Crystal structure of cobalt hydroxide carbonate Co2CO3(OH)2: density functional theory and X-ray diffraction investigation
González-López, J., Cockcroft, J. K., Fernández-González, Á., Jimenez, A. and Grau-Crespo, R.
It is advisable to refer to the publisher's version if you intend to cite from this work. See Guidance on citing. To link to this item DOI: 10.1107/S2052520617007983 Abstract/SummaryThe cobalt carbonate hydroxide Co2CO3(OH)2 is a technologically important solid which is used as precursor for the synthesis of cobalt oxides in a wide range of applications, and it also has relevance as a potential immobilizer of toxic element cobalt in the environment, but its detailed crystal structure is so far unknown. We have investigated the structure of Co2CO3(OH)2 using Density Functional Theory (DFT) simulations as well as Powder X-Ray Diffraction (PXRD) measurements on samples synthesized via deposition from aqueous solution. We consider two possible monoclinic phases, with closely related but symmetrically different crystal structures, based on those of the minerals malachite (Cu2CO3(OH)2) and rosasite (Cu1.5Zn0.5CO3(OH)2), as well as an orthorhombic phase that can be seen as a common parent structure for the two monoclinic phases, and a triclinic phase with the structure of the mineral kolwezite (Cu1.34Co0.66CO3(OH)2). Our DFT simulations predict that the rosasite-like and the malachite-like phases are two different local minima of the potential energy landscape for Co2CO3(OH)2, and are practically degenerate in energy, while the orthorhombic and triclinic structures are unstable and experience barrierless transformations to the malachite phase upon relaxation. The best fit to the PXRD data is obtained using a rosasite model (monoclinic with space group P1121/n and cell parameters a = 3.1408(4) Å, b = 12.2914(17) Å, c = 9.3311(16) Å, γ = 82.299(16)°). However, some features of the PXRD pattern are still not well accounted for by this refinement and the residual parameters are relatively poor. We discuss the relationship between the rosasite and malachite phases of Co2CO3(OH)2 and show that they can be seen as polytypes. Based on the similar calculated stability of these two polytypes, we speculate that some level of stacking disorder could account for the poor fit of our PXRD data. The possibility that Co2CO3(OH)2 could crystallize, under different growth conditions, as either rosasite or malachite, or even as a stacking-disordered phase intermediate between the two, requires further investigation.
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