Applied Clay Science 67–68 (2012) 99–105

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Applied Clay Science

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Research paper

Influence of iron removal on the synthesis of pillared clays: A surface study by

nitrogen adsorption, XRD and EPR
J.G. Carriazo ⁎
Chemistry Department, Science Faculty, Universidad Nacional de Colombia, Carrera 30 # 45-03, Bogotá, Colombia

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

Article history: The present paper reports a surface study on the synthesis of pillared clays before and after removal of iron
Received 1 March 2011 oxides (with sodium dithionite) from the clay used as starting material. Four pillared clays were synthesised
Received in revised form 9 June 2012 with Al- or Al-Fe-polyhydroxocationic solutions: two solids were prepared from the iron-removed clay and
Accepted 16 July 2012
the others from the non-pre-treated clay. All the solids were characterised by X-ray diffraction (XRD), elec-
Available online 5 September 2012
tron paramagnetic resonance (EPR), differential adsorption potential distributions (DAPDs) and fractal
Keywords:
dimension from nitrogen adsorption. The natural clay was also analysed by transmission electron microscopy
Pillared clays (TEM) to verify iron oxide clusters. XRD and EPR analyses revealed that iron-reduction with sodium
Characterisation of pillared clays dithionite, under the studied conditions, did not affect the clay mineral structure and the clay became suc-
Iron-oxide removal cessfully pillared in all cases; however, nitrogen adsorption showed a decrease of external surface areas
Surface study of pillared clays and an increase of micropore areas and volumes as a consequence of chemical pre-treatment. DAPDs indicat-
ed that iron-oxide removal reduced the surface heterogeneity of the pillared clays but enhanced the micro-
pore fraction in the solids.
© 2012 Elsevier B.V. All rights reserved.

1. Introduction previous purification treatments (minimal refining) of natural clays

Modifying clay minerals via pillaring currently constitutes an im-
portant and broad field of materials and surface science research.
Pillared clays are complex microporous systems, having enormous
potential for application in adsorption and catalytic processes
(Carriazo et al., 2008, 2010). Many researchers thus show interest in
clays which have been modified through pillaring and their applica-
tion as catalysts in a wide range of reactions (Carriazo et al., 2005,
2007a, 2007b; Centi and Perathoner, 2008; De Stefanis and
Tomlinson, 2006; Ding et al., 2001; Gil et al., 2000, 2008; Serwicka
and Bahranowski, 2004). Introducing inorganic pillars, in addition to
improving clay mineral strength and stability, increases microporosi-
ty and provides greater surface area on the solid, thereby facilitating
reagents’ access to potentially active sites for the catalysis of some re-
actions (Barrera-Vargas et al., 2007). The synthesis of pillared clays
has been widely described in the literature (Aouad et al., 2005;
Carriazo et al., 2009; Gil et al., 2000; Vicente and Lambert, 2003)
and characterising their porous structure has been recently reviewed
(Gil et al., 2008).
However, the synthesis of pillared clays requires several optimisa-
tions to enable such a procedure to be applied at industrial level and
marketing them in the future. One such improvement is to reduce
⁎ Tel.: +57 1 3165000x14403; fax: +57 1 3165220.
E-mail address: jcarriazog@unal.edu.co.
(Storaro et al., 1996; Vaughan, 1998), such as eliminating organic
matter traces, soluble salts and iron oxides. Surface iron oxides are
commonly removed from some natural clays before pillaring because
it is considered that they affect the synthesis and textural properties
of the final product (pillared clay), but a systematic study have not
been reported in the literature. Previous works use purified clays for
both lab synthesis and preliminary studies of the properties of the re-
sultant solids; however, using raw clays is preferred for scaling-up
the process. Excessive content of iron oxides in natural clays may in-
terfere on both the preparation procedures and the performance
of the final solids synthesised from these clays, because high iron-
oxide content may modify the colloidal and rheological behaviour
of clay suspensions as well as the cation exchange capacity of the
clay mineral present. For more advanced processes, such as catalyst
manufacturing, some good properties of shaped macro-structures
(extruded solids, pellets, agglomerates, monoliths, etc) are desired,
but the high iron content may decrease the mechanical and thermal
stability of the final products. Furthermore, both the acidic and
redox properties of final pillared clays could be modified because of
the high iron content in the starting natural clay.
Iron oxides are usually eliminated from clay minerals by reducing
Fe 3+ to Fe 2+ by sodium dithionite (Na2S2O4) (Bertolino et al., 2010;
Drits and Manceau, 2000; Kunze, 1965), but this process can modify
natural clays' structural and surface properties. In fact, redox reactions
modify the chemical and physical properties of iron-containing smec-
tites, such as cation exchange capacity, specific surface area, swelling
behaviour and ability to fix interlayer cations (Drits and Manceau,

0169-1317/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.clay.2012.07.010
100 J.G. Carriazo / Applied Clay Science 67–68 (2012) 99–105
2000; Komadel et al., 2006; Stucki et al., 2002). Consequently the tex-
ture of iron-removed clays and that of pillared clays synthesised from
these minerals may change. However, most of the studies on the re-
ducing effect of sodium dithionite on clay minerals have been carried
out under inert conditions (using N2 atmosphere) (Anastácio et al.,
2008; Fialips et al., 2002; Komadel et al., 1999; Neumann et al.,
2011; Stucki et al., 1984), and the extent of iron reduction is not
completely understood. So, the effect of sodium dithionite on the
structure and texture of clay minerals under atmospheric air condi-
tions is less known. On the other hand, some models about the reduc-
tion mechanism of iron (III) to iron(II) under inert atmosphere have
been proposed (Drits and Manceau, 2000; Manceau et al., 2000).
Most of the first models assumed that Fe(II) in reduced dioctahedral
smectites was five-coordinated, but Manceau et al. (2000) revealed
that iron is much more likely to maintain six-fold coordination after
complete reduction, with possible migration of some of the iron
atoms from cis- to trans-sites during the reduction reaction, and creat-
ing defects (vacant sites) in the octahedral sheets (Drits and Manceau,
2000; Komadel et al., 2006; Manceau et al., 2000; Stucki et al., 2002).
Recently Neumann et al. (2011) showed that reactions of Fe(II)/
Fe(III) in clay minerals depend on a variety of mineralogical and envi-
ronmental factors, and that iron content, the overall cationic composi-
tion and the location of the negative excess charge determine which
structural Fe(II) arrangement forms during Fe reduction using sodium
dithionite. Furthermore, they suggest that these observations can be
used to refine the current model for structural Fe reduction proposed
by Drits and Manceau (2000). Thus, a model for reduction of iron in an
iron-bearing smectite under air atmosphere is not discussed in the lit-
erature, which makes difficult to predict the extent to which the struc-
ture of this mineral can be altered through the pre-treatment with
sodium dithionite to remove iron oxides before a pillaring process,
since the synthesis of pillared clays, as in the present work, is devel-
oped under atmospheric pressure.
Al- and mixed Al\Fe pillared clays showing an excellent catalytic
activity in environmental oxidation reactions have recently been
synthesised from an iron oxide-rich smectite-type clay (Carriazo et
al., 2005, 2007a); however, for optimising the synthesis, it should
be determined whether removing the natural iron oxides contained
on the surface of this raw clay can enhance or reduce the final pillared
clays’ textural properties. The aim of this paper has thus been to pres-
ent a study of the effect of removing iron-oxides from a clay (under
atmospheric air conditions) on the synthesised pillared-clays’ surface
and textural properties.
2. Experimental
2.1. Pillared clay synthesis
Two pillared clays were synthesised from a bentonite from Valle
del Cauca-Colombia and polyhydroxocationic aqueous solutions of
Al or Al\Fe(10%), as described elsewhere (Carriazo et al., 2005,
2008): Al-Pilc and Al\Fe(10%)-Pilc, labelled here as B-AlNR and
B-AlFeNR respectively. Additionally, the same solids were synthesised
by an identical method but after chemical pre-treatment with sodium
citrate, sodium bicarbonate and sodium dithionite (Na2S2O4) to re-
move the iron oxides from the clay surface, as described in the litera-
ture (Kunze, 1965). These pillared clays are named B-AlR and B-AlFeR
(characters NR and R respectively indicate “non-removed iron-
oxides” or “removed iron-oxides”).
To remove the iron oxides from the clay surface, 10 g of clay was
added to a mixture of 400 mL of 0.3 M sodium citrate solution with
50 mL of 1 N sodium bicarbonate solution (Kunze, 1965). The resul-
tant suspension was heated to 80 °C, and then 10 g of sodium
dithionite was added, maintaining this temperature and a continuous
stirring during 15 min. After this digestion period a volume of 100 mL
of a NaCl saturated solution was added to flocculate the suspension
(Kunze, 1965). The resultant solid was centrifuged at 2200 rpm and
the supernatant extracted, and then washed several times up to the
conductivity of supernatant was closed to that of distilled water. This
procedure of removing iron oxides was repeated on the solid.
2.2. Characterising solids
Transmission electron microscopy (TEM) analysis of the natural-
clay samples was performed using a Philips CM 120 (at 120 kV)
transmission microscope with EDX analyser. The clay samples were
dispersed in ethanol and then placed on a small copper grid covered
with a carbon film. The EPR spectra were obtained on an X-Band
ESP 300 BRUKER spectrometer at 77 K, 100 kHz field modulation
and 9.44 GHz frequency; 10 mW microwave power, 8000 swept
width, 10.25 G modulation amplitude, 40.96 ms time constant and
2 × 10 3 gain were used.
Powder X-ray diffraction (XRD) analysis was carried out in an
X-Pert Pro MPD PANalytical equipment using 2θ geometry and a
Bragg-Brentano configuration at room temperature and using a 0.01
step size and 5 s step time. Nitrogen adsorption isotherms were
taken at 77 K using a Micromeritic TriStar 3000 adsorption analyser
in the 10 −4 to 0.99 P/P0 range. The samples were outgassed at
90 °C for 1 h and then at 350 °C for 8 h. All calculations were devel-
oped assuming both a 16.2 Å 2 area for covering a nitrogen molecule
(N2) and ρ = 0.81 g/cm3 as density of nitrogen condensed in the
pores. α-Curves and t-plots were used to verify the micropore forma-
tion: α-curves were made using a non-porous silica as reference
(Gregg and Sing, 1982), α = Vads/V(0.4), and t-values (thickness of
multimolecular layer) were calculated from Halsey equation:
0 11 =
3
B 5 C
t ¼ −3:54@ B C . Micropore areas and volumes were obtained
PA
Ln
P0
from t-plots. Adsorption potential distribution functions X(A) and the
“characteristic adsorption curves” v(A) were used for evaluating the
solids’ energetic heterogeneity (Carriazo et al., 2008; Jaroniec et al.,
1991, 1996). Total energetic heterogeneity results from both the contri-
bution of functional groups on the surface, impurities and defects, and
the contribution of microporosity (Carriazo et al., 2008; Jaroniec et al.,
1991, 1996). X(A) was expressed as a differential potential distribution
function (Carriazo et al., 2008):
dvðAÞ
X ðAÞ ¼ −
dA
Fractal dimension (D) was determined from adsorption data (P/P0
between 0.08 and 0.2 (Carriazo et al., 2008; Gil et al., 2004), using the
Avnir and Jaroniec equation (Avnir and Jaroniec, 1989; Jaroniec,
1995):
LnðxÞ ¼ K−ð3−DÞLnðAÞ
where x is the adsorbed amount, K is a constant and A is the adsorp-
tion potential.
 
P0
A ¼ −ΔG ¼ RTLn
P
R is the universal gas constant, T is the absolute temperature and
P0 and P are, respectively, the saturation and equilibrium pressures
during gas adsorption.
3. Results and discussion
Microscopic observation (TEM images) showed the existence of
iron-oxide particles on the surface of the natural bentonite-clay
 J.G. Carriazo / Applied Clay Science 67–68 (2012) 99–105 101

Iron oxide particles

200 nm 100 nm
Bentonite Bentonite

Si
O
Intensity

Al Fe

Fe

1.0 2.0 5.0 6.0 7.0

Energy (keV)

Fig. 1. TEM micrographs of iron oxide particles observed on the natural clay (bentonite), and EDX spectrum of the sample.

(Fig. 1). These iron oxides or oxyhydroxides might be hematite, goe-

thite or magnetite (Bertolino et al., 2010) or mixed aluminium-iron 150
g = 4.3
oxide nanoparticles (Schwertmann et al., 2000) supported on the
clay surface. In the present case iron oxide (or mixed aluminium- 100 g = 9.3
g = 2.0
iron oxide) clusters were considered.
Typical values of g = 2.0, g = 4.3 and g = 9.3 for iron paramagnetic 50
Intensity

species were observed from EPR analysis (Fig. 2). The first value (g = B-AlR
2.0) was attributed to iron oxides in cluster form, while g = 4.3 and 0
g = 9.3 were assigned to Fe 3+ in octahedral or tetrahedral chemical B-AlNR
-50
environments (Bertolino et al., 2010; Carriazo et al., 2005). The last
two values could be interpreted as being iron ions in the octahedral -100
sheets (Fe 3+ replacing Al 3+) of the clay mineral (Bertolino et al.,
2010; Carriazo et al., 2005) plus iron ions contained in mixed -150
aluminium-iron oxides deposited on the clay surface. An important 1000 3000 5000 7000
EPR result was the significant decrease of signal intensity (decrease Magnetic field (Gauss)
of area under curve) for the B-AlR and B-AlFeR solids due to clay min-
eral treatment with sodium dithionite. This confirmed an effective re- 150 g = 4.3
moval of iron oxides before synthesis of pillared clay. However, the
smaller reduction of signal intensity for the B-AlFeR sample resulted 100 g = 9.3
g = 2.0
from iron introduction during the course of this solid's synthesis.
Moreover, the EPR spectra indicated that clay mineral structural fea- 50
Intensity

tures were maintained and, therefore, the chemical treatment for

B-AlFeR
iron removal, under these conditions, did not have an apparent effect 0
on the clay mineral structure of the smectite.
-50 B-AlFeNR
XRD analysis revealed the successful synthesis of pillared clay in
all cases. The shift of the 001 diffraction maximum (d001 basal spac-
-100
ing) from 14.7 Å (natural clay) to 17.3 Å for all the modified solids
(Fig. 3a) clearly indicated that the smectite was pillared with the -150
polyoxocationic species (Carriazo et al., 2005, 2007a, 2009). The com- 1000 3000 5000 7000
plete XRD traces (Fig. 3b) did not show other modifications in these Magnetic field (Gauss)
solids’ structure, revealing similar XRD patterns for the pillared
clays synthesised with or without iron removal. Only slightly higher Fig. 2. EPR spectra for the pillared clays.
102 J.G. Carriazo / Applied Clay Science 67–68 (2012) 99–105

55
(a) d=17.3 Å

Volume adsorbed (cm3/g), STP

50 B-AlNR
45
B-AlFeR B-AlR
40
Natural clay
35
Intensity (a. u.)
B-AlFeNR
30
25
B-AlR
20

B-AlNR
15
10
d=14.7 Å 5
Natural clay 0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
0 2 4 6 8 10 12 14 Relative pressure (P/P0)
°2 theta, CuK α
65
(b) 60

Volume adsorbed (cm3/g), STP

B-AlFeNR
B-AlNR - (1) 55
B-AlFeR
B-AlR - (2) 50
B-AlFeNR - (3)
45 Natural clay
B-AlFeR - (4)
40
Intensity (a. u.)

35
30
(4) 25
(3) 20
15
(2) 10
(1) 5
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
0 10 20 30 40 50 60 70 80
Relative pressure (P/P0)
°2 theta, CuK α

Fig. 3. XRD patterns for the pillared clays. a) Amplifying the d001 peak. b) Complete Fig. 4. Nitrogen adsorption isotherms for the natural clay and pillared solids.
diffractograms.

intensity of peaks at ~ 2θ = 21°, 2θ = 26° and 2θ = 28° for the iron-

removed samples was observed, which correspond to quartz and (a) Natural clay
feldspar impurities in the natural clay. The intensity of the diffraction
Volume adsorbed (cm3/g; STP)

60 B-AlNR
maxima of these minerals increases because their surfaces are
cleaned by iron-oxide elimination. This result confirmed that chemi- 50 B-AlR

cal treatment with sodium dithionite did not affect the smectite B-AlFeNR
40
structure. The iron oxide species in the materials were not detected B-AlFeR
by XRD because they were present in small quantities and had poor 30 nonporous silica
(reference)
crystallinity.
20
The nitrogen adsorption isotherms for the natural and pillared
clays are shown in Fig. 4. The isotherms display H3 type hysteresis 10
(IUPAC classification), characteristic of slit shape pores, indicating
that the configuration of parallel plates of clay minerals was 0
0 0.5 1 1.5 2 2.5 3 3.5
maintained (Carriazo et al., 2008). The adsorption capacity of pillared α (Vads/V(0.4))
clays was higher than that of natural clay, due to the formation of mi-
cropores by the effective pillaring. Moreover, a slight difference in (b)
adsorbed volumes was observed between pillared clays synthesised
Volume adsorbed (liquid) (cm3g-1)

with or without iron-oxide removal; the volume adsorbed by B- 0.1 Natural clay
B-AlNR
AlNR was higher than that adsorbed by B-AlR and that of B-AlFeNR 0.09 B-AlR
was higher than B-AlFeR. The α-curves (taking a nonporous silica as 0.08 B-AlFeNR
B-AlFeR
reference) and t-plots (Fig. 5) confirmed the increase of microporos- 0.07
ity of the synthesised solids: when micropores were introduced into 0.06
the solids, adsorption in the low-pressure region was enhanced and 0.05
the (α- or t-) plots were bent, in accordance with previous reports 0.04
(Gregg and Sing, 1982). Pillared clays synthesised after iron-oxide 0.03
elimination thus showed lower nitrogen uptake than their natural 0.02
counterparts; B-AlFeNR was the material having higher apparent 0.01
0
complexity (Fig. 5a). 0 2 4 6 8 10 12 14 16 18 20
Table 1 shows the textural properties of the solids. Specific surface t value (Å)
areas and pore volumes for all the pillared clays increased compared
to the initial natural clay values; BET and external surface areas of Fig. 5. α-curves (a), and t-plots (b) for the pillared solids and the natural clay.
 J.G. Carriazo / Applied Clay Science 67–68 (2012) 99–105 103

Table 1
Textural properties of natural and pillared clays.

Solid BET surface area Micropore area, Smp External surface area, Micropore volume, Vmp Total pore volume (cm3g−1)
(m2g−1) (m2g−1), from t-plot Sext (m2g−1) (cm3g−1), from t-plot from Gurvitsch's method

Natural clay 42.8 3.4 35 0.0012 0.0470

B-AlNR 72.1 74.0 18 0.0262 0.0829
B-AlR 66.6 74.6 13 0.0264 0.0704
B-AlFeNR 76.8 38.2 44 0.0135 0.1032
B-AlFeR 69.3 60.5 25 0.0214 0.0866

B-AlR and B-AlFeR were lower than those of B-AlNR and B-AlFeNR as
a consequence of previous treatment for iron removal, which indi-
cates that treatment with sodium dithionite, under this conditions,
allowed reduction of the free iron-oxides to decrease the number of
adsorption sites on outer smectite surface. Moreover, increase of mi-
cropore areas and volumes were observed for B-AlR and B-AlFeR
regarding B-AlNR and B-AlFeNR, although this result was more evi-
dent between B-AlFeR and B-AlFeNR. Removing iron oxides from
clay surface allowed access of N2 molecules to micropores generated
by the pillaring. Difference between B-AlFeR and B-AlFeNR micropore
areas indicates a higher effect of pore blocking because introducing
iron oxides in the synthesis of pillared clays. The adverse influence
of natural iron-oxide particles on the pillaring with iron species prob-
ably is related to the nucleation of larger iron polyoxocations yielding
larger nanoparticles than those of aluminium oxide, since hydrolysis
of iron cations forms colloidal species with much higher degree of
condensation (Jolivet et al., 2000). On the other hand, the total specif-
ic surface area of the pillared clays is given as the sum of micropore
area plus external surface area (Stotal = Smp + Sext); therefore the
total specific surface area is higher than BET area for all the pillared
clays.
Important differences were observed in the characteristic adsorp-
tion curves for the solids (Fig. 6), indicating a possible surface
0.05
Volume adsorbed (liquid ) (cm3g-1)
energetic variation. Pillared clays showed higher gas adsorption vol-
umes than the natural clay throughout the adsorption potential
values as a consequence of their microporous structure, whilst solids
obtained after iron removal showed lower gas adsorption volumes
than clays pillared without such a chemical treatment probably be-
cause the external specific surface area of former materials was
reduced.
Differential adsorption potential distributions for the pillared
solids (Fig. 7) clearly revealed a shift of the maximum of the curves
to higher adsorption potential values compared to the natural clay
(from 3.3 to 4.0–5.0 kJ/mol), indicating effective formation of micro-
pore structures in the solids. However, the highest derivative values
for B-AlNR and B-AlR in the low pressure region (high adsorption po-
tential values: 4.0–5.0 kJ/mol) suggest the formation of a higher frac-
tion of micropore in these solids than for Al\Fe pillared clays.
Pillaring with iron or aluminium–iron aqueous solutions leads to
the formation of iron oxide nanoclusters on the pillared clays
(Carriazo et al., 2005) which are able to partly block microporosity.
Furthermore, an additional complexity in the high adsorption poten-
tial region was observed for non-pre-treated solid curves (B-AlNR
and B-AlFeNR) (Fig. 7b) showing multimodal functions due to higher
(a)
0.014 Natural clay
B-AlNR

0.012
-dV/dA (mol cm3g-1kJ-1)

Natural Clay B-AlR

B-AlNR B-AlFeNR
0.04 0.010 B-AlFeR
B-AlR

0.008
0.03

0.006
0.02
0.004
0.01
0.002
0 1 2 3 4 5 6
0.00 Adsorption potential (A) (kJ mol-1)
0 1 2 3 4 5 6
Adsorption potential (A) (kJ mol-1)
(b)
0.009
0.05 B-AlNR
Volume adsorbed (liquid) (cm3g-1)

-dV/dA (mol cm3g-1kJ-1)

Natural clay
0.008 B-AlFeNR
B-AlFeNR
0.04
B-AlFeR 0.007

0.03 0.006

0.005
0.02
0.004
0.01
0.003
2 3 4 5
0.00 Adsorption potential (A) (kJ mol-1)
0 1 2 3 4 5 6 h i
ðAÞ
Fig. 7. Differential adsorption potential distributions − dvdA for the natural and pillared
Adsorption potential (A) (kJ mol-1)
clays. a) Complete curves and b) Expansion of an interval for non-pre-treated synthesised
Fig. 6. Characteristic adsorption curves for the solids (natural and pillared clays). solids.
104 J.G. Carriazo / Applied Clay Science 67–68 (2012) 99–105
3.5
3.3
3.1
Ln (V)
2.9
2.7
2.5
6.7 6.9 7.1
Ln (A)
Fig. 8. Linear relationship (Avnir–Jaroniec equation) for determining the fractal dimension of pillared clays by nitrogen adsorption.
heterogeneity on their surface. In this way, lack of removal of iron ox-
ides contributed to higher surface heterogeneity of the pillared clays,
but it reduced the micropore fraction in the as-synthesised solids.
This effect was associated with a variation in the external and
microporo surface areas (Table 1). On the other hand, the rise in ad-
sorption potential distribution functions at low adsorption potential
values (high relative pressures) revealed the multilayer adsorption
and capillary condensation (Carriazo et al., 2008) which was more
important on the natural and Al\Fe pillared clays due to their higher
external surface areas (Table 1).
The fractal dimension (D) determined for the solids (Fig. 8 and
Table 2) showed an increase in surface roughness as a result of the
successful pillaring of the natural clay to produce microporous struc-
tures (D from 2.6941 to 2.8583). In general, D value may vary from 2
to 3, with the lowest value (2) corresponding to a perfectly smooth
surface, and the upper limit (3) corresponding to a totally irregular
or rough surface (Avnir and Jaroniec, 1989; Jaroniec, 1995). D values
for B-AlNR and B-AlR were higher than those for Al-Fe pillared clays,
confirming the higher microporosity of the former solids. Although
these differences in D parameter were important, the fractal dimen-
sion could not verify any variation induced by the iron-oxide removal
pre-treatments, probably because all the synthesised solids have high
microporosity and therefore elevated roughness.
4. Conclusions
In this work, XRD and nitrogen adsorption analyses confirmed the
successful pillaring-intercalation of a Colombian bentonite, which
yielded similar microporous structures with or without previous
chemical treatment with sodium dithionite to remove iron oxides.
The pre-treatment with sodium dithionite did not affect the structure
of smectites in the bentonite. Removal of iron oxides from the clay re-
duced the external surface area and increased the micropore area and
volumes for Al- and Al-Fe-pillared clays (this effect being higher in
the Al-Fe-pillared clay) compared to the solids prepared without
such a treatment. Differential adsorption potential distributions and
the characteristic adsorption curves revealed some variations in ener-
getic terms, indicating that eliminating iron oxides in this bentonite
contributed to a lower surface heterogeneity of pillared clays and in-
creased the fraction of micropores in the solids. These results contrib-
ute in understanding some chemical pre-treatments and optimisation
procedures required for the pillaring of this Colombian bentonite.
Table 2
Fractal dimension (Avnir–Jaroniec equation) of solids studied here.
Solid Equation Fractal dimension (D)
Natural clay y = −0.3059x + 4.9799 2.6941
B-AlNR y = −0.1417x + 4.1129 2.8583
B-AlR y = −0.1464x + 4.0682 2.8536
B-AlFeNR y = −0.2261x + 4.7293 2.7739
B-AlFeR y = −0.2086x + 4.5119 2.7914
⁎
Correlation coefficient.
Natural clay Natural clay
3.5
B-AlNR B-AlFeNR
3.3
B-AlR B-AlFeR
3.1
Ln (V)
2.9
2.7
2.5
7.3 7.5 6.7 6.9 7.1 7.3 7.5
Ln (A)
Acknowledgments
The author gratefully wishes to acknowledge the Universidad
Nacional de Colombia (Bogotá) for supplying the resources for this
scientific investigation.
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