Materials Chemistry and Physics 122 (2010) 491497

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Materials Chemistry and Physics

journal homepage: www.elsevier.com/locate/matchemphys

Blue CoAl2 O4 spinel via complexation method

Ioana Mindru a , Gabriela Marinescu a , Dana Gingasu a , Luminita Patron a, ,
Corneliu Ghica b , Maria Giurginca c
a

Ilie Murgulescu Institute of Physical Chemistry, Splaiul Independentei 202, 060021 Bucharest, Romania
National Institute for Materials Physics, Atomistilor Street, no. 105 bis, P.O. Box Mg-7, Bucharest Magurele R 077125, Romania
c
Politehnica University of Bucharest, Faculty of Chemistry, Polizu Street, no. 1-7, Bucharest, Romania
b

a r t i c l e

i n f o

Article history:
Received 10 June 2009
Received in revised form 26 February 2010
Accepted 16 March 2010
Keywords:
Nanostructure
CoAl2 O4 spinel
Complexation method
X-ray diffraction

a b s t r a c t
Cobalt-aluminate spinel, CoAl2 O4 , has been synthesized by two synthesis variants of the complexation method: tartarate and gluconate routes. The complex precursors have been characterized by IR,
UVvis spectroscopy and thermal analysis. The cobalt-aluminate spinel has been investigated by XRD,
IR, UVvis and luminescence spectroscopy and TEM. The results indicated that in both cases the singlephase nanocrystalline CoAl2 O4 spinel was formed. The average crystallite size from TEM images was in
the range 5060 nm. The emission spectra of CoAl2 O4 in the visible region conrmed the presence of
tetrahedral coordinated Co2+ ion.
2010 Elsevier B.V. All rights reserved.

1. Introduction
The cobalt-blue pigment has been known since Middle Ages. In
1777, Gahn and Wenzel discovered CoAl2 O4 and 30 years later L.J.
Thnard succeeded to reproduce in laboratory the blue colour by
the reaction of cobalt arsenate/cobalt phosphate with alumina, at
high temperature. For this reason, L.J. Thnard has been considered
the inventor of the bright blue cobalt aluminate [1].
Cobalt-aluminate spinel is an idiochromatic (self-coloured)
ceramic pigment, widely used for the coloration of plastics, paint,
bers, paper, rubber, glass, cement, glazes and porcelain enamels
[24]. It is, also, used as humidity sensor [5] and ceramic catalyst
in the CO2 reforming of methane [6].
The normal spinel-CoAl2 O4 has been conventionally synthesized using solid-state reactions at temperatures above 1000 C,
for long periods of time [710]. It was classied as ceramics-grade
pigment. Since 1980, wet-chemical methods have been extensively
applied to synthesize ultrane CoAl2 O4 , among them: coprecipitation method [4,1113], hydrothermal synthesis [14], solgel route
[3,5,1517]. Considerable efforts have been made to develop soft
chemistry routes in which precursors were polynuclear coordination compounds, such as: low temperature combustion synthesis
(LCS) [2,18,19], complexation method [20,21].
In this paper, we report on the synthesis of cobalt-aluminate
spinels, CoAl2 O4 , obtained by thermal decomposition of polynu-

clear multimetallic compounds containing tartarate and gluconate

anions as ligands, respectively.
2. Experimental
2.1. Synthesis of the complex precursors
All chemicals: Al(NO3 )3 9H2 O, Co(NO3 )2 6H2 O, tartaric acid and gluconolactone were of reagent quality (Merck) and were used without further
purications.
The polynuclear coordination precursors were prepared as follows: aluminium(III) nitrate and cobalt(II) nitrate were dissolved in the minimum amount
of water and mixed with an aqueous solution of carboxylic acid in a 2:1:4
(Al(III):Co(II):tartaric acid) ratio and 2:1:8 (Al(III):Co(II):-gluconolactone) ratio,
respectively (-gluconolactone converted into gluconic acid by hydrolysis at 80 C).
Ethanol was added to the nal solution until a pink precipitate was formed. The pH
was raised to 6 by adding NH4 OH:ethanol (1:1). After 24 h at 4 C, the pink precipitate
was ltered and dried over P4 O10 .
The metal content of polynuclear compounds was determined by atomic absorption spectroscopy with an SAA1 instrument; the C, H and N were obtained using a
Carbo Erba Model 1108 CHNS-O elemental analyzer.
Elemental chemical analysis was consistent with the formula:
(NH4 )2 [CoAl2 (C4 O6 H4 )4 (OH)2 ]4H2 O (I): Anal. calcd. Al%: 6.37; Co%: 6.96;
C%: 22.67; N%: 3.30; H%: 4.01; found: Al%: 6.52; Co%: 7.08; C%: 22.74; N%:
3.38; H%: 4.15.
(NH4 )2 [CoAl2 (C6 O7 H11 )5 (OH)5 ]2H2 O (II): Anal. calcd. Al%: 4.33; Co%: 4.73;
C%: 28.90; N%: 2.24; H%: 5.78; found: Al%: 4.68; Co%: 5.12; C%: 28.39; N%:
2.11; H%: 5.52.

2.2. Physical measurements

Corresponding author. Tel.: +40 21 3167912; fax: +40 21 3121147.

E-mail address: Luminita Patron@yahoo.com (L. Patron).
0254-0584/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.matchemphys.2010.03.032

The IR spectra of polynuclear coordination compounds and spinel aluminates

were recorded on KBr pellets with a JASCO FTIR 4100 spectrophotometer in the
4000400 cm1 range.

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I. Mindru et al. / Materials Chemistry and Physics 122 (2010) 491497

Scheme 1.

Absorbtion and uorescence measurements were made with a UV4 UNICAM

spectrophotometer (MgO as a standard), and JASCO FP 6500 spectrouorometer,
respectively.
The thermogravimetric (TG), differential TG (DTG) and differential thermal analysis (DTA) curves were simultaneously recorded under an air atmosphere using a
Shimadzu DTG-TA-51H instrument. The reference material was Al2 O3 . The heating
rate was 10 C min1 in the temperature range 20800 C.

The chemiluminescence measurements were recorded on TD 20/20 chemiluminometer (USA), operating with LH105 M, H2 O2 105 M, tampon solution Tris:HCl
(pH 8.6).
X-ray powder diffraction measurements of spinel aluminates were performed
on a Rigaku-Multiex diffractometer at room temperature using Cu K radiation.
For quantitative analysis a step scanning technique was applied in the 2 range
2080 with a step of 2 min1 .

Scheme 2.

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493

Fig. 1. Diffuse reectance spectra: (a) (NH4 )2 [CoAl2 (C4 O6 H4 )4 (OH)2 ]4H2 O, (b)
(NH4 )2 [CoAl2 (C6 O7 H11 )5 (OH)5 ]2H2 O.

Morphological analysis of the cobalt aluminates was performed using a JEOL

200 CX electron microscope operated at 200 kV, provided with an IXRF EDS unit.
The TEM specimens have been prepared by crushing and depositing the resulting
powder onto holey membrane Cu grids.

Fig. 2. TG, DTG and DTA curves of (a) (NH4 )2 [CoAl2 (C4 O6 H4 )4 (OH)2 ]4H2 O and (b)
(NH4 )2 [CoAl2 (C6 O7 H11 )5 (OH)5 ]2H2 O.

3. Results and discussion

3.1. Characterization of the complex precursors

2Al(III) : 1Co(II) : 8C6 O7 H11

where C6 O7 H11 = gluconate anion

Two types of compounds are obtained:

The successful application of the complexation method for
obtaining aluminate spinel oxides requires two important steps:
(1) a detailed study on the formation of the polynuclear complex
compounds to establish the parameters that inuence the synthesis, such as combination ratio of elements, nature of the ligand, pH
of the reaction medium, temperature, etc.; (2) a study of the thermal
decomposition mechanism accompanied by the characterization of
the mixed oxides.
The polynuclear coordination compounds which may successfully be used as precursors should generate by decomposition only
volatile products. The anions of polycarboxylic and polyhydroxy
carboxylic acids as ligands largely satisfy this requirement. For this
reason, we have selected tartarate and gluconate anions, respectively.
The capacity of these acids to form coordination compounds
is well known [2224]. The study of both tartaric and gluconic
acid solution chemistry has evidenced that the nature of polymeric
species depends on the pH of reaction medium.
The following systems at pH 56 and constant Mn+ /tartaric
acid (gluconic acid) ratio have been studied:
2Al(III) : 1Co(II) : 4C4 O6 H4 2

where C4 O6 H4 2 = tartarate anion

(NH4 )2 [CoAl2 (C4 O6 H4 )4 (OH)2 ]4H2 O

(NH4 )2 [CoAl2 (C6 O7 H11 )5 (OH)5 ]2H2 O

(I)
(II)

Scheme 1 presents the ow chart that lead to the formation of

CoAl2 O4 spinel.
The IR spectra of these polynuclear complex compounds
suggested the coordination of hydroxylcarboxylate anions to
metal ions through both COO and COH groups. The band at
17001730 cm1 assigned to C O of free carboxylic acids, is
replaced in the polynuclear compounds by two intense bands
asym (OCO) (1650 cm1 for I, 1630 cm1 for II) and sym (OCO)
(1390 cm1 for I, 1380 cm1 for II).
On the basis of spectroscopic criteria [25], the magnitude of the
separation  = asym sym may indicate the coordination mode
of carboxylate anions. Values of  > 180 cm1 much higher than
those observed for sodium tartarate ( 120 cm1 ) or sodium
gluconate ( 130 cm1 ) are characteristic for the monodentate coordination of COO groups. The peaks assigned to the CO
stretching vibration of OH secondary groups, which appear at
11501097 cm1 range in the spectra of free acids are splitted and

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Fig. 3. XRD of CoAl2 O4 spinel obtained by thermal decomposition: (a) tartarate complex calcinated at 1000 C/2 h; (b) gluconate complex calcinated at 1000 C/2 h.

shifted towards lower frequencies (11001040 cm1 ) in the case

of the coordination compounds. The splitting can be explained
by a different bonding of OH secondary groups present in the
molecule of hydroxycarboxylate anions, probably to Al3+ and Co2+
ions, respectively.
The absorbance spectra of polynuclear coordination compounds recorded in the range 250850 nm are characterized
by the presence of a band at 525 nm (for compound I)
and 570 nm (for compound II) which can be assigned to
4 T 4 T (P) ( ) transition of octahedral high spin Co(II) (d7 ) ion
1g
1g
3
(Fig. 1) [26].
Preliminary chemiluminescence studies on these two polynuclear complexes are in agreement with the literature data which
revealed the free radical-generating properties of Co2+ ion [27,28].
The negative values obtained for antioxidant assay (AA%: 49.3 for I

and 216.8 for II, respectively) sustained the pro-oxidant character

of Co2+ ion.
In order to establish the decomposition steps and the optimal
conditions for the conversion of polynuclear complex compounds
into cobalt-aluminate spinels, the thermal behaviour of the compounds I, II was investigated. Based on the results of the thermal
analysis (TG, DTG, DTA) (Fig. 2), the following decomposition pathways may be suggested for these compounds (Scheme 2) [29].
These results reveal that the formation temperature of CoAl2 O4
spinel from the gluconate compound is much lower than that
obtained from tartarate compound, probably due to the fact that
the decomposition of gluconate compound can be considered as a
self propagating combustion.
The crystallinity of the samples was improved by 2 h thermal
treatment at 1000 C.

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495

Fig. 4. IR spectra of CoAl2 O4 spinel obtained by thermal decomposition: (a) tartarate complex and (b) gluconate complex calcinated at 1000 C/2 h.

3.2. Characterization of the cobalt-aluminate spinel

The oxide products obtained from tartarate and gluconate
complexes were analyzed by X-ray diffraction, IR, UVvis, photoluminescence spectroscopy and TEM.

Fig. 3 presents the X-ray diffraction patterns of samples obtained

by thermal decomposition of tartarate and gluconate complexes
calcinated at 1000 C/2 h.
The X-ray diffraction patterns conrmed that the samples
consisted in single-phase CoAl2 O4 spinel (JCPDS 44-0160) [4].

Fig. 5. (a and b) UVvis spectra of CoAl2 O4 spinel obtained by thermal decomposition: (a) tartarate complex and (b) gluconate complex calcinated at 1000 C/2 h.

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Fig. 6. Solid-state emission spectra of CoAl2 O4 : (a) ex = 400 nm; (b) ex = 475 nm.

The crystallite size of the CoAl2 O ranged between 26 and

35 nm.
The IR spectra of the nal products were recorded in the
4000400 cm1 range. The IR spectra of CoAl2 O4 obtained by
thermal decomposition of tartarate and gluconate complexes are
presented in Fig. 4. These spectra show the presence of three bands
at 660, 540 and 500 cm1 , respectively. The bands correspond
to the formation of blue CoAl2 O4 spinel [30].
Fig. 5 illustrates the absorbance spectra for CoAl2 O4 spinel
obtained by thermal decomposition of tartarate and gluconate

complexes calcinated at 1000 C/2 h. The broad and intense

absorbtion band in the range 500700 nm could be assigned
to the third transition (3 ) from 4 A2 (F) ground state to the
4 T (P) excited state of tetrahedral Co2+ ion. The ne splitting
1
is due to spin orbit coupling between the excited and the
neighbouring doublet states 2 A1 (G) and 2 T2 (G). Because of both
quartet and doublet states mixing, the spin selection rule is
relaxed and the transition is allowed. The other two transitions
(1 and 2 ) are not observed as they lie in the far infrared
region.

Fig. 7. (a) TEM image of the CoAl2 O4 nanometric powder sample obtained by thermal decomposition of (NH4 )2 [CoAl2 (C4 O6 H4 )4 (OH)2 ]4H2 O calcinated at 1000 C/2 h; (b)
selected area electron diffraction pattern; (c) grain size histogram; (d) EDS spectrum of the CoAl2 O4 sample.

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497

to be suitable for the synthesis of CoAl2 O4 spinel. In general we

can say that both tartarate and gluconate routes lead to the formation of the single-phase CoAl2 O4 spinel. The UVvis spectrum for
CoAl2 O4 conrmed tetrahedral coordination of Co2+ (d7 ) ion which
is responsible for the blue bright colour of spinel oxide (Thenards
blue). Luminescence bands observed in the visible region at 600 and
710 nm are due to transitions from the 2 E(2 G) level to the lower
level 4 A2 (4 F) and from the 4 T1 (4 P) to the 4 A2 (4 F), characteristic
of tetrahedral Co2+ (d7 ) ion. The average crystallite size from TEM
images was in the range 5060 nm.
Acknowledgement
Financial support from the PNII-IDEAS project no. 158/2007.
Fig. 8. The TEM image and the corresponding SAED pattern of the CoAl2 O4 obtained
by thermal decomposition of (NH4 )2 [CoAl2 (C6 O7 H11 )5 (OH)5 ]2H2 O calcinated at
1000 C/2 h.

After a thermal treatment for 2 h/1000 C, CoAl2 O4 revealed

interesting colour changes: from cherry blue to light-blue (royal
blue).
To conrm the existence of tetrahedral Co2+ ions in the CoAl2 O4
spinel, spectra of a powder sample was measured and the results
are shown in Fig. 6. When the excitation wavelength is 400 nm,
the emission spectrum exhibits one peak at 600 nm (Fig. 6(a)).
However, when the excitation wavelength is 475 nm, the emission spectrum presents one emission peak at 710 nm (Fig. 6(b)).
As stated in the literature these emission peaks correspond to the
2 E(2 G) 4 A (4 F) (600 nm) and 4 T (4 P) 4 A (4 F) (710 nm) transi2
1
2
tions of tetrahedral Co2+ ion [31,32], which conrms the presence
of this ion in the resulting spinel powder.
The TEM images shown in Figs. 7 and 8 provide information
about the size and typical morphologies of the CoAl2 O4 spinels
obtained by decomposition of compounds I and II, respectively.
The CoAl2 O4 spinel obtained by decomposition of compound I
consists of nanometric crystal grains (Fig. 7(a)) whose size distribution is represented in Fig. 7(c) and for which average grain size is
63 nm. The selected area electron diffraction pattern indicates the
formation of a unique crystal phase, namely the spinel-CoAl2 O4
with a cell parameter a = 0.81 nm (Fig. 7(b)). Elemental analysis
by EDS reveals the presence of peaks corresponding to Co, Al and
O. Both C and Cu peaks come from the TEM grid provided with a
holey carbon membrane. The Co/Al atomic ratio resulting from the
quantitative analysis of the spectrum is Co/Al = 0.51.
Fig. 8 displays the TEM image of CoAl2 O4 spinel obtained by
thermal decomposition of compound II calcinated at 1000 C/2 h.
The crystallite size is between 35 and 100 nm and the average size
is about 50 nm. As we can see crystallites are welded in large akes
of micron size and also come voids are present in the volume of
each spinel crystallite. These voids are well faceted and have a size
between 5 and 10 nm. The crystallite aggregate have no texture and
the (4 4 0) reections are more intense than usual.
4. Conclusions
From the study carried out in this work the following conclusions can be withdrawn. The complexation method has been found

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