See

discussions, stats, and author profiles for this publication at: https://www.researchgate.net/publication/231377202

One-Pot Synthesis of Ethanolamine-Modified

Mesoporous Silica

Article in Industrial & Engineering Chemistry Research · July 2011

DOI: 10.1021/ie200374r

CITATIONS READS

18 136

5 authors, including:

Pezhman Zarabadi-Poor Alireza Badiei

13 PUBLICATIONS 178 CITATIONS University of Tehran
348 PUBLICATIONS 2,964 CITATIONS
SEE PROFILE

SEE PROFILE

B. D. Fahlman Ghodsi Mohammadi Ziarani

Central Michigan University Alzahra University
82 PUBLICATIONS 776 CITATIONS 279 PUBLICATIONS 1,509 CITATIONS

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Synthesis of bioactive compounds View project

Organic synthesis View project

All content following this page was uploaded by Pezhman Zarabadi-Poor on 10 March 2014.

The user has requested enhancement of the downloaded file.

 ARTICLE

pubs.acs.org/IECR

One-Pot Synthesis of Ethanolamine-Modified Mesoporous Silica

Pezhman Zarabadi-Poor,† Alireza Badiei,*,† Bradley D. Fahlman,‡ Pezhman Arab,† and
Ghodsi Mohammadi Ziarani§
†
School of Chemistry, College of Science, University of Tehran, Tehran, Iran
‡
Department of Chemistry, Central Michigan University, Mount Pleasant, Michigan 48859, United States
§
Department of Chemistry, Faculty of Science, Alzahra University, Tehran, Iran

ABSTRACT: This work represents the first precedent for the one-pot synthesis of ethanolamine-modified mesoporous silica. The
resultant material was characterized by scanning electron microscopy, transmission electron microscopy, infrared spectroscopy, X-ray
diffraction, and BET/BJH surface area/porosity measurements. The successful incorporation of ethanolamine moieties in the structure of
mesoporous silica was confirmed by its subsequent reaction with phenyl isocyanate. The observed morphology of this surface-
functionalized mesoporous silica is significantly different from that of postmodified SBA-15 and also features a greater porosity.

1. INTRODUCTION 2. EXPERIMENTAL SECTION

After the remarkable work of Mobil scientists in discovering
highly ordered mesoporous silicates (M41S), many kinds of meso-
porous materials have been synthesized using the surfactant templat-
ing method.1,2 One of the most studied mesoporous materials is SBA-
15, which was synthesized by Zhao and co-workers using a nonionic
surfactant under acidic conditions.3,4 The large thick-walled pores of
SBA-15 have been found to be suitable for surface modification to
expand the applications for catalysis,5 7 enzyme immobilization,8 10
solid phase microextraction,11,12 and drug delivery.13 15
Typically, two different approaches, namely, grafting (or post-
modification)16,17 and co-condensation (or direct synthesis),18 20
are used for surface modification of mesoporous materials through
the formation of covalent bonds. In the former, the condensation
between free and geminal silanol groups of surface and alkoxy silanes
is used to attach organosilane moieties to the surface of mesoporous
silica.16,17 However, this technique suffers from problems such as
pore blocking,21 limited capacity for functionalization, and multi-
step/time-consuming procedures. To circumvent these problems,
direct synthetic methods have been developed in which the organic
groups are directly incorporated into the mesoporous structure.
These reactions consist of a single-step co-condensation between a
silica source and an organosilane precursor in the presence of a
structure-directing agent. This technique results in higher concen-
trations of functional groups and a more homogeneous surface
coverage.22
Up to now, many organic functional groups, such as
amine,16,17,23 25 carboxylic acid,26 sulfonic acid,27,28 thiol,29 31
vinyl,32 34 and phenyl,33,35,36 have been introduced into the
structure of mesoporous silicas. Recently, we reported the introduc-
tion of a novel functional group, ethanolamine (EA), into the
structure of SBA-15 through a postsynthesis approach.11,12 Inter-
estingly, this modified material has shown promise for many
applications, including use as a nanofiber for solid-phase microex-
traction (SPM).11,12 Herein, we report the synthesis of EA-modified
mesoporous silica (EAMS) through a co-condensation method to
investigate the effects of an alternative synthetic procedure on the
resultant material properties.
2.1. Materials. Tetraethylorthosilicate (TEOS, Merck) as a silica
source, poly(ethylene glycol)-block-poly(propylene glycol)-block-
poly(ethylene glycol) (P123, Aldrich) as a structure-directing agent,
3-[bis(2-hydroxyethyl)amino]propyltriethoxysilane (HPTES, Fluka,
65% in ethanol) as an ethanolamine source, concentrated hydro-
chloric acid (Merck), and ethanol (Merck) were used as received
from suppliers.
2.2. Syntheses. 2.2.1. Synthesis of EAMS (I). A structure-
directing agent (Pluronic P123) was dissolved in a 2 M HCl(aq)
solution at 35 °C. A TEOS/HPTES mixture was added dropwise to
the reaction mixture to reach a final molar composition of TEOS/
HPTES/P123/H2O/HCl = 1:0.07:0.018:113:6.6. The mixture was
stirred for 24 h and then was transferred to a Teflon-lined autoclave.
The sealed autoclave was then heated at 100 °C for 2 days. The
white solid was filtered off and washed with deionized water. The
template was removed by Soxhlet extractor with ethanol for 24 h,
and then the resultant solid (Scheme 1) was dried overnight under
ambient conditions.
2.2.2. Synthesis of EAMS CONHPh (II). EAMS (I), phenyl
isocyanate (1:2 molar ratio), and dry dichloromethane were placed
in a 100 mL round-bottom flask. Then, the reaction mixture was
stirred for 2 h under an inert atmosphere at ambient temperature.
The obtained sample (EAMS CONHPh, II, Scheme 2)) was
filtered, carefully washed, and dried in vacuum.
2.3. Characterization. FTIR spectra of the samples were
recorded on an EQINOX 50 Bruker instrument. Samples were placed
between NaCl disks. N2 adsorption desorption measurements
were performed on a BELSORP-miniII instrument at 196 °C,
with samples degassed at 100 °C before measurements. Struc-
tural parameters (specific surface area, pore volume, pore dia-
meter, and pore size distribution) were calculated using the
Received: February 23, 2011
Accepted: July 29, 2011
Revised: July 29, 2011
Published: July 29, 2011

r 2011 American Chemical Society 10036 dx.doi.org/10.1021/ie200374r | Ind. Eng. Chem. Res. 2011, 50, 10036–10040
Industrial & Engineering Chemistry Research
Scheme 1. Schematic Representation of EAMS (I)
Scheme 2. Schematic Representation of EAMS CONHPh (II)
Brunauer Emmett Teller (BET) and Barrett Joyner Halenda
(BJH) methods using BELSORP-miniII analysis software. The
X-ray diffraction pattern was obtained using a Philips X’PERT
diffractometer with a Cu KR radiation source. Transmission
electron microscopy (TEM) was performed on a Technai G5
instrument at an acceleration voltage of 300 kV. For TEM,
samples were dispersed in ethanol using an ultrasonic bath, and a
drop of the ethanol mixture was placed on a lacey carbon-coated
copper grid for analysis. The morphology of the materials was
investigated with a LEO 1455VP scanning electron microscope
(SEM). Thermogravimetric analysis (TGA) was carried out in a
Perkin-Elmer Pyris Diamond instrument from ambient tempera-
ture to 1000 °C, using a ramp rate of 10 °C/min. Elemental
analyses were performed on a PerkinElmer 2400 series II
CHNS/O elemental analyzer to obtain the C/N ratios of the
synthesized materials.
3. RESULTS AND DISCUSSION
Infrared spectroscopy should be a suitable technique to
ascertain the successful incorporation of HPTES molecules into
the mesoporous silica substrate. However, the product contains
both Si OH and CH2OH groups, which would not allow the
unambiguous determination of reaction success. Hence, we used
a urea formation reaction to unequivocally demonstrate that
CH2OH groups were present in the product and they did not
change during synthesis under acidic conditions.
Accordingly, Figure 1 shows the FTIR spectra for both EAMS
and EAMS CONHPh. Because the EAMS was dried before
reaction with PhNCO, the characteristic water deformation band
at 1640 cm 1 due to physisorbed water has diminished. Addi-
tionally, both materials exhibit ν(Si O) vibration bands at
1100, 960, and 800 cm 1 and weak ν(C H) bands at 2990/
2935 cm 1. However, most diagnostic to confirm the successful
conversion of terminal CH2OH moieties to the urea adduct is
10037
ARTICLE
Figure 1. FTIR spectra of (a) EAMS (I) and (b) EAMS CONHPh (II).
the presence of ν(CdO) for an ester carbonyl group at
1725 cm 1 and ν(CdC) for an aromatic ring at 1440 cm 1.
The nitrogen adsorption desorption isotherms of compound
I are shown in Figure 2. The adsorption desorption isotherms
of SBA-15 and HPTES SBA-1511 are also included to provide
better insight. As can be seen, these isotherms are similar to type IV
standard isotherms, which indicate the presence of mesoporosity in
the sample. The isotherms of compound I and the two other
compounds can be distinguished by the type of hysteresis loop.
SBA-15 and HPTES SBA-15 exhibit H1 hysteresis loops, which is
in consistent with cylindrical pores. In contrast, the observed H3
hysteresis loop in EAMS is related to the presence of a phase mixture
in the product.37 The BJH pore size distribution (Figure 2, inset)
does not show a completely narrow pore size distribution. This
might be a result of the presence of a varying pore/channel system in
the sample, which is consistent with the H3 hysteresis loop.
Structural parameters such as specific surface area, pore
diameter, and pore volume were calculated based on the isotherms
and are reported in Table 1. It is observed that the specific surface
area of EAMS is lower than those of SBA-15 and HPTES SBA-15.
On the other hand, the total pore volume and pore diameter are
higher, which can be considered an advantageous feature of the co-
condensation method.
Figure 3 shows the low-angle XRD pattern of EAMS. Gen-
erally, the SBA-15-type material has three diffraction peaks that
can be indexed as (100), (110), and (200) according to a two-
dimensional hexagonal lattice. A single intense reflection at 2θ ≈
0.8° can be assigned as the (100) peak, whereas two other low-
intensity peaks are also observed at 2θ ≈ 1.7° and 1.9°.29,30 The
other peaks can be observed in this pattern might indicate the
presence of another phase in the EAMS, which is consistent with
the observed N2 adsorption desorption analysis.
Figures 4 and 5 show SEM and TEM images, respectively, of
EAMS. As depicted in Figure 4, the functionalized EAMS material
exhibits a significantly different morphology than SBA-15. In
particular, whereas SBA-15 exhibits a fibrous morphology, EAMS
is observed to present a bulky morphology with a deformed struc-
ture. (Figure 5). This reveals that the addition of HPTES to the
synthesis procedure also significantly altered the morphology of the
product, as well as its composition.
TG and elemental analyses were carried out for further
confirmation of the successful incorporation of ethanolamine
moieties into the mesoporous silica substrate. According to the
TGA curve of EAMS (Figure 6), there is a major weight loss
dx.doi.org/10.1021/ie200374r |Ind. Eng. Chem. Res. 2011, 50, 10036–10040
Industrial & Engineering Chemistry Research ARTICLE

Figure 2. Nitrogen adsorption desorption isotherms of EAMS, as compared to SBA-15. Inset: Corresponding BJH pore size distribution of EAMS.

Table 1. Structural Parametersa Obtained Using the BET and

BJH Methods Based on Sorption Isotherms

DBJH (nm)

SBET (m2/g) adsorption desorption Vtotal (cm3/g)

EAMS 480 9.22 8.06 1.55

SBA-1511 790 8.06 7.06 1.28
HPTES SBA-1511 520 8.06 7.02 0.91
a
DBJH, pore diameter obtained using the BJH method; SBET, specific
surface area obtained using the BET method; Vtotal, total pore volume using
the BET method; all based on adsorption and desorption isotherms.

(12.7%) between 100 and 600 °C corresponding to the elimina-

tion of organic moieties. The removal of physically adsorbed
water and other volatiles occurs below 100 °C. Based on the
molecular weight of EA, the observed mass loss corresponds to 0.87
mmol of HPTES per gram of mesoporous silica. It should be noted
that the dehydroxylation of silanolate groups results in a minor
decrease of the weight above 600 °C, which also makes a small
contribution to the major weight loss.16,17 The C and N contents
Figure 3. Low-angle X-ray diffraction pattern of EAMS.
were obtained by elemental analyses performed on EAMS and
EAMS CONHPh. The corresponding results are given in Table 2.
It should be mentioned that, for both materials, theoretical values
were calculated by considering the organic part of the molecules
attached to the materials to have an acceptable comparison.
The experimental C/N ratios are equal to about 6.7 for
both materials, which are consistent with the calculated results
(C/N = 6). Considering the masses of the samples and the
obtained ratios, the amount of HPTES molecules can be estimated
as around 1 mmol per gram of mesoporous silica, which is in approx-
imate agreement with the value obtained by TGA and can be useful
for removing possible ambiguities. This agreement between the Figure 4. SEM images of (a) SBA-15 and (b) EAMS.

10038 dx.doi.org/10.1021/ie200374r |Ind. Eng. Chem. Res. 2011, 50, 10036–10040

Industrial & Engineering Chemistry Research
Figure 5. TEM micrograph of EAMS (scale bar = 5 nm).
Figure 6. TGA curve of EAMS. Inset: Schematic representation of EAMS.
Table 2. C, N, and C/N Values (in Weight Percentages) in
EAMS and EAMS CONHPh Obtained by Elemental Analysis
C (wt %) N (wt %) (C/N)experimental (C/N)theoreticala
EAMS 5.38 0.80 6.7
EAMS CONHPh 5.45 0.81 6.7
a
Theoretical values were calculated considering the organic parts of the
materials, which are schematically shown for EAMS in Figure 6.
experimental and calculated amounts reveals that the reaction
between EAMS and phenyl isocyanate proceeded almost to com-
pletion. This means that the ethanolamine groups successfully
attached to the surface. Therefore, it can be proposed that the
ethanaolamine groups were accessible and that the phenyl isocya-
nate molecules reacted with them and not with silanol groups.
4. CONCLUSIONS
In conclusion, ethanolamine-modified mesoporous silica has
been successfully synthesized for the first time using a one-pot,
ARTICLE
co-condensation synthetic pathway. The investigation of the
effects of various synthetic parameters on the properties of the
resultant oxide material, and applications for solid-phase micro-
extraction and drug delivery will be the subjects of future reports.
’ AUTHOR INFORMATION
Corresponding Author
*E-mail: abadiei@khayam.ut.ac.ir.
’ ACKNOWLEDGMENT
The authors thank the University of Tehran Research Council
for support of this work. B.D.F. also thanks the National Science
Foundation (CHE0911061) for their support of thin-film and
hafnium precursor synthetic efforts at Central Michigan University.
’ REFERENCES
(1) Beck, J. S.; Vartuli, J. C.; Roth, W. J.; Leonowicz, M. E.; Kresge,
C. T.; Schmitt, K. D.; Chu, C. T. W.; Olson, D. H.; Sheppard, E. W. A
New Family of Mesoporous Molecular Sieves Prepared with Liquid
Crystal Templates. J. Am. Chem. Soc. 1992, 114, 10834.
(2) Kresge, C. T.; Leonowicz, M. E.; Roth, W. J.; Vartuli, J. C.; Beck,
J. S. Ordered Mesoporous Molecular Sieves Synthesized by a Liquid-
Crystal Template Mechanism. Nature 1992, 359, 710.
(3) Zhao, D.; Feng, J.; Huo, Q.; Melosh, N.; Fredrickson, G. H.;
Chmelka, B. F.; Stucky, G. D. Triblock Copolymer Syntheses of Mesopor-
ous Silica with Periodic 50 to 300 Angstrom Pores. Science 1998, 279, 548.
(4) Zhao, D.; Huo, Q.; Feng, J.; Chmelka, B. F.; Stucky, G. D.
Nonionic Triblock and Star Diblock Copolymer and Oligomeric Surfactant
Syntheses of Highly Ordered, Hydrothermally Stable, Mesoporous Silica
Structures. J. Am. Chem. Soc. 1998, 120, 6024.
(5) Rodriguez, I.; Iborra, S.; Corma, A.; Rey, F.; Jorda, J. L. MCM-41-
Quaternary Organic Tetraalkylammonium Hydroxide Composites as
Strong and Stable Brønsted Base Catalysts. Chem. Commun. 1999, 593.
(6) Wang, X.; Lin, K. S. K.; Chan, J. C. C.; Cheng, S. Direct Synthesis
and Catalytic Applications of Ordered Large Pore Aminopropyl-Function-
alized SBA-15 Mesoporous Materials. J. Phys. Chem. B 2005, 109, 1763.
(7) Li, Y.; Feng, Z.; van Santen, R. A.; Hensen, E. J. M.; Li, C. Surface
Functionalization of SBA-15-Ordered Mesoporous Silicas: Oxidation of
Benzene to Phenol by Nitrous Oxide. J. Catal. 2008, 255, 190.
(8) Deere, J.; Magner, E.; Wall, J. G.; Hodnett, B. K. Adsorption and
Activity of Cytochrome c on Mesoporous Silicates. Chem. Commun.
2001, 465.
(9) Lei, C.; Shin, Y.; Liu, J.; Ackerman, E. J. Entrapping Enzyme in a
Functionalized Nanoporous Support. J. Am. Chem. Soc. 2002, 124, 11242.
(10) Fan, J.; Lei, J.; Wang, L.; Yu, C.; Tu, B.; Zhao, D. Rapid and
High-Capacity Immobilization of Enzymes Based on Mesoporous
6.0 Silicas with Controlled Morphologies. Chem. Commun. 2003, 2140.
6.0 (11) Hashemi, P.; Shamizadeh, M.; Badiei, A.; Zarabadi-Poor, P.;
Ghiasvand, A. R.; Yarahmadi, A. Amino Ethyl-Functionalized Nanopor-
ous Silica as a Novel Fiber Coating for Solid-Phase Microextraction.
Anal. Chim. Acta 2009, 646, 1.
(12) Hashemi, P.; Shamizadeh, M.; Badiei, A.; Ghiasvand, A.; Azizi,
K. Study of the Essential Oil Composition of Cumin Seeds by an Amino
Ethyl-Functionalized Nanoporous SPME Fiber. Chromatographia 2009,
70, 1147.
(13) Doadrio, A. L.; Sousa, E. M. B.; Doadrio, J. C.; Perez Pariente, J.;
Izquierdo-Barba, I.; Vallet-RegI, M. Mesoporous SBA-15 HPLC Evalua-
tion for Controlled Gentamicin Drug Delivery. J. Controlled Release
2004, 97, 125.
(14) Xue, J. M.; Shi, M. PLGA/Mesoporous Silica Hybrid Structure
for Controlled Drug Release. J. Controlled Release 2004, 98, 209.
(15) Badiei, A.; Haririan, I.; Jahangir, A.; Mohammadi Ziarani, G.
Incorporation of Ibuprofen into SBA-15; Drug Loading and Releasing
Properties. Dyn. Biochem. Process Biotechnol. Mol. Biol. 2009, 3, 48.
10039 dx.doi.org/10.1021/ie200374r |Ind. Eng. Chem. Res. 2011, 50, 10036–10040
 Industrial & Engineering Chemistry Research ARTICLE

(16) Zhao, X. S.; Lu, G. Q. Modification of MCM-41 by Surface (36) Wang, X.-M.; Du, X.-Z.; Li, C.-l.; Cao, X. Direct Synthesis and
Silylation with Trimethylchlorosilane and Adsorption Study. J. Phys. Characterization of Phenyl-Functionalized SBA-15. Appl. Surf. Sci. 2008,
Chem. B 1998, 102, 1556. 254, 3753.
(17) Maria Chong, A. S.; Zhao, X. S. Functionalization of SBA-15 (37) Sindorf, D. W.; Maciel, G. E. Silicon-29 CP/MAS NMR Studies
with APTES and Characterization of Functionalized Materials. J. Phys. of Methylchlorosilane Reactions on Silica Gel. J. Am. Chem. Soc. 1981,
Chem. B 2003, 107, 12650. 103, 4263.
(18) Burkett, S. L.; Sims, S. D.; Mann, S. Synthesis of Hybrid
Inorganic Organic Mesoporous Silica by Co-Condensation of Siloxane
and Organosiloxane Precursors. Chem. Commun. 1996, 1367.
(19) Macquarrie, D. J. Direct Preparation of Organically Modified
MCM-type Materials. Preparation and Characterisation of Aminopropyl-
MCM and 2-Cyanoethyl-MCM. Chem. Commun. 1996, 1961.
(20) Badiei, A.; Goldooz, H.; Ziarani, G. M.; Abbasi, A. One Pot
Synthesis of Functionalized SBA-15 by using an 8-Hydroxyquinoline-5-
sulfonamide-Modified Organosilane as Precursor. J. Colloid Interface Sci.
2011, 357, 63.
(21) Yoshitake, H. Highly-Controlled Synthesis of Organic Layers
on Mesoporous Silica: Their Structure and Application to Toxic Ion
Adsorptions. New J. Chem. 2005, 29, 1107.
(22) Richer, R. Direct Synthesis of Functionalized Mesoporous
Silica by Non-ionic Alkylpolyethyleneoxide Surfactant Assembly. Chem.
Commun. 1998, 1775.
(23) Huh, S.; Wiench, J. W.; Yoo, J.-C.; Pruski, M.; Lin, V. S. Y.
Organic Functionalization and Morphology Control of Mesoporous
Silicas via a Co-Condensation Synthesis Method. Chem. Mater. 2003,
15, 4247.
(24) Walcarius, A.; Etienne, M.; Lebeau, B. Rate of Access to the
Binding Sites in Organically Modified Silicates. 2. Ordered Mesoporous
Silicas Grafted with Amine or Thiol Groups. Chem. Mater. 2003, 15, 2161.
(25) Varela Guerrero, V.; Shantz, D. F. Amine-Functionalized Ordered
Mesoporous Silica Transesterification Catalysts. Ind. Eng. Chem. Res. 2009,
48, 10375.
(26) Fiorilli, S.; Camarota, B.; Perrachon, D.; Concetta Bruzzoniti,
M.; Garrone, E.; Onida, B. Direct Synthesis of Large-Pore Ethane-
Bridged Mesoporous Organosilica Functionalized with Carboxylic
Groups. Chem. Commun. 2009, 4402.
(27) Melero, J. A.; Stucky, G. D.; van Grieken, R.; Morales, G. Direct
Syntheses of Ordered SBA-15 Mesoporous Materials Containing Are-
nesulfonic Acid Groups. J. Mater. Chem. 2002, 12, 1664.
(28) Shen, J. G. C.; Herman, R. G.; Klier, K. Sulfonic Acid-
Functionalized Mesoporous Silica: Synthesis, Characterization, and
Catalytic Reaction of Alcohol Coupling to Ethers. J. Phys. Chem. B
2002, 106, 9975.
(29) Beaudet, L.; Hossain, K.-Z.; Mercier, L. Direct Synthesis of
Hybrid Organic Inorganic Nanoporous Silica Microspheres. 1. Effect
of Temperature and Organosilane Loading on the Nano- and Micro-
Structure of Mercaptopropyl-Functionalized MSU Silica. Chem. Mater.
2002, 15, 327.
(30) Wei, Q.; Nie, Z.; Hao, Y.; Chen, Z.; Zou, J.; Wang, W. Direct
Synthesis of Thiol-Ligands-Functionalized SBA-15: Effect of 3-Mercap-
topropyltrimethoxysilane Concentration on Pore Structure. Mater. Lett.
2005, 59, 3611.
(31) Miyake, Y.; Yosuke, M.; Azechi, E.; Araki, S.; Tanaka, S.
Preparation and Adsorption Properties of Thiol-Functionalized Meso-
porous Silica Microspheres. Ind. Eng. Chem. Res. 2008, 48, 938.
(32) Babonneau, F.; Leite, L.; Fontlupt, S. Structural Characteriza-
tion of Organically-Modified Porous Silicates Synthesized Using CTA+
Surfactant and Acidic Conditions. J. Mater. Chem. 1999, 9, 175.
(33) Burleigh, M. C.; Markowitz, M. A.; Spector, M. S.; Gaber, B. P.
Direct Synthesis of Periodic Mesoporous Organosilicas: Functional
Incorporation by Co-Condensation with Organosilanes. J. Phys. Chem.
B 2001, 105, 9935.
(34) Kao, H.-M.; Wu, J.-D.; Cheng, C.-C.; Chiang, A. S. T. Direct
Synthesis of Vinyl-Functionalized Cubic Mesoporous Silica SBA-1.
Microporous Mesoporous Mater. 2006, 88, 319.
(35) Bambrough, C. M.; Slade, R. C. T.; Williams, R. T. Synthesis of
a Large Pore Phenyl-Modified Mesoporous Silica and Its Characterization
by Nitrogen and Benzene Sorption. J. Mater. Chem. 1998, 8, 569.

10040 dx.doi.org/10.1021/ie200374r |Ind. Eng. Chem. Res. 2011, 50, 10036–10040

View publication stats