Solid State Sciences 48 (2015) 286e293

Contents lists available at ScienceDirect

Solid State Sciences

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

Cobalt- and iron-based nanoparticles hosted in SBA-15 mesoporous

silica and activated carbon from biomass: Effect of modication
procedure
Tanya Tsoncheva a, *, Izabela Genova a, Daniela Paneva b, Momtchil Dimitrov a,
Boyko Tsyntsarski a, Nicolay Velinov b, Radostina Ivanova a, Gloria Issa a,
Daniela Kovacheva c, Temenujka Budinova a, Ivan Mitov b, Narzislav Petrov a
a
Institute of Organic Chemistry with Centre of Phytochemistry, Bulgarian Academy of Sciences, Acad. G. Bonchev Str., Bl. 9, 1113 Soa, Bulgaria
b
Institute of Catalysis, Bulgarian Academy of Sciences, Acad. G. Bonchev Str., Bl. 11, 1113 Soa, Bulgaria
c
Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, Acad. G. Bonchev Str., Bl. 11, 1113 Soa, Bulgaria

a r t i c l e i n f o a b s t r a c t

Article history: Ordered mesoporous silica of SBA-15 type and activated carbon, prepared from waste biomass (peach
Received 17 March 2015 stones), are used as host matrix of nanosized iron and cobalt particles. The effect of preparation pro-
Received in revised form cedure on the state of loaded nanoparticles is in the focus of investigation. The obtained materials are
21 July 2015
characterized by Boehm method, low temperature physisorption of nitrogen, XRD, UVeVis, FTIR,
Accepted 6 September 2015
Available online 9 September 2015
Mossbauer spectroscopy and temperature programmed reduction with hydrogen. The catalytic behav-
iour of the samples is tested in methanol decomposition. The dispersion, oxidative state and catalytic
behaviour of loaded cobalt and iron nanoparticles are successfully tuned both by the nature of porous
Keywords:
Porous supports
support and the metal precursor used during the samples preparation. Facile effect of active phase
Activated carbon from biomass deposition from aqueous solution of nitrate precursors is assumed for activated carbon support. For the
Iron and cobalt nanoparticles deposition silica based materials the catalytic activity could be signicantly improved when cobalt acetylacetonate
Characterization of hosted nanoparticles is used during the modication. The complex effect of pore topology and surface functionality of different
supports on the active phase formation is discussed.
2015 Published by Elsevier Masson SAS.

1. Introduction suitable host matrix for preparation and stabilization of highly

In the last decade methanol has been considered as suitable
clean and efcient alternative fuel because it can be synthesized
from biomass and other waste products by well-known technolo-
gies and easily converted to hydrogen or synthesis gas in case of
needs [1e3]. Among the various approaches, methanol decompo-
sition has been reported as suitable way to supply vehicles, gas
turbines and fuel cells with hydrogen-containing fuel with a
simultaneous recovering of waste heat in the installations [4e6].
However, the synthesis of cheep, low-temperature and highly
active and selective catalysts for this process is still a matter of
challenge. It is well known, that the application of metals and metal
oxides in nanoscale is a promising way to solve this problem. Or-
dered mesoporous silicas, such as SBA-15, have been reported as
* Corresponding author.
E-mail address: tsoncheva@orgchm.bas.bg (T. Tsoncheva).
dispersed metal/metal oxide particles [7e13]. Their signicantly
large specic surface area and pore volume determined by the
presence of uniform and size-controlled mesopores provides pos-
sibility for ne tuning of the state of loaded particles. Besides,
activated carbons have been widely used as adsorbents, in sepa-
ration processes and in catalysis as catalyst supports [14e16] due to
their high specic surface area, thermal stability, chemical inert-
ness and wide range of variable surface functionality and pore size
distribution. Nowadays, the attempts to reduce the activated car-
bons price focused on their production from agricultural wastes,
such as bagasse and rice husk [17], rice bran [18], coffee husks [19],
olive kernels [20], cherry stones [21], olive stones [22], walnut
shells [23], etc. Recently, we reported our rst results on the pos-
sibility to prepare cheep and effective catalysts for methanol
decomposition on the base of activated carbons, obtained from
waste coal treatment and biomass by-products via their modica-
tion with iron and cobalt nanoparticles [24e26]. The aim of current

http://dx.doi.org/10.1016/j.solidstatesciences.2015.09.001
1293-2558/ 2015 Published by Elsevier Masson SAS.
 T. Tsoncheva et al. / Solid State Sciences 48 (2015) 286e293
paper is to elucidate the effect of preparation procedure on the state
of loaded cobalt and iron species on various porous supports, such
as SBA-15 silica and activated carbon, obtained from waste biomass
(peach shells). For this purpose, the porous supports were treated
with corresponding metal nitrate and acethylacetonate precursors
from aqueous and organic solution, respectively. A complex of
conventional physicochemical techniques, such as Boehm method,
N2 physisorption, XRD, UVevis, FTIR, Moessbauer spectroscopy and
temperature programmed reduction with hydrogen (TPR), was
applied for catalysts characterization. The catalytic behaviour of the
obtained materials was tested in methanol decomposition to CO
and hydrogen.
2. Materials and methods
2.1. Materials
The activated carbon (AC) was produced by one-step process
combining carbonization and activation steps, from crushed peach
stones in the presence of water vapour at 1023 K for 1 h, as
described in [24]. The ow of water vapour was started at 573 K.
Mesoporous silica material SBA-15 was prepared using Pluronic
P123 triblock-co-polymer (EO20PO70EO20) as structure-directing
agent according to the procedure described in [27]. The template
was removed by calcination at 823 K for 6 h. The obtained materials
were modied with Fe and Co by incipient wetness impregnation
with aqueous solution of the corresponding nitrate precursors
(1 ml per 0.5 g support). Analogues modications were obtained by
impregnation of the supports with 0.007 M toluene solutions of the
corresponding acetylacetonate precursors for 4 h at room tem-
perature followed by evaporation at 313 K using a rotary evapo-
rator. The calculated metal content for all materials was 8 wt.%. The
obtained samples were dried at room temperature and then the
decomposition of the metal precursor was carried out under ni-
trogen ow at 773 K for 2 h with temperature increase of 3 Kmin
1.
The metal loading in all materials determined by atomic absorption
analyses (AAS) is listed in Table 1. The samples were denoted as M/
S_X, where S was AC or SBA-15 support, M was Fe or Co and X was
nitrate (N) or acetylacetonate (A) precursor.
2.2. Methods
The atomic absorption analyses were performed on a Pye Uni-
cam SP 192 instrument. The porous structure of selected modi-
cations was studied by nitrogen physisorption at 77 K, carried out in
an automatic volumetric apparatus ASAP 2020 from Micromeritics.
Before the experiments, the samples were treated under vacuum at
523 K overnight. The isotherms were used to calculate the specic
surface area, SBET, and pore volumes of the obtained materials. The
amount of various acidic oxygen-containing functional groups was
determined by Boehm's method using aqueous solutions of
NaHCO3, Na2CO3, NaOH, and C2H5ONa, according to the procedure
described in [28]. The amount of basic sites was determined with
0.05 N HCl [29]. Powder X-ray diffraction patterns were collected
within the range of 5.3 to 80 2q on a Bruker D8 Advance diffrac-
tometer with Cu Ka radiation and LynxEye detector. The average
crystallite size was evaluated by using the Scherrer equation. The
UVeVis spectra were recorded on the powder samples using a Jasco
Table 1
Samples composition determined by AAS.
Sample/M M/AC_A M/SBA-15_A M/AC_N M/SBA-15_N
Fe 2.6 3.3 4.6 3.5
Co 2.4 1.2 2.7 5.6
287
V-650 apparatus. The IR spectra (KBr pellets) were recorded on a
Bruker Vector 22 FTIR spectrometer at a resolution of 1e2 cm
1,
accumulating 64e128 scans. The Mossbauer spectra were obtained
in air at room temperature with a Wissel (Wissenschaftliche Elek-
tronik GmbH, Germany) electromechanical spectrometer working
in a constant acceleration mode. A 57Co/Rh (activity y25 mCi)
source and a-Fe standard were used. The experimentally obtained
spectra were tted by the least square-method. The TPR/TG (tem-
perature-programmed reduction/thermo-gravimetric) analyses
were performed in a Setaram TG92 instrument in a ow of 50 vol%
H2 in Ar (100 cm3 min
1) and heating rate of 5 K min
1.
Methanol conversion was carried out in a xed bed ow reactor
(0.055 g of catalyst), argon being used as a carrier gas
(50 cm3 min
1). The methanol partial pressure was 1.57 kPa. The
catalysts were tested under conditions of a temperature-
programmed regime within the range of 350e770 K with heating
rate of 1 K min
1. On-line gas chromatographic analyses were
performed on HP apparatus equipped with ame ionization and
thermo-conductivity detectors, on a PLOT Q column, using an ab-
solute calibration method and a carbon based material balance.
3. Results and discussion
3.1. SBA-15 and AC supports characterization
Low temperature nitrogen physisorption analyses were per-
formed in order to characterize the texture peculiarities of silica
and carbon supports (Fig. 1) and the main parameters are listed in
Table 2. The isotherm of SBA-15 silica is of IV type with steep step
due to nitrogen condensation at 0.6e0.8 P/P0 and H1 type hyster-
esis loop which according to IUPAC classication can be assigned to
mesoporous materials with uniform cylindrical pores (Fig. 2a,
inset). The isotherm of activated carbon can be indexed as I/IV type
indicating mixed micro-mesoporous structure (Fig. 2b). Both ma-
terials possess almost similar BET surface areas, but about twice is
the found pore volume for SBA-15 due predominantly to the
presence of mesopores. The XRD pattern of SBA-15 in the small
angle region (Fig. 2a, inset) exhibits three well resolved reections,
which are indexed as (100), (110) and (200) planes and conrms the
synthesis of high quality 2D hexagonally ordered mesoporous silica
material. XRD patterns of parent AC (Fig. 2b, inset) represent broad
reections around 26 and 43 2q which are generally assigned to
crystalline carbonaceous structure. In Fig. 3a,b are recorded the
FTIR spectra of the parent supports. The peaks around 1084, 804
and 462 cm
1 in the spectrum of SBA-15 (Fig. 3a) represent the
absorption of SieOeSi skeleton while the band centred around
960 cm
1 typically originates from SieO vibrations in the SieOH
groups. In the spectra of pure activated carbon (Fig. 3b) the band at
1690 cm
1 is attributed to C]O groups, whereas the band at
1530 cm
1 and the broad band around 1200e1000 cm
1 is due to
nas of CeOeC bonds [30]. The weak absorption band around
900e800 cm
1 is due to g(CeH) in aromatic structures, while the
absorption peak at 580 cm
1 belongs to g(OeH) stretching vibra-
tions [30]. More information for the type and the amount of the
accessible surface functional groups on AC was obtained by Boehm
method. Signicant amounts of basic (1.04 meq g
1) and acidic
surface functional groups, mainly carbonyl (1.07 meq g
1) and
hydroxyl (0.29 meq g
1), are registered. The oxygen-containing
functional groups detected on the carbon surface are very impor-
tant for their ion exchange and catalytic properties.
3.2. Iron modications of SBA-15 and AC
In Table 2 are presented data for the nitrogen physisorption
parameters of selected iron modications of AC and SBA-15. The
288 T. Tsoncheva et al. / Solid State Sciences 48 (2015) 286e293

Fig. 1. Nitrogen physisorption isotherms and pore size distribution (incet) for parent SBA-15 silica (a) and AC (b) support.

Table 2 Vmic clearly indicates a preferable location of the iron species into
Nitrogen physisorption data (SBET-specic surface area, Vtotal-total pore volume, the mesopores.
Vmic-micropore volume, Vmes-mesopore volume) for AC and SBA-15 supports and
selected Fe and Co modications.
In Fig. 2 are presented the XRD patterns of the iron modica-
tions of both supports obtained by nitrate and acetylacetonate
Sample SBET, m2/g Vtotal, cm3/g Vmic, cm3/g Vmes, cm3/g Vmic/Vmes precursor. No reections of any metal containing phase are regis-
AC 820 0.41 0.27 0.08 3.4 tered in the XRD patterns of SBA-15 supported modications
SBA-15 807 0.99 0.13 0.86 0.2 (Fig. 2a), which could be due to the formation of very nely
Fe/AC_N 617 0.28 0.24 0.04 6.0
dispersed phase and/or detection limitation (Table 1). The XRD
Co/AC_N 655 0.28 0.20 0.04 5.0
Co/AC_A 346 0.15 0.10 0.02 5.0 pattern of Fe/AC_N (Fig. 2b) represents reections at 30.1, 35.5 ,
Fe/SBA-15_N 716 0.90 0.19 0.66 0.3 43.5 , 56.9 and 62.6 2q which could be assigned to face-centred
Co/SBA-15_N 781 0.92 0.23 0.65 0.4 cubic (fcc) structure of Fe3O4 (JCPDS 19e629). The average particle
size elucidated by Scherrer equation is about 15 nm. The XRD re-
ections are broader and less intensive in the XRD pattern of Fe/
observed decrease in the BET surface area and pore volume as AC_A, indicating higher dispersion of the magnetite phase.
compared to the pure supports is probably due to pore blocking The FTIR spectrum for iron modied AC represents broad bands
after the deposition of the iron phase and this effect is most pro- at about 580e560 cm
1, which are characteristic of the absorption
nounced for the AC support. The increase in the Vmic/Vmes ratio as of FeeO bonds in iron oxide structures (Fig. 3b). The band centred at
compared to the pure supports combined with the slight changes in around 965 cm
1 in FTIR spectra of SBA-15 modications (Fig. 3a)

SBA-15
a x-AC b
AC

0-CoO
u-Co3O4 X -AC
s-Co
0 0-Fe3O4
s
x
Intensity, a.u.
Intensity, a.u.

0 1 2 3 4 5 6
2 Theta, deg 20 30 40 50 60 70 80 90
s X 2 T h e ta , d e g
s
x X
Co/AC_A
Fe/AC_A

x Co/SBA-15_A
0 0 Fe/SBA-15_A
x
x0 0
Co/AC_N
u 0 0x Fe/AC_N
0 0
Co/SBA-15_N
u u Fe/SBA-15_N

10 20 30 40 50 60 70 80 10 20 30 40 50 60 70 80
2 Theta, deg 2 Theta, deg
Fig. 2. XRD patterns of pure AC and SBA-15 supports (inset) and their cobalt (a) and iron (b) modications obtained by various precursors.
 T. Tsoncheva et al. / Solid State Sciences 48 (2015) 286e293
1084
Absorbance, a.u
462
960 SBA-15
804
Fe/SBA-15_N
Co/SBA-15_N
671 573
1400 1200 1000 800 600
-1
Wavenumber, cm
SBA-15
Fe/SBA-15_N
Absorption, a. u.
Fe/SBA-15_A
Co/SBA-15_N
Co/SBA-15_A
200 400 600
Wavelength, nm
Fig. 3. FTIR (a,b) and UVeVis spectra (c,d) of parent and iron and cobalt modications of SBA-15 and AC.
typically originate from SieO vibrations in the SieOH groups [31].
The slight changes in the band for all silica modications compared
to the parent support could be assigned to the metal interaction
with surface SieOH groups with the formation of OeM linkage. The
UVeVis spectra of both iron modications of SBA-15 (Fig. 3c) are
tted with three peaks at about 240, 320 and above 400 nm. The
rst and the second one are generally assigned to mononuclear
Fe3 ions in octahedral coordination and small (FeO)n clusters,
respectively, while the third peak is typical of Fe2O3 bulk particles
[32]. In accordance with XRD analyses, the broad features above
300 nm for both AC modications (Fig. 3d) could be assigned to the
presence of magnetite particles.
In order to describe the state of iron particles more precisely,
Moessbauer spectroscopy was applied. The Moessbauer spectra
(Fig. 4aed) are well tted with doublet and sextet components
which could be ascribed to the presence of iron oxide particles with
different dispersion (Table 3). The main part in the spectra of Fe/
AC_N (Fig. 4a) represents Sx2 and Sxt3 sextets with parameters
corresponding to magnetite phase in consistent with XRD and
UVeVis analyses. The Sx1 sextet with relative weight of about 3%
corresponds to small amount haematite. The appearance of doublet
part in the Moessbauer spectra reveals also presence of ultra
disperse iron oxide particles (D < 10e12 nm) with super-
paramagnetic (SPM) behaviour. The doublet hyperne parameters
in the spectrum of Fe/AC_ (Fig. 4b) are characteristic of Fe3 ions
in tetrahedral and Fe2.5 ions in octahedral coordination and also of
Fe2 ions. The relative part of sextet components for the nitrate
obtained material is about 3.5 times higher as compared to that one
for its acetylacetonate analogue, which conrms the data from the
XRD analyses for the presence of more nely dispersed magnetite
phase in the later sample. At the same time, the Moessbauer spectra
for SBA-15 based iron modications (Fig. 4c,d) consist only of
doublets of Fe3 ions in octahedral coordination. Using coree-
shell model for tting doublet spectra it is possible to estimate
approximately the particle size. The result of equal relative weight
289
1530
a b 1045
1690
AC
Absorbance, a.u
Fe/AC(N)
578
Co/AC(N)
580
2000 1500 1000 500
400 -1
Wavenumber, cm
c d
AC
Absorption, a. u.
Fe/AC_N
Fe/AC_A
Co/AC_N
Co/AC_A
800 200 400 600 800
Wavelength, nm
of core and shell components indicate presence of nely
dispersed iron oxide particles of about 2e4 nm (Table 3).
TPR experiments were performed to characterize the state of the
loaded active phase and the stability of the obtained materials under
reductive conditions (Fig. 5). The TPR-DTG prole of Fe/SBA-15_N
exhibits well dened maximum centred at about 650 K (Fig. 5a).
The observed weight loss during the whole temperature interval is
about 3 times lower than the calculated theoretic one for the
Fe3/Fe0 transition. Less pronounced and shifted to lower tem-
perature DTG effect is registered for its acetylacetonate analogue
(Fig. 5a). Here again, relatively low degree of reduction is detected. In
accordance with Moessbauer, FTIR and UVeVis spectra, these fea-
tures for both iron modied SBA-15 materials probably originate
from the existence of hardly reducible, nely dispersed iron species,
which are in strong interaction with the surface silanol groups.
However, the effect of the iron precursor is well demonstrated for the
carbon based materials (Fig. 5a). Two DTG effects are recognized
when the nitrate precursor was used and only one signicant feature
is registered for the sample obtained from acetylacetonate precursor.
According to Moessbauer data (Fig. 4, Table 3) this could be due to
the reduction of a mixture of haematite- and magnetite-like particles
in different proportion and dispersion. The observed much bigger
weight loss as expected for the reduction of Fe2O3 to metallic iron in
both cases indicates high degree of gasication of the AC, probably
with the catalytic activity of the loaded iron species and this effect
seems to be more pronounced for Fe/AC_A sample.
In Fig. 6 are presented temperature dependencies of methanol
decomposition on various iron modications. In order to precise
the discussion for various materials, the specic catalytic activity
calculated as a conversion per unit metal content (Table 1) is shown
in Fig. 6a. CO, CH4 and CO2 are the only registered carbon con-
taining products and the selectivity to CO, which is closely related
to hydrogen production from methanol, is illustrated in Fig. 6b.
Both iron modications of SBA-15 silica exhibit similar and rela-
tively low catalytic activity and selectivity in methanol
290 T. Tsoncheva et al. / Solid State Sciences 48 (2015) 286e293

Fig. 4. Room temperature Moessbauer spectra of Fe/AC_N(a), Fe/AC_A(b), Fe/SBA-15_N (c) and Fe/SBA-15_A (d).

Table 3
Moessbauer parameters of iron modications of SBA-15 and activated carbon.

Sample Components IS, mm/s QS, mm/s Heff, T FWHM, mm/s G, %

Fe/SBA-15_N Db1-Fe3 SPM core 0.33 0.78 e 0.51 56

Db2-Fe3 SPM shell 0.33 1.26 e 0.69 44
Fe/SBA-15_A Db1-Fe3 SPM core 0.39 0.97 e 0.57 50
Db2-Fe3 SPM shell 0.31 1.03 e 0.64 50
Fe/AC_N Sx1-a-Fe2O3 0.32
0.10 49.8 0.50 3
Sx2-Fe3O4 0.30 0.01 47.6 0.42 10
Sx3-Fe3O4 0.64 0.01 43.7 1.35 61
Db1-Fe3 SPM core 0.34 0.72 e 0.52 12
Db2-Fe3 SPM shell 0.31 1.05 e 0.73 14
Fe/AC_A Sx1-Fe3O4 0.29 0.03 48.8 0.32 6
Sx2-Fe3O4 0.66 0.03 45.6 0.33 13
Db1-Fe3 SPM core 0.33 0.57 e 0.43 36
Db2-Fe3 SPM shell 0.29 0.98 e 0.50 20
Db3-Fe2 1.13 0.58 0.30 7
Db4 eFe2 0.97 1.67 e 0.32 18

isomer shift (IS), quadruple splitting (QS), the effective internal magnetic eld (Heff), the line widths (FWHM), and the relative weight (G).
Db -e doublet part in the spectra; Sx e sextet part in the spectra.

decomposition. The Moessbauer analyses of the used in the cata-
lytic experiments materials clearly show negligible changes with
the loaded iron phase by the inuence of reaction medium, where
only 2 and 10% Fe2 are registered for Fe/SBA-15_A and Fe/SBA-
15_N, respectively. These results support the TPR data for the ex-
istence of strong interaction between the loaded haematite-like
species and surface silanol groups, which stabilize Fe3 species in
highly dispersed state but suppress their redox activity. Taking into
account the nitrogen physisorption data, we do not exclude also
location of haematite nanoparticles in the long mesoporous chan-
nels which makes part of them hardly accessible (Table 2). Among
the AC based materials, the sample obtained by nitrate precursor
possesses signicantly higher catalytic activity but lower selectivity
to CO formation as compared to Fe/AC_A. The Moessbauer study of
the used in catalyses samples demonstrates signicant phase
transformations during the catalytic experiment by the inuence of
the reaction medium. The larger haematite and magnetite particles
(corresponding to the sextet component in the Moessbauer spec-
trum, Fig. 4a and Table 3) in Fe/AC_N are partially transformed to
cementite (Fe3C), while more than 3 fold increase in the relative
part of the portion of relatively large magnetite particles is
observed for Fe/AC_A (Table 3). Hence, the acetylacetonate pre-
cursor provides formation of more nely dispersed magnetite
phase on AC, but on contrary to the silica support, here the inter-
action of iron species with surface acidic groups seems to be
insufcient to preserve the loaded particles against agglomeration
and/or reduction. Moreover, the formation of iron carbide phase
during the catalytic test with the activity of the reduction reaction
medium, which is the case with Fe/AC_N, seems to improve the
catalytic activity. This behaviour is provided also by the less pro-
nounced gasication of AC support as compared to the sample
obtained from acetylacetonate precursor.
 T. Tsoncheva et al. / Solid State Sciences 48 (2015) 286e293 291

Fig. 5. TPR-DTG proles of iron (a) and cobalt (b) modications of SBA-15 and AC.

a 100
20 b
Specific catalytic activity, %

Fe/AC_A
CO Selectivity, %

80
15 Fe/SBA-15_A
Fe/AC_N Fe/AC_A
Fe/SBA-15_N 60 Fe/SBA-15_A
10 Fe/AC_N
Fe/SBA-15_N
40
5
20

0
550 600 650 700 750 0
Temperature, K 600 650 700 750
Temperature, K

60 100
c d
Specific catalytic activity, %

CO Selectivity, %

Co/AC_A 80
Co/SBA-15_A
40 Co/AC_N
60
Co/SBA-15_N

40
20 Co/AC_A
Co/SBA-15_A
20 Co/AC_N
Co/SBA-15_N
0 0
550 600 650 700 750 600 650 700 750
Temperature, K Temperature, K

Fig. 6. The temperature dependencies of specic catalytic activity (a,c) and CO selectivity (b,d) for iron (up) and cobalt (down) modications of SBA-15 and AC.

3.3. Cobalt modications of SBA-15 and AC XRD patterns of all cobalt modications are presented in Fig. 2b.
The reections at 36.5 , 42.2 and 61.4 2q in the pattern of Co/
The data from the nitrogen physisorption analysis for selected AC_N indicate the presence of face centred CoO phase (JCPDS
cobalt modications are listed in Table 2. As in the case of iron 71e1178) with average particle size of 18 nm. The less intensive
modications the observed decrease in the BET surface area and reections at 36.6 , 59.4 and 65 2q which are detected for its SBA-
pore volume evidences deposition of cobalt phase into the porous 15 analogue (Co/SBA-15_N) are typical of Co3O4 spinel oxide (JCPDS
structure. Note that the modication of AC by acetylacetonate 3e1003) with average particles size below 15 nm. The intensive
precursor leads to a signicant decrease in all textural parameters reections at 41.7, 44.1, 47.5 and 75 2q in the pattern of Co/AC_A
which could be due to blocking of micropores or due to structural indicates that the modication of AC with acetylacetonate precur-
collapse of the support. sor provides the formation of metallic Co0 phase (JCPDS 15e0806)
292 T. Tsoncheva et al. / Solid State Sciences 48 (2015) 286e293
with average crystallite size of about 20 nm. On the contrary, the
absence of well distinguished reections in the pattern of its SBA-
15 analogue could be due to the formation of very nely
dispersed cobalt phase.
In order to obtain more information for the state of cobalt
species, UVeVis spectra were recorded (Fig. 3c, d). The peaks at 520,
580 and 630 nm in the spectrum of Co/SBA-15_A (Fig. 3c) are due to
the presence of Co2 ions in tetrahedral coordination, probably
interacting with surface silanol groups [33]. The UVeVis spectrum
of Co/SBA-15_N (Fig. 3c) represents broad absorption band around
470 nm, which can be attributed to octahedrally coordinated Co3
[33]. The band at around 720 nm is ascribed to the electronic
ligand-eld 4A2(F)/4T1(p) transition of Co2 in tetrahedral co- signicant changes with the cobalt phase by the inuence of the
ordination. This is in agreement with FTIR analysis (Fig. 3a) where
the bands at around 670 and 570 cm
1 evidence presence of well
crystallized Co3O4 spinel phase. The observed very low absorption
in the 300e710 nm region in the UVeVis spectra of both AC
modications (Fig. 3d) conrms the data from the XRD study for
the presence of reduced cobalt species.
In Fig. 5b are compared the TPR-DTG proles for the cobalt
modications of SBA-15 and AC. Two reduction effects with max-
ima at 420 and 630 K are observed in the TPR-DTG prole of Co/
SBA-15_N. According to XRD, UVeVis and FTIR data, they corre-
spond to step-wise reduction of Co3O4/CoO/Co. However, only
one broad DTG effect with maximum at 490 K is observed for Co/
SBA-15_A which, in accordance with the UVeVis data, is due to
almost 100% reduction of Co2 to Co0 (Fig. 5b). In the low-
temperature region, the reduction of Co/AC_N is signicantly less
pronounced and shifted to relatively lower temperatures as
compared to Co/SBA-15_N, which according to XRD data, evidences
predominant reduction of CoO. The absence of reduction effects up
to 550 K in the TPR prole of Co/AC_A is in agreement with the XRD
data for the domination of Co0 in this material. The observed strong
weight loss effect above 630 K for both AC modications is assigned
to gasication of activated carbon support.
In Fig. 6c, d are presented the changes in the specic catalytic
activity and CO selectivity in methanol decomposition with tem-
perature for all modications. The signicant shift of the temper- species into the porous support. The transformation of relatively
ature prole to lower temperatures for Co/AC_N evidences that
nitrate precursor ensures formation of highly active cobalt phase on
the activated carbon. Just the opposite its acetylacetonate analogue
(Co/AC_A) possesses extremely low catalytic activity. In accordance
with TPR and XRD analyses, this behaviour could be assigned to
differences in the cobalt phase composition, which is
Table 4
Data from various analyses for different Fe- and Co-modications of activated carbon and SBA-15.
Method of investigation Fe modications
N2 physisorption Location of the active phase into the mesopores of AC and SBA-15
XRD Finely dispersed iron phase for SBA-15 and Fe/AC_A;
Fe3O4 in Fe/AC_N
UVeVis mononuclear Fe3 ions in octahedral coordination, small
(FeO)n clusters, and Fe2O3 bulk particle for SBA-15
modications
Fe3O4 in both Fe/AC modications
Moessbauer Fe3 species with SPM behaviour in Fe/SBA-15(A) and
spectroscopy Fe/SBA-15_N;
Fe3O4 in Fe/AC(N) and Fe3 species with SPM behaviour;
Fe3O4, Fe2 and Fe3 species with SPM behaviour in Fe/AC_A.
TPR Fe2O3 in Fe/SBA-15 strongly interacted with the support;
mixture of Fe species in different oxidative state and
proportion for Fe/AC
Catalysis (specic catalytic Sample Fe/AC_A Fe/SBA-15_A Fe/AC_N Fe/SBA-15_N
activity and selectivity Specic activity 4.8 6.2 17.6 7.7
to CO at 700 K)
Selectivity, % 70 38 17 35
predominantly CoO for the former material and metallic cobalt for
the latter. Moreover, the changes in the textural parameters of the
AC support during the modication with acetylacetonate do not
exclude also signicant location of cobalt particles into the micro-
pores. The effect of cobalt precursor differs essentially when SBA-15
is used as a support. Taking into account the nitrogen physisorption,
spectral, XRD and TPR data (see above) we assume that the ace-
tylacetonate precursor facilitates the formation of more nely
dispersed cobalt phase in Co/SBA-15_A, which is located mainly
into the mesopores of the silica support and ensures better catalytic
activity. The different shape of the temperature dependencies for
AC and SBA-15 supported materials (Fig. 6c) could be due to more
reaction medium on the AC support, which according to the TPR
data could be also accompanied with its gasication.
3.4. Comparison of Fe- and Co-modications
The results from all analyses of Fe- and Co-modications are
summarized in Table 4. Nitrogen physisorption data clearly indicate
deposition of metal containing particles predominantly into the
mesopores in all materials with the exception of Co/AC_A, where
signicant blocking of micropores is observed. XRD, UVeVis,
Moessbauer and TPR analyses indicate that AC support provokes
the deposition of partially or completely reduced metal containing
phases. Magnetite or mixture of magnetite and Fe2 species are
formed when samples are prepared from iron nitrate or acetyla-
cetonate precursor, respectively, while CoO or metallic cobalt are
produced from the corresponding cobalt precursors, respectively.
In contrast, silica support facilitates deposition of nely dispersed
Fe3 species despite the precursor used. Among the cobalt modi-
cations well crystallized spinel Co3O4 phase is registered for the
nitrate obtained one, while the acetylacetonate precursor provokes
the deposition of partially reduced CoO phase. The catalytic
behaviour of cobalt and iron modications is in a complex relation
with the initial composition of the active phase, its transformation
by the inuence of the reaction medium and the location of active
large magnetite particles by the reaction medium to iron carbide,
which is observed for Fe/AC_N, ensures extremely high specic
catalytic activity (Table 4), but low selectivity to CO formation.
Similar facilitated effect of nitrate precursor on the formation of
highly active cobalt phase on AC is observed. The effect of precursor
is small for the iron modications of SBA-15, while the modication
Co modications
Location of active phase into the mesopores for SBA-15 and
Co/AC_N; predominantly blocking of micropores for Co/AC_A
Co3O4 for Co/SBA-15_N; nely dispersed phase in Co/SBA-15_A;
CoO in Co/AC_N; Co in Co/AC_A
Co3O4 for Co/SBA-15_N; Co2 in Co/SBA-15_A; reduced Co
species in AC modications
Co3O4 for Co/SBA-15_N; Co2 in Co/SBA-15_A; CoO for Co/AC_N;
Co for Co/AC_A
Sample Co/AC_A Co/SBA-15_A Co/AC_N Co/SBA-15_N
Specic 2.2 24.9 33.4 17.4
activity
Selectivity, % 78 67 92 91
 T. Tsoncheva et al. / Solid State Sciences 48 (2015) 286e293
with cobalt acetylacetonate ensures higher catalytic activity as
compared to the nitrate analogue. In comparison with the iron
modications, their cobalt analogues exhibit better catalytic ac-
tivity and selectivity in methanol decomposition to CO. This is not
valid only when acetylacetonate precursors are used for AC modi-
cation. As was mentioned above, here the observed extremely low
catalytic activity could be related to signicant reduction trans-
formations of cobalt phase even during the preparation procedure,
which is also combined with its predominant blocking into the
micropores of AC support.
4. Conclusions
The dispersion, oxidation state and catalytic behaviour of loaded
cobalt and iron nanoparticles could by successfully tuned both by
the nature of porous support and the metal precursor used during
the samples preparation. Ordered mesoporous silica provokes the
formation of very nely dispersed haematite-like particles, which
are in strong interaction with the surface silanol groups. The
preparation procedure slightly affects the state of iron particles on
this support. These materials exhibit relatively low catalytic activity
and signicant stability towards the inuence of the reaction me-
dium. Signicantly high catalytic activity, but relatively low selec-
tivity to CO is achieved by deposition of iron phase on activated
carbon from nitrate precursor. The effect of precursor on the for-
mation of cobalt phase on the ordered silica support is much pro-
nounced. The nitrate precursor facilitates the formation of well
crystallized Co3O4 phase, while highly active, nely dispersed
predominantly CoO species are formed from the acetylacetonate
precursor. Activated carbon support provokes the formation of
reduced cobalt phase and it is predominantly CoO or metallic Co for
the nitrate and acetylacetonate precursors, respectively. These
differences in the phase composition ensure signicantly higher
catalytic activity when AC was modied from cobalt nitrate
precursor.
Acknowledgements
Financial support Bulgarian Academy of Sciences (BAS) and
Bulgarian National Scientic Fund (BNSF) at the Ministry of Edu-
cation and Science under Project DFNI-02/2/2014 is gratefully
acknowledged.
References
[1] R. Perez-Hernandez, A.D. Avendano, E. Rosas, V. Rodrguez, Hydrogen pro-
duction by methanol steam reforming over Pd/ZrO2eTiO2 catalysts Lugo, Top.
Catal. 54 (2011) 572e578.
[2] P. Lopez, G.M. Galicia, M.E. Espinosa-Pesqueira, D. Mendoza-Anaya,
Ma.E. Fernandez, A. Gomez-Cortes, J. Bonifacio, G. Martinez-Barrerad, R. Perez-
Hernandez, Hydrogen production from oxidative steam reforming of meth-
anol: effect of the Cu and Ni impregnation on ZrO2 and their molecular
simulation studies, Int. J. Hydrogen Energy 37 (2012) 9018e9027.
[3] A. Szizybalski, F. Girgsdies, A. Rabis, Y. Wang, M. Niederberger, T. Ressler, In
situ investigations of structureeactivity relationships of a Cu/ZrO2 catalyst for
the steam reforming of methanol, J. Catal. 233 (2005) 297e307.
[4] S.T. Yong, C.W. Ooi, S.P. Chai, X.S. Wu, Review of methanol reforming-Cu-
based catalysts, surface reaction mechanisms, and reaction schemes, Int. J.
Hydrog. Energy 38 (2013) 9541e9552.
[5] T.L. Reitz, S. Ahmed, M. Krumpelt, R. Kumar, H.H. Kung, Characterization of
CuO/ZnO under oxidizing conditions for the oxidative methanol reforming
reaction, J. Mol. Catal. A Chem. 162 (2000) 275e285.
[6] T.L. Reitz, P.L. Lee, K.F. Czaplewski, J.C. Lang, K.E. Popp, H.H. Kung, Time-
resolved XANES investigation of CuO/ZnO in the oxidative methanol reform-
ing reaction, J. Catal. 199 (2001) 193e201.
[7] A. Taguchi, F. Schth, Ordered mesoporous materials in catalysis, Microporous
Mesoporous. Mater. 77 (2005) 1e45.
[8] T. Tsoncheva, I. Genova, M. Dimitrov, E. Sarcadi-Priboczki, A.M. Venezia,
D. Kovacheva, N. Scotti, V. Dal Santo, Nanostructured copper-zirconia com-
posites as catalysts for methanol decomposition, Appl. Catal. B Environ. 165
293
(2015) 599e610.
[9] T. Tsoncheva, A. Gallo, I. Genova, I. Spassova, M. Marelli, M. Dimitrov,
M. Khristova, G. Atanasova, D. Kovacheva, D. Nihtyanova, V. Dal Santo, Control
of copper particles deposition in mesoporous SBA-15 silica by modied CVD
method, Inorg. Chim. Acta 423 (2014) 145e151.
[10] T. Tsoncheva, I. Genova, M. Stoyanova, M.M. Pohl, R. Nickolov, M. Dimitrov,
E. Sarcadi-Priboczki, M. Mihaylov, D. Kovacheva, K. Hadjiivanov, Effect of
mesoporous silica topology on the formation of active sites in copper sup-
ported catalysts for methanol decomposition, Appl. Catal. B Environ. 147
(2014) 684e697.
[11] T. Tsoncheva, V. Dal Santo, A. Gallo, N. Scotti, M. Dimitrov, D. Kovacheva,
Structure and catalytic activity of hosted in mesoporous silicas copper species:
effect of preparation procedure and support pore topology, Appl. Catal. A Gen.
406 (2011) 13e21.
[12] T. Tsoncheva, L. Ivanova, J. Rosenholm, M. Linden, Cobalt oxide species sup-
ported on SBA-15, KIT-5 and KIT-6 mesoporous silicas for ethyl acetate total
oxidation, Appl. Catal. B Environ. 89 (2009) 365e374.
[13] R. Khn, D. Paneva, M. Dimitrov, T. Tsoncheva, I. Mitov, C. Minchev, M. Frba,
Studies on the state of iron oxide nanoparticles in MCM-41 and MCM-48 silica
materials, Microporous esoporous Mater. 63 (2003) 125e137.
[14] Y.T. Hung, H.H. Lo, L.K. Wang, J.R. Taricska, K.H. Li, Granular activated carbon
adsorption, in: L.K. Wang, Y.T. Hung, N.K. Shammas (Eds.), Handbook of
Environmental Engineering, vol. 3, Humana Press, Totowa, New Jersey, 2005,
pp. 573e634.
[15] J. Lee, J. Kim, T. Hyeon, Recent progress in the synthesis of porous carbon
materials, Adv. Mater 18 (2006) 2073e2094.
[16] A. Dabrowski, Adsorption-from theory to practice, Adv. Colloid Interface Sci.
93 (2001) 135e224.
[17] D. Kalderis, S. Bethanis, P. Paraskeva, E. Diamadopoulos, Production of acti-
vated carbon from bagasse and rice husks by a single-stage chemical activa-
tion method at low retention times, Bioresour. Technol. 99 (2008)
6809e6816.
[18] R.M. Suzuki, A.D. Andrade, J.C. Sousa, M.C. Rollemberg, Preparation and
characterization of activated carbon from rice bran, Bioresour. Technol. 98
(2007) 1985e1991.
[19] L.C.A. Oliveira, E. Pereira, I.R. Guimaraes, A. Vallone, M. Pereira, J.P. Mesquita,
K. Sapag, Preparation of activated carbons from coffee husks utilizing FeCl3
and ZnCl2 as activating agents, J. Hazard. Mater. 165 (2009) 87e94.
[20] A. Zabaniotou, G. Stavropoulos, V. Skoulou, Activated carbon from olive ker-
nels in a two-stage process: industrial improvement, Bioresour. Technol. 99
(2008) 320e326.
[21] M.G. Lussier, J.C. Shull, D.J. Miller, Activated carbon from cherry stones, Carbon
32 (1994) 1493e1498.
[22] R.V.R.A. Rios, M. Martinez-Escandell, M. Molina-Sabio, F. Rodriguez- Reinoso,
Carbon foam prepared by pyrolysis of olive stones under steam, Carbon 44
(2006) 1448e1454.
[23] M.L. Martinez, M.M. Torres, C.A. Guzman, D.M. Maestri, Preparation and
characteristics of activated carbon from olive stones and walnut shells, Ind.
Crops Prod. 23 (2006) 23e28.
[24] T. Tsoncheva, I. Genova, B. Tsyntsarski, M. Dimitrov, D. Paneva, Z. Cherkezova-
Zheleva, I. Yordanova, G. Issa, D. Kovacheva, T. Budinova, H. Kolev, R. Ivanova,
I. Mitov, N. Petrov, Transition metals modied activated carbons from biomass
and coal treatment products as catalysts for methanol decomposition, Reac.
Kinet. Mech. Cat. 110 (2013) 281e294.
[25] I. Genova, T. Tsoncheva, M. Dimitrov, D. Paneva, B. Tsyntsarski, R. Ivanova,
Z. Cherkezova-Zheleva, T. Budinova, D. Kovacheva, I. Mitov, N. Petrov, Cobalt
ferrite nanoparticles hosted in activated carbon from renewable sources as
catalyst for methanol decomposition, Catal. Commun. 55 (2014) 43e48.
[26] T. Tsoncheva, I. Genova, B. Tsyntsarski, M. Dimitrov, D. Paneva, Z. Cherkezova-
Zheleva, T. Budinova, R. Ivanova, I. Mitov, N. Petrov, Cobalt and iron modied
activated carbon from coal tar pitch: preparation and application as catalysts
for methanol decomposition, J. Porous Mater. 21 (2014) 503e512.
[27] M. Choi, W. Heo, F. Kleitz, R. Ryoo, Facile synthesis of high quality mesoporous
SBA-15 with enhanced control of the porous network connectivity and wall
thickness, Chem. Commun. (2003) 1340e1341.
[28] H.P. Boehm, Chemical identication of surface groups, in: D.D. Eley, H. Pines,
P.B. Weisz (Eds.), Adv. Catal. Related Subjects, vol. 16, Academic Press, New
York, 1966, pp. 179e188.
[29] E. Papier, S. Li, J.B. Donnet, Contribution to the study of basic surface groups on
carbons, Carbon 25 (1987) 243e247.
[30] R. Yang, G. Liu, M. Li, J. Zhang, X. Hao, Preparation and N2, CO2 and H2
adsorption of super activated carbon derived from biomass source hemp
(Cannabis sativa L.) stem, Microporous Mesoporous Mater. 158 (2012)
108e116.
[31] X. Wang, Chemical and morphological characterization of mesoporous ma-
terial supported copper oxide nanoparticles for potential application, J. Porous
Mater. 18 (2011) 623e630.
[32] G. Seong, S. Takami, T. Arita, K. Minami, D. Hojo, A.R. Yavari, T. Adschiri, Su-
percritical hydrothermal synthesis of metallic cobalt nanoparticles and its
thermodynamic analysis, J. Supercrit. Fluids 60 (2011) 113e120.
[33] J. Taghavimoghaddam, G.P. Knowles, A.L. Chaffee, Preparation and charac-
terization of mesoporous silica supported cobalt oxide as a catalyst for the
oxidation of cyclohexanol, J. Mol. Catal. A Chem. 358 (2012) 79e88.