Understanding the microscopic impact of catalysis on the de-hydrogenation process of hydrides is crucial for the development of hydrogen storage materials. In this paper, density functional theory calculations are employed to study the adsorption and dissociation of the AlH₄ cluster, which is the building block of many complex hydrides, on a series of transition metal surfaces. We find that the hybrid bonding of the AlH₄ cluster is weakened when adsorption on metal surfaces and the Al–H bonds are stretched accordingly. This de-hybridization effect enhances from Sc to Ni in correlation with the work function. Based on the results, we predict Ni to be the most effective transition metal in lowering the de-hydrogenation barrier of AlH₄-based hydrides. Detail electronic structure analysis show that the de-hybridization effect mainly resulted from the charge transfer between metals surface and AlH₄ clusters. Our results provide deep insight into improving the properties of hydrogen storage materials.

了解催化对氢化物脱氢过程的微观影响对于储氢材料的开发至关重要。在本文中，密度泛函理论计算用于研究 AlH ₄簇在一系列过渡金属表面上的吸附和解离，AlH ₄簇是许多复杂氢化物的组成部分。我们发现当吸附在金属表面上时，AlH ₄簇的混合键会减弱，Al-H 键相应地拉伸。这种去杂化效应与功函数相关，从 Sc 到 Ni 增强。根据结果​​，我们预测 Ni 是降低 AlH ₄脱氢势垒的最有效过渡金属-基氢化物。详细的电子结构分析表明，去杂化效应主要来自金属表面与AlH ₄簇之间的电荷转移。我们的研究结果为改善储氢材料的性能提供了深刻的见解。