Cu-Al尖晶石的合成及非等温生成动力学分析

Synthesis of Cu-Al spinels and its non-isothermal formation kinetics analysis

以程序升温碳化法合成β-Mo2C载体,采用原位沉淀法制备负载量不同的Au/β-Mo2C催化剂,利用XRD、STEM和氮气吸附-脱附等手段对Au在载体表面的分散性、微观形貌及孔结构等进行表征,并在逆水煤气变换(RWGS)反应中对其高温热稳定性进行了研究。XRD表征结果表明,在34.44°、38.02°、39.44°、52.12°、61.53°、69.62°和74.65°处出现了β-Mo2C对应的(100)、(002)、(101)、(102)、(110)、(103)和(200)晶面的X射线特征衍射峰;同时,未出现Au物种的特征吸收峰,说明Au负载量较低的0.1%和0.5%的催化剂上Au纳米粒子的分散性较好。STEM表征结果也显示,当负载量较低(0.5%、1.0%和2.0%)时,金纳米粒子以2 nm左右的原子簇形式均匀分散并锚定在β-Mo2C载体上。氮气吸附-脱附表征结果表明,催化剂具有良好的介孔结构。反应评价结果表明,0.2%Au/β-Mo2C催化剂在RWGS反应中具有较好的催化活性和较高的CO选择性,且反应后孔结构良好,Au纳米粒子仍然均匀分散,说明Au/β-Mo2C催化剂在此反应中具有较高的催化性能和高温热稳定性。

Cu-Al spinels were synthesized by a solid phase method using Cu(OH)2 and pseudo-boehmite as the raw materials.The effects of synthesis temperature,synthesis time and Cu/Al molar ratio on the formation and properties of Cu-Al spinels were fully investigated by the thermogravimetry(TG/DTG),X-ray diffraction(XRD),H2 temperature programmed reduction(H2-TPR).The non-isothermal kinetics of Cu-Al spinel formation process were analyzed using Coats-Redfern method and two diffusion-controlled kinetic models.Characterization results showed that the Cu-Al surface spinels with unsaturated coordination formed easily at the temperature as low as 400℃,and the content of these surface spinel decreased sharply with the synthesis temperature rising.The hardly-reducible spinel Cu^2+species and easily-reducible spinel Cu^2+species were identified at the synthesis temperature of 700 and 800℃,respectively.The spinel content increased gradually with the synthesis temperature increasing,leading to the formation of Al-rich spinel solid solutions with different Cu/Al molar ratios.At a higher temperature of 1200℃,however,the formation of stoichiometric CuAl2O4 spinel was observed.Hence,the spinel reducibility varied dramatically with the synthesis temperature as illustrated by the drastic change of the molar ratio of hardly-reducible spinel Cu^2+species and easily-reducible spinel Cu^2+species.An appropriate excess of Al3+(Cu/Al=1∶3)could result in the formation of spinel solid solution with more hardly-reducible spinel Cu^2+species,while an excess of Cu^2+would lead to the formation of delafossite-type CuAlO2.Both samples owned low reducibility as compared to the stochiometric CuAl2O4 spinel.Besides,a longer synthesis time would favor the spinel formation as well but to a limited extent.Non-isothermal kinetics analysis showed that the formation process of Cu-Al spinel owned three kinetic regions in terms of synthesis temperature,namely 700-850,850-950 and 950-1200℃,and the apparent activation energies were determined to be 85.2,304.4 and 38.1 kJ/mol,respectively.The diffusion of reactants via product layer could be considered as an one-dimensional diffusion below 950℃,whereas it was more likely to be a three-dimensional diffusion above 950℃,indicating that the product layer became much thicker.