CO–15%CO2混合气体还原碳化MoO2制备Mo2C的动力学机理分析

Kinetics and mechanism of the reduction–carburization processes of MoO2 to Mo2C with CO–15% CO2 mixed gases

  • 摘要: 对CO–15%CO2混合气体还原碳化MoO2制备Mo2C的反应机理及其动力学展开研究并采用热力学软件FactSage 7.3、场发射扫描电子显微镜 (FE-SEM)、X射线衍射(XRD)、热重(TG)、比表面积测试(BET)和模型拟合等手段和方法对实验数据进行分析。结果表明:变温实验中,升温速率越快,MoO2的开始反应温度和完全还原温度越高;恒温实验中,温度越高,MoO2的还原碳化速率越快;反应前后物相组成表明MoO2是经一步反应直接生成Mo2C,没有中间产物金属Mo的生成,并且还发现所得Mo2C基本与MoO2具有一致的片状形貌,但是由于气体的进入与逸出、产物摩尔体积的缩小以及沉积碳的减少,Mo2C颗粒表面会产生微孔和裂纹导致比表面积增长近20倍;动力学分析结果表明该还原碳化过程由形核长大与界面化学反应共同控制,其中形核长大过程占比68.9%,表观活化能为80.651 kJ·mol–1;界面化学反应占比31.1%,表观活化能为121.002 kJ·mol–1

     

    Abstract: Molybdenum carbide (Mo2C), as an alternative to platinum group metals, has been widely used in the hydrocarbon and hydrogen evolution reactions due to its excellent catalytic performance. The exploitation of its preparation method with high efficiency and low cost, therefore, received increasing attention in recent decades. In the current work, the preparation method of Mo2C by reducing MoO2 with CO–15%CO2 mixed gases was proposed, in which the main focus was laid in the reaction kinetics and reduction mechanism studies of the reduction-carburization processes. To determine the isothermal reaction temperature, the nonisothermal reactions of MoO2 in CO–15%CO2 mixed gases under different heating rates (2, 5, 10, and 15 K·min–1) were conducted first. After that, the isothermal reactions in the temperature range from 993 to 1153 K were carried out. Different analytical technologies, such as the thermodynamic calculation, Field emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), Thermogravimetric (TG), Brunauer-Emmett-Teller (BET), and model fitting methods were adopted to analyze the experimental data. The results revealed that both the beginning (953 to 997, 1015, and 1031 K) and ending reaction temperatures (1100 to 1201, 1318, and 1383 K) were gradually increased with the increase of the heating rate (2 to 5, 10, and 15 K·min–1); besides, the reaction rate increased with increasing the temperature was also obtained. Phase transformation process of MoO2 to Mo2C was found to proceed by a one-step reaction (MoO2→Mo2C) without the formation of intermediate product Mo. The study also discovered that both Mo2C and MoO2 maintained the similar platelet-shaped morphology during the reaction process, but partial micro-pores and cracks were formed on the product surface because of the entry of reaction gases and escape of the product gases as well as the shrinking of the molar volume, increasing the specific surface area of the as-obtained Mo2C by nearly 20 times when compared to that of the raw material. Kinetics analysis revealed that the reduction-carburization process of MoO2 to Mo2C were not controlled by a one-step reaction mechanism but by the co-action of nucleation growth and interfacial chemical reactions. It was also discovered that the nucleation growth accounted for 68.9% and the chemical reaction accounted for 31.1%, with the extracted activation energies of 80.651 and 121.002 kJ·mol–1, respectively. The work would make a better understanding of the reaction processes of MoO2 to Mo2C in CO–15%CO2 mixed gases.

     

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