Solid State Sciences 5 (2003) 1471–1474

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The transformation of Cu(OH)2 into CuO, revisited

Yannick Cudennec ∗ , André Lecerf
Groupe de recherche en chimie et métallurgie, institut national des sciences appliquées de Rennes, 20, avenue des buttes de Coësmes,
35043 Rennes cedex, France
Received 21 January 2003; received in revised form 2 September 2003; accepted 23 September 2003

Abstract
Copper hydroxide Cu(OH)2 is metastable. It easily transforms into copper oxide CuO more stable, either in the solid state by a thermal
dehydration or at room temperature, in aqueous basic solutions. In the solid state, the transformation is performed at a relatively low
temperature, 423 K. It is a topotactic or a pseudomorphic transformation owing to clear relationships between axes of the two solids, in
the three directions. The reacting process is described and the corresponding vectorial relations between crystal parameters are proposed. It
is not the same case in aqueous basic solutions. Copper hydroxide gives rise to oxide through the formation of a complex anion, Cu(OH)4 2− ,
by a reconstructive transformation involving a dissolution reaction followed by a precipitation.
 2003 Elsevier SAS. All rights reserved.

Keywords: Copper hydroxide; Copper oxide; Topotactic, pseudomorphic transformations

1. Introduction thought that topotactic reactions do not necessarily need a

three-dimensional similarity between structures.
In previous publications, it was shown that copper hy- The aim of this publication is to propose an explanation
droxide Cu(OH)2 is a metastable phase which easily trans- for transformations of Cu(OH)2 which happen below 473 K,
forms into copper oxide CuO, more stable [1–5]. This trans- a hypothesis of the process which gives rise to CuO from
formation occurs in solid state by thermal dehydration at a Cu(OH)2 in the solid state and to compare it with reactions
relatively low temperature, but exists also in aqueous me- occurring in aqueous solutions at room temperature.
dia at room temperature. In 1970, Günter and Ostwald [5]
published the results of studies about this question. Copper
hydroxide was easily decomposed thermally or by electron 2. Crystal structures of Cu(OH)2 and CuO
irradiation, in an electronic microscope. Thermal decompo-
sition of Cu(OH)2 in the range of 298 to 1273 K in air, In order to understand the transformation on a crystallo-
was followed by means of a high temperature X-ray pow- graphical point of view, it is necessary briefly to describe the
der diffraction camera. At about 323 K a reversible increase crystal structure of the two solids.
of the c parameter of about 1.5% is observed and at 423 K The crystal structure of copper(II) hydroxide is ortho-
the DTA curve is characterized by a large endothermic peak rhombic, space group Cmc21 (No. 36) with a = 2.9471 (Å),
which corresponds to the dehydration of Cu(OH)2 and the b = 10.593 (Å), c = 5.25644 (Å), Z = 4 [6]. It is related
formation of CuO [5]. Another transformation takes place at to lepidocrocite γ -FeO(OH) [4]. The structure presents
a higher temperature (1093 K), giving rise to Cu2 O, but that corrugated layers perpendicular to the b-axis, in which
will not be the matter of this publication. Günter and Ost- copper(II) has a pentahedral surrounding composed of five
wald proposed a hypothesis of a topotactic transformation OH− ions (Cu–O: 1.95, 1.95, 1.97, 1.97 and 2.36 Å). The
between Cu(OH)2 and CuO, which transforms only the a- sixth one is located at a too long distance (Cu–O: 2.92 Å) for
axis of the hydroxide into the [1 1 0] direction of CuO. They being involved in the copper polyhedron (Fig. 1a). Copper
atoms are located at about 0.13 Å of the square basis built
with oxygens.
* Corresponding author. As for the structure of CuO, it was established in 1935 [7]
E-mail address: yannick.cudennec@insa-rennes.fr (Y. Cudennec). and revisited in 1970 [8]. It is monoclinic, space group C2/c
1293-2558/$ – see front matter  2003 Elsevier SAS. All rights reserved.
doi:10.1016/j.solidstatesciences.2003.09.009
1472 Y. Cudennec, A. Lecerf / Solid State Sciences 5 (2003) 1471–1474

Fig. 1. Crystal structures: (a) Cu(OH)2 and (b) CuO.

(No. 15): a = 4.6837 (Å), b = 3.4226 (Å), c = 5.1288 (Å), The loss of water is performed by an oxolation mecha-
β = 99.54 ◦, Z = 4. It is built of crossing bands of copper(II) nism [9], described on Fig. 3, giving rise to O–Cu–O bridges,
with square planar entities CuO4 , linked together by two between former layers of Cu(OH)2 .
opposite edges and spreading out in the directions [1 1 0] and Fig. 3a corresponds to the (a, b)-plane of the structure
[1̄ 1 0] (Fig. 1b). In all crystallized solids, divalent copper of Cu(OH)2. In this structure, layers are shifted of a/2
surroundings are always very distorted by a strong Jahn– along a, explaining why the b parameter corresponds to
Teller effect which often leads to square planar groups, more two interlayer spaces. The oxolation phenomenon involves
stable. a dehydration process and the formation of O–Cu–O bridges
(see Fig. 3(b and c)). Bridges are obtained after the loss
of water molecules followed by a big contraction of the
structure along the [0 1 0] direction (contraction value near
3. Hypothesis of transformation processes in the solid of b/2).
state On Fig. 3d (initial (b, c)-plane of Cu(OH)2), is described
the linkage of CuO4 entities along the c-parameter, which
The structure of Cu(OH)2 , in projection along the a-axis produces a three-dimensional network. Half the rows of
is reported on Fig. 2a. Copper surrounding is a square CuO4 bands are shifted along the [0 1 0] direction (noted
pyramid with four short Cu–O bonds and a medium one shift 1 on Fig. 3d), of a value near 1.4 Å, in order to
at 2.36 Å. At about 323 K, we think that a modification line up copper atoms along the c-direction (this shift of
of surroundings is performed, to give rise to square planar CuO4 groups appears on Fig. 2c). In addition, a second
entities Cu(OH)4 linked together by two opposite edges shift of half the copper atoms (shift 2 on Fig. 3d, of c/4 =
(Fig. 2(b and c)). This modification is reversible and could be 1.3 Å), arises to put these copper atoms at equal distances
responsible, with the thermal dilatation, of the weak increase of four oxygen atoms belonging to four different CuO4
of the c-axis mentioned by Günter et al. [5]. Therefore, groups. Therefore, four new Cu–O bonds are established,
the stability of the structure is only due to the network of obtaining the crossing bands of CuO4 , characteristic of the
hydrogen bonds, so that this structural conformation allows three-dimensional structure of CuO (see the perspective
possibilities of easy shifts of CuO4 groups or Cu atoms, view of Fig. 3e). Obviously, these different contraction and
which promote the evolution towards crystallized CuO at a shifts are simultaneously performed during the oxolation
low temperature. process. They have been disconnected on figures for a better
At the temperature of 423 K, begins the dehydration of understanding of the weak atom displacements during the
transformation.
Cu(OH)2 , characterized by a large endothermic DTA peak,
Vectorial relations between crystal parameters of the
according to the following scheme:
structures of Cu(OH)2 and CuO, corresponding to the
proposed transformation, are reported in Table 1. As it can
Cu(OH)2(s) → CuO(s) + H2 O(g) . be seen, appears the relation between the directions [1 0 0]
 Y. Cudennec, A. Lecerf / Solid State Sciences 5 (2003) 1471–1474 1473

Fig. 2. Cu(OH)2 structural modification at 60 ◦ C: (a) Cu(OH)2 (room temperature) projection along A-axis; (b) Cu(OH)2 (T = 60 ◦ C) long Cu–O bond
breaking. Square–planar surroundings are obtained; (c) perspective view.

Fig. 3. Cu(OH)2 → CuO transformation process: (a) Cu(OH)2 (A, B)-plane; (b) Cu(OH2 ) (A, B)-plane loss of water; (c) CuO (A, B)-plane oxolation process;
(d) CuO (B, C)-plane oxolation process, shift 1: ≈ 1.4 Å, shift 2: C/4 = 1.3 Å; (e) CuO perspective view.

and [1̄ 1 0] of the respective structures of Cu(OH)2 and CuO, at room temperature, without being transformed in CuO.
mentioned by Günter et al. [5]. Nevertheless, at variance Nevertheless, a slow transformation is thermodynamically
to these authors, we propose a three-dimensional structural possible because the solubility found in pure water is more
relationship, with relations between, respectively, [0 0 1] and important for Cu(OH)2 (1.3 × 10−5 mol l−1 ) than for CuO
[1 1 0] and also between [0 1 0] and [0 0 1]. (2 × 10−7 mol l−1 ) [2].
It is quite different in presence of hydroxide ions OH− .
Kinetics of transformation is very fast for the reason that di-
4. Transformation in aqueous solutions valent copper ions are dissolved under the form of tetrahy-
droxocuprate(II) anions Cu(OH)4 2− . In a previous publica-
In previous publications [2,3], we have shown that pure tion [2], we have determined at room temperature, by means
copper hydroxide can stay several months in pure water of an ICP spectrometer, the solubility of divalent copper in
1474 Y. Cudennec, A. Lecerf / Solid State Sciences 5 (2003) 1471–1474

Table 1
Vectorial relations between axes
Cu(OH)2 Cmc21 CuO C2/c Relations between axes Comments
A = 2.9471 Å a = 4.6837 Å
⇔ (−

a + b)/2 (2.90 Å) – As expected, a weak variation is observed along this direction (distance
between copper of neighboring square planar groups)
B = 10.593 Å b = 3.4226 Å
⇔ c
(5.1288 Å)
B – Big contraction of the structure due to the loss of water
C = 5.2564 Å c = 5.1288 Å
⇔ a
+ b
(5.80 Å)
C – Small increase due to the shift of C/4 along C, of half the copper atoms
– β = 99.54◦

the system Na2 O, CuO, H2 O. Concentrations of divalent favors the formation of CuO insofar as atom displacements
copper in soda solutions are found around 10−3 mol l−1 and are reduced during the transformation. Therefore, we think
can reach 6 × 10−2 mol l−1 in very concentrated soda solu- that this structural feature is also an instability factor for
tions. It is clear that copper concentrations can present such Cu(OH)2 .
values only if copper is involved in a complex anion like Even if copper hydroxide decomposes at room tempera-
Cu(OH)4 2− , stabilized by the strong Jahn–Teller effect dis- ture in aqueous soda solutions by a reconstructive transfor-
played by divalent copper, which leads to a square planar mation, a structural relationship exists with CuO. At a higher
surrounding. This anion can be considered as a precursor temperature it is evident that a topotactic or pseudomorphic
entity for the formation of CuO. In fact, a condensation phe- transformation takes place within the solid phase. Neverthe-
nomenon, combined with a loss of two hydroxyl ions and less, the main feature common to the two different routes,
one water molecule, lead to the formation of chains of square performed either in solution or in the solid state, is the for-
planar CuO4 groups and then to solid CuO. Consequently, mation of square planar entities CuO4 , which can be consid-
we think that the transformation of Cu(OH)2 into CuO more ered as the elementary bricks, giving rise to CuO.
stable, in aqueous solution at room temperature, is a recon- For Cornell and Schwertmann [10], a topotactic transfor-
structive transformation involving a dissolution reaction fol- mation involves internal atomic rearrangements with a single
lowed by the precipitation of CuO [3], according to the fol- crystal of the initial phase, transforming into a single crys-
lowing scheme: tal of another phase. In addition, an agreement in three di-
mensions between the initial and the final structure must be
Cu(OH)2(s) + 2 OH−
(aq) Cu(OH)4 2− (aq) obtained, contrarily to Günter and Ostwald [5] who think
that one dimension is enough. Other solid state reactions in
which the end product is not a single crystal but where nev-
CuO(s) + 2 OH−
(aq) + H2 O.
ertheless, there is a clear relationship between crystal axes
of the two structures, could be termed as pseudomorphic.
Thanks to this process the fast transformation of Cu(OH)2
into CuO is possible at room temperature in soda solutions. Acknowledgement

5. Conclusion Thanks to Professor Gérard Férey (Versailles) for his

helpful and valuable comments about these transformation
Copper hydroxide Cu(OH)2 is metastable. This explains processes.
why it is difficult to obtained a pure solid phase. In a recent
publication, we have shown that instability is mainly due References
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