New important applications of copper metal, e.g., in the areas of hydrogen production, fuel cell operation, and spent nuclear fuel disposal, require accurate knowledge of the physical and chemical properties of stable and metastable copper compounds. Among the copper(I) compounds with oxygen and hydrogen, cuprous oxide Cu 2 O is the only one stable and the best studied. Other such compounds are less known (CuH) or totally unknown (CuOH) due to their instability relative to the oxide. Here we combine quantum-mechanical calculations with experimental studies to search for possible compounds of monovalent copper. Cuprous hydride (CuH) and cuprous hydroxide (CuOH) are proved to exist in solid form. We establish the chemical and physical properties of these compounds, thereby filling the existing gaps in our understanding of hydrogen-and oxygen-related phenomena in Cu metal.electronic structure | lattice dynamics | thermodynamic properties | metastability | infrared spectra

Experimental studies have been performed to obtain the unknown cuprous hydroxide compound, which has recently been predicted theoretically (P. A. Korzhavyi et. al., Proc. Natl. Acad. Sci. U. S. A., 2012, 109, 686-689) to be metastable in a solid form. The reduction of Cu(2+) with ferrous ethylenediamine tetraacetate (EDTA) results in the formation of a yellow powder precipitate whose composition corresponds to CuOH × H2O as probed by Fourier Transform Infrared Spectroscopy (FTIR) and cryogenic X-ray Photoelectron Spectroscopy (XPS). A similar compound has been found on the surface of Cu-CuH powder stored in water, as detected by XPS. The reduction of Cu(2+) to Cu(+) with free radicals in aqueous solutions results in a Cu2O precipitate as the final product, while the formation of the yellow cuprous hydroxide colloids may be an intermediate step. Our studies reveal that cuprous hydroxide does exist in a solid form and most likely has a hydrated form, CuOH × H2O.

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