Page 5 of 27 Journal of Materials Chemistry A

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Cite this: DOI: 10.1039/c0xx00000x

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Co3O4 microcubes with exceptionally high conductivity using CoAl
layered double hydroxide precursor via soft chemically synthesized
cobalt carbonate
Churchil A. Antonyraj,a Divesh N. Srivastava,b Gurudas P. Mane,c Sivashunmugam Sankaranarayanan,a
c,d
5 Ajayan Vinu, and Kannan Srinivasana*
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
DOI: 10.1039/b000000x

Cubic micro particles of Co3O4 spinel were synthesized by

calcination of CoCO3 obtained using CoAl layered double
10 hydroxide (LDH) as a unitary precursor through soft-
chemical decomposition. The obtained cobalt spinel showed
an exceptionally high electrical conductivity at room
temperature. This is attributed to high concentrations of
charge carriers (Co4+), unique morphology, high reduction
15 temperature and low activation barrier.

Co3O4 spinel is a well-studied material with diverse applications

such as energy storage and conversion, and catalysis.1-3 It is
potentially explored as a negative electrode in rechargeable
lithium batteries.4 One of the challenges addressed recently is to
20 enhance the electronic conductivity of Co3O4, which is generally
achieved by partially substituting cobalt ions with other metal
ions such as Li, Al, Ga, Ge, and Sn besides transition metal ions
such as Ni.5,6 Among them, substitution of Li offers a significant
increase in the conductivity with respect to neat Co3O4.7 This was
25 attributed to the presence of Co4+ (for charge compensation of
Li+), thus allowing delocalization of holes in the octahedral sites
of the spinel lattice and thereby enhancing the conductivity.8 An
approach has also been made to synthesize nanostructured
composites of Co3O4 with C, Al2O3 etc. to improve conductivity.9
30 Morphology of Co3O4 plays an important role in controlling the
electronic properties, which in turn is governed by the nature of
precursors.2 Being a rarely studied precursor for the synthesis of
Co3O4, morphology of cobalt carbonate (CoCO3) is known to
influence the final property of the spinel.10 Recently, Co3O4
35 spinel derived from CoCO3 showed superior gas sensing
properties.11 It is thus always inquisitive to find a novel synthetic
strategy for Co3O4 with improved electronic properties using
different precursors with tunable morphology.
Layered double hydroxides (LDHs) are ionic lamellar compounds
40 consist of positively charged hydroxide sheets with interlayers
filled with anions and water molecules. LDHs are widely used as
catalysts, catalyst supports, composites, coatings and thin films
for diverse applications.12-16 During our investigation on the
synthesis of CoAl-LDH by different methodologies, urea
45 hydrolysis resulted in the formation of phase pure LDH;
hydrothermal treatment in mother liquor turned this LDH into
cobalt carbonate (denoted here as CoCO3-L).‡
Fig.1 PXRD of (a) CoAl-LDH, (b) CoCO3-C, (c) CoCO3-P, (d) CoCO3-
50 U, (e) CoCO3-L, # Aluminium oxyhydroxide (AlOOH), (Inset is
photograph of synthesized materials)
Heating thus produced carbonate in air topotactically converted it
to Co3O4 spinel with unique microcubic morphology and
unusually high electrical conductivity at room temperature.
55 Furthermore, the electrical conductivity observed is the highest
considering unmodified Co3O4 reported in literature and the
reasons behind thereof are discussed. For comparison, cobalt
carbonate was also synthesized by direct urea hydrolysis of
Co(NO3)2 and co-precipitation which are labelled as CoCO3-U
60 and CoCO3-P, respectively. A commercial cobalt carbonate was
also used, denoted as CoCO3-C (Experimental Section†).
Powder X-ray diffraction pattern (PXRD) showed LDH phase for
the urea hydrolysed sample (Fig. 1, a; JCPDS: 41-1428) and
spherocobaltite phase (CoCO3; Fig. 1, e; JCPDS: 11-0692 whose
65 reflections are indexed) for the sample after hydrothermal
treatment. Less intense reflections of cobalt carbonate phase were
observed for CoCO3-P (crystallite size - 378 Å) and CoCO3-C
(crystallite size - 93 Å) than that of CoCO3-U (crystallite size -
550 Å) and CoCO3-L (crystallite size - 472 Å), suggest the
70 influence of synthesis method in controlling the crystallinity of
the samples. Conversion of LDH into carbonate critically
depended on the hydrothermal treatment temperature wherein the

This journal is © The Royal Society of Chemistry [year] [journal], [year], [vol], 00–00 | 1
 Journal of Materials Chemistry A Page 6 of 27

transformation is complete only above 150 oC (Fig. S1†). CoCO3-
L from LDH had AlOOH as additional poorly crystalline phase
(from Al present in the precursor CoAl-LDH; JCPDS: 21-1307).
To remove this phase, it was treated with dilute HCl (3.3 mM). It
is reported earlier that this concentration does not affect the LDH
shaped morphology. The samples showed surface roughness
60 probably due to the formation of pores created by the CO2
evolution during calcination.

311

440
5

511
500

220

400
structure.17 PXRD revealed that the structure of CoCO3 was intact

422
222
111
and confirmed the absence of aluminium oxide phase after the
d
acid treatment (Fig. S2†). However, SEM-EDAX analysis of the

Intensity, C/s
acid-treated sample (Fig. S3†) showed the presence of aluminium c
10 and cobalt infers the presence of X-ray amorphous aluminium
phase in the material that was not removed by acid treatment.
Strategically, after acid treatment, the material was washed with b
water until neutral pH and then treated with various
concentrations of NaOH (1 M, 50 mM and 5 mM). 5 mM of
15 NaOH was sufficient to remove the aluminium completely.
Simple base treatment alone was not sufficient to completely
remove the AlOOH species. Further, treating washed and dried a
sample after pH adjustment under similar hydrothermal treatment 10 20 30 40 50 60 70
did not yield carbonate phase, instead gave highly crystalline 2 Theta, deg
20 LDH phase. The schematic presentation of experiments Fig. 2 PXRD patterns of (a) Co3O4-C, (b) Co3O4-P, (c) Co3O4-U, (d)
conducted is given in electronic supplementary Information†. Co3O4-L
CoAl-LDH showed platelet-like morphology (Fig. S4a,† 3-5 µm)
aggregated to flower like structure; CoCO3-L showed the layered
structure assembled cubic morphology (Fig. S4b,† 30-50 µm) a b
25 which is completely different from other reported morphologies
of cobalt carbonate.18,19 Formation of such layered cubic structure
is probably due to the sheet-like morphology of the precursor
LDH. In order to discern the reaction mechanism, hydrothermal
treatment of freshly synthesized CoAl-LDH in mother liquor was
30 carried out at different time and the phase formation,
morphology, concentration of metal ions and pH was monitored
(Fig. S5,†). Formation of CoCO3 preceded initially by the partial c d
transformation of carbonate-LDH to nitrate-LDH in 2 h. At 4 h,
transformation of LDH to CoCO3 occurred where the pH was
35 higher (9.0) which showed rectangular to hexagonal nano flakes
that assembled to form micro sheets which overlaid one over the
other forming microcubes. Based on these studies, the reaction
chemistry involved and a schematic mechanism are proposed and
given in Fig. S5,†. Thermal stability of cobalt carbonates varied
65 Fig.3 SEM images of (a) Co3O4-C, (b) Co3O4-P, (c) Co3O4-U, (d) Co3O4-
40 significantly with the synthetic procedure employed. CoCO3-C L (inset: HRSEM images)
showed poor stability, decomposing completely at 349 oC while
CoCO3-L was highly thermally stable (complete decomposition Crystallite sizes of these morphologically different spinels are
at 507 oC), the highest reported in literature so far (Fig. S6†).20,11 265, 224, 255 and 253 Å and surface areas are 23, 25, 15, and 16
A weight loss of 32.9% was observed at 430 oC ascribed to the m2g-1 for Co3O4-C, Co3O4-P, Co3O4-U and Co3O4-L respectively.
45 conversion of CoCO3-L to Co3O4-L and is similar to the 70 Temperature programmed reduction (TPR) profiles of different
theoretically calculated value of 32.5%. Different cobalt Co3O4 displayed two reduction peaks; the first reduction peak
carbonate samples were calcined in air at 500 oC for 3 h which around 240 to 310 oC corresponds to the reduction of Co3O4 to
showed the formation of Co3O4 spinel as elucidated by PXRD CoO, while the subsequent reduction of CoO to Co is observed at
(Fig. 2; JCPDS:42-1467). SEM analysis of these spinels showed 310 to 410 oC (Fig. S7†). The reduction temperatures strongly
50 varied morphology (Fig. 3) depending on the synthesis 75 depended on the morphology wherein Co3O4-L showed the
methodology employed. The unique layered structure assembled highest reduction temperature.22
cubic morphology was retained for Co3O4-L although with Researchers have demonstrated the importance of
significant roughness (craters are clearly visible on the surface of morphologically different Co3O4 materials for various
these particles; Fig. 3d inset). Co3O4-U showed a cubic electrochemical applications.1,20,23 The current-voltage (I-V)
55 morphology made up of highly crystalline small cubes as 80 characteristics of these materials were recorded in ±10 voltage
reported earlier.21 On the other hand, Co3O4-P exhibited uniform window (Fig. 4), using automatic sweep mode. The slopes of the
cuboidal structure piled up together to form micro spheres of I-Vs were found to be linear (R2 = 0.99 or better) in the scanned
irregular shape whereas Co3O4-C displayed a small dumbbell voltage range indicate ohmic nature of the contacts and the

2 | Journal Name, [year], [vol], 00–00 This journal is © The Royal Society of Chemistry [year]
Page 7 of 27 Journal of Materials Chemistry A
existence of a single charge carrier. Co3O4 is a p-type
semiconductor with holes as charge carriers, primarily by Co4+
ions generated through several pathways namely charge
disproportionation, partial substitution of cobalt in tetrahedral
5 sites by monovalent ions such as Li+ and due to excess oxygen
non-stoichiometry.24,25 From the slopes of the I-V curves, the
conductivity of the Co3O4-L is 1 to 5 order of magnitude higher
(8.27×10-4 S/cm) than that of the other Co3O4 materials (1.14×10-
5
S/cm, 6.73×10-9 S/cm and 4.48×10-8 S/cm for Co3O4-U, Co3O4-
10 P and Co3O4-C respectively).
Fig. 4 RT Current-Voltage graphs of (●) Co3O4-P, (▼) Co3O4-C, (■)
Co3O4-U, (▲) Co3O4-L (Inset: expanded region for first three samples)
This value is significantly higher than the classical Co3O4 and
15 compares well with the alkali incorporated Co3O4 obtained
through electrooxidation of CoO.25 The possibility of contribution
from Al in the improved conductivity of Co3O4-L was ruled out
from elemental analysis measurements (<2 wt.%). The electrical
conductance of cobalt oxide materials are best explained by
20 “small-polaron model”, that involves the transport of localized
charge states (holes as charge carriers).26 Unusual high
conductance for this sample is probably due to higher
concentration of charge carriers (here Co4+) and unique layered
cubic morphology that imparts better p-type electrical
25 conductivity. This was supported through iodometric titration
measurements that showed higher value of Co4+ (Table 1S†). It is
worth noting here that the higher reduction temperature exhibited
by Co3O4-L (Fig. S7†) supports facile formation of Co4+ by
oxidation of Co3+. Further, the conductivity of Co3O4 increased
30 with an increase in calcination temperature for CoCO3-L (Table
2S†).25 The conductance recorded as a function of temperature
showed an increase with an increase in temperature that confirms
the semiconducting nature. The energy of activation calculated
from the slope of ln(ρ/T) vs. 1/T plot (Fig. S8†) was 0.50 eV,
35 0.70 eV, 0.58 eV and 0.17 eV for Co3O4-C, Co3O4-P, Co3O4-U
and Co3O4-L respectively. The low activation energy observed
for Co3O4-L correlates well with the enhanced conductivity of
this sample.25
Conclusions
40 In conclusion, we have successfully demonstrated the synthesis
of crystalline cubic micro particles of Co3O4 using CoAl-LDH as
the unitary precursor via CoCO3 for the first time. Exceptionally
This journal is © The Royal Society of Chemistry [year]
high electrical conductivity at room temperature was noted for
this spinel and is attributed to higher charge carriers, unique
45 morphology, low band gap, and higher reduction temperature.
Such unusual properties possessed by this sample even without
additional doping may find application as electrodes in batteries
or supercapacitors with improved practical efficiency.
50 Acknowledgements
The authors thank reviewers for their constructive suggestions that have
helped in improving the scientific quality of the manuscript. The authors
thank Council of Scientific and Industrial Research (CSIR), New Delhi
55 for funding this work. C. A. A. thanks CSIR, New Delhi for the award of
a Senior Research Fellowship (31/28(95)/2008-EMR-1.
Notes and references
a
Discipline of Inorganic Materials & Catalysis, Central Salt and Marine
Chemicals Research Institute , Council of Scientific and Industrial
60 Research (CSIR), GB Marg, Bhavnagar 364002, India, * Tel: +91-278-
2567760 ext. 7030. Fax: +91-278-2567562.
E-mail: skannan@csmcri.org; kanhem1@yahoo.com;
b
Analytical Discipline and Centralized Instrument Facility, Central Salt
and Marine Chemicals Research Institute, Council of Scientific and
65 Industrial Research (CSIR), GB Marg, Bhavnagar 364002, India
c
International Center for Materials Nanoarchitectonics, World Premier
International Research Center, National Institute for Materials Science,
1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan
d
Multifunctional Nanoporous Materials Group, Australian Institute for
70 Bioengineering and Nanotechnology (AIBN), The University of
Queensland, Corner College and Cooper Roads, Brisbane Qld 4072,
Australia
† Electronic Supplementary Information (ESI) available: [Synthetic
75 procedures, reaction chemistry, mechanistic studies, PXRD, FT-IR, SEM-
EDAX, HRSEM, DTGA, TPR, elemental analysis, oxygen content
analysis and electrical conductivity measurements of various materials.].
See DOI: 10.1039/b000000x/
‡ Hydrothermal treatment of thoroughly washed urea-hydrolysed sample
80 (and not in mother liquor) did not result in the formation of cobalt
carbonate, but yielded a highly crystalline LDH. This provides evidence
that the pH of the solution during hydrothermal treatment is critical for
obtaining carbonate.
85 1 B. Guo, C. Li, and Z. Yuan, J. Phys. Chem. C, 2010, 114, 12805.
2 T. Zhu, J. S. Chen and X. W. Lou, J. Mater. Chem., 2010, 20, 7015.
3 X. Xie, Y. Li, Z. Liu, M. Haruta and W. Shen, Nature, 2009, 458,
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4 B. C. Yu, J. O. Lee, J. H. Song, C. M. Park, C. K. Lee and H. J. Sohn,
90 J. Solid State Electrochem., 2012, 16, 2631.
5 D. Pyke, K. K. Mallick, R. Reynolds and A. K. Bhattacharya, J.
Mater. Chem., 1998, 8, 1095.
6 J. A. K. Tareen, A. Małecki, J. P. Doumerc, J. C. Launay, P. Dordor,
M. Pouchard and P. Hagenmuller, Mater. Res. Bull., 1984, 19, 989.
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11 C. C. Li, X. M. Yin, T. H. Wang and H. C. Zeng, Chem. Mater.,
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2010, 49, 6020.
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and K. Kaneda, Angew. Chem. Int. Ed., 2010, 49, 5545.
14 C. A. Antonyraj, P. Koilraj and S. Kannan, Chem. Commun., 2010,
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15 J. Han, Y. Dou, M. Wei, D. G. Evans and X. Duan, Angew. Chem.

Int. Ed., 2010, 49, 2171.
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5 17 N. Iyi, T. Matsumoto, Y. Kaneko and K. Kitamura, Chem. Mater.,
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10 20 M. Y. Nassar and I. S. Ahmed, Polyhedron, 2011, 30, 2431.
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4 | Journal Name, [year], [vol], 00–00 This journal is © The Royal Society of Chemistry [year]
 Journal of Materials Chemistry A Page 10 of 27

Electronic Supplementary Information

Co3O4 microcubes with exceptionally high conductivity using

CoAl layered double hydroxide precursor via soft chemically
synthesized cobalt carbonate

Churchil A. Antonyraj,a Divesh N. Srivastava,b Gurudas P. Mane,c Sivashunmugam

Sankaranarayanan,a Ajayan Vinu,c,d and Kannan Srinivasana*
a
Discipline of Inorganic Materials & Catalysis, Central Salt and Marine Chemicals Research
Institute, Council of Scientific and Industrial Research (CSIR), GB Marg, Bhavnagar 364002,
India
b
Analytical Discipline and Centralized Instrument Facility, Central Salt and Marine
Chemicals Research Institute, Council of Scientific and Industrial Research (CSIR), GB
Marg, Bhavnagar 364002, India
c
International Center for Materials Nanoarchitectonics, World Premier International Research
Center, National Institute for Materials Science, 1-1 Namiki, Tsukuba, Ibaraki 305-0044,
Japan
d
Multifunctional Nanoporous Materials Group, Australian Institute for Bioengineering and
Nanotechnology (AIBN), The University of Queensland, Corner College and Cooper Roads,
Brisbane Qld 4072, Australia

Corresponding Author Information

* Tel: +91-278-2567760 ext. 7030. Fax: +91-278-2567562. E-mail: skannan@csmcri.org;
kanhem1@yahoo.com;

S1
Page 11 of 27 Journal of Materials Chemistry A

Experimental
Synthesis of LDH and its decomposition to cobalt carbonate: CoAl-LDH was synthesized
using urea hydrolysis method by taking 0.27 M of Co(NO3)2, 0.135 M of Al(NO3)3 and 1.584
M of urea in 200 ml of water and N2 gas was purged for 30 min to remove dissolved O2 and
CO2. This mixture was kept in a round-bottomed flask (500 ml) attached to a reflux
condenser at 90 oC for 30 h with stirring under N2 atmosphere. One portion (150 ml) of this
was filtered, washed with distilled water till neutral pH and dried in vacuum at room
temperature and the sample was named here as CoAl-LDH.
Decomposition of CoAl-LDH was done by taking another portion (50 ml) of LDH
synthesized with mother liquor into a Teflon-lined autoclave (70 ml) and heated at different
temperatures ranging from 120 to 200 oC for 12 h. After cooling to room temperature, the
solid precipitate was collected by filtration, washed with deionized water and dried in
vacuum at room temperature and the sample treated at 150 oC is named as CoCO3-decomp.
750 mg of this sample is treated with 300 ml of 3.3 mM HCl for 6 h, washed till pH neutral
and treated subsequently with 300 ml of 5 mM of NaOH for 6 h to remove AlOOH and
amorphous alumina phases to obtain highly pure and crystalline CoCO3-L.

Urea hydrolysis: 0.135 M of Co(NO3)2 and 1.584 M of urea in 50 ml of water were taken in a
Teflon-lined autoclave and heated at 150 oC for 12 h. The solid precipitate is collected by
filtration, washed with deionized water and dried in vacuum at room temperature. The sample
was named as CoCO3-U.

Co-precipitation:1M solution of Co(NO3)2 was slowly (1 ml min-1) and simultaneously

mixed with 2 M (NH4)2CO3 in a Schott autotitrator at a constant pH of 7.5 ± 0.1 under
stirring at room temperature. The sample was aged in the mother liquor at 90 oC for 30 h,
filtered off, washed with deionized water and dried in vacuum at room temperature. The
sample was named as CoCO3-P.

Commercial cobalt carbonate is purchased from sd-fine chem. pvt. Ltd., India and named
here as CoCO3-C.
Calcination of cobalt carbonate to cobalt oxide spinel:
Thus obtained CoCO3 samples were heated in a muffle furnace at a heating rate of 5 oC/min
till 500 oC in static air and kept at that temperature for 3 h for complete decomposition to
Co3O4. The corresponding samples are named as: Co3O4-L, Co3O4-U, Co3O4-P and Co3O4-C.

Elemental analysis for cobalt and aluminium in cobalt oxides was determined using
inductivity coupled plasma optical emission spectrometry (ICP-OES: Perkin Elmer, OES,
Optical 2000 DV) by dissolving the sample in adequate quantity of mineral acid.
The reaction chemistry and schematic presentation of experiments performed are given
below:

S2
 Journal of Materials Chemistry A Page 12 of 27

Schematic Presentation of Experiments

Conductance measurement: Co3O4 pellets were made by taking 75% of Co3O4, 20%
graphite and 5% PTFE and pelletized at an applied pressure of 5 tones. The electrical
measurements (Source Meter Unit - Keithley – 2635A) were done in a custom made pellet
holder of Teflon with stainless steel contacts. The whole system was placed in an airtight
controlled heating apparatus. I-V characteristics were recorded at different temperatures after
stabilizing at each temperature for 10 minutes. The current-voltage (I-V) characteristics were
recorded in ±10 voltage window. The readings were recorded at the end of one second with
applied voltage and the whole scan was completed in 21 seconds. The measurements were
done in duplicate and the error in the current measured was ± 3%.

S3
Page 13 of 27 Journal of Materials Chemistry A

Figure S1

*
1000
*
* * * *#*
Intensity, C/s

# # # # * **
# d

+ * * * * * *
# # # #* * **
# c
+
*+ + + ++
+ +* *
+ + + ++ b
a
10 20 30 40 50 60 70
2 Theta, deg
Fig. S1 PXRD patterns of (a) CoAl-as-synthesized (90 oC), (b) hydrothermal of “a” at 120
o
C , (c) hydrothermal of “a” at 150 oC, (d) hydrothermal of “a” at 200 oC (*Cobalt carbonate
(Spherocobaltite), # Aluminium oxyhydroxide (AlOOH), + Hydrotalcite)

S4
 Journal of Materials Chemistry A Page 14 of 27

Figure S2

*
1000

* * * * * * * ** c
Intensity, C/s

# # # # #
a

10 20 30 40 50 60 70
2 Theta, deg

Fig. S2 PXRD patterns of (a) CoCO3-L, (b) CoCO3-L after acid treatment, (c) CoCO3-L after
acid and base treatment (* Cobalt carbonate (Spherocobaltite), # Aluminium oxyhydroxide
(AlOOH))

S5
Page 15 of 27 Journal of Materials Chemistry A

Figure S3

Element Weight Atomic

% %
CK 26.16 46.02
OK 28.59 37.76
Co K 45.25 16.23
Total 100.00
Element Weight Atomic
% %
OK 67.09 78.30
Al K 30.04 20.79
Co K 2.88 0.91
Total 100.00

Fig. S3 SEM-EDAX images of CoCO3-L after acid treatment

S6
 Journal of Materials Chemistry A Page 16 of 27

Figure S4

a b

Fig. S4 HRSEM images displaying the morphological changes occurred during the soft
chemical decomposition (a) CoAl-LDH to (b) CoCO3-L

S7
Page 17 of 27 Journal of Materials Chemistry A

Figure S5
Formation mechanism of CoCO3 through soft-chemical decomposition of CoAl-LDH
+ - Hydrotalcite * 12 h

104
* - Cobalt carbonate
200 10 h
# - Aluminum oxyhydroxide
8h

110
012

122
116
113
*

202

Transmittance,%
024
*

214
# #
Intensity,c/s

* * # 6h
# * # * * * 12 h
4h
10 h

8h 2h
6h 0h
+ 4h

+ 2h
+
+ + ++ 0h
4000 3500 3000 2500 2000 1500 1000 500
10 20 30 40 50 60 70 -1
2 Theta, deg Wave number, cm

PXRD and FT-IR spectra of the as-synthesized CoAl-LDH sample (marked as 0 h) and after
its hydrothermal treatment in mother liquor at indicated time

PXRD and FT-IR results showed partial conversion of carbonate containing CoAl-LDH to
nitrate containing LDH upon hydrothermal treatment of as-synthesized sample after 2 h. This
was supported by the appearance of d003 basal reflection around 8.7 Å in PXRD and a band
observed at 1385 cm-1 (indicated as red arrow) in FT-IR, characteristic of nitrate containing
LDH materials.1 No significant change in the pH was noted during (see figure below) this
time however with subtle increase in the Co/Al atomic composition as determined through
ICP-OES analysis. Formation of nitrate containing CoAl-LDH through urea hydrolysis at
high temperature is known earlier.2 On increasing time to 4 h, a sharp increase in the pH was
noted (to 9.0) that did not change with its further increase. This could be due to the formation
of ammonium carbonate which probably then reacted with nitrate containing LDH, possibly
through dissolution-reprecipitation resulting in cobalt carbonate and aluminium oxyhydroxide
(see PXRD and FT-IR of 4 h sample). Since solubility of nitrate containing LDH is higher
than its corresponding carbonate from3, feasibility of this reaction would be better. On further
increase in time (up to 12 h), crystallization of cobalt carbonate takes place (as evidenced
from the increase in the intensity of reflections in PXRD) where assembling of rectangular to
hexagonal nano flakes to micro sheets occurs which then overlay one over the other forming
microcubes (morphology changes and schematic mechanism are given below).

ICP-OES analysis of solids and supernatant solutions obtained after hydrothermal treatment
of freshly synthesized CoAl-LDH in mother liquor at various time
Treatment Co/Al atomic Co in supernatant Al in supernatant
time (h) ratio in solid* (mg/L) (mg/L)
0 2.3 80.9 0.0
2 3.1 91.7 0.1
4 3.3 1.7 0.0
6 4.0 1.0 0.1
8 11.4 1.0 0.0
10 14.3 1.0 0.0
12 8.2 0.9 0.1
*The variation in Co/Al atomic ratio for solids after 4 h could be due to heterogeneity of the samples having
multiple phases

Supernatant solution at different time interval and values indicated are pH of the solution

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 Journal of Materials Chemistry A Page 18 of 27

Morphological (SEM) changes during the formation of CoCO3 through soft-chemical

decomposition of CoAl-LDH and schematic mechanism

Reaction Chemistry

90 oC
CO(NH2)2 + 3H2O 2NH4+ + CO2 + 2OH-
90 oC
2NH4+ + CO2 + 2OH- 2NH4+ + CO32- + H2O
90 oC
4Co(NO3)2 + 2Al(NO3) 3 + CO32- + 14NH4+ Co4Al2(OH)12.CO3.x H 2O + 14NH 4NO3
o
150 C
Co4Al2(OH)12.CO3.x H 2O + NH4NO3 Co6Al2(OH)12.NO3.x H2O + NH4CO3
In mother liquor
150 oC
2Co6Al2(OH)12.NO3.x H2O + 12CO32- 12CoCO3 + 2AlOOH + Al2O3
In mother liquor
500 oC
6CoCO3 + O2 2Co3O4 + 6CO2

(1) S. Huang, H. Peng, W.W. Tjiu, Z. Yang, H.Zhu, T. Tang, T. Liu, J. Phys Chem. B, 2010, 114, 16766.
(2) J.B. Han, J. Lu, M. Wei, Z.L. Wang, X. Duan, Chem. Commun., 2008, 5188.
(3) R.K. Allada, A. Navrotsky, H.T. Berbeco, W.H. Casey, Science, 2002, 296, 721.

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Page 19 of 27 Journal of Materials Chemistry A

Figure S6

c
dW/dT

100 200 300 400 500 600 700 800

o
Temperature, C
Fig. S6 DTGA profiles of (a) CoCO3-C, (b) CoCO3-P, (c) CoCO3-U, (d) CoCO3-L

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 Journal of Materials Chemistry A Page 20 of 27

Figure S7

H2 consumption (a.u)

c
b

a
100 200 300 400 500 600 700 800
o
Temperature, C
Fig. S7 TPR profiles of (a) Co3O4-C, (b) Co3O4-P, (c) Co3O4-U, (d) Co3O4-L

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Page 21 of 27 Journal of Materials Chemistry A

Estimation of Co4+ by oxygen content analysis through iodometric titration

Oxygen content analysis was carried out as reported.4 50 mg of material was dissolved in 10
ml of HCl (35.4 %) containing KI (10 g/L) in a tightly packed container for 4-6 h (complete
dissolution). The Co ions (Co3+ and Co4+) in higher oxidation states are reduced to Co2+ and
forms stoichiometric amount of iodine in the solution. The liberated iodine was titrated
against standard sodium thiosulpate solution (0.025 M) using freshly prepared starch as
indicator. Excess oxygen present in the sample is due to the presence of Co4+ that results in
high electrical conductivity. Titrations were done in triplicate and the average values are
reported and the variation in the titre values is ± 0.1 ml.

2Co3+ + 3I- → 2Co2+ + I3-

Co4+ + 3I- → Co2+ + I3-

I3- + 2S2O32- → 3I- + S4O62-

Table 1S Oxygen content and calculated formula of different Co3O4 materials by iodometry

Oxygen
Material Calculated Formula#
content
Co3O4-C 4.03 Co2+Co3+1.95Co4+0.05O4.03
Co3O4-P 4.00 Co2+Co3+2.00Co4+0.00O4.00
Co3O4-U 4.03 Co2+Co3+1.94Co4+0.06O4.03
Co3O4-L 4.08 Co2+Co3+1.84Co4+0.16O4.08
#
values rounded to two significant figures

(4) K. Conder, E. Pomjakushina, A. Soldatov, E. Mitberg, Mater. Res. Bull., 2005, 40, 257.

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 Journal of Materials Chemistry A Page 22 of 27

Effect of calcination temperature on the conductivity of Co3O4

In order to study the effect of calcination temperature which is known to influence the
electrical conductivity of the oxide samples, CoCO3-L was thermally treated at three different
temperatures (based on thermogravimetric analysis) namely 400, 500 and 650 oC in air for 3
h and the obtained oxide samples were assessed for electrical conductivity measurements.
The results showed an increase in the conductivity with an increase in calcination
temperature (Table 2S) probably due to an increase in the concentration of Co4+ as reported
earelier.5

Table 2S Specific conductivity of Co3O4 obtained by calcining CoCO3-L at different

temperatures

Calcination Specific conductivity

Temp (oC) (S/cm)

400 7.67×10-4
500 8.27×10-4
650 13.44×10-4

(5) M. Douin, L. Guerlou-Demourgues, M. Menetrier, E. Bekaert, L. Goubault, P. Bernard and C. Delmas,

Chem. Mater., 2008, 20, 6880.

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Page 23 of 27 Journal of Materials Chemistry A

Figure S8

Co3O4-C Co3O4-P
4.00 5.00
4.00 R² = 0.8539
3.00
3.00
ρ/T)

ρ/T)
2.00 R² = 0.9771
log(ρ

log(ρ
2.00
1.00R² = 0.9991
1.00
0.00 0.00
-1.00 -1.00
0.0015 0.002 0.0025 0.003 0.0035 0.0015 0.002 0.0025 0.003 0.0035
1/T 1/T

Co3O4-U Co3O4-L
4.00 1.50
3.00 R² = 0.9548 R² = 0.9207
1.00
ρ /T)

ρ/T)
2.00
log(ρ

log(ρ 0.50
1.00
0.00 0.00
-1.00 -0.50
0.0015 0.002 0.0025 0.003 0.0035 0.0015 0.002 0.0025 0.003 0.0035
1/T 1/T

Fig. S8 The electrical conductivity of Co3O4 materials at different temperatures – Small-

polaron model

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