Materials Chemistry and Physics 60 (1999) 39±43

Preparation and characterization of a higher cobalt oxide

St.G. Christoskovaa,*, M. Stoyanovaa, M. Georgievaa, D. Mehandjievb
a
Department of Physical Chemistry, Paisii Hilendarski University of Plovdiv, 4000 Plovdiv, Bulgaria
b
Institute of General and Inorganic Chemistry, Acad. G. Bonchev Str. bl. 11, 1040 So®a, Bulgaria

Received 7 July 1998; received in revised form 4 January 1999; accepted 20 February 1999

Abstract

The present paper describes the synthesis of a higher cobalt oxide system obtained from a solution technique. Low-temperature cobalt
oxide system has been prepared by the reaction of sodium hydroxide and NaOCl with a cobalt nitrate aqueous solution. The composition of
solid phase obtained under certain conditions is investigated by X-ray, IR, XPS- and atomic absorption spectral analyses, magnetic
measurements and chemical analysis. The results obtained show that a Co oxide system may be achieved, in which Co ions are mainly in
the highest oxidation state (‡ 4) and in octahedral coordination. The proposed method leads to the obtaining of highly active low-
temperature catalysts for oxidation of toxic substances (phenols, alcohols, aldehydes, CNÿ and S2ÿ) in an aqueous medium in the absence
of gaseous phase oxygen. # 1999 Elsevier Science S.A. All rights reserved.

Keywords: Cobalt oxide; XPS; Magnetic measurements; Oxidant

1. Introduction CoO2 has been readily formed by the reaction of laser-

vaporised metal atoms with oxygen and characterized by
Recently, the preparation, characterization and applica- ESR-spectroscopy [10].
tion of the Co oxide systems have attracted an increasing The oxidation of Co(II) hydroxide with hypochlorite,
interest [1±6]. The studies show that they can be used as persulphate or permanganate ions gives a precipitate
catalysts in various processes. The Co oxide systems used as believed to be a mixture of Co2O3aq and CoO2aq [11].
catalysts in oxidation reactions and described in the litera- Co2O3 has been obtained by electrochemical deposition
ture have a spinel structure, the contents of which may be on Pt electrodes from strong concentrated Co(II) solutions at
shown with the formula Xtetr(II)Y2oct(III)O4 allowing three high anodic density [12,13].
basic combinations of X and Y ions. The catalytic activity of Co2O3 for the liquid phase
A number of authors support the theory that the ions in oxidation of acrolein [14], the wet oxidation of strong waste
tetrahedral coordination are inactive or have a negligible water [15] and the reduction of nitrogen oxide by carbon
contribution to the total activity [5,7±9]. This fact could be monoxide has been studied [16].
explained with stronger metal(II)±oxygen bonds due to In this paper we describe the synthesis of a novel low-
lower valency and coordination number. The high catalytic temperature heterogeneous catalystÐa higher Co oxide. We
activity of the spinels in oxidation processes is related to the aimed at obtaining information about the phase composition
weaker Y(III)±O bond, i.e. to the higher oxidation state of and structure of the catalyst by means of several experi-
the metal cation. Experimentally this has been con®rmed by mental methods.
Jacobs et. al. [5]. Shelef et al. [7] also prove, using the LEIS The conditions under which the synthesis is carried out
method, that the high activity of spinel structure Co oxides is determine basic advantages in comparison with other meth-
due to the octahedrally coordinated Co ions [7,9]. Similar ods for obtaining of higher cobalt oxides:
conclusions have been reached in [8].
 an active phase with non-stationary surface properties is
In the specialised literature methods for obtaining of
formed, which changes slightly in the process of oxida-
higher cobalt oxidesÐCoO2 and Co2O3 have been described
tion proceeding at temperatures close to room tempera-
[10±13].
tureÐtypical of low-temperature catalysts;
 an amorphous and highly disperse oxide system is
*Corresponding author. obtained. The amorphous state makes each active site

0254-0584/99/$ ± see front matter # 1999 Elsevier Science S.A. All rights reserved.
PII: S 0 2 5 4 - 0 5 8 4 ( 9 9 ) 0 0 0 5 3 - X
40 S.G. Christoskova et al. / Materials Chemistry and Physics 60 (1999) 39±43

of the catalyst structurally and chemically isotropic Total cobalt content was determined by atomic absorp-
which is the basis for high selectivity in oxidation tion measurement carried out with a Spectro-Flama IOP-
processes. OES spectrometer at the corresponding resonance wave-
length.
The total `active' oxygen content was determined by a
2. Experimental direct iodine method [20]. The sample (0.1 g) was dissolved
in dilute (1 : 10) sulphuric acid containing 2 g of potassium
The low-temperature cobalt oxide system was obtained by iodide. The solution was magnetically stirred and after a
the precipitation±oxidation process in an aqueous solution. complete decomposition the liberated iodine was titrated
A cobalt nitrate solution (0.4 M) is added to a mixture of with standardised 0.1 N sodium thiosulphate.
aqueous solutions of NaOH (4 M) and NaOCl (1 M). NaOH The amount of surface active oxygen was measured by
was used as a precipitating agent instead of NH4OH in order the hydrazine method [21]. A measured amount of 0.1 N
to avoid the formation of water-soluble Co(II) ammonia hydrazine sulphate solution is allowed to react with a known
complexes. The precipitation was carried out at 708C and weight of a catalyst sample for about 20 min in a closed
pH ˆ 9.0 under constant stirring. The resulting black pre- vessel. The residual hydrazine after ®ltration was titrated
cipitate was allowed to stay in the mother liquor for 1 h. against 0.1 iodine solution at pH ˆ 7.2.
Then it was ®ltered, washed with distilled water until The infrared spectra were recorded with a model 1750
negative reaction for NO3ÿ and Clÿ and dried at 908C Perkin Elmer FTIR spectrophotometer in KBr tablets. The
for 6 h. tablets were prepared according to a procedure described
The difference between the presented preparation method elsewhere [22]. The applied procedure led to the obtaining
and the method described in Ref. [11] is that the processes of of IR spectra free from undesirable bands of adsorbed water
precursor forming Co(OH)2 and its further oxidation pro- (water may be adsorbed during mixing and pelleting).
ceed simultaneously. A periodic precipitation method with a The XPS spectra were registered with an ESCALAB II
reverse order of applying of the precipitation agent to the electron spectrometer using Al K radiation. Corrections
system is used, i.e. Co2‡ ! OHÿ ‡ OClÿ. This favours the related to a charge on the samples were made with respect to
obtaining of hydrophilic precipitates. The OH groups, the position of the C 1s peak at 284.6 eV. The energy
included in the oxide system and thus increasing its activity differences were determined with an accuracy of  0.1 eV.
in the oxidation processes, take part in the oxidation The ESR spectra were recorded with a Bruker ER-200
mechanism [17]. On the other hand, the Co(II) ions act DSRC apparatus.
as a catalyst in the decomposition of NaOCl producing Magnetic measurements were carried out according to the
highly reactive nascent oxygen. The latter increases the Faraday method in a special equipment. Speci®c magnetic
oxidation state of the cobalt ions in the oxide system and susceptibility (s) was measured in the temperature range of
ensures a high concentration of ionic oxygen species (Oÿ, 290±490 K with a magnetic ®eld intensity varying from
O2ÿ) on its surface and plays a main role in the oxidation 2  103 to 10  103 Oe. Molar magnetic susceptibility (M,
catalysis [18]. cm3 molÿ1) was calculated from the experimental values for
The synthesized Co oxide system was characterized by s. The effective magnetic moment (eff, BM) was esti-
X-ray analysis, IR spectroscopy and electron spin resonance mated from the slope of the 1/M vs. temperature plot.
(ESR) spectroscopy, X-ray photoelectron spectroscopy
(XPS), magnetic and atomic absorption measurements
and chemical analysis. Data obtained were compared with 3. Results
that of a reference sample of Co3O4 (E. Merck, Germany)
analyzed by the same methods. 3.1. Chemical analysis
Chemical analysis of the synthesized Co oxide system
includes determination of total cobalt content and `active' The results concerning the content of total (O*) and
oxygen content. The `active' oxygen is the percentage of surface `active' oxygen (Os*) as well as the Co content in
excess oxygen above that required by the lowest stable the synthesized Co oxide system and in the Co3O4 are
valency state [19]. presented in Table 1.

Table 1
Chemical analysis data of Co oxide system and Co3O4

Catalyst Total active oxygen [O*] Surface active oxygen [Os*] Co content
ÿ1 ÿ1
gOg cat % gOg cat % g Co gÿ1cat

Co oxide system 0.0946 9.45 0.0437 4.37 0.325

Co3O4 0.0103 1.03 0.009 0.98 0.734
 S.G. Christoskova et al. / Materials Chemistry and Physics 60 (1999) 39±43 41

It is seen from Table 1 that the Co oxide system has a high

O* content (9.45%); however, the amount of Os* is approxi-
mately 50% of the total active oxygen. Both these factors
determine its high activity in liquid phase oxidation reac-
tions in contrast to Co3O4, which is characterized by much
lower active oxygen (total and surface) content. Considering
the chemical analysis and thermal analysis data, published
in Ref. [23], the composition of the synthesized Co oxide
system may be expressed with the gross formula
CoO1.78
5
2H2O.
The chemical analysis data were used for the interpreta-
tion of the results obtained from the magnetic measure-
ments.
Fig. 2. IR spectrum of Co oxide system.
3.2. X-ray analysis

The synthesized Co oxide system is amorphous in con- oxide system may be more accurately expressed with the
trast to Co3O4 and Co2O3 which have a well-de®ned crystal formula Co‡20.24Co‡40.76O1.78
5
2H2O.
structure. Co3O4 belongs to the spinel-type oxides and
Co2O3 is supposed to have the hexagonal lattice structure 3.4. IR-spectral analysis
[24]. The fresh sample, heated at a temperature above
2508C, undergoes changes in its composition and structure Since the Co oxide system was amorphous, its IR spec-
and turns into a cobalt cobaltite with a spinel structure [23]. trum could present information about the phase composition
as well as the way oxygen is bound to the metal ions. The IR
3.3. Magnetic measurements spectra of Co oxide system and Co3O4 are illustrated in
Figs. 2 and 3.
Fig. 1 presents the s vs. temperature and 1/M vs. Comparing the two IR spectra one can note an essential
temperature plots for the Co oxide system. deviation. Evidently (Fig. 2) the synthesized sample does
The plots on Fig. 1(a) show that the synthesized cobalt not have a spinel structure characteristic of Co3O4. The IR
oxide system is paramagnetic. The linear course of the 1/M spectrum of Co3O4 (Fig. 3) displays two distinctive bands
vs. temperature plot (Fig. 1(b)) is evidence that the Curie± originating from the stretching vibrations of the metal±
Weis law is obeyed in the whole studied temperature inter- oxygen bond [25,26]. The ®rst band  1 at 571 cmÿ1 is
val, which allows us to calculate the effective magnetic associated with the BOB3 vibrations in the spinel lattice,
moment. The value obtained (eff ˆ 2.96 BM) leads to the where B denotes the Co cations in an octahedral position, i.e
assumption that cobalt ions in the sample are in (‡ 2) and Co(III) ions. The second band  2 at 664 cmÿ1 is attributed to
(‡ 4) state of oxidation. Considering the results of the the ABO3 vibrations, where A denotes the metal ions in a
magnetic measurements the Co2‡/Co4‡ ratio is calculated tetrahedral position. The comparison of the two spectra
to be 0.24 : 0.76. That is why the composition of the cobalt shows a single wide and highly intensive absorption band
at 586 cmÿ1 in the IR spectrum of the Co oxide system
instead of  1 and  2. We assume that this band is due to the
stretching vibrations of the bond between the surface

Fig. 1. Temperature dependencies on the (a) specific magnetic suscept-

ibility and on (b) the molar magnetic susceptibility. Fig. 3. IR spectrum of Co3O4.
42 S.G. Christoskova et al. / Materials Chemistry and Physics 60 (1999) 39±43

weak satellite band [29]. Some authors claim that on the

basis of XPS measurements Co2O3 and Co3O4 which con-
tain both Co2‡ and Co3‡ could not be distinguished by a
chemical shift or satellite [29]. This suggests that the surface
layer of Co3O4 is similar to that of Co2O3. The estimated
2p3/2±2p1/2 spin orbit splitting is 14.8 eV in the Co oxide
system compared with 15.1 eV in the Co3O4 [30] and Co2O3
[29].
The discrepancies in the XPS spectra between the Co
oxide system and Co3O4 and Co2O3, i.e. the observed
differences in binding energies and in spin-orbit splitting,
indicate chemical dissimilarities of surface composition in
the two samples and suggest that the synthesised Co oxide
Fig. 4. Co 2p XPS spectrum Co oxide system.
system contains cobalt in a higher oxidation state than the
Co3O4, i.e. exceeding (‡ 3).
cation±oxygen, affected by the available oxygen in the The O 1s spectrum of a cobalt oxide system (Fig. 5)
oxide. The above-mentioned band is similar to the BOB3 exhibits a single peak located at 531.3 eV. Similar to the
vibrations in the spinel lattice of Co3O4, but has been nickel oxide system, obtained by the same method, we
displaced by 15 cmÿ1 into the higher frequency area. The attribute the 531.3 eV peak to both OH groups and Oÿ(or
displacement observed leads to the assumption that the Co O22ÿ) species on the oxide's surface [31]. We should recall
ions in Co oxide system are in an oxidation state higher than that XPS is sensitive to only the outermost ca. 20A Ê of the
(‡ 3). Since the sample is amorphous, the presence of the solid, i.e. this spectra describe only the surface properties of
absorbency band at 586 cmÿ1 is likely to be due to the the systems.
presence of randomly oriented octahedra, i.e. cobalt is There is a correlation between the observed O (1s)
situated in oxygen octahedral environment [27]. binding energy and the amount of negative charge (i.e.
degree of oxidation) available for delocalisation on the
3.5. X-ray photoelectron spectroscopy oxygen atoms in each of the species. It is established that
both Oÿ and O22ÿ (with a maximum charge per oxygen
The Co2p and O 1s XPS spectra of cobalt oxide system atom of ÿ1) have the same binding energy as OHÿ, i.e.
are shown in Figs. 4 and 5. 531.5 eV [31]. The Oÿ species present at a zinc oxide
The binding energy of the Co2p3/2 and Co2p1/2 peaks surface, have also been shown to have an O (1s) peak at
(Fig. 4) is 780.9 and 795.7 eV, respectively, in the studied 531.5 eV [32].
sample. The Co2p3/2 spin-orbital component has a weak
satellite located about 6.7 eV above the main peak. Mean-
while, in Co3O4 the spectrum presents a main Co2p3/2 peak 4. Discussion
at a lower binding energy (780.1 eV) and a much smaller
satellite than in the cobalt oxide system [28]. Co2O3 has a The main point of the cobalt oxide system synthesis is the
Co2p3/2 spectrum with a main peak at 779.4 eV and very oxidation of the Co(OH)2 precursor with a strong oxidant.
As a result of the electron transfer between the hydroxide
and the oxygen from the oxidant, the oxidation state of the
metal cations increases and a high concentration of electro-
philic oxygen species ÿOÿ, O2ÿ, Oÿ2, i.e. active oxygen, is
achieved on the oxide surface. These effects are of great
importance to the complete oxidation catalysts.
Considering the results of the IR-, XPS, ESR-spectro-
scopic investigations of the synthesized oxide system, we
suggest that only Oÿ oxygen forms are present on its
surface. The presence of a single absorption band in the
IR region, in which the stretching vibrations of the surface
metal±oxygen bond are registered, proves the availability of
an energetically homogeneous surface oxygen in the Co
oxide system.
The absence of an absorption band at 1070 cmÿ1 in the IR
spectrum [33] as well as the lack of asymmetric ESR signals
at g ˆ 2.008 and g ˆ 2.03 [34] gives a reason to assume that
Fig. 5. O 1s XPS spectrum of Co oxide system. there are no charged molecular forms of adsorbed oxygen on
 S.G. Christoskova et al. / Materials Chemistry and Physics 60 (1999) 39±43 43

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