Langmuir 2003, 19, 3019-3024

3019

Selective Adsorbents from Ordered Mesoporous Silica

Ka Yee Ho, Gordon McKay, and King Lun Yeung*
Department of Chemical Engineering, The Hong Kong University of Science and Technology,
Clear Water Bay, Kowloon, Hong Kong, SAR-P.R. China
Received October 17, 2002. In Final Form: January 6, 2003
Ordered mesoporous silica adsorbents were prepared by grafting amino- and carboxylic-containing
functional groups onto MCM-41 for the removal of Acid blue 25 and Methylene blue dyes from wastewater.
The amino-containing OMS-NH2 adsorbent has a large adsorption capacity and a strong affinity for the
Acid blue 25. It can selectively remove Acid blue 25 from a mixture of dyes (i.e., Acid blue 25 and Methylene
blue). The OMS-COOH is a good adsorbent for Methylene blue displaying excellent adsorption capacity
and selectivity for the dye. The better selectivity of the OMS-based adsorbents means longer operating
life and less maintenance. Furthermore, these adsorbents can be regenerated by simple washing with
alkaline or acid solution to recover both the adsorbents and the adsorbed dyes.

1. Introduction
The ordered mesoporous materials (e.g., M41S, FSM,
HMS, and SBA) belong to an important class of molecular
sieve materials. Their large surface area, ordered pore
structure, and nanometer-sized pores offer a unique
environment for chemical separations1 and reactions.2-4
The concept of supramolecular templating has enabled
the design of mesoporous silica with adjustable pore sizes
and structures.5,6 Chemical modifications of the pore with
metals,7,8 metal oxides,9,10 and organic moieties1,11,12 are
successful in tailoring the physical, chemical, and catalytic
properties of these materials. The two main obstacles for
the widespread industrial application of OMS are its cost
and stability. In the manufacture of the ordered mesoporous silica, the surfactant template accounts for more
than 80% of the cost. Nondestructive methods for the
removal and recovery of the surfactants and the use of
cheaper polymer substitutes have substantially cut the
cost of the OMS.13-15 Better thermal and hydrothermal
stability were obtained by postsynthesis treatment of the
OMS with organic solvent containing metal alkoxides,16
salt solution,17 and organosilanes.18
The bulk of the adsorption and transport studies on
MCM-41 were conducted for gases19-22 with very few works
* To whom correspondence should be addressed. Tel: 8522358-7123; Fax: 852-2358-0054; E-mail: kekyeung@ust.hk.
(1) Thomas, J. M. Nature 1994, 368, 289.
(2) Corma, A.; Navarro, M. T.; Pariente, J. P. J. Chem. Soc., Chem.
Commun. 1994, 147.
(3) Shinoda, T.; Izumi, Y.; Onaka, M. J. Chem. Soc., Chem. Commun.
1995, 1801.
(4) Kloetstra, K. R.; Vandenbroek, J.; van Bekkum, H. Catal. Lett.
1997, 47, 235.
(5) Vartuli, J. C.; Schmitt, K. D.; Kresge, C. T.; Roth, W. J.; Leonowicz,
M. E.; McCullen, S. B.; Hellring, S. D.; Beck, J. S.; Schlenker, J. L.;
Olson, D. H.; Sheppard, E. W. Chem. Mater. 1994, 6, 2317.
(6) Biz, S.; Occelli, M. L. Catal. Rev.sSci. Eng. 1998, 40, 329.
(7) Okumura, M.; Tsubota, S.; Iwamoto, M.; Haruta, M. Chem. Lett.
1998, 315.
(8) Long R. Q.; Yang, R. T. Catal. Lett. 1998, 52, 9.
(9) Mulukutla, R. S.; Asakura, K.; Namba, S.; Iwasawa, Y. J. Chem.
Soc., Chem. Commun. 1998, 14, 1425.
(10) Grubert, G.; Rathousky, J.; Schulzekloff, G.; Wark, M.; Zukal,
A. Microporous Mesoporous Mater. 1998, 22, 225.
(11) Van Rhijn, W.; De Vos, D.; Bossaert, W.; Bullen, J.; Woulters,
B.; Grobet, P.; Jacob, P. Stud. Surf. Sci. Catal. 1998, 117, 183.
(12) Koyano, K. A.; Tatsumi, T.; Tanaka, Y.; Nakata, S. J. Phys.
Chem. B 1997, 101, 9436.
(13) Kawi, S.; Lai, M. W. CHEMTECH 1998, 28, 26.
(14) Chen, C. Y.; Li, H. A.; Davis, M. E. Microporous Mater. 1993,
2, 17.
(15) Whitehurst, D. D. U.S. Patent 5,143,879, 1992.

dealing with the liquid-phase system.23-25 However, the

most promising applications of these materials are for
liquid-phase separations and reactions. OMS materials
can play a vital role in the green production of high
value fine chemicals and pharmaceuticals.26 The OMS
has been used as either substitute catalyst or support
matrix for homogeneous catalyst, therefore significantly
reducing the needs for these hazardous materials in fine
chemical production.27 Two other applications involving
liquid-phase systems demonstrate the potential of OMS
technology in separation and pollution problems. It also
emphasizes the importance of the adsorption and diffusion
processes in the performance of the OMS. Recent work by
Hata and co-workers28 has reported that Taxol can be
efficiently recovered from the extraction solvent by using
OMS with tailored pore structure. The anticancer drug
Taxol was obtained at a high purity. Feng et al.23 have
shown that mercapto-functionalized OMS are effective
adsorbents for the removal of mercury and other heavy
metals from water. Simply changing the pH of the washing
solution allows the total regeneration of the modified
mesoporous silica adsorbent and full recovery of the
adsorbed metals.
Although further cost reduction is needed for the
economical application of OMS material to general
environmental problems, there are many specific cases
where OMS technology is urgently needed. These include
(16) McCullen S. B.; Vartuli, J. C. U.S. Patent 5,156,829, 1992.
(17) Ryoo, R.; Jun, S. J. Phys. Chem. B 1997, 101, 317.
(18) Tatsumi, T.; Koyano, K. A.; Tanaka, Y.; Nakata, S. Stud. Surf.
Sci. Catal. 1998, 117, 143.
(19) Rathousky, J.; Zukai, A.; Franke, O.; Schulz-Ekloff, G. Faraday
Trans. 1995, 91, 937.
(20) Llewellyn, P. C.; Schuth, F.; Grillet, Y.; Rouqoerol, F.; Rouquerol,
J.; Unger, K. K. Langmuir 1995, 11, 574.
(21) Branton, P. J.; Hall, P. G.; Sing, K. S. W.; Reichert, H.; Schuth,
F.; Unger, K. K. Faraday Trans. 1994, 90, 2965.
(22) Branton, P. J.; Hall, P. G.; Treguer, M.; Sing, K. S. W. Faraday
Trans. 1995, 91, 2041.
(23) Feng, X.; Fryxell, G. E.; Wang, L. Q.; Kim, A. Y.; Liu, J.; Kemner,
K. M. Science 1997, 276, 923.
(24) Derylo-Marczewska, A.; Goworek, J.; Borowka, A.; Kusak, R.
Proceedings of the Second Pacific Basin Conference on Adsorption Science
and Technology; Brisbane, Australia, 2000.
(25) Nooney, R. I.; Kalyanaraman, M.; Kennedy, G.; Maginn, E. J.
Langmuir 2001, 17, 528.
(26) Biz, S.; Occelli, M. L. Catal. Rev.sSci. Eng. 1998, 40, 329.
(27) Zhao, X. S.; Lu, G. Q.; Millar, G. J. Ind. Eng. Chem. Res. 1996,
35, 2087.
(28) Hata, H.; Saeki, S.; Kimura, T.; Sugahara, Y.; Kuroda, K. Chem.
Mater. 1999, 11, 1100.

10.1021/la0267084 CCC: $25.00 2003 American Chemical Society

Published on Web 02/14/2003

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Ho et al.

ultrapure water purification and reuse in semiconductor

industry, treatment of pharmaceutical wastewater discharge, and recovery of toxic homogeneous catalysts used
in fine chemical production. In most industrial wastewaters, the removal of one or two problematic pollutants
from the effluent can mean a significant saving in the
treatment cost. In some instances, their removal permits
the discharge of the rest of the effluent for municipal
treatment. Dyes used in the textile industry are one such
example. This work investigates the possibility of designing selective adsorbents for the Acid blue 25 and Methylene
blue dyes using ordered mesoporous silica.
2. Experimental Section
2.1 Synthesis and Characterization of Mesoporous
Silica. Mesoporous MCM-41 has been successfully prepared
using different synthesis procedures and conditions.27 For this
study, the MCM-41 powder was crystallized from an alkaline
solution containing tetraethyl orthosilicate (TEOS, 98%, Aldrich),
cetyltrimethylammonium bromide (CTABr, 99.3%, Aldrich),
ammonium hydroxide (NH4OH, 28-30%, Fisher Scientific), and
deionized water in the mole ratio of 6.45 TEOS: 1 CTABr: 292
NH4OH: 2773 H2O. After 16 h of crystallization at room
temperature, the MCM-41 powder was filtered, washed, and dried
before it was calcined in a furnace at 823 K for 24 h to remove
the organic template. Different chemical moieties could be grafted
onto the surface of MCM-41 to alter its surface properties.29-32
Amino- and carboxylic-containing mesoporous silicas were
selected as candidate adsorbents and were prepared using the
following procedures. OMS-NH2 was obtained when 2.5 g of
calcined MCM-41 was refluxed in 250 mL of dry toluene solution
containing 0.1 mole of 3-aminopropyltrimethoxysilane (97%,
Aldrich) at 383 K for 18 h. After cooling to room temperature,
the powder was collected by centrifugation at 10 000 rpm for 5
min with repeated washing using dry toluene. The preparation
of OMS-COOH involves two steps. A CN-containing organic
was first grafted onto the MCM-41 by reflux of 2.5 g powder in
250 mL of dry toluene containing 0.1 mole of 3-(triethoxysilyl)propionitrile (98%, Aldrich) at 381 K for 18 h under nitrogen
atmosphere. After recovery by centrifugation, the powder was
dried at 373 K for 24 h to obtain CN-MCM-41. The cyanide
group was then hydrolyzed to carboxylic acid by reflux with 50%
sulfuric acid (95-97%, BDH) at 408 K for 3 h. The sample was
then collected, washed, and dried to obtain OMS-COOH powder.
The powder morphology and crystal structure of the mesoporous materials were characterized by electron microscopy and
X-ray diffraction. For analysis by transmission electron microscopy (TEM, JEOL JEM-2010), the powder sample was suspended
in methanol and transferred onto a carbon-coated (10 nm) copper
grid. The sample was allowed to dry at room temperature before
TEM imaging. The particle size was confirmed by scanning
electron microscopy (JEOL JSM-6300). The phase structure and
pore size of the mesoporous silica were evaluated from the X-ray
diffraction pattern obtained from Philip 1080 X-ray diffractometer
equipped with a CuKR radiation source and a graphite monochromator. The BET surface area of the mesoporous silica was
measured by Coulter SA 3100 nitrogen physi-adsorption apparatus. The surface composition and chemistry of MCM-41 was
investigated by X-ray photoelectron spectroscopy (Physical
Electronics PHI 5600) and Fourier transform infrared spectroscopy (Perkin-Elmer model GX 2000). Thermogravimetric and
differential thermal analyses (TGA/DTA, Setaram 92-18) were
useful methods for fingerprinting and quantifying the types of
organic moieties present on the MCM-41 surface. In these
experiments, the powder sample was placed in a platinum holder
and heated from 298 to 1073 K at a heating rate of 5 K/min in
(29) Macquarrie, Duican J. J. Chem. Soc., Chem. Commun. 1996,
1961.
(30) Butterworth, A. J.; Clark, J. H.; Walton, P. H.; Barlow, S. J.
Chem. Soc., Chem. Commun. 1996, 1859.
(31) Elings, J. A.; Ait-Meddour, R.; Clark, J. H.; Macquarrie, D. J.
J. Chem. Soc., Chem. Commun. 1998, 2707.
(32) Jaroniec, C. P.; Kruk, M.; Jaroniec, M. J. Phys. Chem. B 2001,
105, 5503.

Figure 1. (a) Molecular formula and (b) UV-visible spectra

of Acid blue 25 and Methylene blue dyes.
Table 1. Characteristic Properties of Dye Molecules
dyes
molecular weight (g/mol)
molecular size ()
characteristic wavelength, (nm)

Acid blue 25 Methylene blue

416.39
14
257
602-618

319.85
15
291
622

air. Alpha alumina powder was used as a standard reference

material for DTA.
2.2 Liquid-Phase Adsorption Study. The adsorption properties of ordered mesoporous silicas (i.e., OMS, OMS-NH2, and
OMS-COOH) were investigated for two different organic dyes,
the Acid blue 25 (45%, Aldrich) and Methylene blue (Aldrich).
The molecular structures of the two dyes are shown in Figure
1a and some of their characteristic properties are listed in Table
1. The adsorption isotherms were obtained for 0.1 g of adsorbent
in 100 mL aqueous solution with dye concentrations of 20-1000
mg/L. The solutions were placed in a shaker bath and allowed
to equilibrate at constant temperature of 295 ( 2 K for 12 days.
The dye concentration was measured by UV/visible spectrophotometer (Perkin-Elmer 550S). Instead of using the longer
characteristic wavelengths of the dyes at 600-620 nm where
there is a severe overlap in their signals (Figure 1b), we have
chosen the characteristic wavelengths of 257 nm for Acid blue
25 and 291 nm for Methylene blue for this study. Both signals
display good linear relationship between intensity and dye
concentration. The possible recovery and reuse of adsorbent and
dye were also examined. In these experiments, 0.1 g of spent
adsorbent was washed at different pH (i.e., 10 mL wash solution).
The amount of dye recovered was measured by UV/visible
spectrophotometer and the amount of remaining dye in the
adsorbent was determined by TGA method.
The adsorption capacity and selectivity of OMS for binary dye
mixtures were determined by agitating 0.1 g of adsorbent powder
in 100 mL dye solutions containing mole ratios of Acid blue 25
to Methylene blue of 0:100, 20:80, 40:60, 60:40, 80:20, and 100:0
for 12 days at constant temperature of 295 ( 2 K. The individual
dye concentration in the mixture was calculated using the optical
densities of the dyes at the specified wavelength.

CA ) (kB2d1 - kB1d2)/(kA1kB2 - kA2kB1)

(1)

CB ) (kA1d2 - kA2d1)/(kA1kB2 - kA2kB1)

(2)

Adsorbents from Ordered Mesoporous Silica

Langmuir, Vol. 19, No. 7, 2003 3021

where CA is the concentration of Acid blue 25; CB is the

concentration of Methylene blue; kA1, kA2, kB1, and kB2 are the
calibration constants for the dyes at their characteristic absorption wavelength (i.e., 1 and 2); d1 and d2 are the optical densities
at the two wavelengths 1 and 2.

3. Results and Discussion

3.1 Mesoporous Silica Powders. Mesoporous silica
prepared from alkaline solution has a plate-like morphology as shown in the SEM picture in Figure 2a. The plates
have an average diameter of 0.9 m and a thickness of
about 0.1 m. TEM analysis indicates that the individual
particles have a hexagonal shape (cf. Figure 2a inset).
The mesoporous silica displays the characteristic X-ray
diffraction pattern of MCM-4133 as shown in Figure 2b.
The presence of both (110) and (200) diffraction peaks are
evidence of good crystallinity of the prepared powder. The
DTA plot in Figure 2c shows that the organic template
molecules have been completely removed during the
calcination. The calcined sample has a BET surface area
of 1071 m2/g and a pore volume of 0.3805 cm3/g. The pore
size of the MCM-41 powder can be calculated from the
X-ray diffraction interplanar spacing (Figure 2b) using
the equation,34

Wd ) cd(FVp/(1 + FVp))1/2

(3)

where Wd is the pore size, Vp is the primary mesoporous

volume (0.3805 cm3/g from N2 physisorption), F is the pore
wall density (ca. 2.2 cm3/g for siliceous materials), d is the
XRD(100) interplanar spacing (i.e., 35.36 for the sample),
and c is a constant dependent on the assumed pore
geometry and is equal to 1.155 for hexagonal models. From
the equation, the pore size of the mesoporous silica is 27.57
. Routine chemical analysis of the sample by energydispersive X-ray spectrometer (EDXS) and XPS detected
only silicon and oxygen atoms with carbons from adsorbed
ambient carbon dioxide and hydrocarbons as the main
surface impurities. The FTIR spectrum of the powder
displays the characteristic bands for Si-OH groups at
3674, 948, and 802 cm-1 (Figure 2d).
Amino and carboxylic functional groups were grafted
onto the ordered mesoporous silicas to create adsorbent
materials that have specific affinity for the target pollutants, Acid blue 25 and Methylene blue dyes. The particle
morphology remains unchanged after grafting R-NH2 and
R-COOH functional groups onto the mesoporous silica.
However, a decrease in the (100) peaks signal was
observed after the chemical modification (Figure 2b). The
decrease in the crystallinity is more likely due to the
inherent disorder introduced by the modification process
rather than due to the collapse in the pore structure of the
mesoporous silica. The DTA plots for the mesoporous silica
containing different chemical moieties display distinct
patterns (Figure 2c). The OMS-NH2 has two sharp peaks
at 575 and 602 K and a broad shoulder centered at 816
K, whereas OMS-COOH has a small peak at 593 K and
a large peak located at 725 K. Table 2 shows that the BET
surface areas of OMS-NH2 and OMS-COOH are smaller
than the precursor powder. Both modified mesoporous
silicas have a smaller pore diameter of about 25.5 . The
Fourier transform infrared spectrum of OMS-NH2 shows
that the characteristic peaks at 1590, 3300, and 3435 cm-1
for R-NH2 are partially obscured by adsorbed water, but
the CO stretching band at 1718 cm-1 is clearly evident in
(33) Zhao, X. S.; Lu, G. Q.; Whittaker, A. K.; Millar, G. J.; Zhu, H.
Y. J. Phys. Chem. B 1997, 101, 6525.
(34) Jaroniec, M.; Kruk, M.; Sayari, A. Mesoporous Mol. Sieves 1998,
117, 325.

Figure 2. (a) Scanning electron microscopy picture of MCM41 adsorbent powder (OMS) after air calcination. Figure inset
is a transmission electron microscopy picture of a MCM-41
particle. (b) X-ray diffraction pattern for OMS, OMS-NH2, and
OMS-COOH adsorbents. (c) Differential thermal analysis plots
for OMS, OMS-NH2, and OMS-COOH adsorbents. (d) Fourier
transformed infrared spectra for OMS, OMS-NH2, and OMSCOOH adsorbents.

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Ho et al.

Table 2. Properties of Ordered Mesoporous Silica Adsorbents

sample

BET
surface area (m2/g)

pore sizea (nm)

OMS
OMS-N H2
OMS-C OOH

1071
774
757

2.76
2.57
2.55

concentration of organic surface

functional groupb
(mmol/g)
(groups/nm2)
0
2.226
1.343

maximum adsorption capacity

(mg/g, T ) 295 K)
Acid blue 25
Methylene blue

0
1.7
1.0

15
256
7

54
90
113

The pore size was calculated using eq 3. b The concentration of the surface chemical groups was calculated from the TGA data.
Table 3. Adsorption Capacity of Carbon-Based
Adsorbents for Acid Blue 25 and Methylene Blue Dyes
maximum adsorption
capacity (mg/g)
adsorbent

Acid blue 25

bagasse pitha
pithb
activated petroleum cokec
activated carbon (granular)d

21.7
17.5

Methylene blue

100
80-300

Reference 35. b Reference 36. c Reference 37.

Reference 38.

Table 4. Recovery of Spent Adsorbents

Methylene
Acid blue
blue in
25 in
wash
pH of
wash
a
b
wash solution regeneration (%) solutionc regenerationb (%)
solution (ppm)
OMS-NH2
OMS-COOH
(ppm)
pH 2
pH 4
pH 7
pH 10

Figure 3. Equilibrium adsorption isotherms of (a) Acid blue

25 and (b) Methylene blue dyes on OMS (4), OMS-NH2 (0),
and OMS-COOH (O) from single dye solutions.

the OMS-COOH sample (Figure 2d). The amount of

functional group grafted onto the mesoporous adsorbent
was calculated from the TGA measurements and is listed
in Table 2. The 2.23 mmol/g of RNH2 grafted onto the
OMS-NH2 gave a surface concentration of amino groups
of 1.7 per nm2 compared to 1 carboxylic group per nm2 for
OMS-COOH.
3.2 Adsorption Properties of Mesoporous Silica
Powders. 3.2.1 Single Dye Adsorption. Figure 3a displays the equilibrium adsorption isotherms for Acid blue
25 at 295 K for the OMS, OMS-NH2, and OMS-COOH
adsorbent powders. It is clear from the figure that the
adsorption capacity of OMS-NH2 for Acid blue 25 is
significantly higher than both the unmodified OMS and
OMS-COOH. An adsorption capacity of 250 mg or 0.6
mmol of Acid blue 25 per gram of OMS-NH2 was obtained.
Although the amount of Acid blue 25 adsorbed is less than
the amount of available NH2 sites (i.e., 0.6 vs 2.23 mmol/
g), calculation indicates that at the maximum adsorption
capacity there is a monolayer surface coverage. The
adsorption capacity of OMS-NH2 for the acid dye is also
higher than the reported values for several carbon-based
adsorbents (Table 3).35-38 The initial adsorption rates of
Acid blue 25 (i.e., C0 ) 150 ppm) on OMS, OMS-NH2, and
OMS-COOH are 0.4, 66, and 76 ppm dye/h per gram of
adsorbent, respectively. The large adsorption capacity and
relatively rapid adsorption rate of OMS-NH2 makes it
an attractive adsorbent for the removal of acid dye
(35) McKay, G.; Geundi, M. EL; Nassar, M. M. Trans. I Chem. E
1996, 74, 277.
(36) Chen, B.; Hui, C. W.; Mckay, G. Chem. Eng. J. 2001, 84, 77.
(37) Shawwa, R.; Smith, W.; Sego, C. Water Res. 2001, 35, 745.
(38) Potgieter, J. H. J. Chem. Educ. 1991, 68, 349.

1.82
7.91
13.01
20.87

0.23
1.02
1.67
2.71

25.26
3.11
1.34
1.78

12.14
1.49
0.64
0.85

a Concentration of Acid blue 25 dye in 10 mL of wash solution

used for regenerating OMS-NH2 adsorbent. b Amount of dye
removed from the adsorbent based on TGA measurement. c Concentration of Methylene blue dye in 10 mL of wash solution used
for regenerating OMS-COOH adsorbent.

pollutants from effluents, which is an acknowledged

problem in the textile industry.
Figure 3b shows that Methylene blue dye has good
affinity for the carboxylic acid group grafted onto OMSCOOH. This can be attributed to the weak Lewis base
characteristic of Methylene blue and to the cationicanionic interaction between the dye molecule and the
surface moiety. This adsorbent displays higher adsorption
capacity for the Methylene blue than both OMS-NH2 and
unmodified MCM-41. At the maximum adsorption capacity, about 0.3 mmol/g of Methylene blue were adsorbed on
OMS-COOH. Although the adsorbates occupy less than
a quarter of the available COOH sites, the surface coverage
is close to a monolayer. It has been well established that
the adsorbed Methylene blue on hydroxylated surface (e.g.,
MCM-41) is usually coordinated to four surface hydroxyl
groups.39 It is possible that the Methylene blue molecule
adsorbed on OMS-COOH is also coordinated to four
COOH sites. The initial adsorption rates of Methylene
blue (i.e., C0 ) 150 ppm) on OMS, OMS-NH2, and OMSCOOH are 4, 45, and 210 ppm dye/h per gram of adsorbent,
respectively. It is clear from Figure 3 that the starting
precursor material MCM-41 is a poor adsorbent for both
dyes. Simply grafting select functional groups (e.g., RNH2
and RCOOH) onto MCM-41creates new, high surface area
adsorbents that have selective affinity for Acid blue 25
(i.e., OMS-NH2) and Methylene blue dyes (i.e., OMSCOOH). The adsorbent and dyes could be recovered by
simply washing with alkaline or acid solution. Table 4
lists the concentration of the recovered dye and the
percentage of dyes removed from the adsorbent after a
(39) Kaewprasit, C.; Hequet, E.; Abidi, N.; Gourlot, J. P. J. Cotton
Sci. 1998, 2, 164.

Adsorbents from Ordered Mesoporous Silica

Langmuir, Vol. 19, No. 7, 2003 3023

Table 5. Effect of Repeated Wash on Dye Recovery and

Adsorbent Regeneration
no. of
washing

recovery (%)
of Acid blue 25
from OMS-NH2a

recovery (%)
of Methylene blue
from OMS-COOHb

1
2
3
4
5

2.71
6.17
8.84
11.85
14.99

12.14
24.53
35.59
46.61
57.51

a Recovery from pH 10 wash solution and calculated from

material balance. b Recovery from pH 2 wash solution and calculated from material balance.

single stage washing of the adsorbent using wash solutions

with different pH. Methylene blue dye and MCM-COOH
can be easily recovered and regenerated by acid wash,
whereas Acid blue 25 is more strongly adsorbed on MCMNH2. A single acid wash was able to remove 12% of
adsorbed Methylene blue dyes that were adsorbed on
OMS-COOH. Using a more alkaline solution (pH > 10),
15% recovery of acid blue 25 can be obtained from single
washing, but dissolution of the silica matrix is also more
likely to occur at this pH. Table 5 suggests that repeated
washing is a better alternative and could lead to complete
regeneration of adsorbent. These recovery and regeneration values are better than for typical carbonaceous
adsorbents, which require harsher regeneration conditions
(e.g., steam treatments). After washing, there was no
decrease in the number of functional groups in OMSNH2, but there is a loss of 35% for the OMS-COOH. The
latter is mainly due to the detachment of the chemical
moiety from the pore wall during the acid wash.
3.2.2 Binary Dyes Adsorption. The single dye adsorption
experiments indicate that OMS-NH2 has a higher affinity
for Acid blue 25 than Methylene blue dye. Similarly, OMSCOOH has a higher adsorption capacity for Methylene
blue than Acid blue 25. To test the performance of these
mesoporous silica adsorbents for selective dye removal,
adsorption experiments were conducted using solutions
containing a mixture of Acid blue 25 and Methylene blue
dyes. Figure 4 displays the equilibrium adsorption isotherms for Acid blue 25 and Methylene blue dyes obtained
from these experiments. Figure 4a shows that OMS-NH2
remains the best adsorbent for the Acid blue 25. Its
adsorption performance is comparable to that obtained
from the single dye adsorption experiment (cf. Figure 3a).
On the other hand, the adsorption capacity of the other
two mesoporous silica adsorbents displays significantly
higher values for the mixture compared to the single dye
experiment. This synergistic effect can be more easily
explained if we also take into account the adsorption
properties of the adsorbents for Methylene blue (Figure
4b). The plots show that the adsorption performance of
OMS-NH2 for Methylene blue is enhanced by the presence
of Acid blue dye in the mixture. Although the competitive
adsorption of Acid blue 25 and Methylene blue dyes on
OMS-NH2 could not be ruled out, the adsorption data
suggest that it is more likely that we have a multilayer
adsorption. The strong affinity of the Acid blue 25 dye for
the amino groups on the adsorbent means that the first
monolayer of adsorbed molecules will consist mainly of
Acid blue 25 molecules. This may also explain why the
equilibrium adsorption isotherms for Acid blue 25 are the
same for the single and binary dyes mixtures. The
adsorbed dye molecules will change the chemical characteristics of the adsorbent and being acidic and anionic
in nature, they could further interact with the basic and
cationic Methylene blue dyes in the solution leading to
multilayer adsorption and to the observed enhancement

Figure 4. Equilibrium adsorption isotherms of (a) Acid blue

25 and (b) Methylene blue dyes on OMS (4), OMS-NH2 (0),
and OMS-COOH (O) from binary dye mixtures.

in the adsorption of Methylene blue on OMS-NH2. A

separate experiment was conducted wherein acid blue 25
(C0 ) 2.4 mM) was first adsorbed on OMS-NH2 and the
dye-modified OMS was then used as adsorbent for
Methylene blue (C0 ) 2.4 mM). 0.69 mmol/g (286 mg/g)
of Acid blue 25 was adsorbed on OMS-NH2 and an
additional 0.64 mmol/g (223 mg/g) of Methylene blue was
adsorbed on the dye-modified OMS. This clearly demonstrates that preadsorbed Acid blue 25 on OMS-NH2
changes the chemistry and adsorption properties of the
adsorbent and that Methylene blue can be adsorbed on
top of the Acid blue 25 layer.
The same phenomenon could also explain the adsorption
of Acid blue 25 on OMS-COOH (cf. Figure 4a). The
adsorption behavior of Methylene blue dye on OMSCOOH from single and binary dye mixtures are similar.
Both reach a maximum adsorption capacity of about 100
mg per gram of adsorbent. The single dye experiment
clearly shows that the Acid blue dye does not have any
affinity for the carboxylic acid groups grafted onto OMSCOOH. However, in the presence of Methylene blue, nearly
50 mg of Acid blue 25 was adsorbed per gram of the
adsorbent. This strongly suggests that the adsorption of
Acid blue 25 onto OMS-COOH is mediated by the
adsorbed Methylene blue dyes. This is confirmed in an
experiment wherein Methylene blue was preadsorbed on
OMS-COOH (0.38 mmol/g or 123 mg/g) and the dyemodified OMS adsorbent was used to adsorb Acid blue 25
from a solution. An additional 0.38 mmol/g (160 mg/g)
of Acid blue 25 was adsorbed on the dye-modified
adsorbent. The adsorption of Acid blue 25 on unmodified
MCM-41 from the mixture of dyes also displays an
improvement compared to the value obtained from the
single dye experiment (cf. Figures 4a and 3a). However,
the adsorption isotherms of the two dyes from the mixture suggest that there is competitive adsorption between
Acid blue 25 and Methylene blue on OMS adsorbent
(cf. Figure 4b). This may be because the native hydroxyl
groups on MCM-41 do not have a strong affinity for either
dye.

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Langmuir, Vol. 19, No. 7, 2003

4. Concluding Remarks
This work demonstrates that selective adsorbents could
be prepared from the ordered mesoporous silica (i.e., MCM41) by grafting chemical moieties that have specific affinity
for the target molecules. The Acid blue 25 represents an
important class of dye pollutants that cannot be effectively
removed by traditional carbonaceous adsorbents such as
activated carbons and peat. The amino-modified OMSNH2 has a strong affinity and adsorption capacity for acidic
dye molecules and could efficiently remove Acid blue 25
from a mixture. Similarly, OMS containing grafted
carboxylic groups (OMS-COOH) is a good adsorbent for
the removal of Methylene blue dyes and displays comparable adsorption capacity as the commercial adsorbents
but with better selectivity. A better selectivity means that
the OMS-based adsorbents have longer operating life and
require less maintenance, thus resulting in lower capital
and operating cost. Also unlike the existing adsorbents,
the OMS-based adsorbents can be regenerated by a simple
washing procedure.
One additional advantage of using ordered mesoporous
silica is that it provides an ideal material for studying
adsorption and diffusion phenomena. Today, most adsorbents possess complex pore structure that is populated

Ho et al.

by myriad of chemical groups. It is difficult if not impossible

to accurately describe the different adsorption sites,
chemical interactions, and transport processes in these
materials. The cylindrical pore structure and high degree
of pore symmetry found in OMS are ideal for testing
various existing adsorption and diffusion models. The
simple pore geometry is amenable to mathematical
description and the amorphous state of the pore wall
approximates an ideal Langmuir surface. The ability to
introduce well-defined functional groups is invaluable for
developing mathematical model for surfaces with multiple
adsorption sites. This will allow the systematic study of
the nature of interaction between different surface sites
and lead to the design of better adsorbent materials. This
work constitutes the first step toward this goal.
Acknowledgment. The authors would like to gratefully acknowledge the funding from the Hong Kong
Research Grant Councils (grant RGC-HKUST 6037/00P).
We also thank the Material Characterization and Preparation Facility at the HKUST for the use of XRD, TEM,
SEM, EDXS, XPS, and TGA/DTA equipment.
LA0267084