| 能量最低构型Ca2B4团簇的储氢性能 |
| Hydrogen Storage Capabilities of the Low-Lying Ca2B4 Clusters |
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| 摘要: 基于密度泛函理论，研究了Ca2B4团簇的几何结构、电子特征和储氢性能。前2个与第4个能量最低构型Ca2B4 01、Ca2B402和Ca2B4 04有很高的热力学稳定性，分别最多可以吸附12、12和10个氢分子，达到16.3%、16.3%和14.0%的储氢量，超过了美国能源部提出的目标(5.5%）。Ca2B4 01(H2)12、Ca2B4 02(H2)12和Ca2B4 04(H2)10的平均每个氢分子吸附能量分别为0.58~4.21 eV、0.54~3.69 eV和0.10~0.12 eV。玻恩-奥本海默分子动力学模拟表明，Ca2B4 01和Ca2B4 02可作为潜在吸附氢气的候选目标，而Ca2B4 04不行。吉布斯自由能校正的氢吸附能结果表明，在101 325 Pa下，Ca2B4 01和Ca2B4 02吸附12个氢气分子有较大的可调节的温度范围。 |
| 关键词: 储氢 密度泛函理论 吸附 分子动力学 吉布斯自由能 |
| 基金项目: 运城学院基础研究课题(No.CY-2020018)、山西省基础研究课题(No.20210302124345)、山西省省筹留学人员回国专项课题(No.NO2020-140)与山西省应用基础研究计划面上青年项目(No.201901D211460)资助。 |
| Abstract: The structural feature and electronic property of Ca2B4, as well as its potential for hydrogen storage, have been studied using density functional theory. The first, second, and fourth low-lying isomers Ca2B401, Ca2B4 02, and Ca2B404 have high stabilities in thermodynamics and can adsorb 12, 12, and 10 H2 molecules with respective H2 gravimetric uptake capacity of 16.3%, 16.3%, and 14.0%, which far exceeds the target (5.5%) proposed by the US department of energy (DOE). The average absorption energies per H2 molecule are in the range of 0.58-4.21 eV for Ca2B4 01(H2)12, 0.54-3.69 eV for Ca2B4 02(H2)12, and 0.10-0.12 eV for Ca2B4 04(H2)10. Born-Oppenheimer molecular dynamic (BOMD) simulations indicate Ca2B401 and Ca2B4 02 are promising candidates for adsorbing hydrogen, but Ca2B4 04 is not. The results of hydrogen adsorption energies with Gibbs free energy correction indicate that 12 H2 molecules on Ca2B4 01 and Ca2B4 02 are energetically favorable with a wide range of temperatures at 101 325 Pa. |
| Keywords: hydrogen storage density functional theory absorption molecular dynamic Gibbs free energy |
| 投稿时间：2022-01-16 修订日期：2022-04-21 |
| 摘要点击次数: 601 |
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| 唐玉朋,赵燕飞,杨海英,李楠.能量最低构型Ca2B4团簇的储氢性能[J].无机化学学报,2022,38(7):1391-1401. |
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| Support information: 相关附件： 220019_Surpporting_information-wjhxxb_revison.doc |
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