Toso Stefano, Imran Muhammad, Mugnaioli Enrico, Moliterni Anna, Caliandro Rocco, Schrenker Nadine J, Pianetti Andrea, Zito Juliette, Zaccaria Francesco, Wu Ye, Gemmi Mauro, Giannini Cinzia, Brovelli Sergio, Infante Ivan, Bals Sara, Manna Liberato
Department of Nanochemistry, Istituto Italiano di Tecnologia, Via Morego 30, 16163, Genova, Italy.
International Doctoral Program in Science, Università Cattolica del Sacro Cuore, 25121, Brescia, Italy.
Nat Commun. 2022 Jul 8;13(1):3976. doi: 10.1038/s41467-022-31699-1.
Colloidal chemistry grants access to a wealth of materials through simple and mild reactions. However, even few elements can combine in a variety of stoichiometries and structures, potentially resulting in impurities or even wrong products. Similar issues have been long addressed in organic chemistry by using reaction-directing groups, that are added to a substrate to promote a specific product and are later removed. Inspired by such approach, we demonstrate the use of CsPbCl perovskite nanocrystals to drive the phase-selective synthesis of two yet unexplored lead sulfochlorides: PbSCl and PbSCl. When homogeneously nucleated in solution, lead sulfochlorides form PbSCl nanocrystals. Conversely, the presence of CsPbCl triggers the formation of PbSCl/CsPbCl epitaxial heterostructures. The phase selectivity is guaranteed by the continuity of the cationic subnetwork across the interface, a condition not met in a hypothetical PbSCl/CsPbCl heterostructure. The perovskite domain is then etched, delivering phase-pure PbSCl nanocrystals that could not be synthesized directly.
胶体化学通过简单温和的反应可制备出大量材料。然而,即便只有少数几种元素,也能以多种化学计量比和结构进行组合,这可能会导致杂质甚至错误产物的生成。在有机化学中,长期以来人们通过使用反应导向基团来解决类似问题,这些基团被添加到底物中以促进特定产物的生成,随后再将其去除。受此方法启发,我们展示了利用CsPbCl钙钛矿纳米晶体来驱动两种尚未被探索的硫氯铅化物:PbSCl和PbSCl的相选择性合成。当在溶液中均匀成核时,硫氯铅化物会形成PbSCl纳米晶体。相反,CsPbCl的存在会引发PbSCl/CsPbCl外延异质结构的形成。相选择性由跨界面阳离子子网络的连续性保证,这一条件在假设的PbSCl/CsPbCl异质结构中无法满足。然后对钙钛矿域进行蚀刻,得到无法直接合成的纯相PbSCl纳米晶体。