The rational design of efficient bimetallic nanoparticle (NP) catalysts is challenging due to the lack of theoretical understanding of active components and insights into the mechanisms of a specific reaction. Here, we report the rational design of nanoreactors comprising hollow carbon sphere-confined PtNi bimetallic NPs (PtNi@HCS) as highly efficient catalysts for hydrogen generation via ammonia borane hydrolysis in water. Using both density functional theory calculations and molecular dynamics simulations, the effects of an active PtNi combination and the critical synergistic role of a hollow carbon shell on the molecule diffusion adsorption behaviors are explored. Kinetic isotope effects and theoretical calculations allow the clarification of the mechanism, with oxidative addition of an O–H bond of water to the catalyst surface being the rate-determining step. The remarkable catalytic activity of the PtNi@HCS nanoreactor was also utilized for successful tandem catalytic hydrogenation reactions, using in situ-generated H₂ from ammonia borane with high efficiency. The concerted design, theoretical calculations, and experimental work presented here shed light on the rational elaboration of efficient nanocatalysts and contribute to the establishment of a circular carbon economy using green hydrogen.

中文翻译：

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将理论与纳米反应器概念相结合，合成空心碳球封装的 PtNi 合金以增强氢气的产生

由于缺乏对活性组分的理论理解和对特定反应机制的深入了解，高效双金属纳米颗粒（NP）催化剂的合理设计具有挑战性。在这里，我们报告了包含空心碳球限制的 PtNi 双金属纳米粒子（PtNi@HCS）的纳米反应器的合理设计，作为通过氨硼烷在水中水解产生氢气的高效催化剂。利用密度泛函理论计算和分子动力学模拟，探讨了活性 PtNi 组合的影响和空心碳壳对分子扩散吸附行为的关键协同作用。动力学同位素效应和理论计算可以阐明该机制，其中水的 O-H 键氧化加成到催化剂表面是速率决定步骤。PtNi@HCS纳米反应器的卓越催化活性也被用于成功的串联催化氢化反应，利用氨硼烷原位产生H ₂，效率很高。这里提出的协调设计、理论计算和实验工作揭示了高效纳米催化剂的合理阐述，并有助于建立使用绿色氢的循环碳经济。