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Journal Article

Structural Effects of Cu/Zn Substitution in the Malachite-Rosasite System

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Behrens,  Malte
Inorganic Chemistry, Fritz Haber Institute, Max Planck Society;

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Girgsdies,  Frank
Inorganic Chemistry, Fritz Haber Institute, Max Planck Society;

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Citation

Behrens, M., & Girgsdies, F. (2010). Structural Effects of Cu/Zn Substitution in the Malachite-Rosasite System. Zeitschrift für anorganische und allgemeine Chemie, 636(6), 919-927. doi:10.1002/zaac.201000028.


Cite as: http://hdl.handle.net/11858/00-001M-0000-0011-2A45-8
Abstract
Synthetic zincian malachite samples (Cu1-xZnx)2(OH)2CO3 with x = 0, 0.1, 0.2 and 0.3 were characterized by powder X-ray diffraction and optical spectroscopy. The XRD patterns of the samples up to x = 0.2 indicate single phase materials with an approximately linear dependence of the refined lattice parameters on the zinc content. In contrast, the sample with a nominal zinc content x = 0.3 shows the formation of a small amount of aurichalcite (Zn,Cu)5(OH)6(CO3)2 as an additional phase. Based on the lattice parameter variations, the zinc content of the zincian malachite component in this sample is estimated to be x ≈ 0.27, which seems to represent the maximum possible substitution in zincian malachite under the synthesis conditions applied. The results are discussed in relation to preparation of Cu/ZnO catalysts and the crystal structures of the minerals malachite and rosasite. One striking difference between these two structurally closely related phases is the orientation of the Jahn-Teller elongated axes of the CuO6 octahedra in the unit cell, which seems to be correlated with the placement of the monoclinic β angle. The structural and chemical relationship between these crystallographically distinct phases is discussed using a hypothetical intermediate Zn2(OH)2CO3 phase of higher orthorhombic symmetry. In addition to the crystallographic analysis, optical spectroscopy proves to be a useful tool for estimation of the Cu:Zn ratio in (Cu1-xZnx)2(OH)2CO3 samples.