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Zr-SBA Catalyst Pentru Reactia Prins
Zr-SBA Catalyst Pentru Reactia Prins
www.rsc.org/catalysis PAPER
Mesoporous Zr-SBA-15 as a green solid acid catalyst for the Prins
reactionw
Dong Minh Do, Stephan Jaenicke and Gaik-Khuan Chuah*
Received 13th February 2012, Accepted 25th March 2012
DOI: 10.1039/c2cy20084h
Published on 27 March 2012. Downloaded on 17/03/2017 12:09:01.
Mesoporous Zr-SBA-15 platelets were prepared with different pore dimensions from 4 to 8 nm
by the simple procedure of varying the amount of water in the synthesis gel. Narrow pore size
distributions were obtained for water–tetraethoxysilane ratios between 208 and 639, but samples
formed using a lower ratio of 100 had a broad pore size distribution. Thermogravimetric
measurements showed that the interaction between the Pluronic template and the inorganic
framework was affected by the amount of water in the synthesis gel. More zirconium was
incorporated into the silica framework when the synthesis was conducted in a more dilute system.
The Zr-SBA-15 obtained from this synthesis forms platelets with relatively short channels.
The catalytic activity was tested for C–C-coupling (Prins reaction). The terpene alcohol Nopol,
the product of an intermolecular Prins reaction between b-pinene and paraformaldehyde, could
be obtained with excellent selectivity. The mesoporous structure of the catalyst together with the
presence of zirconium in the silica framework, which confers strong Lewis acidity as well as
weak Brønsted acidic sites, are essential for the activity and selectivity of the reaction.
Introduction catalysts have been prepared by loading this metal onto high
surface area supports like MCM-41, SBA-15 or kenyaite
Acid-catalyzed reactions are important in petrochemical and (a sodium silicate) through ion exchange, incipient wetness
fine chemical synthesis.1 Using solid acids instead of mineral impregnation and chemical vapor deposition14–17 and by incor-
acids offers green synthetic routes to the desired chemicals, due poration into the silica framework of mesoporous SBA-15.18 In
to ease of product isolation, minimization of waste in work-up particular, Corma and Renz19 reported that Sn-MCM-41 was very
and reuse of catalysts. Hence, efficient and selective solid acids active in the Prins reaction of b-pinene with paraformaldehyde,
are desired. An example of an acid-catalyzed C–C coupling forming Nopol with a 94% selectivity at 93% conversion.
reaction is the Prins reaction where aldehydes are added to The use of butylnitrile instead of toluene as a solvent improved
alkenes.2 Different products such as 1,3-diols, 1,3-dioxanes or the selectivity by moderating the strength of the acidic sites at
unsaturated alcohols can be formed, depending on the reaction the catalyst.
conditions.3,4 Various acids have been reported such as hydro- Non-tin-containing heterogeneous catalysts reported for Nopol
chloric acid, alkyl aluminium chlorides,5,6 stannic chloride,7–9 synthesis include mesoporous iron phosphate,20 mesoporous
indium chloride in ionic liquids,10 and heteropolyacids.11 The Zn-Al-MCM-41,21 ZnCl2 impregnated Indian Montmorillonite,22
Prins reaction of b-pinene with paraformaldehyde is used in the and Fe–Zn double cyanide.23 However, mesoporous iron
synthesis of Nopol, a bicyclic unsaturated primary alcohol phosphate gave only Nopol yields of 2–85% at a catalyst to
(Scheme 1). Its ester with acetic acid, nopyl acetate, is an substrate ratio of 3.3 : 5 mmol.20 An even higher catalyst to
artificial fragrance compound which is found in the formulations substrate molar ratio (6.6 : 5) was required to reach 100% conver-
of many household products such as pesticides, detergents, soaps sion. Similarly, the use of Al-MCM-41 and Zn-Al-MCM-41 gave
and polishes.12 Normally, Nopol is synthesized in homogeneous Nopol yields of 27–84% but at a catalyst : substrate ratio of 0.2 g
systems using either ZnCl2 or acetic acid as the catalyst, or by (B 3.3 mmol) : 0.75 mmol.21
autoclaving the mixture of formaldehyde and b-pinene for
several hours at 150–230 1C.13 As tin was found to be active
for the homogeneously-catalyzed reaction,7–9 various supported
This journal is c The Royal Society of Chemistry 2012 Catal. Sci. Technol., 2012, 2, 1417–1424 1417
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We have found that hydrous zirconia and Zr-zeolite beta are for 8 h (or 24 h) before hydrothermal treatment at 100 1C for
good catalysts for the intramolecular Prins cyclisation of 24 h in a Teflon-lined autoclave. The solid was recovered by
citronellal to isopulegols.24,25 These catalysts possess strong filtration, washed, dried at 100 1C, and calcined at 550 1C for
Lewis acid sites and weak Brønsted sites, both of which are 8 h to remove the organic template. The amount of water was
essential for the reaction.24 Further studies using mesoporous varied from 6.67 ml to 56.67 ml to give H2O/Si molar ratios of
TUD-1 with framework incorporation of Al and Zr showed 100, 208, 423 and 639. The molar composition of the synthesis
the presence of synergy between the Brønsted and Lewis gel was 0.017 Pluronic : 1 TEOS : 0.10 ZrOCl28H2O : 7.77
acid sites when applied as catalysts in the cyclisation of HCl : 100–639 H2O. The samples are labeled as 10Zr-w-t where
citronellal.26 However, when used in the more challenging 10 denotes the Si/Zr ratio, w the H2O/Si ratio and t represents
intermolecular Prins reaction between b-pinene and paraformal- the aging time of the synthesis gel. A catalyst with a lower
dehyde, no synergy was observed.27 To investigate if there zirconium content, 50Zr-423-24, was also prepared.
are other suitable catalysts besides the tin-based ones for inter- A procedure for Al-SBA-1544 was adapted for the prepara-
molecular Prins reactions, we focused on zirconium-containing tion of non-platelet mesoporous zirconium silica (10ZrMPS,
materials. The bulky size of b-pinene necessitates the use of Si/Zr = 10). The molar composition of the gel was 0.016
mesoporous catalysts, as previous studies with this substrate have Pluronic : 1 TEOS : 0.10 ZrOCl28H2O : 0.56 HCl : 77 H2O. A
Published on 27 March 2012. Downloaded on 17/03/2017 12:09:01.
shown a higher reaction rate with Sn-MCM-41 than with mixture of 2 g Pluronic P123 in 27.6 ml water was stirred at
microporous Sn-beta.19 room temperature for 3 h before adding 2.4 ml of 5 M HCl,
Among the mesoporous materials, SBA-15 with tunable 4.82 ml TEOS and 0.696 g zirconium oxychloride. The
pore sizes of 4–10 nm arranged in a 2D-hexagonal p6mm solution was stirred for 4 h, hydrothermally treated in a
structure has received much attention in the past decade Teflon-lined autoclave at 100 1C for 2 days before calcination
because of its relatively large pore size and high hydrothermal at 500 1C for 8 h.
stability in comparison with other mesoporous silica materials.
While the synthesis of the pure silica mesoporous material is
Characterization of samples
easily carried out in the presence of an appropriate surfactant,
it has low catalytic activity due to the lack of acidic sites. The The zirconium and silicon content of the samples was determined
incorporation of other metal ions such as zirconium into the by inductively coupled plasma-atomic emission spectroscopy
framework provides Lewis acidity. Mesoporous zirconium- (ICP-AES) after dissolving a weighed amount in HF. X-ray
doped silica is of interest due to the catalytic activity of the diffraction measurements were carried out using a Siemens
metal28–33 and the possibility of forming strong solid acids by D5005 diffractometer equipped with a copper anode and variable
sulfation.34–37 Recently, several novel routes have been developed slits. A step size of 0.0041/step and 0.021/step was used for 2y
for direct synthesis of Zr-SBA-15. For example, Newalkar et al.38 between 0.5–61 and 6–701, respectively. The morphology of the
reported the direct synthesis of Zr-SBA-15 with Si/Zr of 10–80 samples was measured using a scanning electron microscope
using microwave irradiation. The materials formed had thicker (JEOL JSM-5200). The UV-Vis absorption spectra were
walls than those formed by conventional synthesis.39 Materials measured against a barium sulfate reference using a Shimadzu
with high zirconium content (Si/Zr 5–9) were prepared by Du spectrophotometer (UV-2450) equipped with a diffuse-reflectance
et al.40 using urea as a pH adjustor. Cheng and coworkers41 cell. 29Si MAS NMR spectra were measured on a Bruker
showed that the synthesis of Zr-SBA-15 from the zirconium DRX-400 wide-bore solid state spectrometer operating at a
precursor ZrOCl28H2O was possible in the absence of HCl. resonance frequency of 79.46 MHz with a spinning rate of
However, the addition of HCl changed the morphology of the 8 kHz, a pulse length of 4 ms and a recycle time of 20 s. 4 mm
materials from rod-like structures to hexagonal platelets with rotors were used and the 29Si chemical shifts are reported
short mesochannels of 150–350 nm in length, perpendicular to relative to tetramethylsilane. The interaction between Pluronic
the hexagonal planes.42 Due to their structure, these platelet and the inorganic silica–zirconia was studied using thermo-
materials were less susceptible to diffusion limitations and pore gravimetric analysis-mass spectrometry (TGA-MS, MS-Pfeiffer
blockage than conventional rod or fibre-like SBA-15. Hence, Thermo Star) and simultaneous differential thermal analysis-
these materials are potentially useful catalysts in the intermole- thermogravimetric analysis (DTA-TGA, SDT 2960). Prior to
cular Prins reaction, where both the nature and strength of the the measurements, the as-synthesized sample was kept at 100 1C
acidic sites are essential for the formation of Nopol.43 In this for 30 min before heating to 600 1C in air at a rate of 10 1C min1.
study, we varied the water content in the synthesis gel and The evolution of water (m/z 18) and carbon dioxide
examined its effect on the pore size of the materials. (m/z 44) was monitored by the online mass spectrometer.
The adsorption of b-pinene and formaldehyde on 10Zr-423-8
was investigated by DTA-TGA. The catalyst was first im-
Experimental pregnated with b-pinene or formaldehyde in toluene and dried
at room temperature under nitrogen before thermogravimetric
Preparation of zirconium-incorporated SBA-15
analysis. A blank run was carried out using only the catalyst.
First, 0.5 g Pluronic P123 was added to a solution containing The presence of residual products on the catalyst after the
3.33 ml concentrated HCl (12 M) in water. After stirring the reaction was similarly studied. A heating rate of 10 1C min1 in
mixture for 4 h to obtain a clear solution, 1.15 ml tetraethyl nitrogen from room temperature to 500 1C was used.
orthosilicate (TEOS) and 0.162 g zirconium oxychloride The nitrogen adsorption–desorption isotherms were carried
(ZrOCl28H2O) were added. The mixture was stirred at 35 1C out using a Micromeritics Tristar 3000. Samples were degassed
1418 Catal. Sci. Technol., 2012, 2, 1417–1424 This journal is c The Royal Society of Chemistry 2012
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1420 Catal. Sci. Technol., 2012, 2, 1417–1424 This journal is c The Royal Society of Chemistry 2012
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Lewis/Brønstedc
Sample Si/Zr pHa Acidityb (mmol g1)
Solid 25 1C 100 1C
Fig. 6 Ammonia TPD of 10Zr-w-24 and 10ZrMPS samples.
10Zr-100-24 18.4 0.17 0.17 12.5 3.3
10Zr-208-24 17.9 0.33 0.31 11.2 4.3
10Zr-423-24 14.6 0.65 0.33 14.5 4.1 the samples (Fig. S5w). The adsorption of pyridine at Lewis
10Zr-639-24 13.1 0.73 0.43 15.7 6.1 acid sites is indicated by bands at B1440–1450 cm1 and
10Zr-208-8 12.9 0.33 0.51 N.D. N.D. 1600–1610 cm1, while the pyridinium ion formed by adsorp-
10Zr-423-8 16.4 0.65 0.35 N.D. N.D.
10ZrMPS 15.4 — 0.32 N.D. N.D. tion of pyridine at Brønsted acid sites shows a band at
Zr-beta 100 — — 8.3 2.5 B1540–1550 cm1. The peak at B1491 cm1 is attributed to
a
In the synthesis gel. b From NH3 TPD. c From pyridine IR mea- both Brønsted and Lewis acidities. The incorporation of zirconium
surements. N.D: not determined. into the silica framework can result in the generation of Brønsted
acid sites as suggested by Tanabe et al.45 The relative density
of Lewis/Brønsted acid sites were obtained from the bands
These bands broadened and merged together in the zirconium- B1445 cm1 and B1545 cm1 after normalizing with the
containing samples. The smaller bands centered at 800 and respective molar extinction coefficients.46 Lewis acidity was
458 cm1 are assigned to Si–O–Si symmetric stretching and predominant in all the samples (Table 2). The density of Lewis
rocking modes, respectively, and they also broadened with a acid sites increased with the amount of water in the synthesis
slight decrease in intensity when zirconium was introduced gel while samples formed with less water had more Brønsted
into the silica framework. The 29Si MAS spectra show peaks of acidity. Evacuation of the samples at 100 1C resulted in the
Q4 and Q3 (Si with four and three neighbouring Si) with only a removal of pyridine bound to weak Lewis acid sites, so that
small Q2 peak. The higher intensity of the Q3 peak over Q2 the Lewis/Brønsted ratio decreased.
supports the presence of isolated zirconium ions in the silica
matrix (Fig. S4w).
Catalytic activity
The acidity of the samples was assessed by ammonia
temperature-programmed desorption (Fig. 6). Desorption of The catalytic activity of the 10Zr-SBA catalysts was tested in
ammonia occurred between 170 and 470 1C, showing that the the liquid phase Prins condensation of paraformaldehyde and
samples have a range of acidic sites. The density of acid sites b-pinene to form Nopol (Table 3). The samples exhibited good
increased from 0.17 mmol g1 in 10Zr-100-24 to 0.43 mmol g1 activity. Conversions of 54–74% were obtained after 6 h when
for 10Zr-639-24. This is due to the incorporation of more the reaction was carried out at 80 1C. At 100 1C, the conversion
zirconium into the silica framework as the water content in increased to 69–95%. The highest activity was observed for
the synthesis gel increased. The pyridine IR measurements catalysts formed with H2O/Si of 208 and 423. For samples
indicate the presence of both Brønsted and Lewis acid sites in prepared at H2O/Si of 423, the conversion decreased from 74%
This journal is c The Royal Society of Chemistry 2012 Catal. Sci. Technol., 2012, 2, 1417–1424 1421
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1422 Catal. Sci. Technol., 2012, 2, 1417–1424 This journal is c The Royal Society of Chemistry 2012
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Acknowledgements
Financial support from National University of Singapore under
grant number R-143-000-418-112 is gratefully acknowledged.
This journal is c The Royal Society of Chemistry 2012 Catal. Sci. Technol., 2012, 2, 1417–1424 1423
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