Microporous and Mesoporous Materials 234 (2016) 392e400

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Microporous and Mesoporous Materials

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

Sol-gel synthesis, characterization and catalytic activity of silica

aerogels functionalized with copper(II) complexes of cyclen and
cyclam

czi b, Istva
Helga Fruzsina Bereczki a, 1, Lajos Daro
n Fa

bia

n a, Istva

n La
r a, *

za
a
Department of Inorganic and Analytical Chemistry, University of Debrecen, Egyetem t
er 1., H-4032 Debrecen, Hungary
b
Department of Solid State Physics, University of Debrecen, Bem t

er 18/b., H-4026 Debrecen, Hungary

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

Article history: Mesoporous silica aerogels covalently functionalized with Cu(II) complexes of cyclen (1,4,7,10-
Received 6 May 2016 tetraazacyclododecane) and cyclam (1,4,8,11-tetraazacyclotetradecane), denoted as CuAM12 and
Received in revised form CuAM14, respectively, have been first prepared. Monolithic materials were synthesized from
18 July 2016
alkoxysilane-anchored macrocyclic complexes and TMOS through the base catalyzed sol-gel method
Accepted 19 July 2016
Available online 28 July 2016
followed by a supercritical CO2 drying. Presence of organic moieties in the silica structure was confirmed
by FT-IR measurements, the amount of incorporated copper was determined by ICP-OES technique,
resulting in 1.310 ± 0.028 and 2.060 ± 0.025 wt% copper for CuAM12 and CuAM14, respectively). Surface
Keywords:
Mesoporous silica aerogel
morphology was characterized by nitrogen adsorption/desorption porosimetry and scanning electron
Covalently bound cyclam and cyclen microscopy. Catalytic activities of the aerogels CuAM12 and CuAM14 were evaluated by oxidation of
complex phenol with eco-friendly reagent hydrogen peroxide, without buffering or using organic co-solvents.
Phenol oxidation and mineralization Control experiments using unbound macrocyclic complexes in the homogenous phase were also con-
Heterogeneous catalysis ducted. Surprisingly, results revealed that the functionalized aerogels' turnover frequencies (TOF) were
Confinement effect approximately 7e15 times higher than that of the free complexes in the homogeneous phase. The in-
crease was attributed to the confinement effect. Reusability studies showed that the catalysts remained
active even after four cycles completed. Certain reduction of catalytic activity was observed in the
repeated cycles, which was the combined effect of poor mechanical properties of the aerogel, splitting-
off and leaching of the less-bound surface macrocycles, and extensive adsorption of the oxidation
products.
© 2016 Elsevier Inc. All rights reserved.

1. Introduction
Aerogels have drawn significant attention in the past few de-
cades in the fields of chemical and engineering sciences. The term
aerogel was first proposed by S. S. Kistler [1] in 1931 to designate
gels in which the liquid was replaced by gas, without collapsing the
gel solid network. The method, which enables the production of
these materials possessing extremely low bulk density and high
porosity, is called supercritical drying and is used until today.
Recognizing the unique properties of aerogels such as very low
* Corresponding author.

za
E-mail address: lazar@science.unideb.hu (I. La
r).
1
Present address: Section of Electron Spectroscopy and Materials Science,

r 18/c, H-4026
Institute for Nuclear Research, Hungarian Academy of Science, Bem te
Debrecen, Hungary.
thermal conductivity [2], high adsorption capacity [3] etc., Kistler
was quick to propose most of the potential industrial applications
for aerogels, for instance, as catalysts, thickening agents, insulating
materials, or water repellants when they were hydrophobic [4].
Over the years, silica aerogels found applications as thermal in-
sulators of windows [5] and thermoelectric devices [6], acoustic
barriers [7], or in Cherenkov radiation detectors [8].
Silica aerogels are synthesized by the acid- or base-catalyzed
sol-gel process, usually starting from a tetraalkoxy silane, which
allows their easy chemical modification with various organic tri-
alkoxysilanes resulting in materials with dramatically different
properties. Although a great number of functionalized aerogels
have been synthesized earlier [9,10], the full potential of these
materials has not yet been explored. The majority of the studies
focused on the development of hydrophobicity [11e13], since
sensitivity to water is one of the biggest setbacks that practically

http://dx.doi.org/10.1016/j.micromeso.2016.07.026
1387-1811/© 2016 Elsevier Inc. All rights reserved.
 H.F. Bereczki et al. / Microporous and Mesoporous Materials 234 (2016) 392e400
hinder utilization. Currently, one of the most promising areas of
investigation is the design of controlled release drug delivery sys-
tems [14e18], but other examples have also appeared suggesting
the use of functionalized silica aerogels for adsorption [19e22],
immobilization scaffolds for enzymes [23,24], stationary phases in
microfluidic devices [25], inorganic fillers in reinforced polymer
composites [26,27] or as catalysts [28].
Cyclen, cyclam, and their derivatives are tetraaza macrocyclic
chelators widely used mainly in magnetic resonance imaging and
in radiopharmaceuticals [29]. These compounds bind strongly to a
wide range of transition metal ions that still remain catalytically
active in oxidative processes. Therefore, these compounds are
suitable candidates for anchoring metal ions to silica surfaces in
such a firm way that any metal leakage can be avoided. Although
functionalizing various types of supports with catalytic metal
complexes has been extensively reported in the literature [30e32],
only few examples can be found where cyclam complexes were
covalently bound to mesoporous silica materials [33e35]. These
materials were tested as gas chromatography stationary phases
[36] or selective metal adsorbents [37]. Besides characterization of
the prepared materials, Sujandi et al. [35] investigated the catalytic
performance during the oxidation of ethylbenzene leading to
promising results. To the best of our knowledge, the synthesis of
mesoporous silica aerogel functionalized with cyclen has not yet
been published.
The removal of phenol and its derivatives from wastewaters has
been the subject of outstanding interest in the past few decades,
since these compounds are extremely toxic. In 2008, the European
Commission listed several phenolic compounds as priority pollut-
ants in a directive [38]. Currently, several technologies are used for
the mineralization of phenol, including different oxidation treat-
ments that are based on the high reactivity of oxyradicals [39].
Among oxidation agents, hydrogen peroxide is widely investigated
[40e43] due to its eco-friendly nature.
In this paper, we report for the first time, the synthesis and
characterization of silica aerogels functionalized with the copper(II)
complexes of cyclen and cyclam, as well as an investigation of their
catalytic performance and reusability for the oxidation of phenol
with hydrogen peroxide.
2. Experimental
2.1. Materials
Tetramethyl orthosilicate (TMOS), (3-chloropropyl)trimethox-
ysilane (CPTMS), (3-glycidoxypropyl)trimethoxysilane (GPTMS),
N,N-diisopropylethylamine (DIPEA), acetonitrile and cupric acetate
were purchased from Sigma-Aldrich. 1,4,7,10-
tetraazacyclododecane (cyclen) and 1,4,8,11-
tetraazacyclotetradecane (cylam) were purchased from CheM-
atech (Dijon, France). Ammonium carbonate, potassium dihy-
drogen phosphate and phosphorous acid (85%) were obtained from
Merck (Darmstadt, Germany). HPLC grade methanol and technical
grade solvents (acetone, methanol) were purchased from Molar

sztelek, Hungary). Double deionized water was
Chemicals Ltd. (Hala
prepared by a MilliQ equipment. Argon gas cylinders (99.996%) and
carbon dioxide cylinders (Biogon-C, 99.5%) equipped with a dip
tube were purchased from Linde Ga
z Magyarorsza
g Zrt. (Debrecen,
Hungary).
2.2. Synthesis of functionalized silica aerogels
Functionalized silica aerogels were prepared by the base-
catalyzed sol-gel method. In the first step, the macrocyclic com-
pound (cyclam or cyclen) was functionalized with a reactive silane
393
coupling agent (CPTMS or GPTMS), which was followed by complex
formation by adding copper(II) ions to the solution. Upon intro-
ducing the main silane component (TMOS) and the catalyst (if
necessary) into the mixture, gel formation occurred. The gel was
then subjected to a gradual solvent exchange process and super-
critical CO2 drying.
Synthesis of aerogels modified with the Cu(II) complex of
cyclam was carried out in the following way. Cyclam (227 mg,
1.13 mmol) was dissolved in dry acetonitrile (15.0 ml, 285 mmol),
then CPTMS (0.206 ml, 1.13 mmol) and DIPEA (0.590 ml, 3.45 mmol)
were added to the solution. The mixture was refluxed for 48 h
under argon gas atmosphere, then evaporated to dryness. Next, the
as-prepared solid was dissolved in methanol (5.00 ml, 123 mmol),
and mixed with cupric acetate (187 mg, 1.03 mmol) which was
dissolved in the mixture of methanol (20.0 ml, 492 mmol) and
water (3.00 ml, 166 mmol). Thus, a dark purple solution was ob-
tained. Finally, TMOS (3.80 ml, 25.6 mmol) and ammonium car-
bonate solution (1.00 ml, 1,04 mol L
1, 1.04 mmol) were added
under vigorous stirring. The resulting mixture was immediately
poured in a plastic mold, where gelation took place. The dark-
purple colored alcogel was aged for 24 h in the mold, and then
placed into methanol. After subjecting the gel to a step-by-step
solvent exchange process, where the original solvent of the alco-
gel (methanol and water) was gradually replaced by acetone in four
consecutive steps, the gel was soaked in 2 L of freshly distilled
acetone for at least three days. Finally, supercritical drying was
performed using carbon-dioxide the same way we published
earlier [26]. The resulting aerogel was labeled CuAM14.
The synthesis of the aerogel CuAM12 functionalized with the
copper(II) complex of cyclen ([cyclen-Cu]) was carried out similarly
as CuAM14, with the following modifications. First, cyclen (199 mg,
1.15 mmol) was dissolved in the mixture of water (8.00 ml,
443 mmol) and methanol (15.8 ml, 389 mmol). To this solution,
GPTMS (1.00 ml, 4.53 mmol) was added under argon atmosphere,
and the mixture was stirred at room temperature for 20e30 min. In
the second step, cupric acetate (211 mg, 1.16 mmol) dissolved in
water (5.00 ml, 277 mmol) was added. Immediate complex for-
mation was accompanied by a color change (from colorless to dark-
blue). As the final step, TMOS (3.78 ml, 25.6 mmol) was introduced,
and the mixture was poured in a plastic mold. Due to the highly
basic nature of [cyclen-Cu], gelation took place in a short time
without the addition of any further catalyst. After 24 h of aging, the
dark blue-colored alcogel was placed in methanol. Gradual solvent
exchange steps and supercritical drying was performed as
described above for CuAM14. The obtained gel was denoted
CuAM12.
2.3. Characterization
IR spectra were recorded on a Nicolet Nexus FT-IR Spectrometer.
All the mesoporous materials samples were prepared as KBr diluted
pellets. Copper contents were determined at the analytical lines of
copper (324,754 nm and 327,395 nm) by an Agilent Technologies
ICP-OES 5100 SVDV spectrometer calibrated to certified copper
standards. The samples were digested prior to analysis by using a
Milestone ETHOS UP high performance microwave digestion sys-
tem in a mixture of nitric acid (4.00 ml, 65%) and hydrogen
peroxide (1.00 ml, 30%). Scanning electrone microscopy (SEM)
studies were performed by a Hitachi S-4300 instrument (SEM)
equipped with a Bruker energy dispersive X-ray spectroscope. The
monolithic aerogel samples of approximately 2e4 mm sizes were
embedded in a low melting point alloy (Wood's metal). All surfaces
were covered by a sputtered gold conductive layer. 5e10 kV
accelerating voltage was used for the high resolution pictures. Ni-
trogen gas porosimetry measurements were performed on a
394 H.F. Bereczki et al. / Microporous and Mesoporous Materials 234 (2016) 392e400
Quantachrome Nova 2200e surface area and porosity analyzer
(Quantachrome Instruments, Boynton Beach, FL, USA) after the
samples were outgassed under vacuum at 100  C for 24 h. All cal-
culations were performed by using the NovaWin 11.0 software
(Quantachrome Instruments, Boynton Beach, FL, USA). Surface
areas were calculated by the multi-point Brunauer-Emett-Teller
(BET) method. Pore size distributions were determined by the
Barret-Joyner-Halenda (BJH) method. Adsorption film thickness
was calculated by the de Halsey method [44]:
t ¼ 3:54½5=2:303 log ðp0 =pÞ1=3
where t is the film thickness p is the gas vapor pressure, and p0 is
the saturation pressure of adsorbent.
High pressure liquid chromatographic (HPLC) measurements
were performed by a Jasco chromatograph equipped with an ERC
3315 degassing module, a Jasco LG-980-02 low-pressure gradient
valve unit, a Jasco PU-980 pump, a Jasco AS-1555 autosampler, a
Jasco UV-975 UVevis detector and Jasco ChromPass software.
Phenomenex Lichrosphere 5 RP-18e (4.6 mm  150 mm, 5 mm) was
used. All measurements were carried out at ambient temperatures.
The applied eluent was 40% methanol e 60% potassium dihydrogen
phosphate (0.025 mM)/phosphoric acid (0.52 mM) buffer (pH 4).
The wavelength of detection was typically 254 nm 20 ml of sample
was injected.
Mass spectrometric measurements were performed by
MicroTOF-Q type Qq-TOF MS instrument (Bruker Daltonik, Bremen,
Germany). The instrument was equipped with an electrospray ion
source where the spray voltage was 3 kV. Nitrogen was utilized as
drying gas. The drying temperature was 180  C and the flow rate
was 4.0 L/min. Mass spectra were recorded by means of a digitizer
at a sampling rate of 2 GHz and evaluated with the DataAnalysis 3.4
software from Bruker.
In the reaction mixtures used for the catalytic studies, the
concentrations of the applied cupric acetate, [cyclen-Cu] and
[cyclam-Cu] solutions and the weights of the functionalized silica
materials were adjusted to give copper:phenol ¼ 1:99 wt ratios.
2.4. Catalytic tests and identification of oxidation products
Catalytic activity of the aerogels was measured by the oxidation
of phenol with hydrogen peroxide in aqueous solutions. In a typical
run, phenol solution (10.66 ml, 906 ppm) was placed in a flask, along
with the appropriate amount of ground catalyst and hydrogen-
peroxide (1.00 ml, 10.3 M). The phenol to hydrogen peroxide molar
ratio was set to 1:100, while copper to phenol weight ratio was kept
constant at 1:99. Throughout the reaction, the temperature was
70.0  C. The mixture was thermally equilibrated for 30 min before
hydrogen peroxide was added to start the reaction. 700 ml aliquots of
samples were taken after 1, 3, 5, 7, 10, 15, 20, 30, 40, 50 and 60 min
and centrifuged. Supernatant solutions were collected and subse-
quently frozen by liquid nitrogen. Samples were melted directly
before HPLC analysis. For comparison purposes, homogenous-phase
catalytic reactions using copper acetate, [cyclam-Cu] and [cyclen-
Cu] as catalysts were carried out, using the same concentrations
and sample preparation method as described above.
In order to identify oxidation products, identical reaction mix-
tures were prepared under the same experimental conditions as
described above. Samples after 20, 60, 120 and 240 min were taken
and evaluated by ESI-MS.
2.5. Reusability studies
To examine the catalytic stability of the prepared aerogel ma-
terials, four successive experiments were performed. Experimental
conditions and concentrations were the same as described in Sec-
tion 2.4., with the sole exception that copper:phenol weight ratio
was set to 5:95. After the first reaction, the catalyst was separated
from the reaction mixture by centrifugation and 700 ml of the su-
pernatant solution was collected for HPLC analysis. The catalyst was
washed with water three times, and then the wet gel was placed
back into the flask along with the usual amount of phenol and
hydrogen peroxide to start the next cycle.
Leaching of copper complexes from the catalysts were investi-
gated according to the following procedure. First, reaction mixtures
were prepared as described in Section 2.4. The reactions were
allowed to proceed for 240 min at standard conditions. Afterwards,
the mixture was centrifuged and the supernatant solutions were
carefully collected. The obtained solution was filtered through a
PTFE membrane filter (pore size: 0.45 mm) prior to analysis. Copper
concentrations were determined by MP-AES technique.
3. Results and discussion
3.1. Preparation
Incorporation of copper(II) complexes of the macrocyclic com-
pounds cyclen and cyclam through covalent bonds in mesoporous
silica aerogels was accomplished by the sol-gel method. The hy-
drolysis and polycondensation of TMOS and the functionalized
trialkoxy silanes took place simultaneously, resulting in a highly
uniform distribution of the macrocycles (Scheme 1). While the
reaction of commercially available silica gels with the same
macrocyclic silane coupling reagents may led to a surface coverage
of the available pore walls only, co-gelation of the reactants gave
full in-depth functionalization of the silica network.
The synthesis route applied can be summarized in three major
steps. In the first step, the macrocyclic compounds were function-
alized with the appropriate coupling agent (CPTMS or GPTMS).
Secondly, the preparation of copper(II) complexes was accom-
plished by the addition of equimolar amount of cupric acetate.
Successful complex formation was indicated by a dramatic color
change (from colorless to dark blue or purple). In the third step of
the preparation, the main silane component (TMOS) and the co-
catalyst ammonium carbonate (if needed), were added to the sys-
tem to induce hydrolysis and polycondensation. Finally, after
ageing, a solvent exchange process was performed, where the
parent solvent (methanol/water mixture) was gradually replaced
by acetone. Supercritical carbon dioxide drying resulted in mono-
lithic aerogels, their photographs are shown in Fig. 1.
In both cases, discoloration of the wash solvents was observed,
indicating that a certain amount of the macrocyclic complex failed
to become covalently bound to the silica backbone. However, after a
period of time the discoloration gradually diminished while the
alcogels stayed purple/blue. Obviously, the non-bound complexes
were washed out of the gel-structure.
3.2. Structural studies
Copper content of the materials was determined after nitric acid
and hydrogen peroxide microwave digestion by ICP-OES technique
(Table 1.). Based on these results it is possible to compare the effi-
ciencies of complex incorporation. The functionalization was more
effective (61%) in the case of CuAM14, yielding a copper content of
2.09 wt%. For CuAM12, copper content was 1.31%, which means that
43% of [cyclen-Cu] was successfully incorporated.
Covalent chemical bonding of the macrocycle rings to the
anchoring silane reagents (Scheme 1) was monitored by 1H NMR
technique. After their complexation with copper ions, 1H NMR was
no longer appropriate to monitor the chemical reactions, due to the
 H.F. Bereczki et al. / Microporous and Mesoporous Materials 234 (2016) 392e400
Scheme 1. Synthetic pathways of aerogels CuAM12 and CuAM14, functionalized with macrocyclic complexes [cyclen-Cu] and [cyclam-Cu], respectively. For solvents, catalysts and
reaction times (t), see Section 2.2.
Fig. 1. Photographs of (a) CuAM14 and (b) CuAM12. against a metric-ruler.
paramagnetic effect of the copper ions. Thus, FT-IR spectra of the
aerogel materials were recorded (Fig. 2.). For comparison, FT-IR
spectrum of an unmodified silica aerogel (denoted Aer blank)
395
Table 1
Copper content of the prepared macrocyclic silica aerogels determined by ICP-OES.
Material Copper content (weight%) Incorporated copper (%)
Theoretical Measured
CuAM12 3.06 1.31 ± 0.028 43
CuAM14 3.43 2.09 ± 0.025 61
prepared by our group earlier [26] is also presented. The intense
broad band at approximately 1040 cm
1 present in all spectra can
be attributed to the SieOeSi antisymmetrical stretching vibration.
Between 2850 and 2950 cm
1, two or three weak bands can be
observed for CuAM14, CuAM12, while they are absent in the spectra
of their parent materials. These peaks can be attributed to aliphatic
CeH stretching vibrations, and certainly arise due to
functionalization.
The porosity of the materials was characterized by nitrogen
adsorption/desorption porosimetry. For samples CuAM12 and
CuAM14, the isotherms (Fig. 3a) can be classified [45] as type IV,
which is typical of mesoporous silica materials. The sharply
increasing adsorption isotherms above p/p0 ¼ 0.9 in both cases
indicate the presence of macropores, while hysteresis loops starting
at low relative pressures (p/p0 ¼ 0.25e0.30) indicate microporosity.
Individual contributions of micro-, meso- and macropores to the
total pore volume were estimated as follows. By applying the t-plot
396 H.F. Bereczki et al. / Microporous and Mesoporous Materials 234 (2016) 392e400

Fig. 2. FT-IR spectra of an unmodified natural silica aerogel (blank) as well as func-
tionalized aerogels CuAM12 and CuAM14.

method, micropore volumes were calculated with the reference to

standard nitrogen adsorption data for non porous silica provided by
the software. The sums of micro- and mesopore volumes were
determined by calculating the pore volumes at p/p0 ¼ 0.96 from the
desorption branches of the isotherms. By taking the total pore
volumes into account, individual meso- and macropore volumes
could be obtained. Results are presented in Table 2. It can be seen,
that in both cases, the majority of pore volume (86.5% and 83.2% for
CuAM12 and CuAM14, respectively) can be attributed to meso-
pores, and around 12% to macropores. The contribution of micro-
pores to the total pore volume is not significant in the case of
CuAM12 (0.86%), while it is around 5% in the case of CuAM14.
The calculated BET surface areas area was 367.4 and
500.2 m2 g
1 for CuAM14 and CuAM12, respectively (Table 2). SEM
images (Fig. 4bec) also reveal large macropores with pore di-
ameters of as high as 1 mm. Pore size distribution curves were
calculated by the BJH method for the desorption branches.
Although the curves, due to the limitations of the BJH method,
might not reflect all aspects of internal pore structures of the
samples, the data obtained are in good correlation with the BET
specific surface areas calculated from the adsorption branches. For
CuAM14, the contribution of mesopores (2e50 mn range) to the Fig. 3. aeb: (a) Nitrogen adsorption/desorption isotherms of aerogels CuAM12 and
total pore volume is nearly uniform, no dominant pore diameter CuAM14 (a). Pore size distribution dV(log d) curves of CuAM12 and CuAM14 calculated
from the desorption branch of isotherms by the BJH method (b).
can be identified. However, a shallow maximum can be observed at
23.4 nm. Aerogel CuAM12 also shows a wide pore size distribution
curve. However, in this case, one dominant maximum at 19.9 nm Table 2
can be clearly distinguished. Summary of nitrogen adsorption/desorption porosimetry results.
Surface morphology of silica aerogels was studied by scanning
CuAM12 CuAM14
electron microscopy. For comparison, SEM image of an unmodified
SBET (m2 g
1)a 500.2 367.4
natural silica aerogel prepared by a similar base-catalyzed sol-gel
dmean (nm)b 19.9 23.4c
method is also provided (Fig. 4aec). The structure of a typical un- Vtotal (cm3 g
1) 1.972 0.7844
modified aerogel (Fig. 4a) consists of interconnected networks of Vmicropores (cm3 g
1) 0.017 0.040
overlapping and nearly uniformly sized globuli with diameters of Vmesopores (cm3 g
1) 1.706 0.6528
30e80 nm. The space in between them fall mostly in the mesopores Vmacropores (cm3 g
1) 0.249 0.0916

range, interrupted by a number of macropores. SEM images of a

CuAM12 and CuAM14 reveal significantly different structures. In
the case of CuAM14, the primer globuli form large aggregates (with
roughly 420e580 nm diameters), arranged randomly, creating
highly interconnected networks of macropores and cavities. A
similar, but less pronounced tendency can be observed in the case
of CuAM12. Here, both the aggregates and the macroporous
channels appear to be smaller, ca. half the size of the previous
ones.In both functionalized aerogels the presence of larger
Calculated by the BET method.
b
Calculated by the BJH method.
aggregates is most likely the consequence of the fact that copper
complex formation took place in aqueous media. There, beside
complexation, hydrolysis of the silane reagent and poly-
condensation of the silanols resulted in formation of partly con-
nected sol particles, which grew larger later in the reaction mixture.
 H.F. Bereczki et al. / Microporous and Mesoporous Materials 234 (2016) 392e400 397

Fig. 5. Kinetic curves representing the progress of phenol conversion over time with
the aerogel catalysts CuAM12 and CuAM14, as well as the free macrocyclic complexes
[cyclam-Cu] and [cyclen-Cu], and cupric acetate at 70  C. (Initial concentrations of
phenol were 906 ppm, and the phenol-to-hydrogen peroxide molar ratio was set to
1:100, while the copper-to-phenol weight ratio was kept at a constant value of 1:99).

Kinetic curves of phenol conversion are shown in Fig. 5. As ex-

pected, none of the prepared catalysts could exceed the perfor-
mance of free copper(II) ions in the homogeneous phase. However,
copper ions can not be removed from the solution by physical
treatments, thus its application in real samples would be disad-
vantageous. The most interesting feature of our finding is revealed
when the kinetic curves of [cyclen-Cu] and [cyclam-Cu] were
compared to those of CuAM12 and CuAM14, respectively. While
both [cyclen-Cu] and [cyclam-Cu] performed quite poorly by
degrading only ca. 16 and 21% of phenol in 60 min, CuAM12 and
CuAM14 converted 4.6 and 4.4 times more (ca. 95 and 71% of the
original value), respectively. In order to make catalytic perfor-
mances even more comparable, we estimated the rates of phenol
degradation by simple linear regression (Fig. 6.). Fitting was per-
formed through a set of points selected from the initial linear
segments of the kinetic curves. The calculated turnover frequencies
(TOF) (derived from the slopes divided by the number of moles of
the catalytic sites), and regression coefficients of the fittings are
shown in Table 3. As can be seen, the TOF for CuAM14 and CuAM12
are ca. 15 and 7 times higher than that of free [cyclam-Cu] and

Fig. 4. aec: SEM images of (a) an unmodified natural silica aerogel (scalebar 500 nm),
(b) CuAM14 (scalebar 2 mm), and (c) CuAM12 (scalebar 1 mm).

3.3. Catalytic activity

Catalytic performance was evaluated through the oxidation of

phenol in aqueous solutions with environmentally friendly oxi-
dizong agent hydrogen peroxide. For comparison, control experi-
ments using copper acetate, unbound [cyclam-Cu] and [cyclen-Cu]
complexes, as well as blank (no catalyst) experiment with hydrogen
peroxide alone were carried out. We have studied the catalytic
performances at the original self-pH of phenol solution without
buffering or adding organic solvents, in order to keep the condi- Fig. 6. Linear trendlines fitted to points selected from the vicinity of the inflexion
tions quite similar to the natural waters polluted with phenols. points of S-shaped kinetic curves of CuAM12, CuAM14, [cyclam-Cu] and [cyclen-Cu].
398 H.F. Bereczki et al. / Microporous and Mesoporous Materials 234 (2016) 392e400

Table 3 both different selectivity and increased activity [49e53]. The

Turnover frequencies (TOF) of free and immobilized copper complexes and regres- remarkable increase of the performances of the macrocyclic aero-
sion coefficients of fitting calculated from the kinetic curves.
gels over the free [cyclen-Cu] and [cyclam-Cu] complexes can be
Material TOF (s
1)a Regression coefficient of linear fitting attributed to their immobilization combined with the confinement
CuAM12 2.240$10
2 0.9922 effect.
[cyclen-Cu] 0.328$10
2 0.9609 The S-shape of all curves recorded either for both the free and
CuAM14 6.396$10
2 0.9751 the immobilized macrocyclic complexes in Fig. 5 indicate a char-
[cyclam-Cu] 0.415$10
2 0.9814
acteristic autocatalytic reaction mechanism, which does not change
a
1
s ¼ micromoles of phenol converted by 1 mmol of complex-bound copper per upon immobilization.
second.
Oxidation products were identified by HPLC and ESI-MS mea-
surements (Scheme 2). Samples were taken at 20, 60, 120 and
[cyclen-Cu] complexes in the homogeneous phase, respectively. 240 min. Besides the peak of hydroquinone/catechol, in the case of
That was quite unexpected, as the conversion rate of a both aerogels, a series of organic acids were detected including
homogeneous-phase catalyst in general decreases significantly, acrylic acid, malonic acid, maleic acid, succinic acid and oxalic acid.
when it is immobilized on a solid surface. Evaluating the relative intensities of the peaks of the above
This dramatic increase in performance can be attributed to the mentioned oxidation products, we assume that the oxidation
so called “nest effect”. The “nest effect” or confinement effect was mechanism (presented in Scheme 2) includes quinone formation,
first proposed and later further extended by E.G. Derouane et al. followed by ring opening and stepwise oxidation and degradation
[46e48]. The concept suggests that the sorption equilibrium con- steps, which finally lead to a mixture of biodegradable and envi-
stant and thus the local concentration of the chemical species ronmentally friendly short-chained carboxylic acids.
involved are increased by the curvature of the pore walls, which For both CuAM12 and CuAM14, in the first 60 min, the con-
affect reaction kinetics, both activity and selectivity. Later on, the centration of hydroquinone/catechol gradually decreases, while the
confinement effects were extended to mesoporous materials by concentrations of acrylic acid, malonic acid, maleic acid and suc-
other groups, presenting experimental evidences with respect to cinic acid are on the rise. From this point on, hydroquinone/

Scheme 2. Proposed degradation pathways of phenol by hydrogen peroxide in the presence of CuAM12 and CuAM14 catalysts, determined by LC-MS.
 H.F. Bereczki et al. / Microporous and Mesoporous Materials 234 (2016) 392e400
Fig. 7. Conversion of phenol in reusability tests of CuAM12 and CuAM14 in four
consecutive steps, after 1 h reaction time.
catechol and organic acids are further oxidized which is indicated
by the appearance of oxalic acid at 120 min. At 240 min, only oxalic
acid and acetic acid are present in the reaction mixture, and thus
the mineralization of phenol is completed. It can be concluded that
under these circumstances, using aerogel catalysts, phenolic con-
tent can be fully transformed into non-toxic short chained car-
boxylic acids in 240 min.
3.4. Reusability
Reusability tests were conducted with CuAM12 and CuAM14 in
four consecutive cycles (Fig. 7). As it can be seen in Fig. 7, both
aerogels preserved their activity even after four complete reaction
and separation cycles. A decrease in the catalytic performance was
observed in both cases. For CuAM14, the decrease stopped at ca.
50% conversion rate in the third cycle, while this value was only 15%
for CuAM12 in the last cycle.
There are several possible explanations for the decrease in the
catalytic performance. Most likely, oxidation byproducts adsorb on
the aerogel surface, gradually blocking the active sites. This theory
is supported by the observation of the color change of the catalyst:
after Cycle 1, CuAM12 and CuAM14 both suffered only a minor
brownish discoloration while still retaining their original colors
(light purple and blue, respectively). However, during the forth-
coming cycles, the discoloration intensified resulting in dark-brown
catalysts. The brownish color can be attributed to 1,4-
benzoquinone, as well as a number of oligomeric/polymeric in-
termediates [54]. This concept is further promoted by one of our
recent works [55] dealing with photocatalytic titania-silica hybride
aerogels. There we found that a portion of the substrate molecules
involved in the photocatalytic reactions irreversibly adsorbed on
the aerogel surface, and thus in situ poisoned the suspended aer-
ogel catalyst.
On the other hand, the gradual decrease of the catalytic activ-
ities can be attributed to an experimental artifact as well. According
to our experience, one of the greatest shortcomings of working
with silica aerogel particles is stemming from their poor mechan-
ical properties and extreme sensitivity to any kind of wetting liq-
uids [52]. In a stirred reactor aerogel particles start crumbling into
ever smaller sized particles, and a part of them cannot be settled
completely by a standard laboratory centrifuge. A portion of the
catalyst, which is still suspended in the supernatant could be lost
during the washing and refilling processes between two cycles.
Additionally, moderate solubility of the amorphous silica aerogel
skeleton in water [26] may also contribute to the effect. The
399
solubility is expected to be higher for mono-functionalized cyclen
attached to only one [SiO3R] silicon atom, then with the CuAM14
aerogel, wherein the macrocycle is covalently bound through four
silicon atoms.
In an attempt to further investigate the causes of gradual
degradation of catalytic activity, leaching experiments were con-
ducted. Catalytic mixtures described in Section 2.4 were prepared
and the reactions were allowed to progress for 240 min, after which
copper concentrations were determined by MP-AES. Results show
that for CuAM12 and CuAM14, 34.7% and 64.5% of copper com-
plexes were released, respectively. The difference between CuAM12
and CuAM14 can be attributed to the larger number of anchoring
sites in CuAM12, allowing lower release ot the bound macrocycle.
However, these results appear to be contradictory with the fact that
its reusability is poorer than that of CuAM14. The explanation of
this phenomenon possibly lies in the much higher relative ratio of
small mesopores (<10 nm) in the total pore volume of CuAM14,
which provide the necessary confined space for the catalytic pro-
cess which, combined with the ab ovo higher activity of the 14-
membered macrocyclic complex, results in a more sustainable
catalyst.
4. Conclusion
Copper(II) complexes of macrocycles cyclen and cyclam have
been successfully incorporated in mesoporous silica aerogels
through covalent bonds. The results show that, covalently func-
tionalized aerogels CuAM12 and CuAM14 gave ca. 7 and 15 times
higher rate of catalytic conversion of phenol compared to free
[cyclen-Cu] and [cyclam-Cu] complexes in the homogenous phase.
The increased performance of the heterogeneous catalysts can be
attributed to and explained by the confinement effect. Regarding
reusability, the catalysts remain active even after four cycles
completed. Although a decrease in activity can be observed for
CuAM12, phenol conversion with CuAM14 seems to be stabilized in
the third and fourth cycle at ca. 50% of the original activity.
The newly synthesized macrocyclic aerogel catalysts meet most
of the requirements set towards the ideal wastewater-treatment
catalyst of the future. The fine structure provides extra advan-
tages of aerogel catalysts over traditional surface-functionalized
silicas like widely controllable pore sizes, tunable pore size distri-
butions, and higher load of the catalytically active species. Catalytic
performances are remarkable, especially in the light of low copper
contents in these materials. Using the green oxidant hydrogen
peroxide only, these macrocycle-functionalized silica aerogels do
not require any additives or buffering to mineralize phenol and may
serve as efficient and eco-friendly catalysts for the removal of
phenol-like toxic pollutants from wastewaters.
Acknowledgement
The authors thank Lajos Nagy for ESI-MS, and Sa
ndor Harangi
and Edina F. Baranyai for ICP-OES measurements. Financial support
from the Hungarian Scientific Research Fund (OTKA) grant No. NK-
105156 and Richter Gedeon Talentum Alapítva
ny is gratefully


acknowledged. The work is supported by the. TAMOP-4.2.2.A-11/1/
KONV-2012-0036 project. The project is co-financed by the Euro-
pean Union and the European Social Fund.
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.micromeso.2016.07.026.
400 H.F. Bereczki et al. / Microporous and Mesoporous Materials 234 (2016) 392e400

References [28] M.D. Gonza
lez, P. Salagre, E. Taboada, J. Llorca, E. Molins, Y. Cesteros, Appl.
Catal. B Environ. 136e137 (2013) 287e293.
[29] R. Delgado, V. Fe
lix, L.M.P. Lima, D.W. Price, Dalton Trans. (2007) 2734e2745.
[1] S.S. Kistler, Nature 127 (1931) 741.
[30] Y. Zhang, Y. Zhang, L. Wang, H. Jiang, C. Xiong, Industrial Eng. Chem. Res. 54
[2] S.S. Kistler, A.G. Caldwell, Industrial Eng. Chem. 26 (1934) 658e662.
(2015) 5894e5900.
[3] S.S. Kistler, E.A. Fischer, I.R. Freeman, J. Am. Chem. Soc. 65 (1943) 1909e1919.
[31] W.A. Wani, S. Prashar, S. Shreaz, S. Go
mez-Ruiz, Coord. Chem. Rev. 312 (2016)
[4] N. Leventis, M.M. Koebel (Eds.), Aerogels Handbook, Springer, 2011.
67e98.
[5] M. Rubin, C.M. Lampert, Sol. Energy Mater. 7 (1983) 393e400.
[32] J.M. Thomas, R. Raja, J. Organomet. Chem. 689 (2004) 4110e4124.
[6] J. Sakamoto, J.-P. Fleurial, J. Paik, J. Snyder, S. Jones, T. Caillat, NASA TechBriefs
[33] R.J.P. Corriu, A. Mehdi, C. Reye
, C. Thieuleux, New J. Chem. 27 (2003) 905e908.
NPO-40630, 2006.
[34] M. Makowska-Janusik, A. Kassiba, N. Errien, A. Mehdi, J. Inorg. Organomet.
[7] M. Gronauer, J. Fricke, Acta Acustica united Acustica 59 (1986) 177e181.
Polym. Mater. 20 (2010) 761e773.
[8] C.A. Alexa, G.M. Huber, G.J. Lolos, F. Farzanpay, F. Garibaldi, M. Jodice, A. Leone,
[35] E.A. Sujandi, D.-S. Prasetyando, S.-C. Han, S.-E. Lee, Park, Catal. Today 141
R. Perrino, Z. Papandreou, D.L. Humphrey, P. Ulmer, R. DeLeo, Nucl. Instrum.
(2009) 374e377.
Methods Phys. Res. A 365 (1995) 299e307.
[36] P. Bielecki, W. Wasiak, J. Chromatogr. A 1217 (2010) 4648e4654.
[9] A. Venkateswara Rao, G.M. Pajonk, S.D. Bhagat, P. Barboux, J. Non-Crystalline
[37] G. Ye, F. Bai, G. Chen, J. Wei, J. Wang, J. Chen, J. Mater. Chem. 22 (2012)
Solids 350 (2004) 216e223.
20878e20880.
[10] R. Al-Oweini, H. El-Rassy, J. Mol. Struct. 919 (2009) 140e145.
[38] Official J. Eur. Union 348 (2008).
[11] H. Yokogawa, M. Yokoyama, J. Non-Crystalline Solids 186 (1995) 23e29.
[39] N.S. Inchaurrondo, P. Massa, R. Fenoglio, J. Font, P. Haure, Chem. Eng. J.
[12] N.D. Hegde, A.V. Rao, Appl. Surf. Sci. 253 (2006) 1566e1572.
198e199 (2012) 426e434.
[13] M.-L. Liu, D.-A. Yang, Y.-F. Qu, J. Non-Crystalline Solids 354 (2008) 4927e4931.
[40] F. Adam, J.-T. Wong, E.-P. Ng, Chem. Eng. J. 214 (2013) 63e67.
[14] M. Alnaief, S. Antonyuk, C.M. Hentzschel, C.S. Leopold, S. Heinrich, I. Smirnova,
[41] A. Kumar, D. Srinivas, J. Mol. Catal. A Chem. 368e369 (2013) 112e118.
Microporous Mesoporous Mater. 160 (2012) 167e173.
[42] K. Yube, M. Furuta, K. Mae, Catal. Today 125 (2007) 56e63.
[15] M. Alnaief, I. Smirnova, J. Non-Crystalline Solids 356 (2010) 1644e1649.
[43] S. Zhou, Z. Qian, T. Sun, J. Xu, C. Xia, Appl. Clay Sci. 53 (2011) 627e633.
[16] Z. Ulker, C. Erkey, J. Control. Release 177 (2014) 51e63.

pez-Periago, J. Saurina, A. Roig, C. Domingo, [44] G. Halsey, J. Chem. Phys. 16 (1948) 931.
[17] N. Murillo-Cremaes, A.M. Lo
[45] K.S.W. Sing, D.H. Everett, R.A.W. Haul, L. Moscou, R.A. Pierotti, J. Rouque
rol,
J. Supercrit. Fluids 73 (2013) 34e42.
T. Siemieniewska, Pure Appl. Chem. 57 (1985) 603e619.
[18] G. Caputo, M. Scognamiglio, I. De Marco, Chem. Eng. Res. Des. 90 (2012)
[46] E.G. Derouane, J. Catal. 100 (1986) 514e544.
1082e1089.
[47] E.G. Derouane, J.B. Nagy, Chem. Phys. Lett. 137 (1987) 341e344.
[19] N.N. Linneen, R. Pfeffer, Y.S. Lin, Chem. Eng. J. 254 (2014) 190e197.
 [48] E.G. Derouane, J.-M. Andre, A.A. Lucas, J. Catal. 110 (1988) 58e73.
[20] S. Standeker, Z. Novak, Z. Knez, J. Colloid Interface Sci. 310 (2007) 362e368.
 [49] S. Valange, R. Palacio, A. Charmot, J. Barrault, A. Louati, Z. Gabelica, J. Mol.
[21] S. Standeker, A. Veronovski, Z. Novak, Z. Knez, Desalination 269 (2011)
Catal. A Chem. 305 (2009) 24e33.
223e230.
[50] F. Bosc, D. Edwards, N. Keller, V. Keller, A. Ayral, Thin Solid Films 495 (2006)
[22] G. Qin, Y. Yao, W. Wei, T. Zhang, Appl. Surf. Sci. 280 (2013) 806e811.
272e279.
[23] S. Gao, Y. Wang, T. Wang, G. Luo, Y. Dai, Bioresour. Technol. 100 (2009)
[51] Y. Rao, J. Kang, M. Trudeau, D.M. Antonelli, J. Catal. 266 (2009) 1e8.
996e999.
[52] T. Komatsu, T. Kishi, T. Gorai, J. Catal. 259 (2008) 174e182.
[24] Z. Novak, M. Habulin, V. Krmelj, Z. Knez, J. Supercrit. Fluids 27 (2003)
[53] H. Zhang, Y.M. Wang, L. Zhang, G. Gerritsen, H.C.L. Abbenhuis, R.A. van Santen,
169e178.

spa
r, A. Nagy, I. La

za

r, J. Chromatogr. A 1218 (2011) 1011e1015. C. Li, J. Catal. 256 (2008) 226e236.
[25] A. Ga
[54] J. Poerschmann, U. Trommler, J. Chromatogr. A 1216 (2009) 5570e5579.
[26] I. L
aza
r, H.F. Bereczki, S. Mano
, L. Daro

czi, G. De

ak, I. F

abi

tony,
an, Z. Cserna

za
[55] I. La
r, J. Kalma
r, A. Peter, A. Szila
gyi, E. Gyo
} ri, T. Ditro

i, I. F

abi

an, Appl. Surf.
Polym. Compos. 36 (2015) 348e358.
Sci. 356 (2015) 521e531.
[27] J.K. Floess, R. Field, S. Rouanet, J. Non-Crystalline Solids 285 (2001) 101e108.