【摘要】 采用2种密度泛函方法模拟了金属硼球烯TM₈B₆（TM=Ni、Pd）的储氢性能。结果表明，超原子Ni₈B₆和Pd₈B₆能够分别吸附40和32个氢分子，储氢密度可达13.134%和6.562%。Ni₈B₆（H₂）₄₀和Pd₈B₆（H₂）₃₂的平均吸附能满足可逆储氢标准。多种波函数分析结果表明，极化效应与库巴斯机制共同主导了氢分子与母体结构之间的相互作用。同时，系统分析了常压下温度对TM₈B₆储氢容量的影响，并通过原子中心密度矩阵传播动力学模拟验证了氢气吸附与解吸循环的可逆性。利用被吸附氢分子数量与温度和压力之间的关系绘制的三维图对TM₈B₆的吸附氢分子能力进行了热力学分析。结果显示，在0.5 MPa和358 K条件下，大部分吸附的氢分子能够被释放。另外，与单体相比，二聚体（TM₈B₆）₂的储氢密度略有下降。更多还原

【Abstract】 Two density functional theory methods were employed to evaluate the H₂ storage capabilities of metalloborospherenes TM₈B₆（TM=Ni, Pd）. Consequently, the superatoms Ni₈ B₆ and Pd₈B₆, which accommodate 40 and 32 H₂ molecules, respectively, exhibit gravimetric H₂ uptake capacities of 13.134% and 6.562%, respectively. The average binding energies of Ni₈B₆（H₂）₄₀and Pd₈B₆（H₂）₃₂fall within the optimal range for reversible H₂ storage applications. The interactions between H₂ molecules and the parent structures were characterized using various wave function analysis methods. Polarization effects, alongside the Kubas mechanism, are pivotal to the adsorption of H₂ on TM₈B₆. Moreover, the investigations examine the effect of temperature on the H₂ storage capacity of TM₈B₆ at atmospheric pressure. Atom-centered density-matrix propagation molecular dynamics simulations confirm the reversibility of H₂ adsorption and desorption cycles. The thermodynamic analyses of the desorption behavior of H₂ molecules were conducted via a three-dimensional graph, plotted based on the relationship between the number of adsorbed H₂ molecules and temperature as well as pressure, revealing that the majority of adsorbed H₂ molecules can be released at 0.5 MPa and 358 K. Compared to the respective monomeric counterparts, the H₂ storage densities of（TM₈B₆）₂ dimers exhibit a slight reduction.更多还原