Separation and Purification Technology xxx (2015) xxx–xxx

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Separation and Purification Technology

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

Fe/Al binary oxide aerogels and xerogels for catalytic oxidation

of aqueous contaminants
Yue Li a, Fernando Hung b, Louisa J. Hope-Weeks b, Weile Yan a,⇑
a
Department of Civil and Environmental Engineering, Texas Tech University, TX 79409, United States
b
Deparment of Chemistry and Biochemistry, Texas Tech University, TX 79409, United States

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

Article history: Iron oxides and supported iron materials have been widely used as heterogeneous catalysts to oxidize
Received 16 April 2015 aqueous organic contaminants in the presence of H2O2. One approach to enhance the catalyst perfor-
Received in revised form 18 August 2015 mance is to synthesize micro- or meso-porous iron oxides with large surface areas and to control surface
Accepted 24 September 2015
composition and catalyst structure through the use of two metal constituents. In this study, xerogels and
Available online xxxx
aerogels of Fe/Al binary oxides were synthesized using a propylene oxide-driven sol–gel method. The
effect of synthesis parameters including the ratio of Fe to Al in the precursor solutions, annealing temper-
Keywords:
ature, and drying method were varied independently. The resultant solids were evaluated for their ability
Aerogel
Xerogel
to catalyze H2O2 activation and phenol oxidation. The ratio of Fe/Al was found to have a prominent effect
Iron oxide catalyst on the catalytic activity of the solids, with an optimal activity occurring at an intermediate Fe loading
Peroxide activation reflecting the important of Fe dispersion. Higher annealing temperature led to enlarged pore size that
Phenol oxidation facilitates access to the internal reactive surface. Xerogels, despite having moderately smaller surface
Catalytic oxidation areas than the aerogel counterparts, exhibited consistently higher oxidant generation efficiency and phe-
nol oxidation rates, indicating it is a more favorable method for making porous iron-containing materials
for catalytic wet oxidation applications.
Ó 2015 Elsevier B.V. All rights reserved.

1. Introduction synthesis reactions (e.g., Fischer–Tropsch synthesis and selective

High surface-area ceramic or metal oxides materials have found
important applications in gas storage, energy-harvesting, catalysis,
and chemical separation [1–5]. Among these materials are a class
of sol–gel derived materials known as aerogels which exhibit low
densities and have exceptionally high surface areas and porosities.
The analogous xerogel materials often exhibit slightly higher den-
sities and lower surface areas. However, they possess greater
mechanical strengths and are easier to manufacture than their
aerogel counterparts. A variety of single or mixed metal oxide aero-
gels and xerogels find favorable uses in heterogeneous catalysis
applications because of their exceptionally high surface-area-to-
volume ratio, good thermal stability, and well-controlled pore
structure and pore size distributions [1,6].
In the past few decades, iron-based catalysts have received
much attention owing to the natural abundance of the element
iron, its benign environmental character, and labile redox activity.
These qualities render iron a central catalyst in many biological
enzymes (e.g., the heme-containing cytochromes) and chemical
⇑ Corresponding author.
E-mail address: weile.yan@ttu.edu (W. Yan).
C–H bond oxidation) [7–9]. The use of iron in environmental
decontamination is best known through the Fenton chemistry, in
which catalytic activation of hydrogen peroxide by Fe(II) or Fe
(III) species generates reactive oxygen species that are able to
degrade organic contaminants at high efficiencies [10,11]. Tradi-
tional Fenton oxidation system using dissolved iron has limited
applications in large-scale environmental applications due to the
requirement of acidic media and the challenges associated with
catalyst separation and regeneration [12–14]. Considerable efforts
have been focused on using solid-phase iron (mainly as Fe(III)) to
enable efficient activation of H2O2 to form reactive oxidants such
as hydroxyl radicals for the oxidation of aqueous contaminants
[15,16]. Compared to the classical Fenton reaction, activation of
H2O2 by heterogeneous catalysts does not require strict pH control,
is more specific for the intended contaminants through appropri-
ate design of the catalysts, and the process is amenable to reuse
in continuous operation (e.g., in fluidized or fixed-bed reactors).
However, bulk iron oxides (such as hematite and goethite) are
known to be relatively inefficient in converting H2O2 to reactive
oxidants [20]. Ample studies have attempted to create more active
iron catalysts by immobilizing Fe(III) on ion exchange membranes
[12], or disperse it on inorganic solids such as silica, alumina, clay

http://dx.doi.org/10.1016/j.seppur.2015.09.056
1383-5866/Ó 2015 Elsevier B.V. All rights reserved.

Please cite this article in press as: Y. Li et al., Fe/Al binary oxide aerogels and xerogels for catalytic oxidation of aqueous contaminants, Separ. Purif. Technol.
(2015), http://dx.doi.org/10.1016/j.seppur.2015.09.056
2 Y. Li et al. / Separation and Purification Technology xxx (2015) xxx–xxx
minerals, and synthetic zeolites [17–19,15,16]. In particular, a
strong synergy between Fe(III) and aluminum oxide supports has
been noted in several recent studies. The synergistic effect is attrib-
uted to improved iron catalyst dispersion on alumina surface and
to the Lewis acidity of Al(III) that facilitates iron redox cycling
[19,21].
The most common approach to prepare supported Fe(III) cata-
lysts is via wet impregnation of aqueous Fe(III) onto pre-formed
solid supports. Despite of its simple procedures, wet impregnation
does not afford much control over the morphology of Fe(III) depos-
its and the catalyst-support interactions are limited to a finite
amount of surface area, restricting further catalyst improvement.
Synthesizing highly porous Fe(III)/Al(III) mixed oxides via a one-
pot sol–gel method offers an attractive alternative. In this study,
we employed a facile epoxide-driven sol–gel process to prepare a
series of high surface-area Fe(III)/Al(III) mixed oxide aerogels and
xerogels. In our method, epoxide was used as a proton-
scavenger, which can drive the olation and oxolation of Al(III)
and Fe(III) in a controlled manner to form very small colloidal par-
ticles of oxy-hydroxy Al/Fe polymers. The gels formed are dried
under ambient atmosphere to form xerogels. Alternatively, sol-
vents are extracted by exchange with supercritical CO2 to create
highly porous particles known as aerogels. The activities of these
xerogels and aerogels were evaluated in a wet oxidation system
using H2O2 as a source of oxidant and phenol as a model aqueous
contaminant. Key synthesis parameters such as the ratio of Fe(III)
to Al(III) in the precursor mixture and annealing temperature were
varied and their effects on catalyst activity were investigated.
2. Materials and methods
2.1. Chemicals
Iron chloride hexahydrate, FeCl3
6H2O (Mallinckrodt) and alu-
minum nitrate nonahydrate, Al(NO)3
9H2O (Spectrum) were used
as precursors. Propylene oxide (ACROS Organics, 99.6%) and iso-
propanol were used as received without further purification. Dis-
tilled deionized water (DDI) was used for the preparation of all
solutions. Phenol and sodium bicarbonate were obtained from
Riedel-de Haën and Fisher, respectively. Hydrogen peroxide
(H2O2) was from 3% w/w aqueous solution (Fisher).
2.2. Preparation of iron oxide and aluminum oxide aerogels and
xerogels
In a typical experiment to prepare a 1:1 ratio Fe/Al xerogel,
FeCl3
6H2O (0.2703 g, 1 mmol) and Al(NO)3
9H2O (0.3751 g,
1 mmol) were dissolved in isopropanol (4 mL), followed by addi-
tion of 10 equivalents (i.e. 20 mmol) of propylene oxide (PO,
1.39 mL). The composite was then vortexed for 10 s and then
set aside to gel undisturbed for 24 h. Gels were obtained within
3–10 min. The red monolithic gels were then dried under the hood
for 24 h. A similar procedure was followed to prepare 1:4 and 4:1
ratios of Fe/Al xerogels. The as-prepared xerogels were annealed in
a muffle furnace under static air by ramping a specific temperature
at a rate of 2 °C min–1. The gels were held at the temperature (400,
500, 600, 700, and 800 °C respectively) for 6 h and then cooled to
room temperature at a rate of 2 °C min–1.
In a typical synthesis batch to prepare a 1:1 ratio Fe/Al aerogel,
FeCl3
6H2O and Al(NO)3
9H2O were dissolved in isopropanol, fol-
lowed by addition of 10 equivalents of propylene oxide (PO). The
composite was then vortexed for 10 s and then set aside to gel
undisturbed for 24 h. Thereafter, the gels were washed in acetone
baths over a week and then transferred to SPI-DRYTM critical point
driers. During the super critical drying process, the solvent in the
Please cite this article in press as: Y. Li et al., Fe/Al binary oxide aerogels and xerogels for catalytic oxidation of aqueous contaminants, Separ. Purif. Technol.
(2015), http://dx.doi.org/10.1016/j.seppur.2015.09.056
gels was exchanged with liquid CO2 over 3–4 days, and then the
extractor was brought beyond the critical point (40 °C, 1200 psi)
and vented slowly to ambient pressure over 6–8 h. The as-
prepared aerogels were annealed in a muffle furnace under static
air by ramping a specific temperature at a rate of 2 °C min–1. The
gels were held at the temperature for 6 h and then cooled to room
temperature at a rate of 2 °C min–1.
2.3. Batch experiments
Batch experiments were performed in 40-mL clear glass vials
(Kimble Chase) at room temperature (22 ± 1 °C). Due to concern
over possible photo-activity of the Fe(III)-containing aerogel and
xerogel materials, all vials were wrapped with aluminum foil to
prevent light exposure. 100 mg of the aerogel or xerogel powder
was introduced into 25 mL of 0.17 mM phenol solutions. Each solu-
tion was amended with 0.1 mM sodium bicarbonate as a back-
ground electrolyte. The use of bicarbonate stabilizes solution pH
and the concentration is typical of carbonate presence in surface
freshwater at neutral pH. Higher concentration of bicarbonate is
known to impose a strong radical scavenging effect and was not
evaluated in this study [22,23]. At time zero, a small aliquot
(500 lL) of 3% H2O2 solution was injected to reach a concentration
of 17.6 mM, and the reaction mixture was agitated on a mechanical
shaker at 250 rpm. At predetermined time intervals, samples were
withdrawn and filtered through 0.2 lm PTFE filters (MillexÒ-LG,
Millpore) into amber HPLC samples vials. The samples were then
spiked with 32 lL of methanol (99.9%, Fisher) to quench further
reactions in the mixture.
2.4. Analytical methods
Aqueous phenol, intermediate products (e.g., p-benzoquinone
and hydroquinone) and H2O2 concentrations were analyzed with
a high-performance liquid chromatography system (Agilent HPLC
1100 series) equipped with a C-18 column (Alltech 5 lm,
4.6  25 mm) and a diode array detector (DAD) containing a tung-
sten and a deuterium lamp for visible and UV absorbance measure-
ments. Isocratic elution with 30% acetonitrile and 70% DDI acidified
with 10 mM of HCl was performed at a flow rate of 0.8 mL/min.
Phenol, hydroquinone, and H2O2 concentrations were quantified
with their UV absorbance at 220 nm based on 4-point calibration
curves. p-Benzoquinone was measured at 255 nm.
2.5. Physical characterizations
The powder X-ray diffraction patterns of the samples were
recorded with a Rigaku Ultima III diffractometer using Cu Ka radi-
ation. To prepare the samples, they were first finely ground before
being packed in a zero-background Pt sample holder. The collec-
tion was taken at a 2h range of 20–80° at a step-width of
0.03° s1. The diffraction patterns were then identified by compar-
ison to the phases in the International Centre for Diffraction Data
(ICDD) powder diffraction file (PDF) database. The specific surface
area, pore volume and average pore sizes were all obtained from
the N2 adsorption/desorption analyses conducted at 77 K on a
NOVA 4200e model surface area/pore size analyzer (Quan-
tachrome Instrument Corp.). Brunauer–Emmett–Teller (BET) speci-
fic surface areas were calculated from data points taken at relative
pressures between 0.05 and 0.30 of the adsorption branch of the
isotherm. The pore volume, pore sizes and average size distribution
was taken from the desorption branch of the isotherm. Prior to
physisorption analysis, the samples were placed on degas for
24 h at 80 °C. Each set of measurements was taken with an equilib-
rium time of 600 s, which resulted in a total experimentation time
of 9–18 h per sample. Dry and crushed samples were also
 Y. Li et al. / Separation and Purification Technology xxx (2015) xxx–xxx 3

characterized for surface morphology with a field-emission scan- annealed at 800 °C for 6 h. Fig. 1 shows the PXRD pattern observed
ning electron microscope (SEM, Hitachi S-4700) at an accelerating for the different Al/Fe xerogels samples annealed at 800 °C. We
voltage of 2 kV. observed that the crystallinity of the material increases with a
decreasing amount of Al present in the sample due to the inherent
amorphous nature of aluminum oxide. The xerogel with the highest
3. Results and discussion
fraction of Al, corresponding to an Al/Fe ratio of 4:1, has no identifi-
able peaks above the background (spectrum not shown). Fe/Al sam-
3.1. Catalyst characterization
ple (1:1 ratio) shows to be the more crystalline with reflections
corresponding mainly to aluminum iron oxide (AlFeO3, PDF# 30–
Preparation of iron and aluminum oxide xerogels and aerogels
24). Further increasing the iron leads to well defined diffraction
was achieved using the epoxide-addition method. Here, by pre-
peaks that can be attributed to hematite (a-Fe2O3) and AlFeO3.
forming the nanostructured colloidal particles by sol–gel synthesis,
The absence of a pure iron oxide phase in Al/Fe 1:1 sample indicates
higher surface areas can be attained, even in the case of xerogels,
that the two metal ions form homogeneous mixed oxides and there
where collapse of the pore structure by rapid evaporation of the
is no phase segregation when the Al to Fe ratio is 1:1. This property
solvent tends to provide a rather non-porous material. The well-
may be attributable to similar hydrolysis and condensation rates of
established epoxide-driven polycondensation of metal salt precur-
Al and Fe ions in the synthesis mixture. As illustrated in Fig. 2, SEM
sors was chosen because of its proven efficacy in a wide variety of
characterization of the Al/Fe 1:1 xerogel reveals a clean, smooth-
transition metal systems, its simplicity, and its versatility for the
textured material with primary particles of approximately 60–
preparation of binary metal oxide systems. In this method, the
100 nm in diameter. In comparison, the solids prepared at a higher
epoxide is added to a solution of the metal salts (FeCl3
6H2O and
or lower Al/Fe ratio contains significant surface heterogeneity with
Al(NO)3
9H2O) to promote the steady formation of colloidal oxy-
a large quantity of small formations (less than 10 nm) littered on the
hydroxy metallate polymers. The mechanism has been previously
surface of the primary particles. The bimodal distribution of particle
described [3,24], and relies on the epoxide acting as a proton scav-
sizes may arise from the presence of multiple solid phases when Al
enger for the system, thereby irreversibly driving forward the ola-
or Fe is at a significant excess relative to the other.
tion and oxolation reactions that form the inorganic polymer.
The N2 adsorption–desorption isotherms of the Fe/Al xerogel
Because the epoxide mediates the polymerization, very small col-
and aerogel samples exhibit type IV hysteresis typical for meso-
loidal particles are formed, which facilitate the formation of high
porous materials. The BET surface areas and pore radii of the xero-
surface area materials.
gels show a direct dependence on the annealing temperature used
To determine the ideal temperature at which the desired binary
during the synthesis (Table 1). Accordingly, the decrease in surface
metal oxide phase is observed, iron/aluminum xerogels in a 1:1
and porosity with increasing temperatures are due to grain growth
ratio were prepared and annealed at 400, 500, 600, 700, and
and densification effects as it has been previously reported else-
800 °C for 6 h, the crystallinity of the annealed samples was inves-
where. Aerogel is typically characterized by BET surface areas on
tigated using powder X-ray diffraction (PXRD). The samples showed
the order of 100 m2/g and are much higher than their xerogel
to be amorphous after annealing at different temperatures except at
counterparts [1]. In this study, the aerogel annealed at 800 °C has
the highest temperature (800 °C), at which point the particles exhi-
a moderate increase in surface area and pore size compared to
bit reflections corresponding to aluminum iron oxide. Aluminum/
the equivalent xerogel material. The relatively small surface area
iron xerogels in a 1:4 and 4:1 ratios were then prepared and
observed for the aerogel is believed to be caused by the high
80 annealing temperature used.
1:1 AlFeO3
70
1:4 HemaƟte 3.2. Effect of Fe(III)/Al(III) ratio on catalyst activity
Rela ve Intensity (a.u.)

60
Phenol oxidation in the presence of different xerogel is shown
50
in Fig. 3. Control experiment reacting phenol and H2O2 (as Control
40 1 in Fig. 3a) shows there is no oxidation of phenol in the absence of

30 Table 1
Physical properties of the annealed xerogel and aerogel solids (Fe/Al = 1:1).
20
Sample/annealing Surface area Average pore Pore volume
10 temperature (m2/g) size (nm) (cm3/g)
Xerogel 400 °C 260 4.3 0.332
0
Xerogel 500 °C 238 4.7 0.403
20 30 40 50 60 70
Xerogel 600 °C 195 5.8 0.369
2Ɵ (degrees) Xerogel 700 °C 64 12.2 0.308
Xerogel 800 °C 40 12.0 –
Fig. 1. Powder X-ray diffraction patterns for the Al/Fe annealed samples at 800 °C Aerogel 800 °C 76 20.9 0.302
for 6 h.

Fig. 2. SEM micrographs of (a) Al/Fe 1:4, (b) Al/Fe 1:1, and (c) Al/Fe 4:1. The solids were annealed at 700 °C for 6 h. Scale bars correspond to 500 nm.

Please cite this article in press as: Y. Li et al., Fe/Al binary oxide aerogels and xerogels for catalytic oxidation of aqueous contaminants, Separ. Purif. Technol.
(2015), http://dx.doi.org/10.1016/j.seppur.2015.09.056
4 Y. Li et al. / Separation and Purification Technology xxx (2015) xxx–xxx
Fig. 3. (a) Phenol oxidation catalyzed by Fe/Al xerogels of varying composition, (b)
reaction intermediates of the xerogel having an Fe/Al ratio of 1:1, and(c) oxidant
consumption efficiency determined by the ratio of phenol oxidized over H2O2
consumed (both in mM). Xerogel loading was 4 g/L. Initial concentrations of phenol
and H2O2 were 0.17 mM and 17 mM, respectively. Solids were annealed at 800 °C.
the catalysts. Mixing the catalysts with phenol solutions without
adding H2O2 (as Control 2 in Fig. 3a) indicates negligible removal
of phenol due to background adsorption. As shown in Fig. 3a, the
ratio of Al(III) and Fe(III) precursors used during xerogel synthesis
has a marked effect on their catalytic activity. The most reactive
catalyst was made of equivalent molar concentration of Al(III)
and Fe(III). This xerogel was able to oxidize over 62% of phenol
within 24 h. In comparison, solids with a Fe/Al ratio of 1:4 or 4:1
degraded 13% and 15% of the initial amount of phenol, respectively.
p-benzoquinone and hydroquinone were the two major intermedi-
ates detected by HPLC analysis. The same compounds were formed
during phenol oxidation in Fenton reaction systems [25]. The con-
centrations of the intermediates for the xerogel having a Fe/Al ratio
of 1:1 were shown in Fig. 3b. Note that the total concentration of
the two intermediates is substantially lower than the amount of
phenol initially present in the solution. This is due to that p-
benzoquinone and hydroquinone were rapidly oxidized, giving rise
to small molecule organic acids that cannot be detected by HPLC,
before their mineralization to CO2.
With hydrogen peroxide as the oxidant, an important indicator
of the catalyst performance is related to the efficiency of peroxide
Please cite this article in press as: Y. Li et al., Fe/Al binary oxide aerogels and xerogels for catalytic oxidation of aqueous contaminants, Separ. Purif. Technol.
(2015), http://dx.doi.org/10.1016/j.seppur.2015.09.056
conversion to reactive oxygen species (ROS) versus its unproduc-
tive decomposition to oxygen and water. The reactions of Fe(III)
with H2O2 can be described by Eq. (1), in which ‘‘” denotes
surface-residing species [15,13]. The Fe(II) formed reacts with
another molecule of H2O2 to produce hydroxyl radical (OH).
 FeIII þ H2 O2 ! FeII þ O2 þ Hþ ðpH > 5Þ ð1Þ
 FeII þ H2 O2 ! FeIII þ  OH þ OH ð2Þ
Free or surface-bound OH are thought to be the key ROS responsi-
ble for the degradation of organic compounds [26–28]. However,
competing reactions (Eqs. (3) and (4)) may consume ROS and result
in a net loss of H2O2 (Eq. (5)).
 FeIII þ O2 ! FeII þ O2 ð3Þ
 FeII þ  OH þ Hþ ! FeIII þ H2 O ð4Þ
2H2 O2 ! O2 þ H2 Oðnet reaction by combining Reactions 1  4Þ
ð5Þ
The efficiency of oxidant consumption, defined as the ratio of phe-
nol oxidized over the total loss of H2O2 in the solution, is a complex
function of the solution pH, Fe(III)/H2O2 ratio, as well as the nature
of the catalysts [26,11,29]. As all three solids were evaluated under
similar reaction conditions, the difference in H2O2 utilization effi-
ciency observed here can be attributed mainly to catalyst activity.
As indicated in Fig. 3c, xerogel with an Fe/Al ratio of 1:1 outper-
formed two other particles by attaining an ROS generation effi-
ciency of 0.94%. This value is close to the ROS yield of Fe(III)-
embedded synthetic aluminosilicates reported in a prior study
[15]. For the other two solids, xerogel with an Fe/Al ratio of 4:1
has significantly higher oxidant productivity than its Al-enriched
counterpart although the phenol degradation performance of the
two solids was similar. This shows that given the amount of H2O2
consumed, the former (Xerogel with Fe/Al at 4:1) is more efficient
at producing reactive oxidants versus unproductive decomposition
of H2O2 to water and O2. The trend of phenol degradation with Fe
(III) content observed here points to the existence of an optimal
Fe/Al composition. The optimal ratio of Fe/Al in the binary structure
likely promotes the formation of more active Fe(III) species result-
ing in more rapid and efficient ROS generation. It has been reported
that Reaction (1) is preceded by formation of an inner-sphere com-
plex between Fe(III) and H2O2 [30,31]. For facile complexation to
occur, Fe(III) has to possess vacant coordination position or bound
with labile ligands (e.g., H2O) [13]. The active Fe structure should
also be able to minimize unproductive dissociation of H2O2 (Reac-
tion (3) and (4)). As such, the coordination environment and disper-
sion state of surface Fe species are critical factors controlling the Fe
activity for H2O2 activation. In line with these considerations, Fe(III)
chelated with suitable ligands (e.g., EDTA) or dispersed on solid sub-
strates (e.g., alumina or aluminosilicates) is known to possess sig-
nificantly higher activity and selectivity for ROS generation over
unproductive H2O2 decomposition than bulk Fe(III) (oxyhydr)oxides
[10,18,21,32]. In this study, we postulate that the ratio of Fe/Al may
have a strong effect on Fe(III) hydrolysis and polymerization,
thereby affecting the structural organization of Fe(III) species in
the solid phase. Increasing the Fe(III) loading may increase the
number of reactive Fe(III) sites, yet at the same time, promote the
formation of large Fe(III) clusters that are catalytically unreactive.
The two competing effects would suggest the existence of an opti-
mal Fe(III) loading, which was observed to be around an Fe/Al ratio
of 1:1 in this study.
 Y. Li et al. / Separation and Purification Technology xxx (2015) xxx–xxx
Fig. 4. Effect of annealing temperature of xerogel (Fe/Al = 1:1) on phenol degrada-
tion rates. Xerogel loading was 4 g/L. Initial concentrations of phenol and H2O2 were
0.17 mM and 17 mM, respectively.
3.3. Effect of annealing temperature on catalyst activity
Fig. 4 shows phenol oxidation by xerogel that had undergone
annealing at different temperatures. No appreciable improvement
in catalyst activity can be discerned at an annealing temperature
between 400 and 600 °C. Annealing at 700 °C brought about a
sharp increase in reactivity. Further increasing the annealing tem-
perature to 800 °C results in a moderate increase in phenol oxida-
tion rate. The trend suggests significant structural transformation
had occurred at approximately 700 °C. To understand this effect,
gas adsorption analysis was performed on these solids and the
results are shown in Table 1. The surface area was found to
decrease progressively from 260 to 40 m2/g with an increasing
annealing temperature, indicative of material sintering. The aver-
age pore size measured by N2 adsorption does not decrease as
would be expected for high temperature annealing. Instead, we
saw a biphasic behavior that coincides with the trend of phenol
oxidation rate. Specifically, the pore size was largely unaffected
between 400 and 600 °C. Annealing at 700 °C led to a significant
enlargement of the pore size from 5.8 nm to 12.2 nm, and pore size
was more or less constant going up to 800 °C. Within this temper-
ature window, pore volume decreased moderately by approxi-
mately 20%. Taking together the changes in surface area, pore
size, and pore volume, the transition temperature of 700 °C seems
to correspond to coalescence of micropores into meso- or macro-
pores while the porous network structure of the xerogel material
was largely intact (i.e. no significant loss of total pore space). This
expansion of pore diameter greatly enhances the diffusion of reac-
tants in the aqueous phase into the interior space of the xerogel,
which more than compensates the loss in surface area.
3.4. Performance of aerogels vs. xerogels
Aerogel and xerogel are broadly used synthesis routes for pro-
ducing high surface-area metal oxides. The two methods adopt
similar gelling procedures but differ in the drying processes. Com-
pared to xerogels, the solvent of which is removed through room
temperature evaporation, aerogel synthesis entails days of contact-
ing the gels with liquid CO2. This critical point drying step offers
the benefit of minimizing pore structure collapse due to solvent
excavation. However, it is a lengthy process incurring high costs,
and is therefore difficult to be applied at large scales [33,24]. Fol-
lowing our observation that aqueous phenol oxidation rates are
largely controlled by the mesopores (>10 nm in diameter) instead
of relying on micropores as in typical gas phase reactions, it is of
interest to examine whether aerogel would be of advantage over
xerogel in the aqueous system studied here. Fig. 5 compares the
Please cite this article in press as: Y. Li et al., Fe/Al binary oxide aerogels and xerogels for catalytic oxidation of aqueous contaminants, Separ. Purif. Technol.
(2015), http://dx.doi.org/10.1016/j.seppur.2015.09.056
5
Fig. 5. Comparison between xerogel and aerogel (Fe/Al ratio is 1:1 for both) for
phenol degradation at 24 h. The solid loading was 4 g/L. Initial concentrations of
phenol and H2O2 were 0.17 mM and 17 mM, respectively.
amount of phenol degradation at 24 h by aerogel and xerogel pre-
pared under two annealing temperature (700 °C and 800 °C). Also
illustrated in this figure are H2O2 utilization efficiencies in various
experiments (scaled up by 100 times). At both temperatures, xero-
gel has delivered higher phenol oxidation rates and greater oxidant
generation efficiency than its aerogel counterpart. This is some-
what unexpected, as N2 adsorption data indicates that aerogel
offers a significantly higher surface area (76 vs. 40 m2/g), greater
average pore size (20 nm vs. 12 nm) and comparable pore volume
than its xerogel counterpart (Table 1). While the cause for this
behavior is unclear and requires further investigations, aerogel
producing consistently lower oxidant efficiency (i.e. higher H2O2
decomposition) is perhaps attributable to significant aggregation
of Fe(III) at the surface due to the prolonged solvent exchange pro-
cess. From a practical point of view, the high surface area-
normalized reactivity of xerogel is desirable because of the mate-
rial’s simpler processing requirements and greater scalability.
4. Conclusions
Fe/Al mixed metal oxide xerogels and aerogels were prepared
by a facile propylene-oxide-enabled sol–gel process to generate a
series of high surface-area heterogeneous catalysts for water
decontamination applications. The molar ratio of Fe and Al and
the annealing temperature were varied independently to assess
the effect of synthesis parameters on the crystallinity, surface area,
and pore structure of the resultant materials. The catalytic activity
of the xerogels and aerogels were assessed using phenol as a model
organic contaminant and H2O2 as a source of oxidants. The results
indicate that the activity and oxidant utilization efficiency of the
binary metal oxides are sensitive to Fe/Al ratio. Optimal catalyst
performance was observed at an intermediate Fe/Al ratio, with
higher Fe loading contributing to the formation of discrete hema-
tite crystallites that are less catalytically active. Increasing anneal-
ing temperature of the xerogels led to more efficient phenol
oxidation, which was attributed to enlarged average pore size that
facilitates the access of aqueous reactants to the internal pore sur-
face. Despite having moderately smaller surface areas, xerogels
possess higher catalytic activity for phenol oxidation than the aero-
gel counterparts. Considering their simpler processing needs, xero-
gels represent a more viable approach to preparing reactive and
environmentally benign catalysts for water treatment.
Acknowledgement
The financial support by the U.S. National Science Foundation
(CHE-1308726) is greatly appreciated by WLY.
6 Y. Li et al. / Separation and Purification Technology xxx (2015) xxx–xxx

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Please cite this article in press as: Y. Li et al., Fe/Al binary oxide aerogels and xerogels for catalytic oxidation of aqueous contaminants, Separ. Purif. Technol.
(2015), http://dx.doi.org/10.1016/j.seppur.2015.09.056