Journal of Porous Materials

https://doi.org/10.1007/s10934-018-0659-3

Liquid phase oxidation of cyclohexane over mesoporous cobalt

silicates molecular sieves synthesized in strong acidic media
by assembly of preformed CoS-1 precursors with triblock copolymer
A. Ziouèche1 · L. Chérif‑Aouali1 · A. Bengueddach2

© Springer Science+Business Media, LLC, part of Springer Nature 2018

Abstract
Cobalt–incorporated mesoporous silica materials [MCoS(n), n = Si/Co = 20; 60] have been successfully prepared in strong
acidic media by assembly of preformed CoS-1 precursors with triblock copolymer of the Pluronic type (P123) by a two steps
procedure. They were characterized by various techniques including XRD, BET, FT-IR spectroscopy and diffuse reflectance
UV–Vis (DRUV–Vis). The results show that the calcined MCoS materials contain Co(II) ions in tetrahedral environments
under low and high Co content and the mesoporous walls contain the MFI structure building units. Liquid phase oxidation
of cyclohexane using TBHP as oxidant was investigated on MCoS(n). The major products detected are cyclohexanone and
cyclohexanol in all cases. The MCoS(n) catalysts are more active when water free TBHP was used and the conversion of
cyclohexane increases when cyclohexane to TBHP molar ratio increases from 1:1 to 1:2, while the cyclohexanol selectivity
decreases, which is ascribed to a further oxidation of cyclohexanol to cyclohexanone. The catalytic activity of MCoS(n)
materials is enhanced as the cobalt content increases. It is worth noting that MCoS(20)is more active than Co-SBA15(20).
The most active catalyst MCoS(20) acts as truly heterogeneous catalyst and was very stable after four runs.

Keywords Zeolite precursors · CoS-1 · Mesoporous · Oxidation · Cyclohexane

1 Introduction reaction conditions, catalyst separation from the product

and the environmental pollution, various research groups
Heterogeneous selective oxidation reactions have an increas- were focused on the development of transition metal-based
ing importance for the modern chemical industry [1]. The heterogeneous catalysts using environmentally friendly
cyclohexane oxidation products, cyclohexanol and cyclohex- oxidants, such a molecular oxygen and peroxides [3–11].
anone, are important intermediates in the production of adi- Titanium silicalite (TS-1) was the first example of a redox
pic acid and caprolactam, which are the key precursors for molecular sieve, which exhibited an activity in the liquid
the manufacture of nylon-6 and nylon-6,6 polymers. The phase oxidation of hydrocarbons with hydrogen peroxide
main catalytic system presently used for industrial cyclohex- under mild conditions [12, 13]. The success of TS-1 moti-
ane oxidation is carried out over homogeneous cobalt salts vated various research groups to investigate a wide range
at temperature above 423 K and 1–2 MPa pressure with of metal-incorporated mesoporous and microporous alu-
< 10% conversion and 70–85% selectivity to cyclohex- minosilicates molecular sieves (M-SBA-15,M-MCM-41,
anone and cyclohexanol [2]. However, due to the limita- M- KIT-6,M-MCM-48, M-ZSM-5, where M stands for
tions of this process, viz, high-cost, low conversion, extreme Au, Ag, V, Cr, Cu, Co, Fe, etc.), for cyclohexane oxida-
tion [14–20]. Reddy et al. [19] reported that Co-SBA-15
catalysts prepared by direct synthesis are more active for
* L. Chérif‑Aouali cyclohexane oxidation than those prepared by post-synthetic
[email protected] procedure, 2 wt% Co- SBA-15 catalyst exhibited the highest
1
Laboratoire de catalyse et synthèse en chimie organique PB activity 9.4% conversion of cyclohexane and 78% selectivity
119, Université de Tlemcen, Tlemcen, Algeria to cyclohexanone. Porous materials afford highly dispersed
2
Laboratoire de chimie des matériaux, Université d’Oran, metal oxide species which are the key parameter in the rather
Oran, Algeria difficult oxidation of cycloalkanes. In the last two decades an

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 Journal of Porous Materials

increasing interest can be observed for the design and syn- 2.2 Characterization
thesis of metal-containing mesoporous materials, in order
to overcome the diffusion limitations in zeolite micropores The X-ray diffraction (XRD) patterns were recorded on
[21–24]. However, although the heteroatoms are introduced a D5000 Siemens powder diffractometer equipped with
into mesoporous materials, they do not show as high cata- copper anode. The scattering intensities were measured
lytic activity as they do in zeolites, which can be attributed over an angle range of 1°< 2θ < 70° with a step size
to the amorphous nature of the pore walls. Several research Δ(2θ) = 0.02° and a step time of 8 s.
groups have explored various synthesis pathways in order Diffuse reflectance Infrared Fourier transform (DRIFT)
to introduce some structural order into the amorphous pore spectroscopy measurement were recorder using KBr pel-
walls of mesoporous catalysts and to enhance their activity lets technique in the 1500–400 cm−1 range using a Perkin
for a wide range of reactions [25–29]. Elmer FT-IR spectrophotometer.
In this work, we report the synthesis of mesoporous Nitrogen adsorption/desorption measurement were per-
Cobalt silicate (MCoS) by the assembly of CoS-1 nano- formed using Quantachrome Autosorb by N ­ 2 physisorp-
clusters with triblock copolymers [Pluronic type (P123)] in tion at liquid nitrogen temperature. The pore size dis-
strongly acidic media and their catalytic activity in the liquid tribution curves of the samples were estimated from the
phase oxidation of cyclohexane using TBHP as oxidant. adsorption branch using Barrett–Joyner–Helenda (BJH)
method, and specific surface areas were calculated by the
Brunauer–Emmet–Teller (BET) method.
Diffuse reflectance UV–Vis (DRUV–Vis) spectra were
2 Experimental section recorded using a Perkin-Elmer Lambda 800 spectrometer
in the wavelength range 200–800 nm.
2.1 Mesoporous materials preparation Cobalt content in the calcined catalyst was determined
by atomic absorbance analysis using Perkin–Elmer Ana-
Mesoporous cobalt silicate were synthesized according to lyst 300 spectrometer after dissolution of the samples in
the following procedure developed by Xiao in the synthesis HF solution [31].
of mesoporous ferrisilicate [26]:

(1) The zeolite precursor solution with CoS-1 building 2.3 Catalytic reactions
units were prepared by dissolving a calculated amount
of cobalt nitrate, in order to obtain a well defined Si/ The oxidation of cyclohexane was carried out in a Teflon-
Co ratio equal to 20 and 60, in 12 ml H ­ 2O. Then, 6 ml lined autoclave. In order to obtain an anhydrous system,
of tetapropylammonium hydroxide aqueous solution a solution of TBHP in cyclohexane was used, prepared as
was added dropwise, followed by the addition of 5.6 g follows: 18.5 mmol cyclohexane and 18.5 mmol of com-
of tetraethyl-orthosilicate under stirring. The mixture mercial TBHP (70 wt% in water, Aldrich) or 37 mmol
was transferred into an autoclave at 373 K for 3 h to get were mixed in a closed Erlenmeyer flask and magnetically
precursor solution. stirred for 24 h. The organic phase was then separated
(2) In order to obtain the mesophase, 2.5 g of from the aqueous phase. Concentration of TBHP in the
­EO20PO70EO20 (Pluronic 123) was dissolved in the cyclohexane was determined by iodometric titration and
solution of 60 ml of H ­ 2O and 15 ml of 10M HCl, fol- adjusted by adding additional cyclohexane to maintain 1:1
lowed by addition of the precursor solution obtained in or 1:2 molar ratio of cyclohexane to TBHP.
step one. The mixture was stirred at 313 K for 20 h, and In a typical reaction, 10 ml of solvent (acetonitrile) was
then transferred into autoclave for additional reaction at then added to the TBHP–cyclohexane mixture, and 0.100 g
373 K for 24 h. After cooling to room temperature the catalyst was added at the end (MCoS was heated at 373 K
solid product was filtered and dried at room tempera- overnight before being used in the reaction). The auto-
ture in air. Template removal was achieved by calcina- clave was submerged in a thermostated oil bath at desired
tion in air at 823 K for 5 h (heating rate: 1 K min−1). temperature (373 K). The reaction was continued for 8 h.
The samples were called MCoS (20) and MCoS (60). After the reaction was over, the catalyst was filtered and
the product mixture was directly analysed by gas chro-
For comparison purposes, references cobalt-substituted matography (GC 14-B Shimadzu Instrument Corporation,
mesoporous Co-SBA-15 catalysts with Si/Co = 20 and 60 in Japan) equipped with a FID detector using HP-FFAP capil-
gel, were synthesized using the pH-adjusting direct hydro- lary column (M/S.Zebron), having dimension of 0.30 mm
thermal method according to the published procedure [30]. i.d. × 0.25 µm × 30 m long. A blank cyclohexane oxidation
The pH value of the system was adjusted to 3.

13
Journal of Porous Materials

reaction over SBA-15 was also carried out under the same compared to conventional SBA-15, which could be ascribed
reaction conditions. to the difference between the nanoclustered CoS-1 units used
for MCoS and the nonstructured silicon species used for
SBA-15; the stronger rigidity and bigger volume of the MFI
3 Results and discussion nanoclusters make assembly with tri block copolymers more
difficult, resulting in some disorder in MCoS [25, 29]. The
3.1 Characterization of mesoporous materials wide-angles XRD pattern of MCoS(20) (Fig. 1b) reveals the
presence of ­Co3O4 [32]. The absence of MFI structure peak
3.1.1 XRD ssuggests that MCoS(20) is pure mesoporous phase. This
result should be attributed to the duration of first crystalliza-
X ray diffraction patterns of the SBA-15 and MCoS(20) tion step; it was not enough for the formation of the zeolite
materials are shown in Fig. 1; MCoS(20) shows a low angle phase. The zeolite seed were therefore used up as structural
reflections indexed as (100), (110), and (200) (Fig. 1a), building units for the construction of mesoporous materials
which can be associated with the hexagonal symmetry during the second crystallisation [33]. Also the strong acidic
characteristic of mesoporous SBA-15. We can note that the condition of the second step in the preparation procedure
higher ordered Bragg’s reflections (110) and (200) are hardly prevents the formation of zeolite crystals [29, 34].
visible, indicating the less ordered mesostructure of MCoS

3.1.2 N2 adsorption–desorption isotherms

(A)
The ­N2 adsorption–desorption isotherms for SBA-15 and
100 MCoS materials are shown in Fig. 2. MCoS materials
show similar shape of the isotherms (type IV) to that of
SBA-15. However, the pore size distributions (Fig. 3) of
the MCoS materials are broader than that of the SBA-15
110 200
material; this result is attributed to some disorder in the
(a)
products. Both materials MCoS(n) have nearly the same
mesoporous size, centred at mean value of 3.9 nm as
determined from BJH. MCoS materials show smaller pore
diameters than that of SBA-15 (5.9 nm). This decreasing
(b)
in pore size results from an increased wall thickness with
zeolite nanoparticles embedded in the mesoporous mate-
0,5 1,0 1,5 2,0 2,5 3,0 3,5 4,0 4,5 5,0 rial walls [35]. The textural properties of all the materials
are reported in Table 1.
2 theta (degree)

(B)
volume adsorbed (cm3/g)

(a)

(a) (b)

(c)
(b)

10 20 30 40 50 60 70 0,0 0,2 0,4 0,6 0,8 1,0

2 theta (degree) Relative pressure P/Po

Fig. 1  XRD patterns of: SBA15 (a) and MCoS(20) (b), a low angles; Fig. 2  Adsorption–desorption isotherms of nitrogen on siliceous
b high angles SBA-15 (a), MCoS(20) (b) and MCoS(60) (c) samples at 77 K

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 Journal of Porous Materials

(a)
(a)
Pore volume (cm3/gA°)

(b) (b)

Intensity (a.u.)
(c)

(c)

0 2 4 6 8 10 12 14 16 18 400 600 800 1000 1200 1400

Pore diameter (nm)
Wavenumber cm-1

Fig. 3  Pore size distribution curves for SBA-15 (a), MCoS(20) (b)
and MCoS(60) (c) samples Fig. 4  FT-IR of SBA-15 (a), MCoS(20) (b) and MCoS(60) (c)

3.1.3 FT‑IR spectroscopy

Comparison between the FTIR spectra of SBA-15 and

MCoS (Fig. 4) shows an additional band at about 555 cm−1, (a)

which is characteristic of 5-rings of zeolite structure as

Absorbance

reported by other authors [29, 35, 36].

The comparison of the FT-IR spectra of SBA-15 and
MCoS with various Si/Co (Fig. 4) shows also the shift to
(b)
higher frequency region of the band assigned to the asym-
metric stretching vibrations (Si–O–Si). This observed shift
for MCoS samples, is an indication that a part of cobalt is
incorporated into the mesoporous framework and Co–O–Si
bonds are formed [37]. The band assigned to the Si–OH is
also shifted to high frequency which can be attributed to the 350 400 450 500 550 600 650 700 750 800

presence of cobalt in the framework probably incorporated Wavelength (nm)

via Co–O–Si bonds, similar to the observations of Bendahou
et al. for LaSBA-15 [38]. Fig. 5  The diffuse reflectance UV–Visible spectra of calcined,
MCoS(20) (a) and MCoS(60) (b)
3.1.4 DR UV–Vis

The DR UV–Vis spectra of calcined MCoS(20) and 587 nm, and 655 nm), which can be attributed to the
4
MCoS(60) samples are shown in Fig. 5. The UV–Vis spec- A2(F) → 4T1(P) transition of C
­ o2+ ions in tetrahedral envi-
tra of MCoS sample display three absorption peaks (514 nm, ronment [37, 39–43]. MCoS(20) shows an other absorption

Table 1  Textural properties Si/Co gel Wt (%) BET area Pore volume Pore
of purely siliceous SBA-15, mixture ­(m2 g−1) ­(cm3 g−1) diameter
MCoS(20) and MCoS(60) (nm)

SBA-15 – – 883 1.01 5.90

MCoS 20 0.98 515 0.95 3.7
MCoS 60 0.49 531 0.91 3.9
Co-SBA15(n) (pH = 3) 20 0.031 718
Co-SBA15(n) (pH = 3) 60 0.023 702

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Journal of Porous Materials

peak at around 464 nm which can be assigned to C­ o3+ in an and cyclohexanol in all case (Tables 2, 3, 4, 5), with trace
octahedral environment in the mixed spinel oxide C ­ o 3O 4 amount of others products undefined by GC. It can be seen
[37, 44]. This band indicate that MCoS(20) contain ­Co3O4 from Table 2 that the MCoS(n) catalysts are more active
particles as mentioned in XRD analysis. Other authors [32, when water free TBHP was used. For example the con-
45–47] attribute the presence of absorption bands at around versions of cyclohexane over MCoS(20) using water free
420–475 nm and 700–760 nm to ­Co3O4. TBHP and a TBHP water solution (70% in water) reached
13.7% and 9.9%, respectively. An analogous behaviour was
3.2 Catalytic activity for cyclohexane oxidation found in the epoxidation of cyclohexene and was ascribed
to a competitive adsorption between water and TBHP on Ti-
The performance of the MCoS(n) catalysts was tested in the MCM-41 [48, 49]. Table 2 also shows the effect of cyclohex-
liquid-phase oxidation of cyclohexane using TBHP as oxi- ane to TBHP molar ratio on the oxidation of cyclohexane
dizing agent. The major products detected are cyclohexanone at 373 K for 8 h. As can be seen from this table the con-
version of cyclohexane over MCoS(n) catalysts increases
when cyclohexane to TBHP molar ratio increases from 1:1
Table 2  Catalytic oxidation of cyclohexane by MCoS
to 1:2, the conversion increases from 13.7 to 22.3% over
Catalyst (TBHP/C6H12) X% Sol Sone Sbyproducts MCoS(20). At the same time, the cyclohexanol selectivity
MCoS(60) 1 6.6 55.6 42.1 2.3
decreases with increasing cyclohexane to TBHP molar ratio,
MCoS(20) 1 9.9 44.1 53.8 2.1
while the cyclohexanone selectivity increases. Augmenta-
MCoS(60) 1* 10.2 35.3 62.2 2.5
tion in the amount of oxidant give rise to more radicals and
MCoS(20) 1* 13.7 38.8 57.9 3.3
thus enhancing the conversion [50]. The observed higher
MCoS(60) 2* 15.6 23.2 73.7 3.1
cyclohexanone selectivity in the presence of higher amounts
MCoS(20) 2* 22.3 26.7 68.6 4.7
of TBHP could be ascribed to further oxidation of cyclohex-
Co- 1* 7.1 50.5 45.7 3.8 anol to cyclohexanone [50, 51].
SBA-15(20) Table 2 shows that Co content (Si/Co) has an important
(pH = 3) effect on the conversion but little effect on selectivity. In all
SBA-15 1 - cases, MCoS(20) is more active than MCoS(60), which is
interpreted by the availability of more actives sites for the
TBHP/C6H12: molar ratio
The catalytic activities reported as conversion (X%) and selectivity
(S%) calculated are as follows:
Coane −Coane
X% conversion of cyclohexane ∶ X = Coane
× 100, where
Coane , Cfane concentration of the initial and final cyclohexane respec-
Table 4  Recycling catalytic test
tively
Cfol −Cool
Sol ∶ selectivity of cyclohexnol ∶ Sol = × 100, where Catalyst Cycle X% Sol Sone Sbyproducts
Coane −Cfane

Cool , Cfol concentration of the initial and final cyclohexanol MCoS(20) 1 22.6 26.7 68.6 4. 7
Cfone −Coone
Sone ∶ selectivity of cyclohexane ∶ Sone = × 100, where MCoS(20) 2 20.1 27.3 67.8 4.9
Coane −Cfane
MCoS(20) 3 19.6 25.6 70.6 3.8
Coone , Cfone concentration of the initial and final cyclohexanone
MCoS(20) 4 19.3 26.1 69.7 4.2
Reaction conditions: catalyst mass = 0.100 g; temperature = 373 K;
and reaction time = 8 h Reaction conditions: catalyst mass = 0.100 g; temperature = 373 K
*Denote water free TBHP (TBHP in cyclohexane) and reaction time = 8 h

Table 3  Effect of reaction times Catalyst (TBHP/C6H12) TIME X% Sol Sone Sbyproducts
on cyclohexane reaction
MCoS(60) 2* 3 3.7 55.3 43.6 1.1
MCoS(20) 2* 3 6.4 58.9 39.7 1.6
MCoS(60) 2* 6 11.1 35.4 63.2 1.4
MCoS(20) 2* 6 15.3 46 0.1 51.6 2.3
MCoS(60) 2* 8 15.6 23.2 73.7 3.1
MCoS(20) 2* 8 22.6 26.7 68.6 4. 7
MCoS(60) 2* 14 19.2 21.5 74.7 3.8
MCoS(20) 2* 14 28.8 22.9 72.8 4.3

Reaction conditions: catalyst mass = 0.100 g; temperature = 373 K

13
 Journal of Porous Materials

Table 5  Leaching catalytic Catalyst (TBHP/C6H12) TIME X% Sol Sone Sbyproducts

study
MCoS(20) 2* 1 1.7 66.3 32.9 0.8
Filtrat without MCoS(20) 8 1.9 67.9 31.5 0.6

Reaction conditions: catalyst mass = 0.100 g; temperature = 373 K

reaction in the catalyst [52]. It can be seen from Table 2 that cyclohexane to TBHP molar ratio increases from 1:1 to
MCoS(20) is more active than Co-SBA15(20) in the liquid- 1:2, while the cyclohexanol selectivity decreases, which is
phase oxidation of cyclohexane using TBHP as oxidizing ascribed to a further oxidation of cyclohexanol to cyclohex-
agent. MCoS(20) shows 13.7% conversion and 99% selec- anone. It is worth noting that MCoS(20) is more active than
tivity to cyclohexanone and cyclohexanol, while the con- Co-SBA15(20). The most active catalyst MCoS(20) acts as
version reaches 7.1% over Co-SBA-15(20) under the same truly heterogeneous catalyst and was very stable after four
conditions. Co-SBA-15 catalyst prepared by direct synthesis runs, hence it is a potential candidate for the oxidation of
exhibited 9.4% conversion of cyclohexane and 95% selectiv- cycloalkanes with TBHP under mild conditions.
ity to cyclohexanone and cyclohexanol at 433 K and 1 MPa
of ­O2 [19].
The effect of reaction time on the cyclohexane oxida-
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