Formation of paratacamite nanomaterials via the conversion of aged and oxidized copper nanoparticles in hydrochloric acidic media

Abstract

Nanoparticles and nanostructured aggregates of paratacamite are prepared in acidic solutions through the conversion of copper-based nanoparticles. Aged and oxidized copper nanoparticles with an average primary particle size of ∼15 nm, when combined with hydrochloric acid solutions in the range of 0.025 to 0.1 M, show interesting behavior yielding both a change in nanoparticle primary size, as measured by an electrospray scanning mobility particle sizer, and in chemical composition to produce a copper chloride hydroxide mineral identified as paratacamite (γ-Cu2(OH)3Cl) by powder X-ray diffraction of the dehydrated solid sample. Taken together, these data suggest that paratacamite nanoparticles in solution can aggregate to yield microporous paratacamite materials. Microporous paratacamite was characterized by several techniques including X-ray diffraction, transmission electron microscopy, energy dispersive X-ray analysis, electron energy loss spectroscopy, X-ray photoelectron spectroscopy and surface area measurements. Oxidation of these copper-based nanoparticles with molecular oxygen and the role of the oxidized layer in the formation of paratacamite have been investigated. Comparison to microscale copper particles showed there is unique oxidation behavior of nanoscale copper particles that results in unique reaction chemistry of oxidized nanoscale copper particles with hydrochloric acid solutions to form paratacamite. This study provides a new route for the formation of paratacamite nanomaterials that can be used in a wide range of chemically interesting applications including hydrogen storage materials and as a heterogeneous catalyst for the synthesis of green solvents such as dimethyl and diethyl carbonates. Additionally, this study suggests a potentially new pathway for the degradation of art objects and ancient artifacts as well as other cultural heritage materials containing small copper particles that has not been previously considered.