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CO–15%CO2混合氣體還原碳化MoO2制備Mo2C的動力學機理分析

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

  • 摘要: 對CO–15%CO2混合氣體還原碳化MoO2制備Mo2C的反應機理及其動力學展開研究并采用熱力學軟件FactSage 7.3、場發射掃描電子顯微鏡 (FE-SEM)、X射線衍射(XRD)、熱重(TG)、比表面積測試(BET)和模型擬合等手段和方法對實驗數據進行分析。結果表明:變溫實驗中,升溫速率越快,MoO2的開始反應溫度和完全還原溫度越高;恒溫實驗中,溫度越高,MoO2的還原碳化速率越快;反應前后物相組成表明MoO2是經一步反應直接生成Mo2C,沒有中間產物金屬Mo的生成,并且還發現所得Mo2C基本與MoO2具有一致的片狀形貌,但是由于氣體的進入與逸出、產物摩爾體積的縮小以及沉積碳的減少,Mo2C顆粒表面會產生微孔和裂紋導致比表面積增長近20倍;動力學分析結果表明該還原碳化過程由形核長大與界面化學反應共同控制,其中形核長大過程占比68.9%,表觀活化能為80.651 kJ·mol–1;界面化學反應占比31.1%,表觀活化能為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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