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

Matteo Ceppatelli (), Demetrio Scelta, Manuel Serrano-Ruiz, Kamil Dziubek, Gaston Garbarino, Jeroen Jacobs, Mohamed Mezouar, Roberto Bini and Maurizio Peruzzini
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Matteo Ceppatelli: European Laboratory for Non-linear Spectroscopy
Demetrio Scelta: European Laboratory for Non-linear Spectroscopy
Manuel Serrano-Ruiz: Institute of Chemistry of OrganoMetallic Compounds, National Research Council of Italy
Kamil Dziubek: European Laboratory for Non-linear Spectroscopy
Gaston Garbarino: European Synchrotron Radiation Facility
Jeroen Jacobs: European Synchrotron Radiation Facility
Mohamed Mezouar: European Synchrotron Radiation Facility
Roberto Bini: European Laboratory for Non-linear Spectroscopy
Maurizio Peruzzini: Institute of Chemistry of OrganoMetallic Compounds, National Research Council of Italy

Nature Communications, 2020, vol. 11, issue 1, 1-11

Abstract: 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.

Date: 2020
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DOI: 10.1038/s41467-020-19745-2

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