Bull. Chem. Soc. Ethiop. 2005, 19(2), 197-112.

ISSN 1011-3924
Printed in Ethiopia 2005 Chemical Society of Ethiopia

IN SITU AND POST REACTION COBALT-INCORPORATION INTO

AMINOPROPYL-MODIFIED PERIODIC MESOPOROUS ORGANOSILICA
MATERIALS

Alufelwi M. Tshavhungwe and Neil J. Coville*

DST/NRF Centre of Excellence in Strong Materials and the Molecular Sciences Institute,
School of Chemistry, University of the Witwatersrand, Johannesburg, 2050, South Africa

(Received March 1, 2005; revised May 4, 2005)

ABSTRACT. Bifunctional periodic mesoporous organosilica materials with and without cobalt ion
incorporation were synthesized by co-condensation of 1,2-bistrimethoxysilylethane (BTME) with 3-
aminopropyltriethoxysilane (APTS) in the presence of cetyltrimethylammonium bromide. Cobalt
was incorporated onto APTS-modified ethylene-bridged silica materials by in situ and by incipient
wetness addition methods. The periodicity of the new materials is indicated by the presence of low
angle diffraction peaks found in the XRD profiles (pore size ca. 40 nm). The surface area, pore
volume and pore diameter of the new ethylene-bridged silica materials decreased with increasing
loading of APTS as well as after cobalt incorporation. Thermogravimetric analysis and Raman
spectroscopy show that the surfactant is removed by solvent extraction. Cobalt ion incorporation is
confirmed by Raman spectroscopy and UV-vis diffuse reflectance spectroscopy.

KEY WORDS: Bifunctional periodic mesoporous organosilica, 1,2-bistrimethoxysilylethane,

3-aminopropyltriethoxysilane, Sol-gel, Cobalt

INTRODUCTION

The sol-gel method is widely used to synthesise periodic mesoporous organosilica (PMOs)
materials containing both bridging organic functional moieties in the framework and terminal
organic functional groups protruding into the channel pores [1 – 20]. The large ordered pore
sizes of PMOs make these materials very attractive for applications such as catalyst supports,
sensors and adsorbents for heavy metal ions. Periodic ethylene-bridged silica materials, by far
the most widely studied PMO, has been modified by co-condensation of 1,2-
bistrialkoxysilylethane precursors with various trialkoxyorganosilanes in the presence of
surfactants [21 – 32]. Organosilane precursors co-condensed with bistrialkoxysilylethane include
3-glycidoxypropyltrimethoxysilane [21], 3-cyanopropyltriethoxysilane [22], N-(2-aminoethyl)-
3-aminopropyltrimethoxysilane [H2N-(CH2)-NH(CH2)3] [26], N-[3-(trimethoxysilyl)propyl]-
ethylenediamine [27] and mercaptopropyltrimethoxysilane [HS-(CH2)3-] [26, 31, 32].
PMO materials containing “nitrogen-bearing” functional groups (e.g. cyano- (CN) [22],
amines (NH) [24 – 27, 33], etc) have also received some attention. Asefa et al. prepared periodic
mesoporous aminosilicas that contain amine functional groups in the framework of a
mesoporous network via thermal ammonolysis of periodic mesoporous organosilicas (PMOs)
under a flow of ammonia gas [33]. Burleigh and co-workers described the preparation of a
porous organosilica by co-condensation of bistriethoxysilylethane and N-(2-aminoethyl)-3-
aminopropyltrimethoxysilane, N-[3-(trimethoxysilyl)propyl] ethylenediamine or Cu(II)-
complexed N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine under acidic and basic
conditions [24 – 27].

__________
*Corresponding author. E-mail: [email protected] or [email protected]
Fax: +27 11 717 6749. Tel.: +27 11 717 6738.
198 Alufelwi M. Tshavhungwe and Neil J. Coville

For catalytic applications, aminopropyl-functionalised amorphous and ordered mesoporous

silicas have been the most widely studied organic-inorganic hybrid solids [34]. These organic-
inorganic hybrids have been used as catalysts for the Knoevenagel condensation of various
aldehydes and ketones with ethyl cyanoacetate [35 – 37] as well as for base-catalysed reactions
such as the nitroaldol condensation and Michael addition reactions [38, 39].
Although unfunctionalized silica materials, including ordered mesoporous silicas (MCM 41)
have been used as supports for cobalt-based catalysts in the Fischer Tropsch (FT) synthesis [40 –
42], there are very few reports in the literature on cobalt incorporation into periodic mesoporous
organosilica materials. Further, amine functionalised silicas have not been used in the FT
reaction.
Herein we report on the synthesis and characterization of organosilica materials synthesized
by co-condensation of 1,2-bistrimethoxysilylethane (BTME) with 3-aminopropyltriethoxysilane
(APTS) in the presence of hexadecyltrimethylammonium bromide (cetyltrimethylammonium
bromide, CTAB) as the surfactant both in the presence and absence of cobalt ions. The
molecular structures of these silica precursors and the surfactant are shown in Scheme 1. Cobalt
ion was added to the formed silicas to generate Co supported catalysts for use in Fischer-
Tropsch (FT) synthesis [43 – 47]. 3-Aminopropyltriethoxysilane (APTS) has a terminal amine
group which may be beneficial for binding metals and this is one of the aspects of APTS which
we wish to explore in this study.
The FT studies are a continuation of previous studies on Co supported catalysts [48, 49]. To
the best of our knowledge, this is the first report on the synthesis of cobalt ion incorporated
APTS-modified ethylene-bridged silica.

EXPERIMENTAL

Chemicals

1,2-bistrimethoxysilylethane (BTME), hexadecyltrimethylammonium bromide (CTAB) and

cobalt nitrate hexahydrate were obtained from Aldrich; 3-aminopropyltriethoxysilane (APTS)
was obtained from ABCR (Germany). All chemicals were used as received.

Synthesis

APTS-functionalized ethylene-bridged silica materials. PMOs were prepared using a modified

method based on that reported by Ozin and co-workers [23]. A series of APTS-modified
ethylene-bridged silica materials were prepared starting with a mole ratio of
BTME:APTS:CTAB:NH4OH:H2O = 1: x: 0.275: 64: 218 (where x = 0, 0.476, 0.714, and
0.952). In a typical synthesis, CTAB (0.36 g; 0.98 mmol) was dissolved in a solution consisting
of water (14 mL) and 28 % ammonium hydroxide (8 mL; 0.229 mol). The mixture was stirred
for 45 minutes. The pH of the solution was estimated by pH paper to be approximately 10. A
mixture of BTME (0.9 mL, 3.57 mmol) and APTS [varying amounts: 0.8 mL (3.40 mmol), 0.6
mL (2.55 mmol) and 0.4 mL (1.70 mmol)] was added dropwise to the stirred mixture. These
materials are denoted as BAA(1:1), BAA(1:0.7) and BAA(1:0.5), respectively (see section
Nomenclature for a description of notation used). Stirring was continued for a further 1 hour,
followed by ageing at 80 oC for 4 days. The solid was suction filtered in a Buchner funnel and
washed with an excess of water. The solid was dried in air overnight to give the required
material (between 1 and 2 g).

Bull. Chem. Soc. Ethiop. 2005, 19(2)

 In situ and post reaction cobalt-incorporation into mesoporous organosilica materials 199

Surfactant extraction. A portion of the as synthesized sample (0.5 g) was stirred in a solution of
concentrated HCl (5 mL) in methanol (200 mL) at 50 oC for 2 days. The solid was suction
filtered in a Buchner funnel, washed with water and finally with methanol (200 mL) and then
dried in air. Mass losses of between 20 and 40 % were observed after surfactant extraction.
Extracted materials are denoted as BAE(1:1), BAE(1:0.7) and BAE(1:0.5), respectively.

In situ cobalt incorporated APTS-functionalized ethylene-bridged silica. Cobalt incorporated

APTS-modified ethylene-bridged silica materials were synthesized by adding cobalt nitrate [0.1
g; 0.34 mmol] to a reaction mixture of CTAB (0.36 g; 0.98 mmol), water (28 mL) and 28 %
ammonium hydroxide (8 mL; 0.229 mol). A mixture of BTME and APTS (BTME:APTS = 1:1
or 1:0.5) was then added dropwise to the mixture. The procedure, including solvent extraction,
was continued as described above for the synthesis of APTS-modified ethylene-bridged silica
materials. The APTS-modified ethylene-bridged silica materials synthesized in this manner are
denoted as 6.7CoBAE(1:1)-in situ and 6.7CoBAE(1:0.5)-in situ. The corresponding ethylene-
bridged silica (not modified) is denoted as 6.7CoBE-in situ.

Post reaction cobalt incorporated APTS-functionalized ethylene-bridged silica. Cobalt

incorporated aminopropyl-modified ethylene-bridged silica was prepared using the incipient
wetness impregnation method. An aminopropyl-modified ethylene-bridged silica [BAE(1:1)]
having a BET surface area, pore volume and desorption BJH pore diameter of 389 m2/g, 0.27
cm3/g and 3.0 nm, respectively, was used as the support. Different amounts of cobalt nitrate,
Co(NO3)2.6H2O, (0.1 g and 0.2 g) were dissolved in deionised water and impregnated into the
support (0.3 g) using incipient wetness to give materials with 6.7 % and 13.5 % cobalt.
Materials were dried at 120 oC for 12 hours. Materials synthesized in this manner are denoted as
6.7CoBAE(1:1)-imp and 13.5CoBAE(1:1)-imp.

Nomenclature. The percentage APTS indicates the percentage of APTS expressed per mole of
silicon atoms in the BTME and APTS organosilica precursors {% APTS = [100 x (mol Si in
APTS)/(2 x moles Si in BTME + mol Si in APTS)]}. The moles of BTME are multiplied by 2
because each BTME molecule supplies two moles of Si whereas an APTS molecule supplies
one. The notation used to identify the samples is as follows: A = APTS, B = BTME, Co =
cobalt, A = as synthesized, and E = extracted. The mole ratio of BTME to APTS in the reaction
mixture is given in parenthesis. Numerical figures preceding Co refer to the percentage of cobalt
in the sample in cobalt incorporated samples. The method used to incorporate cobalt is
identified by imp (impregnated) or in situ after the name. For example, BAE(1:0.5) refers to an
extracted (E) sample synthesized from APTS (A) and BTME (B) in which the ratio of BTME to
APTS is 1:0.5. 6.7CoBAE (1:1) – imp, refers to a cobalt incorporated (6.7 % Co), extracted (E)
material synthesized from APTS (A) and BTME (B) in a 1:1 ratio in which cobalt was supported
by impregnation (imp).

Characterization

Powder X-ray diffraction. Powder X-ray diffraction measurements were made on a Phillips
PW1710 diffractometer with Cu K-α radiation ( = 1.5443 Å). Powdered disc samples were
analysed at a scan speed of 5o s-1 in the 1.5 – 10o or 1.5 – 70o 2 range at a generator voltage of
40 kV and a generator current of 20 mA.

Nitrogen sorption. The nitrogen adsorption and desorption isotherms were measured at –196 oC
using a Micromeritics ASAP2010 instrument. Prior to adsorption measurements, all samples
were degassed for 12 hours at 120 oC. The BET surface area was calculated from the adsorption
Bull. Chem. Soc. Ethiop. 2005, 19(2)
200 Alufelwi M. Tshavhungwe and Neil J. Coville

isotherm in a relative pressure range from 0.001 to 0.20. The total pore volume was evaluated
from the amount of nitrogen adsorbed at a relative pressure of 0.98. The average pore diameter
was evaluated by the BET method (4V/A). The pore size distribution was obtained from analysis
of the adsorption and desorption branches of the isotherm using the Barrett-Joyner-Halenda
(BJH) method.

Thermogravimetric analysis. Thermogravimetric analyses were performed with a Perkin Elmer

Pyris 1 TGA Thermogravimetric analyser using nitrogen or air as the purge gas at a heating rate
of 5 oC per minute.

Raman spectroscopy. Measurements were made using the micro-Raman attachment of a Jobin-
Yvon T64000 Raman spectrometer, configured in single spectrograph mode. A grating with 600
grooves/mm was used to disperse the spectrum onto a charge coupled device (CCD) detector.
The laser spot size on the sample was ~1.5 microns in diameter, and the excitation wavelength
was 514.5 nm from an argon ion laser.

Scanning electron microscopy. SEM images were recorded on a JSM 840 Scanning Electron
Microscope with an acceleration voltage of 10 kV and a working distance of 15 mm. Prior to
measurements, the samples were sprinkled on a disk smeared with carbon and then coated with
gold.

UV-vis diffuse reflectance spectroscopy. UV-Vis diffuse reflectance spectra were recorded with
a Cary-5E Varian spectrometer equipped with a Praying–Mantis diffuse reflectance attachment.
BaSO4 was used as reference.

RESULTS AND DISCUSSION

Synthesis

Addition of a mixture of BTME and APTS to a basic solution of CTAB formed white solid
materials. A gel formed immediately for samples containing large amount of APTS. For all
mixtures, precipitation started within 30 minutes after addition of the silica precursor. Addition
of cobalt nitrate to the mixture yielded dark brown/black materials for CoBAE(1:0.5)-in situ and
CoBAE(1:1)-in situ. The base-catalysed surfactant-templated formation of APTS-modified
periodic mesoporous ethylene-bridged silica is proposed to form from micelles [50] as
illustrated in Scheme 1.

Powder X-ray diffraction

APTS-modified ethylene-bridged silica. Powder XRD was used to probe the periodicity of the
mesoporous materials. Periodic mesoporous materials display a very high intensity peak at
around 2θ = 2o, together with low intensity peaks below 8o [50, 51]. The prominent low angle
peak at approximately 2θ = 2o indicates the presence of uniformly sized pores for ordered
materials. XRD patterns (shown in Figure 1) show relatively broad low angle peaks compared to
that of hexagonal MCM 41 materials. The absence of higher angle reflections suggests the lack
of long range order. The most intense peak was arbitrarily assigned as the d (100) peak. Powder
XRD patterns of the as synthesized and the solvent extracted APTS-modified ethylene-bridged
silica samples in which the BTME:APTS mole ratio is 1:1 are shown in Figure 1 (D and C,
respectively; d values of 3.9 and 4.1 nm, respectively). Corresponding values obtained for a
Bull. Chem. Soc. Ethiop. 2005, 19(2)
 In situ and post reaction cobalt-incorporation into mesoporous organosilica materials 201

related amine-functionalised material synthesized by Burleigh et al. [26] are 4.3 nm and 4.4 nm,
respectively, and suggests equivalent structures.

CH3
N+ CH3 Br- (CTAB)
CH3
H2O + NH4OH

Supramolecular formation

(R'O)3Si Si(OR')3 (BTME)

Hydrolysis and +
Condensation
H2N Si(OCH3)3 (APTS)

Surfactant micelle

Organosilica

Surfactant
Removal Solvent Extraction (HCl/MeOH)

Organosilica
H2N

Peiodic Mesoporous Organosilica Si

O
Si Si O Si Si
where organosilica consists of units

Scheme 1. Reaction scheme showing the formation of periodic mesoporous aminopropyl-

modified ethylene-bridged silica. Note that the framework is made up of units of
H2NCH2CH2CH2SiO3 and O3SiCH2CH2SiO3.

As expected for organic-functionalized silicas synthesized via co-condensation [23, 52], the
position of the d (100) peak shifts to higher angles (implying lower d values) as the amount of
APTS added increased (Table 1). This shift corresponds to the reduction in the interplanar
spacing from about 4.9 to 3.9 nm for BAE(1:0.5) and BAE(1:1), respectively. The same
behaviour was observed for BTME silica modified by co-condensation with various

Bull. Chem. Soc. Ethiop. 2005, 19(2)

202 Alufelwi M. Tshavhungwe and Neil J. Coville

organosilanes including 3-glycidoxypropyltrimethoxysilane [21] and 3-cyanopropyltriethoxy-

silane [22].
From the above data it can be seen that the amount of APTS has an effect on the pore
structure of the silica material. It is assumed that the major effect arises from an interaction of
the CTAB micelle with the APTS that modifies the micelle structure, leading to the loss of long
range order. Increasing the amount of APTS may cause an increase in the number of
electrostatic interactions between the aminofunctional group of APTS and the quartenary
ammonium head group of the surfactant, which can result in a change in the density of silanol
groups in the surfactant silicate interface, thereby requiring fewer surfactant molecules for
charge balance. This situation leads to contraction of the micelle size in hybrid mesoporous
materials with higher concentrations of APTS [22, 53]. However, further work on this and other
related systems will need to be performed to confirm this suggestion.
It was also observed that when the ratio of surfactant to silica precursors was changed, by
increasing the amount of surfactant while keeping the amount of silica precursors constant, the
d100 peak observed in the surfactant-containing material (with a reduced intensity) disappeared
after solvent extraction.

Co-incorporated APTS-modified ethylene-bridged silica. The XRD pattern of a solvent-

extracted material synthesized in the presence of cobalt nitrate (0.1 g) using a BTME:APTS
mole ratio of 1:0.5, CoBAE(1:0.5)-in situ, displays an intense diffraction peak with a lattice
spacing, d100, of 4.78 nm at 1.85o (Figure 1B). This value is slightly higher than that of
BAE(1:05) (Figure 1A), by ~0.1 nm. As shown in Figure 1 (insert), the material obtained by
impregnating 0.3 g of the material prepared from a BTME:APTS mole ratio of 1:1 with 0.1 g
cobalt nitrate [6.7CoBAE(1:1)] does not show any low angle diffraction peaks, suggesting loss
of mesophase for this sample. Similar results were reported for other Co-impregnated ethylene-
bridged silica materials [54].

Table 1. Structural properties of organosilica materials.

Sample and % APTSa SAb PVc APDd Dad e Ddesf d100g (nm)
(m2/g) (cm3/g) (nm) (nm) (nm)
BAE(1:1) [32 %] 389 0.27 2.78 2.1 – 2.2 (2.0) 3.0 – 2.9 ( 3.0) 3.92 (4.11)
BAE(1:0.7) [26 %] 426 0.30 2.83 1.7 – 1.7 (1.7) 2.6 – 2.1 (2.3) h 4.38
BAE(1:0.5) [19 %] 470 0.45 3.82 2.8 – 2.6 (2.7)h 3.2 – 3.1 (3.2) 4.93
BE 672 0.71 4.24 2.2 – 2.1 (2.2) 3.3 – 3.2 (3.3) 4.75 (4.42)
13.5CoBA(1:1) – imp 181 0.14 2.53 2.0 – 1.8 (1.9) 3.1 – 3.0 (3.1)
6.7CoBAE(1:1)-imp. 250 0.17 2.76 1.9 – 1.8 (1.8) 3.2 – 3.1 (3.1)
6.7CoBAE(1:1)-in situ 308 0.19 2.52 -i - 4.34
6.7CoBE - in situ 438 0.48 4.34 2.5 – 2.4 (2.4) 3.2 – 3.1 (3.1) 4.45
a
Values in square brackets are % APTS = [100 x (mol Si in APTS)/(2 x moles Si in BTME + mol Si in
APTS, b SA = BET Surface Area, c PV = Total Pore volume (cm3/g), d APD = Average Pore Diameter, e Dad
= BJH Adsorption Pore Diameter, f Ddes = BJH Desorption Pore Diameter, g d100 = XRD lattice parameter
of extracted samples. The value of the corresponding as synthesized sample is given in parenthesis. h Broad
PSD ‘mesopore’ peak. i Not determined, 5-point BET method was used to determine surface area.

Bull. Chem. Soc. Ethiop. 2005, 19(2)

 In situ and post reaction cobalt-incorporation into mesoporous organosilica materials 203

6.7CoBAE(1:1)

0 2 4 6 8 10
o
2 THETA ( )

A BAE(1:0.5)
INTENSITY

B CoBAE(1:0.5)-in situ

C BAE(1:1)

D BAA(1:1)

1 2 3 4 5 6 7
o
2 THETA ( )

Figure 1. XRD patterns for aminopropyl-functionalized ethylene-bridged silicas. A = extracted

APTS-modified ethylene-bridged silica (BTME:APTS = 1:0.5); B = extracted APTS-
modified ethylene-bridged silica (BTME:APTS = 1:0.5) prepared in the presence of
0.1 g cobalt nitrate; C and D = extracted and as-synthesised APTS-modified ethylene-
bridged silicas (BTME:APTS = 1:1), respectively. Insert: APTS-modified ethylene-
bridged silica (BTME:APTS = 1:1) impregnated with 0.1 g cobalt nitrate.

Nitrogen sorption

APTS-modified ethylene-bridged silica. Nitrogen adsorption-desorption isotherms for extracted

aminopropyl-modified ethylene-bridged silica samples with BTME:APTS mole ratios of 1:0.5,
1:0.7 and 1:1 in the synthesis gels are shown in Figure 2 (A, B and C, respectively). All the
materials exhibit Type IV isotherms with a narrow pore size distribution according to the
IUPAC classification, which is typical for mesoporous materials [55]. The shape of the
hysteresis loop (Type H4) observed for BAE (1:1) and BAE (1:0.7) is consistent with the
presence of ‘ink-bottle’ pores having a narrow entrance and wide interior.
The structural properties (BET surface area, average pore diameter, pore volume and lattice
parameter) of these materials are listed in Table 1. BJH desorption PSDs with maxima ranging
between 3.3 (for the unmodified ethylene-bridged silica material) and 3.0 nm (for the material
with BTME:APTS =1:1) are obtained. (Table 1, Figure 2). The corresponding pore diameters
obtained from the adsorption isotherm are 2.2 and 2.0 nm, respectively. The pore diameters
derived from the adsorption isotherm are lower than the corresponding values obtained from the
desorption isotherm by about 1 nm (Table 1). The surface area and total pore volume decrease
significantly after co-condensation with increasing amount of APTS. The same behaviour was
observed for ethylene-bridged silica modified by co-condensation of BTME with 3-
glycidoxypropyltrimethoxysilane [21].

Co-incorporated APTS-modified ethylene-bridged silica. Shown in Figure 3 (A and B) are

isotherms of the materials prepared by impregnating 0.3 g samples of an APTS-modified
ethylene-bridged silica [(BAE(1:1), BET surface area = 389 m2 g-1, and pore volume = 0.27 cm3
Bull. Chem. Soc. Ethiop. 2005, 19(2)
204 Alufelwi M. Tshavhungwe and Neil J. Coville

g-1] with 0.1 and 0.2 g of cobalt nitrate, yielding materials with 6.7 % [6.7CoBAE(1:1)] and
13.5 % [13.5CoBAE(1:1)] cobalt, respectively. The shape of the isotherm is not affected by post
reaction cobalt incorporation. The effect of incorporating cobalt nitrate onto amine-
functionalized materials on the surface area is clearly observed from the isotherms. The surface
area and total pore volume decreased significantly after cobalt incorporation (Table 1). The
decrease in surface area and pore volume as the amount of Co loading increases suggests that
Co particles were deposited in the pores of the organosilica materials [56].
The surface areas and pore volumes of the materials prepared by the impregnation method
are lower than the corresponding values of the materials prepared by the in situ procedure (see
Table 1). For example, the cobalt incorporated APTS-modified ethylene-bridged silica material
synthesized in the presence of 0.1 g cobalt nitrate [6.7CoBAE(1:1) - in situ] has a higher surface
area (308 m2/g) compared to the material impregnated with an equivalent amount of cobalt
nitrate (250 m2/g for 6.7CoBAE(1:1) - imp). This arises since in the impregnation method all the
Co nitrate fill the pores while in the in situ method some of the Co is incorporated in the
framework to form Co-O-Si bonds and hence the Co does not block the pores as effectively.

200
A
180
Volume Adsorbed (cm /g)

160
3

140 B
120 C
100 0.10

80 0.08
D
0.06
60 0.04
E
40 0.02
0.00

20 2 3 4 5
Pore diameter
6 7

0
0.0 0.2 0.4 0.6 0.8 1.0
Relative pressure (P/Po)

Figure 2. N2 adsorption desorption isotherms and BJH pore size distributions derived from
desorption isotherms for APTS-modified ethylene-bridged silica and Co-incorporated
APTS-modified ethylene-bridged silica materials. A, B and C are isotherms of APTS-
modified ethylene-bridged silica with BTME:APTS mole ratios of 1:0.5, 1:0.7, and
1:1, respectively. D and E are BJH desorption PSDs for BAE1:1 and BAE(1:0.5),
respectively.

Thermogravimetric analysis

APTS-modified ethylene-bridged silica. TGA (under N2) was used to monitor the decomposition
characteristics of the APTS-modified ethylene-bridged silica materials before and after solvent
extraction. Analysis was conducted from room temperature to 1000 oC. Thermograms and
derivative thermograms of samples prepared from a mixture of APTS and BTME are shown in
Figure 4. The results for as-synthesized and solvent extracted APTS-modified ethylene-bridged
silica materials prepared from a mixture with BTME:APTS = 1:1 are summarised in Table 2.
The profiles indicate that the organosilica materials all have similar thermal stability, with
distinct mass losses, associated with the organic groups in the materials. Whereas the extracted

Bull. Chem. Soc. Ethiop. 2005, 19(2)

 In situ and post reaction cobalt-incorporation into mesoporous organosilica materials 205

ethylene-bridged silica loses no weight in the range 262 – 370 oC [21], the solvent extracted
APTS-modified ethylene-bridged silica materials lose mass in this region (Figure 4). The mass
loss in this region decreases with decreasing amount of APTS used during synthesis and is
consequently attributed to loss of the aminopropyl functional group. The onset of aminopropyl
group decomposition overlaps with the decomposition of surfactant molecules in as-synthesized
materials. The mass losses obtained in the temperature range 100 – 400 oC for materials with
BTME:APTS mole ratios of 1:1 and 1:0.5 [BAE(1:1) and BAE(1:0.5)] are 17 and 24 %,
respectively. All extracted APTS/BTME samples lose between 10 and 12 % of their masses due
to framework ethylene group decompostion at temperatures between 400 and 800 oC. Another
observation is that APTS/BTME samples lose more weight (due to methanol and ethanol
desorption) below 100 oC compared to BTME samples. This is expected as the material formed
from co-condensation of APTS and BTME is more hydrophilic than that prepared from BTME
alone [26].

120
A
100
Volume Adsorbed (cm /g)
3

80 B

0.12
Pore Volume (cm /g-nm)

60 0.10
0.08
3

0.06 C
40 0.04
0.02 D
0.00

20 2 3 4 5 6 7 8 9 10
Pore diameter (nm)

0.0 0.2 0.4 0.6 0.8 1.0

Relative pressure (P/Po)

Figure 3. N2 adsorption desorption isotherms and BJH pore size distributions derived from
desorption isotherms for Co-incorporated APTS-modified ethylene-bridged silica
materials. A and B are isotherms of APTS-modified ethylene-bridged silica with
BTME:APTS mole ratio of 1:1 impregnated with 6.7 % and 13.5 % cobalt,
respectively. C and D are BJH desorption PSDs for 6.7CoBAE(1:1)-imp and
13.5CoBAE(1:1)-imp, respectively.

Table 2. TGA results of as-synthesized and solvent-extracted APTS-modified ethylene-bridged silica

materials prepared from a mixture with BTME:APTS = 1:1.

Temperature % Mass loss of as % Mass loss of solvent Source of mass loss

range (oC) synthesized material extracted material
25 – 175 5% 10 % Desorption of water, ethanol and
methanol
175 – 250 50 % 2% Surfactant decomposition
250 – 370 17 % 13 % Decomposition of surfactant and
aminopropyl functional group
370 – 600 5.5 % 12 % Decomposition of ethylene groups
from the ethylene-bridged silica
network

Bull. Chem. Soc. Ethiop. 2005, 19(2)

206 Alufelwi M. Tshavhungwe and Neil J. Coville

0 200 400 600 800 1000

2
A
100 0

DERIVATIVE WEIGHT % (% min )

-1
-2

WEIGHT LOSS %
80
-4
B
C -6
60
D -8
BAE(1:0.7)
BAE(1:0.5) -10
40 BAA(1:1)
BAE(1:1) -12
E
20 -14
-16
0 200 400 600 800 1000
o
TEMPERATURE / C

Figure 4. TGA curves and derivative thermograms for APTS-modified ethylene-bridged silica
materials. A = derivative TGA curve of BAE(1:1); B, C, D and E are TGA curves of
BAE(1:0.5), BAE(1:1), BAE(1:0.7) and BAA(1:1), respectively.

Co-incorporated APTS-modified ethylene-bridged silica. TGA curves of cobalt incorporated

ethylene-bridged silica materials prepared by impregnation of 0.3 g ethylene-bridged silica
samples with 0.1 and 0.2 g cobalt nitrate are shown in Figure 5. The mass loss at temperatures
between 100 and 300 oC observed in materials obtained by impregnation is due to loss of
products associated with the decomposition of the nitrate ions and water. Sample
6.7CoBAE(1:1) loses half (16 %) the mass lost by 13.5CoBAE(1:1) (30%) in agreement with
the ratio of cobalt nitrate used for the impregnation. The other mass losses observed are similar
to those associated with the hybrid support.

100 13.5CoBAE(1:1)
6.7CoBAE(1:1)
90

80
% MASS

70

60
A
50

40 B
0 200 400 600 800 1000 1200 1400
o
TEMPERATURE ( C)

Figure 5. TGA curves for solvent extracted APTS-modified ethylene-bridged silica materials
impregnated with cobalt nitrate. A = 6.7CoBAE(1:1) and B = 13.5CoBAE(1:1).

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 In situ and post reaction cobalt-incorporation into mesoporous organosilica materials 207

Raman spectroscopy

APTS-modified ethylene-bridged silica. Raman spectroscopy was used to identify functional

groups associated with the new materials. Raman spectra of solvent extracted APTS-modified
ethylene-bridged silica [BAE (1:0.5)] as well as solvent extracted ethylene-bridged silica (BE)
are shown in Figure 6. After solvent extraction the peaks associated with CTAB had disappeared
while those due to the C-H vibrations of the BTME and APTS ethylene groups (2885 cm-1) are
still to be seen (Figure 6) [57, 58]. The intensity of the Raman peaks indicative of the amine
functional group, observed between 3250 and 3500 cm-1, increases with an increasing amount of
APTS in the reaction mixture. The absence of peaks between 600 and 700 cm-1 (which are
observed in the spectra of silicon precursors) indicates considerable hydrolysis and condensation
of the methoxy and ethoxy groups of the silicon precursors. Whereas single peaks are observed
in the range 1200 – 1300 (due to symmetric CH vibrations of Si–CH2– groups) and 1400 – 1600
cm-1 (due to asymmetric CH vibrations of Si–CH2– groups) in the spectrum of ethylene-bridged
silica, doublets appear in the spectra of APTS-modified ethylene-bridged silica materials,
indicating that the methylene groups in the framework and those due to the aminopropyl group
are not equivalent (Figure 6). Bands due to Si-O vibrations are observed at 798, 956, 1078 and
1147 cm-1.

Co-incorporated APTS-modified ethylene-bridged silica. Incorporation of Co into ethylene-

bridged silica and APTS-modified ethylene-bridged silica yielded a material that has peaks at
686 cm-1 and at 480 cm-1, indicative of Co3O4 [59]. However, no evidence for the presence of
Si-O-Co-O-Si species was evident.

16000
BAE(1:0.7)
12000
8000
4000
0

10000 0 500 1000 1500 2000 2500 3000 3500 4000

INTENSITY

8000
6000 BAE(1:0.5)
4000
2000
0
-2000
0 500 1000 1500 2000 2500 3000 3500 4000
28000
24000
20000 BE
16000
12000
8000
4000
0

0 500 1000 1500 2000 2500 3000 3500 4000

-1
WAVENUMBER (cm )
Figure 6. Raman spectra for solvent extracted ethylene-bridged silica (BE) and APTS-modified
ethylene-bridged silica [BAE(1:0.5) and BAE(1:0.7)] materials.

Bull. Chem. Soc. Ethiop. 2005, 19(2)

208 Alufelwi M. Tshavhungwe and Neil J. Coville

UV-Vis diffuse reflectance spectroscopy

Co-incorporated APTS-modified ethylene-bridged silica. UV-Vis diffuse reflectance spectra of

aminopropyl-modified ethylene-bridged silica materials impregnated with cobalt nitrate (0.1 and
0.2 g cobalt precursor per 0.3 g organosilica) as well as that of unsupported cobalt nitrate
hexahydrate are presented in Figure 7. The absorption band at 428 nm is due to the formation of
Co3O4, where a migration of Co to octahedral sites has occurred [59]. The UV-vis diffuse
reflectance spectroscopy thus confirms the presence of Co3O4.

12.5
A

10.0
B

7.5
INTENSITY

A 6.7CoBAE(1:1)
B 13.5CoBAE(1:1)
5.0
C Co(NO3)2

2.5
C

0.0
200 250 300 350 400 450 500 550
WAVELENGTH (nm)

Figure 7. UV-VIS diffuse reflectance spectra of unsupported cobalt nitrate and supported cobalt
nitrate.

Scanning electron microscopy (SEM)

APTS-modified ethylene-bridged silica. Typical scanning electron microscopy (SEM) images of

ethylene-bridged silica, APTS-modified ethylene-bridged silica and cobalt incorporated APTS-
modified ethylene-bridged silica materials are shown in Figure 8. The SEM image of an
ethylene-bridged silica sample displays predominantly spherical particles with diameters in the
range 11.1 to 21.8 m. Smaller particles, with diameters ranging between 1.67 and 3.89 m,
dominate after modifying ethylene-bridged silica with APTS.

Co-incorporated APTS-modified ethylene-bridged silica. Cobalt impregnated materials,

6.7CoBAE(1:1) and 13.5CoBAE(1:1), show spherical particles with diameters in the 1.67 –
5.56 m and 0.6 – 4.7 m range, respectively. Particles with “shell-like” morphology are also
observed for cobalt impregnated materials.

Bull. Chem. Soc. Ethiop. 2005, 19(2)

 In situ and post reaction cobalt-incorporation into mesoporous organosilica materials 209

A B

C D

Figure 8. SEM micrographs of ethylene-bridged silica, APTS-modified ethylene-bridged silica

and cobalt incorporated APTS-modified ethylene-bridged silica materials. A =
ethylene-bridged silica (BE), B = In situ Co incorporated ethylene-bridged silica
[6.7CoBAE(1:1) - in situ], C = APTS-modified ethylene-bridged silica [BAE(1:0.7)],
D = cobalt impregnated APTS-modified silica [6.7CoBAE(1:1) - imp], and E = Cobalt
impregnated APTS-modified ethylene-bridged silica [13.4CoBAE(1:1) - imp].

Bull. Chem. Soc. Ethiop. 2005, 19(2)

210 Alufelwi M. Tshavhungwe and Neil J. Coville

CONCLUSIONS

Bifunctional periodic mesoporous organosilica materials consisting of ethylene groups (in the
framework) and aminopropyl groups in the channels were synthesized. Cobalt incorporated
APTS-modified ethylene-bridged silica materials were synthesized in situ by adding cobalt
nitrate to the reaction mixture. Cobalt was also supported on APTS-modified materials by using
the incipient wetness impregnation method. Cobalt incorporation led to a collapse in the
periodicity of the materials, as shown by the disappearance of the XRD peak observed at 2 =
2o. Cobalt ion incorporation was confirmed by Raman spectroscopy and UV-vis diffuse
reflectance spectroscopy. The amount of APTS and cobalt incorporation determined the pore
size, surface area and pore volume of the new material in a predictable manner.

ACKNOWLEDGEMENTS

We wish to thank the NRF, THRIP, Sastech, the University, the Mellon Foundation and DAAD
for financial assistance.

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