本文采用电弧熔炼法制备具有单一C14 Laves相结构的TixZr1-xMnFe(x=0、0.25,摩尔分数)吸气合金,在660~700 ℃下用自制的简易Sieverts型恒容设备对ZrMnFe进行CO2气体吸附反应测试,研究其吸附性能及其吸附CO2气体的行为。结果表明：随温度升高,CO2吸附量先增大后减小,在680 ℃时的最大吸附量为3.869 mmol/g,此时吸附性能最好。进行Ti掺杂获得TixZr1-xMnFe吸气合金后,吸附量较掺杂前提升19.2%,但前8 h的吸附速率从0.301 mmol/(g∙h)降低到0.119 mmol/(g∙h)。结合第一性原理对吸附机理进行研究,通过吸附能比较得出最佳吸附位置为ZrMnFe (110)表面水平取向的空位,吸附能为5.531 eV。对态密度进行研究发现,ZrMnFe (110)表面和CO2气体分子之间的相互作用主要由O的2s轨道和Zr原子的4p、4d轨道的杂化导致。
In this paper, TixZr1-xMnFe (x=0, 0.25, mole fraction) inspiratory alloy with a single C14 Laves phase structure was prepared by arc melting method. CO2 gas adsorption reaction for ZrMnFe was tested by a self-made simple Sieverts constant volume equipment between 660-700 ℃, to study the adsorption performance as well as the adsorption behavior to CO2 gas. The results show that with the increase of temperature, the adsorption capacity of CO2 increases first and then decreases, and the maximum adsorption capacity is 3.869 mmol/g at 680 ℃, showing the best adsorption performance. After obtaining TixZr1-xMnFe alloy by Ti doping, the adsorption capacity increases by 19.2% compared with that before doping, but the adsorption rate decreases from 0.301 mmol/(g·h) to 0.119 mmol/(g·h) in the first 8 h. The adsorption mechanism was studied based on the first principles, by comparing the adsorption energies, we obtained the optimal adsorption position which is the horizontal orientation vacancy on the surface of ZrMnFe (110), and the adsorption energy is 5.531 eV. Under the study to density of state, it was found that the interaction between the surface of ZrMnFe (110) and CO2 gas molecules is mainly because of the hybridization of 2s orbitals of O and 4p and 4d orbitals of Zr atom.
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