seVeral Rh metal clusters

    Model Diameter/nm Number of atoms Work function
    Rh13 0.6 13 4.039
    Rh43 1.0 43 4.130
    Rh55 1.2 55 4.177
    Rh165 1.8 165 4.317
    Rh(rods) 16 4.418
    下载: 导出CSV

    表  2  Rh16/In2O3上的吸附能、吸附位和反应种类的结构参数

    Table  2  Structural parameters of adsorption energies, adsorption sites and reaction types on Rh16/In2O3

    Specie Eads/eV Site Bond length (Å) and bond angle (°)
    CO2 −1.16 interface d(Rh−O)=2.126;d(In−O)= 2.247;
    d(Rh−C)=1.973;∠Oa−C−Ob=121.9°
    H(1/2 H2) −0.68 Rh metal d(Rh−H)=1.709/1.772
    H2O −0.83 In2O3 interface d(In−O)= 2.352
    HCOOH −0.94 In2O3 interface d(In−O)=2.314
    CH2O −1.51 Rh metal d(Rh−O)=2.016;d(Rh−C)=2.149/2.124
    CH3OH −1.43 In2O3 interface d(In−O)= 2.264;d(O−H)= 1.577
    CO −2.57 Rh metal d(Rh−C)=1.964/1.982
    下载: 导出CSV

    表  3  HCOO 途径中甲醇合成所涉及的基本步骤的反应能ΔE 和势垒Eb

    Table  3  Reaction energy ΔE and potential barrier Eb of the basic steps involved methanol synthesis in the HCOO pathway

    Elementary reaction step Eb/eV E/eV
    CO2* + H* → HCOO* + * 0.69 −0.86
    HCOO* + H* → H2COO* + * 1.72 0.17
    H2COO* + H* → H2COOH* + * 0.97 0.41
    H2COOH* + *→CH2O*+ OH* 0.79 −0.06
    HCOO* + H* → HCOOH* + * 1.15 0.14
    HCOOH* + * → HCO* + OH* 0.54 −1.02
    HCO* + H* → CH2O* + * 1.10 −0.06
    CH2O* + H* → CH3O* + * 1.07 0.57
    CH3O* + H* → CH3OH* + * 0.30 0.10
    CH2O* + H* → CH2OH* + * 1.02 0.20
    CH2OH* + H* → CH3OH* + * 0.37 0.10
    下载: 导出CSV

    表  4  COOH途径中甲醇合成所涉及的基本步骤的反应能 ΔE 和势垒Eb

    Table  4  Reaction energies ΔE and potential barriers Eb for the basic steps involved in methanol synthesis in the COOH pathway

    Elementary reaction step Eb/eV E/eV
    CO2* + H* → COOH* + * 0.99 −0.70
    COOH* + H* → HCOOH* + * 0.88 0.14
    HCOOH* + *→HCO* + OH* 0.68 −1.01
    COOH* + * → CO* + OH* 0.51 −1.88
    HCO* + H* → CH2O* + * 1.10 −0.06
    下载: 导出CSV

    表  5  RWGS + CO-Hydro 通道中甲醇合成所涉及的基本步骤的反应能 ΔE和能垒 Eb

    Table  5  Reaction energy ΔE and energy barrier Eb for the basic steps involved in methanol synthesis in the RWGS +CO-Hydro channel

    Elementary reaction step Eb/eV E/eV
    CO2* + H* → COOH* + * 0.99 −0.70
    COOH* + * → CO* + OH* 0.51 −1.88
    CO* + H* → HCO* + * 1.37 −1.01
    HCO* + H* → CH2O* + * 1.10 −0.06
    CO2* + * → CO* + O* 2.18 −1.18
    CO* +O* → C* + O* 2.94 0.72
    下载: 导出CSV
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  • 收稿日期:  2024-03-07
  • 修回日期:  2024-04-16
  • 录用日期:  2024-04-16
  • 网络出版日期:  2024-06-04

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