Sodreau Alexandre, Zahedi Hooman Ghazi, Dervişoğlu Rıza, Kang Liqun, Menten Julia, Zenner Johannes, Terefenko Nicole, DeBeer Serena, Wiegand Thomas, Bordet Alexis, Leitner Walter
Department of Molecular Catalysis, Max Planck Institute for Chemical Energy Conversion, 45470, Mülheim an der Ruhr, Germany.
Institute of Technical and Macromolecular Chemistry, RWTH Aachen University, Worringerweg 2, 52074, Aachen, Germany.
Adv Mater. 2023 Dec;35(49):e2306621. doi: 10.1002/adma.202306621. Epub 2023 Oct 22.
Metal chloride complexes react with tris(trimethylsilyl)phosphine under mild condition to produce metal phosphide (TMP) nanoparticles (NPs), and chlorotrimethylsilane as a byproduct. The formation of Si-Cl bonds that are stronger than the starting M-Cl bonds acts as a driving force for the reaction. The potential of this strategy is illustrated through the preparation of ruthenium phosphide NPs using [RuCl (cymene)] and tris(trimethylsilyl)phosphine at 35 °C. Characterization with a combination of techniques including electron microscopy (EM), X-ray absorption spectroscopy (XAS), and solid-state nuclear magnetic resonance (NMR) spectroscopy, evidences the formation of small (diameter of 1.3 nm) and amorphous NPs with an overall Ru P composition. Interestingly, these NPs can be easily immobilized on functional support materials, which is of great interest for potential applications in catalysis and electrocatalysis. Mo P and Co P NPs can also be synthesized following the same strategy. This approach is simple and versatile and paves the way toward the preparation of a wide range of transition metal phosphide nanoparticles under mild reaction conditions.
金属氯化物配合物在温和条件下与三（三甲基硅基）膦反应，生成金属磷化物（TMP）纳米颗粒（NPs），并产生副产物氯代三甲基硅烷。比起始的M-Cl键更强的Si-Cl键的形成是该反应的驱动力。通过在35℃下使用[RuCl（对异丙基苯）]和三（三甲基硅基）膦制备磷化钌NPs，说明了该策略的潜力。结合电子显微镜（EM）、X射线吸收光谱（XAS）和固态核磁共振（NMR）光谱等技术进行表征，证明形成了具有整体Ru P组成的小尺寸（直径1.3 nm）无定形NPs。有趣的是，这些NPs可以很容易地固定在功能载体材料上，这对于催化和电催化的潜在应用具有重要意义。Mo P和Co P NPs也可以按照相同的策略合成。这种方法简单且通用，为在温和反应条件下制备多种过渡金属磷化物纳米颗粒铺平了道路。
