Postsynthetic transformations are key to the colloidal synthesis of functional nanocrystals by offering a way to complex shapes, heterostructures, and chemical compositions. They however remain inaccessible to whole families of solids, especially those relying on covalent bonds, which crystallize at temperatures that common solvents cannot stand. Herein we show that in inorganic molten salts above 500 °C, such transformations can be triggered to deliver metallo-covalent nanocrystals previously unattainable. By incorporating silicon and phosphorus into metal nanoparticles, we synthesize nickel silicophosphide nanocrystals and demonstrate how distinct chemical bonds involving silicon or phosphorus drive their electrocatalytic properties for alkaline water oxidation and hydrogen evolution. These bonds also determine the synthesis pathway, from sequential incorporation of p-block elements to topotactic transformations not reported before. The ability to run such complex postsynthetic reactions of nanoparticles into molten salts paves the way to increasing complexity in compositions and chemical bonding in nanocrystals for energy conversion.

中文翻译：

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进和出：穿梭共价纳米晶体中的原子，从熔盐合成到水分解电催化

合成后转化是功能性纳米晶体胶体合成的关键，它为复杂的形状、异质结构和化学成分提供了一种方法。然而，它们仍然无法被整个固体家族接触，尤其是那些依赖于共价键的固体，共价键在普通溶剂无法承受的温度下结晶。在此，我们表明，在 500 °C 以上的无机熔盐中，可以触发这种转变以产生以前无法实现的金属共价纳米晶体。通过将硅和磷掺入金属纳米颗粒中，我们合成了硅磷化镍纳米晶体，并展示了涉及硅或磷的不同化学键如何驱动它们进行碱性水氧化和析氢的电催化特性。这些键还决定了合成途径，从 p 区元件的顺序掺入到以前未报道的拓扑转化。将纳米颗粒的这种复杂的合成后反应运行成熔盐的能力为增加纳米晶体中用于能量转换的成分和化学键的复杂性铺平了道路。