Laboratoire Hétéroéléments et Coordination, Ecole Polytechnique, CNRS, Palaiseau, France.
Dalton Trans. 2013 Sep 21;42(35):12667-74. doi: 10.1039/c3dt50686j.
Stoichiometric reactions of Pd(0) nanoparticles with various amounts of white phosphorus (P4) are an efficient route to convert them into the corresponding Pd phosphides Pd(x)P(y). Formation of crystallized palladium phosphide nanoparticles is a two-step process, which allows exploring in detail the phase transitions of the Pd(x)P(y) system, from amorphous Pd-P nanoparticles (formed in a first step at moderate temperature) to crystallization (at higher temperature). The second temperature was found to be strongly dependent on the Pd/P ratio: PdP2, Pd5P2 and Pd3P stoichiometries form the amorphous phases, but only PdP2 and Pd5P2 could be further crystallized from them. Although it exists as a bulk crystalline material, Pd3P could only be crystallized by starting from the more Pd-rich Pd6P composition. Phase-to-phase transformations from P-poor phosphides (Pd3P and Pd5P2) to the P-rich PdP2 were also demonstrated, and a first Pd-P phase diagram at the nanoscale was tentatively produced.
Pd(0)纳米颗粒与不同量的白磷 (P4) 的化学计量反应是将其转化为相应的 Pd 磷化物 Pd(x)P(y)的有效途径。结晶钯磷化物纳米颗粒的形成是一个两步过程，这使得可以详细研究 Pd(x)P(y) 系统的相变，从非晶态 Pd-P 纳米颗粒（在中等温度下的第一步形成）到结晶（在更高温度下）。发现第二温度强烈依赖于 Pd/P 比：PdP2、Pd5P2 和 Pd3P 化学计量形成非晶相，但只有 PdP2 和 Pd5P2 可以从它们进一步结晶。尽管它作为块状晶体材料存在，但 Pd3P 只能从更富 Pd 的 Pd6P 组成开始结晶。还证明了从贫磷化物 (Pd3P 和 Pd5P2) 到富磷化物 PdP2 的相到相转变，并且初步在纳米尺度上产生了 Pd-P 相图。
