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High pressure synthesis of phosphine from the elements and the discovery of the missing (PH3)2H2 tile.


ABSTRACT: 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.

SUBMITTER: Ceppatelli M 

PROVIDER: S-EPMC7705733 | biostudies-literature | 2020 Nov

REPOSITORIES: biostudies-literature

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High pressure synthesis of phosphine from the elements and the discovery of the missing (PH<sub>3</sub>)<sub>2</sub>H<sub>2</sub> tile.

Ceppatelli Matteo M   Scelta Demetrio D   Serrano-Ruiz Manuel M   Dziubek Kamil K   Garbarino Gaston G   Jacobs Jeroen J   Mezouar Mohamed M   Bini Roberto R   Peruzzini Maurizio M  

Nature communications 20201130 1


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 (PH<sub>3</sub>)<sub>2</sub>H<sub>2</sub>, a crystalline van der Waals (vdW) compound (I4cm) made of PH<sub>3</sub> and H<sub>2</sub> 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 ro  ...[more]

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