High pressure synthesis of phosphine from the elements and the discovery of the missing (PH3)2H2 tile.
Matteo CeppatelliDemetrio SceltaManuel Serrano-RuizKamil Filip DziubekGaston GarbarinoJeroen JacobsMohamed MezouarRoberto BiniMaurizio PeruzziniPublished in: Nature communications (2020)
High pressure reactivity of phosphorus and hydrogen is relevant to fundamental chemistry, energy conversion and storage, and materials science. Here we report the synthesis of (PH3)2H2, a crystalline van der Waals (vdW) compound (I4cm) made of PH3 and H2 molecules, in a Diamond Anvil Cell by direct catalyst-free high pressure (1.2 GPa) and high temperature (T ≲ 1000 K) chemical reaction of black phosphorus and liquid hydrogen, followed by room T compression above 3.5 GPa. Group 15 elements were previously not known to form H2-containing vdW compounds of their molecular hydrides. The observation of (PH3)2H2, identified by synchrotron X-ray diffraction and vibrational spectroscopy (FTIR, Raman), therefore represents the discovery of a previously missing tile, specifically corresponding to P for pnictogens, in the ability of non-metallic elements to form such compounds. Significant chemical implications encompass reactivity of the elements under extreme conditions, with the observation of the P analogue of the Haber-Bosch reaction for N, fundamental bond theory, and predicted high pressure superconductivity in P-H systems.
Keyphrases
- high temperature
- small molecule
- high resolution
- ionic liquid
- high throughput
- room temperature
- public health
- single cell
- single molecule
- climate change
- cell therapy
- molecular dynamics simulations
- magnetic resonance imaging
- gold nanoparticles
- bone marrow
- density functional theory
- raman spectroscopy
- risk assessment
- dual energy
- carbon dioxide