David
Skoda
ab,
Ales
Styskalik
ab,
Zdenek
Moravec
a,
Petr
Bezdicka
c,
Michal
Babiak
ab,
Mariana
Klementova
c,
Craig E.
Barnes
d and
Jiri
Pinkas
*ab
aDepartment of Chemistry, Masaryk University, Kotlarska 2, CZ-61137 Brno, Czech Republic. E-mail: jpinkas@chemi.muni.cz
bCEITEC MU, Masaryk University, Kamenice 5, CZ-62500 Brno, Czech Republic
cInstitute of Inorganic Chemistry of the ASCR, v.v.i., CZ-25068 Husinec-Rez, Czech Republic
dDepartment of Chemistry, University of Tennessee, Knoxville, TN 37996-1600, USA
First published on 25th February 2016
A novel non-hydrolytic sol–gel (NHSG) synthesis of mesoporous aluminosilicate xerogels is presented. The polycondensation between silicon acetate, Si(OAc)4, and tris(dimethylamido)alane, Al(NMe2)3, leads to homogeneous aluminosilicate xerogels containing Si–O–Al linkages through dimethylacetamide elimination. The addition of Pluronic P123 and F127 templates provides stiff gels that are, after calcination at 500 °C, converted to stable mesoporous xerogels with a high surface area (>600 m2 g−1) and wormhole-type pores (d = 5.9 nm). The xerogels exhibit high catalytic activity in aminolysis of styrene oxide (82% conversion) with the turnover frequency up to 100.
Recently, Liu13 has obtained Al-rich mesoporous aluminosilicates with improved hydrothermal stability by assembling zeolite Y and beta precursors in the walls of mesophases. For example, the retaining ratio of the total surface area was 33% after hydrothermal treatment in 100% water vapor at 800 °C for 15 h. This group also reported a pH-adjusting method24 based on the assembly of beta zeolite. An approach recently published by Enterría25 provides a simple strategy based on the overgrowing mesoporous silica (MCM-48) on crystalline zeolite particles. For this purpose, preformed zeolite is added to mesoporous silica gel, which results in materials with a microporous zeolitic core and a mesoporous silica cover (MCM-48).
The methods and procedures mentioned above all involve hydrolytic reactions. Aluminosilicates can also be successfully prepared by non-hydrolytic routes. With these methods, it is possible to overcome the problems of different hydrolysis rates and subsequent phase separation. These techniques allow reaction control on atomic scale and homogeneous dispersions of silicon and aluminum atoms in the gel network may be achieved. One type of non-hydrolytic sol–gel (NHSG) reaction is alkylhalogenide elimination.26 In this method, condensations between SiCl4, AlCl3, Al(OiPr)3, and Si(OiPr)4 in ethers or CH2Cl2 provide monolithic homogeneous aluminosilicate gels27 (Scheme 1).
This non-hydrolytic sol–gel technique has also been applied to the preparation of highly active mesoporous metathesis catalysts MoO3–SiO2–Al2O328 and Re2O7–SiO2–Al2O3.29 Mullite precursor gel synthesis was described from AlCl3 and TEOS in Et2O and CCl4 in an autoclave at 110 °C.30
Catalytic efficiency of aluminosilicates was determined by a variety of test reactions. Kim reported Friedel–Crafts acylation of bulky aromatic compounds in MFI zeolite nanosponge,31 Neves32 used mesoporous aluminosilicates with acid sites for conversion of furfuryl alcohol to ethyl levulinate and Robinson described the alcoholysis and aminolysis of styrene oxide promoted by mesoporous aluminosilicate catalysts.33,34
We have recently reported that non-hydrolytic acetamide elimination35 can be successfully used for the synthesis of mesoporous titanium silicate36 and zirconium silicate materials.37 In contrast to conventional hydrolysis-based routes for the preparation of SBA-15 and MCM-41 materials, our approach excludes hydrolytic steps and the reactions proceed only by condensation of metal amide with silicon acetate.
The work presented here introduces this novel non-hydrolytic acetamide elimination for the preparation of aluminosilicate xerogels with a high Al content in the framework. This effective one-pot reaction can be extended by the use of templates. With the Pluronic block copolymers we are able to obtain homogeneous xerogels which exhibit their mesoporous character even after calcination at 700 °C and convert to mullite only at 980–1000 °C. We have successfully used these materials as catalysts for aminolysis34,38 and alcoholysis33 of styrene oxide and for the conversion of styrene oxide to phenylacetaldehyde.39
Chemicals, such as Pluronic P123 (EO20PO70EO20Mav = 5845 g mol−1), Pluronic F127 (EO100PO65EO100Mav = 12600 g mol−1), tris(dimethylamido)aluminium Al(NMe2)3 (99%), styrene oxide (97%), aniline (97%), methanol, and nonane, were purchased from Sigma-Aldrich. Si(OAc)4, Si2O(OAc)6, Me3SiOAc, and Si2(CH2)2(OAc)6 were synthesized according to the published procedures.40 Toluene, methanol, and isopropanol were dried by standard methods and distilled before use. Pluronic P123 and F127 were dried under vacuum at 60 °C, dissolved in dry toluene, and stored as 20.17 and 19.61 wt% solutions, respectively.
The single-crystal X-ray diffraction data were collected at 120 K using Rigaku diffraction system (MicroMax007HF DW rotating anode source with multilayer optic, partial χ axis goniometer, Saturn 724+ HG detector and Cryostream cooling device). Molybdenum Kα radiation (λ = 0.71075 Å) was used. CrystalClear (Rigaku 2014) and CrysAlisPro (Agilent Technologies 2013) software packages were used for data collection and data reduction. The structure was solved using SHELXT43 program and refined (full matrix least-squares refinement on F2) using SHELXL program. Both symmetrically independent cation fragments were disordered. One Me3Si-moiety of one anionic fragment was also refined as disordered. Disordered fragments were treated by geometrical similarity restraints and by ADP restraints. All non-hydrogen atoms were refined anisotropically. All hydrogen atoms (of methyl and hydroxyl groups) were placed at calculated positions and refined as riding and rotating, with their Uiso set to 1.5Ueq of carrier atom.
In reactions without a template, the yield of the product as well as the mass of starting precursors were precisely weighed to allow gravimetric estimation of the degree of condensation, DC = 100(ntotal − nresidual)/ntotal, where ntotal is the molar amount of organic groups in the starting materials and nresidual is molar amount of residual organic groups in the xerogel based on the difference between theoretical and experimental yields. As the condensation reactions were never quantitative, the degree of condensation represents the relative difference between the maximum theoretical loss of Me2NC(O)CH3 (eqn (1)) in comparison to what is experimentally observed. This difference also defines the number of acetoxy groups on silicon and dimethylamido groups on aluminium that are left in the matrix.
NMR: 13C CPMAS (SiAl1, ppm) δ 21.9 (CH3C(O) – bidentate), 24.1 (CH3C(O) – monodentate), 33.4, 35.3 (CH3N), 38.2 (CH3N), 170.7 (CH3C(O) – monodentate), 179.4 (CH3C(O) – bidentate); 29Si CPMAS (ppm) δ −89; 27Al MAS (ppm) δ 0 (AlVI = 6-coordinated Al), 29 (AlV = 5-coordinated Al), 54 (AlIV = 4-coordinated Al).
TG/DSC (air, 5 °C min−1) weight loss at 1000 °C 53.83%.
BET: SA = 607 m2 g−1, C = 146, Vtot = 0.35 cm3 g−1, d = 2.4 nm.
Aluminosilicate xerogel C2SiAl with Si2(CH2)2(OAc)6 precursor was prepared with the same procedure and under same conditions as in the case of SiAl1 xerogel. See Table 1.
Sample | Si precursor | n Si [mmol] | n Al [mmol] | Ala mol% | Template | n template [mmol] | TG residual mass at 1000 °C [%] | TG residual mass calc.b [%] |
---|---|---|---|---|---|---|---|---|
a Nominal Almol% = nAl/(nAl + nSi). b Based on AlxSiyOz (see text) in precursors. | ||||||||
SiAl1 | Si(OAc)4 | 3.907 | 5.018 | 56.2 | — | — | 46.17 | 45.10 |
C2SiAl | Si2(CH2)2(OAc)6 | 5.108 | 5.100 | 49.9 | — | — | 50.09 | 40.45 |
SiAl2 | Me3SiOAc | 13.726 | 4.478 | 24.6 | — | — | 7.71 | — |
SiAlP1 | Si(OAc)4 | 5.029 | 3.460 | 40.8 | P123 | 0.239 | 19.92 | 18.74 |
SiAlF1 | Si(OAc)4 | 5.025 | 3.416 | 40.5 | F127 | 0.111 | 19.36 | 15.70 |
SiAlP2 | Si(OAc)4 | 3.825 | 5.206 | 57.6 | P123 | 0.128 | 31.78 | 26.64 |
SiAlF2 | Si(OAc)4 | 3.894 | 5.114 | 56.8 | F127 | 0.064 | 29.94 | 29.36 |
SiAlP3 | Si2O(OAc)6 | 2.312 | 2.418 | 51.1 | P123 | 0.071 | 30.49 | 35.59 |
SiAlF3 | Si2O(OAc)6 | 5.236 | 5.112 | 49.4 | F127 | 0.068 | 31.78 | 39.34 |
NMR: 13C CPMAS (SiAlF2, ppm) δ 26.9 (CH3C(O)), 40.7 (CH3N), 74.1 (CH2O), 79 (CHO), 173.3 (CH3C(O) – monodentate), 184.6 (CH3C(O) – bidentate); 29Si CPMAS (SiAlF2, ppm) δ −87; 27Al MAS (SiAlF2, ppm) δ 2 (AlVI), 32 (AlV), 61 (AlIV).
TG/DSC: (air, 5 °C min−1) weight loss at 1000 °C 70.06%.
Portions of dried xerogel were calcined in a tube furnace under air at 500 and 700 °C for 3 h.
BET: (sample calcined at 500 °C) SA = 477 m2 g−1, C = 54, Vtot = 0.53 cm3 g−1, d = 5.9 nm.
ICP OES (sample calcined at 500 °C) wt%: Al 25.34 ± 0.04, Si 18.98 ± 0.01.
Hydrothermal stability was studied after calcination at 500 °C. The xerogel was kept in refluxing water for 24 hours. Then, water was evaporated and the sample was dried under vacuum at 100 °C. Changes in the xerogel porosity and structure were studied by N2 porosimetry and MAS NMR spectroscopy.
Calcined samples are labeled with a number corresponding to the particular calcination temperature, e.g. SiAlF1-500, water-treated samples are labeled with H, e.g. SiAlF2-500H.
Reactions with the P123 template were carried out under the same conditions as in the case of F127. Aluminosilicate xerogels from Si2O(OAc)6 precursor were prepared according to same protocol as in the case of SiAlF2 sample. For details see the Table 1.
EI-MS (m/z): 589 [Al2(OSiMe3)6H]+ (10%); 574 [Al2(OSiMe3)5OSiMe2H]+ (100%); 485 [Al2(OSiMe3)4OSiMe2H]+ (20%); 411 [Al2(OSiMe3)4H]+ (50%).
3Si(OAc)4 + 4Al(NMe2)3 → Al4Si3O12 + 12Me2NC(O)CH3 | (1) |
(AcO)3SiOSi(OAc)3 + 2Al(NMe2)3 → Al2Si2O7 + 6Me2NC(O)CH3 | (2) |
(AcO)3Si–(CH2)2–Si(OAc)3 + 2Al(NMe2)3 → Al2Si2(CH2)2O6 + 6Me2NC(O)CH3 | (3) |
The reaction proceeds with the formation of Si–O–Al network and release of dimethylacetamide which was confirmed by GC-MS (Fig. 2S†) and 1H NMR analysis of volatiles separated from the reaction mixture. In the case of the reaction with excess Si(OAc)4, a small amount of acetic acid was observed in GC-MS.
Hexaacetoxydisiloxane (AcO)3SiOSi(OAc)3 (eqn (2)) and bis(triacetoxysilyl)ethane (AcO)3Si–(CH2)2–Si(OAc)3 (eqn (3)) were used for the modification of porosity and optimizing of the Si/Al ratio. Eqn (1) represents a complete condensation of functional groups to Si–O–Al network and quantitative elimination of dimethylacetamide. However, under experimental conditions, the condensation is incomplete (Scheme 2), and degree of condensation (DC) for the reaction without a template was 56%.
![]() | ||
Scheme 2 Synthesis of aluminosilicate gel with four-, five-, and six-coordinate Al atoms and residual acetate and dimethylamide groups. |
Reaction parameters are summarized in Table 1. Systems without the templates produced yellowish turbid gels which were dried under vacuum for 24 h to form yellow powders. With the use of templates, stiff and transparent yellow gels were obtained. These gels were dried to form yellow-orange rubbery or glassy products. Dried xerogels were afterwards calcined in a tube furnace at 500 °C for 3 h in air to remove the templates. The resulting yellowish powders possessed surface areas that were substantially improved and pore sizes corresponded to mesoporous region (see below).
To study the condensation, a model reaction between Me3SiOAc and Al(NMe2)3 was carried out. It provided molecular ionic compound [Me(C)OHNMe2]+ [Al(OSiMe3)4]− (1) (Fig. 1 and 1S†). Crystallographic details and IR spectrum of 1 are summarized in ESI (Table 1S, Fig. 3S†). A similar compound has been prepared by Chisholm from Me3SiOH and Al(NMe2)3.45 This product shows that condensation between acetoxy and dimethylamido groups takes place forming Si–O–Al bonds.
IR spectra of all dried products were recorded to identify Si–O–Al heterolinkages and also the residual organic groups. Fig. 2 illustrates IR spectra of non-templated and F127 templated dried samples synthesized by NHSG reactions. The absence of OH bands attests to the truly non-aqueous nature of the xerogel synthesis. Vibrational bands located at 1030–1000 cm−1 are attributed to Si–O–Si and Si–O–Al bonds on the basis that introduction of Si–O–Al bonds in a SiO2 matrix shifts the absorption maxima toward the lower wavenumbers.46–48 Besides the bonds mentioned above, vibrational bands of residual organic groups were observed as well. Dimethylamido groups give rise to vibrational bands at 1250–1270, 1370–1380, 1510–1520, and 2970–2980 cm−1.49–51 Acetoxy moieties are characterized by the asymmetric and symmetric COO stretches at 1580–1590 and 1460–1470 cm−1, respectively. The difference between symmetric and asymmetric carboxylate vibrational bands is 120–130 cm−1 and according to Deacon–Phillips rules, this is indicative of the bidentate bridging mode on a metal center.52,53 Pluronic templates P123 and F127 are represented by vibrational bands of C–O–C bonds at 1090–1105 cm−1 and CH3 at 2860–2880 cm−1.54
The thermal behavior of the prepared products was studied by TG/DSC analysis in air. Residual masses are summarized in Table 1. These values are in an agreement with the calculated residual masses corresponding to aluminosilicate AlxSiyOz, where x, y, and z represent moles of aluminium, silicon, and oxygen in precursors. For example, the TG residual mass of sample SiAlF2 (Table 1) is 29.94% while the calculated residual mass of aluminosilicate is 29.36%. TG curves (Fig. 4S†) of xerogels synthesized without the templates display mass losses in two steps. The first mass loss is observed between 50–225 °C (21–26%) and the second one between 230–500 °C (24%). These steps are connected with oxidation of residual dimethylamido and acetoxy moieties. In the case of templated samples the highest mass losses (52–56%) are observed between 200–450 °C. Xerogels with a lower content of Al show the highest mass loss between 125–400 °C (68–72%). A lower decomposition temperature than in the previous case could be explained by the oxidation of unreacted monodentate acetoxy groups bound to silicon. DSC curves of the templated samples (SiAlP2, SiAlF2) with 57–58 mol% of Al show exothermic peaks at 995 and 985 °C for the xerogel with F127 and P123 copolymer, respectively. This observation could be connected to crystallization of the mullite phase.46–48
Solid state NMR spectroscopy (Table 2) was employed for in-depth characterization of the aluminosilicate xerogel matrix. 13C CPMAS NMR spectrum of non-templated sample (SiAl1) displayed resonances of residual organic groups (Fig. 5S†). Resonances at 33.1, 35.0, and 37.8 ppm are attributed to dimethylamido groups while the acetoxy groups in bidentate and monodentate coordination are characterized by the CH3 resonances at 22.0 and 24.1 ppm, respectively. The COO resonances of acetate groups in unidentate and bidentate mode were observed at 170.4 and 179.5 ppm, respectively. Similar resonances of residual N(CH3)2 (34.1, 37.4 ppm), CH3 (20.7, 23.1 ppm) and COO (169.8, 179.0 ppm) were observed also in the 13C CPMAS spectrum of the xerogel synthesized from bis(triacetoxysilyl)ethane (C2SiAl). The ethylene (CH2–CH2) bridge is characterized by the signal at 7.5 ppm. In the 13C CPMAS NMR spectrum of F127 templated xerogel (SiAlF2, Fig. 5S†), the presence of residual organic moieties was observed as well. The N(CH3)2 groups are seen at 40.8 ppm and CH3 of acetoxy species are displayed at 27.3 ppm. The carboxylate function features weak signals at 173.2 and 183.2 ppm. The template carbons are represented by chemical shifts at 21.0 (CH3CHO), 74.1, 76.8, and 78.8 ppm (CH2O and CH3CHO).55
Sample | Chemical shift [ppm] | |||||
---|---|---|---|---|---|---|
29Si CPMAS | 27Al MAS | |||||
SiAl1 | −89 | 53 | 28 | 0 | ||
C2SiAl | −54 | 54 | 29 | −1 | ||
SiAlF1 | −106 | −97 | 54 | −2 | −4 | |
SiAlF1-500 | −97 | 61 | 32 | 2 | ||
SiAlF2 | −88 | 61 | 32 | 2 | ||
SiAlF2-500 | −90 | 64 | 33 | 4 | ||
SiAlF3 | −90 | 61 | 30 | 0 | ||
SiAlF3-500 | −93 | 69 | 34 | 4 |
The 29Si CPMAS NMR spectrum of non-templated sample (SiAl1) shows a broad signal with the maximum at −89 ppm (Fig. 3). Compared to SiO2 (−110 ppm)56,57 and Si(OAc)4 (−96 ppm) a downfield shift is observed. This shift is caused by the presence of Si–O–Al linkages in the xerogel network.58–6029Si CPMAS NMR spectrum of the sample C2SiAl with ethylene (CH2–CH2) bridges displays a broad signal with the maximum at −54 ppm (Fig. 3). 29Si CPMAS NMR data of templated samples displays a broad signal at −87 ppm assigned to Si(OSi)(OAl)3 species (Fig. 3).58,59 Similar resonances were observed after calcination at 500 °C of these templated samples (Fig. 4). The resonance at −90 ppm in 29Si CPMAS NMR corresponds to Si(OSi)(OAl)358,59 In the case of templated samples with a lower Al content (SiAlF1), 29Si CPMAS displays a signal with maximum at −106 ppm and a shoulder at −97 ppm. This shift could be caused by the formation of Si–O–Si bonds because of excess Si(OAc)4 (Fig. 3). Comparison of 29Si CPMAS NMR spectra before and after calcinations for the templated samples SiAlF1, 2, 3 indicates there are not major differences (Fig. 4).
![]() | ||
Fig. 4 29Si CPMAS NMR spectra of calcined (500 °C) aluminosilicate xerogels synthesized with F127 template. |
27Al NMR spectra of dried xerogels provide information about the coordination number of Al atoms in the aluminosilicate network. 27Al spectra of dried non-templated xerogels (SiAl1, C2SiAl) illustrate three signals attributed to 4-coordinated (AlIV, 53 ppm), 5-coordinated (AlV, 28 ppm) and 6-coordinated (AlVI, 0 ppm) Al3,58,61 (Fig. 6S†). 27Al MAS NMR spectra of dried templated samples (SiAlF2, 3) show also the resonances for AlIV (58 ppm), AlV (31 ppm), and AlVI (2 ppm) atoms in the framework (Fig. 6S†). No significant change in the 27Al MAS NMR spectra of calcined templated xerogels was observed and Al signals were found at 62 ppm (AlIV), 33 ppm (AlV), and 4 ppm (AlVI).5827Al MAS NMR spectrum of the sample SiAlF1 (lower Al content) displays signals for AlIV at 54 ppm and for AlVI at −2 and −4 ppm. After calcination of this sample, the resonances at 61 ppm (AlIV), 32 ppm (AlV), and 2 ppm (AlVI) were observed (Fig. 5). Chemical shifts of xerogel samples are summarized in Table 2. From these NMR data we can conclude, that the calcined xerogels still contain Si–O–Al bonds and no phase separation takes place during the calcination. The 27Al NMR and EPR observations made by Chen et al. show association of five-coordinated aluminum atoms to Lewis acid sites.62 Hence, the effect of different aluminum coordination and their acid–base properties on the catalytic activity is a very interesting subject. 27Al MAS spectrum of hydrothermally treated sample SiAlF2-500H shows intensity decrease of signal corresponding to 5-coordinated Al while the signal of 6-coordinated Al atoms increased (Fig. 7S†). This change is caused by coordination of water and –OH groups. Solid state MAS NMR spectra of the samples synthesized with the P123 template are similar and thus are not shown here.
![]() | ||
Fig. 5 27Al MAS NMR spectra of calcined (500 °C) aluminosilicate xerogels synthesized with F127 template. |
A very important feature of these aluminosilicate xerogels is their porosity. High surface area materials with mesopores provide better catalytic efficiency for the processing of bulky organic molecules. We investigated the N2 adsorption/desorption isotherms of the non-templated and templated samples (Table 3). The results show that xerogels synthesized without copolymer templates exhibit high surface areas after drying and feature the type-II isotherms63 (Fig. 6). Equivalent BET surface areas of xerogels prepared from Si(OAc)4 (SiAl1) and from the ethylene bridged acetoxysilane (C2SiAl, Fig. 8S†) were 607 and 517 m2 g−1, respectively. However the pore diameters correspond to micropores in both materials. After calcination of the C2SiAl sample at 200 °C, surface area decreased considerably to 36 m2 g−1. This change can be explained by the framework collapse while the ethylene bridging groups are oxidized. Interestingly, according to the NLDFT method, the pore diameter increased and shifted to the mesopore region (4.8 nm).
Sample | Template | Al mol% | SA (BET) [m2 g−1] | V [cm3 g−1] | d [nm] |
---|---|---|---|---|---|
SiAl1 | — | 56.2 | 607 | 0.34 | 2.4 |
C2SiAl | — | 49.9 | 517 | 0.38 | 2.9 |
SiAlP1-500 | P123 | 42.2 | 429 | 0.37 | 4.9 |
SiAlF1-500 | F127 | 40.6 | 381 | 0.37 | 4.9 |
SiAlP2-500 | P123 | 59.3 | 591 | 0.53 | 4.9 |
SiAlF2-500 | F127 | 58.1 | 477 | 0.53 | 5.9 |
SiAlF2-700 | F127 | 58.1 | 424 | 0.41 | 5.1 |
SiAlF2-500H | F127 | 58.1 | 166 | 0.28 | 6.1 |
SiAlP3-500 | P123 | 54.1 | 627 | 0.55 | 4.9 |
SiAlF3-500 | F127 | 50.7 | 442 | 0.46 | 5.3 |
SiAlF3-500H | F127 | 50.7 | 171 | 0.31 | 6.1 |
An improvement in morphological properties is achieved through the use of Pluronic templates (Table 3). With this approach, framework collapse during heat treatment is avoided and high surface areas are achieved after calcination at 500 °C. The shape of isotherms corresponds to type IV with the H2 hysteresis consistent with significant mesopore content and narrower pore size distributions (Fig. 6 and 9S†).63 Calcined xerogel SiAlP2-500 synthesized with the P123 template containing 59.3 mol% of Al exhibits surface area of 591 m2 g−1 and the pore volume 0.53 cm3 g−1. If (AcO)3SiOSi(OAc)3 is used as the silicon precursor, the surface area increases to 627 m2 g−1. This change can be caused by better crosslinking due to a higher number of functional groups. Pore diameters of these calcined samples calculated by the NLDFT method are between 4.9 and 5.9 nm (Table 3). In the case of the aluminosilicates synthesized with the F127 template, surface areas in the range 381–477 m2 g−1 are achieved with a pore diameter of 4.9–5.9 nm (Fig. 10S†). We observed that with increasing Al content the surface areas and pore volumes increased as well. Pore diameters do not change with different Si/Al ratios for P123 but increased for F127. For classification of thermal stability, we calcined the sample SiAlF2 at 700 °C for 3 h and remeasured N2 adsorption isotherms (Fig. 7). Its surface area reached 424 m2 g−1 (Vtot = 0.41 cm3 g−1) which is about 53 m2 g−1 lower than in SiAlF2-500 and the pore volume and diameter decreased (Fig. 8, Table 3) and the distribution is narrower. To investigate hydrothermal stability, the sample SiAlF2-500 was exposed to boiling water for 24 h (Fig. 7). The surface area after this test was reduced to 166 m2 g−1 and pore volume to 0.28 cm3 g−1. The pore size distribution maximum moved to 6.1 nm and the mesoporous character was preserved (Fig. 8). Compared to this sample, the hydrothermally treated sample (SiAlF3-500H) synthesized with (AcO)3SiOSi(OAc)3 exhibits also loss of surface area and pore volume while pore diameter increased (Table 3, Fig. 11S†).
![]() | ||
Fig. 7 N2 adsorption/desorption isotherms of aluminosilicate xerogel SiAlF2 calcined at 500 (top) and 700 °C (middle). Sample SiAlF2-500H after hydrothermal treatment (bottom). |
![]() | ||
Fig. 8 NLDFT pore diameters (adsorption branch) of aluminosilicate xerogels: SiAlF2 calcined at 500 and 700 °C. Sample SiAlF2-500H after hydrothermal treatment. |
SAXS measurements of the calcined samples SiAlP2-500 and SiAlF2-500 synthesized with the P123 and F127, respectively, show a weak scattering maximum at 0.42° (0.06 Å−1) (Fig. 9). This behavior points to the mesoscopic ordering with the uniform pore channels in the xerogel.
![]() | ||
Fig. 9 SAXS pattern of calcined aluminosilicate xerogel SiAlP2-500. NLDFT pore diameter distribution (inset). |
The morphology of calcined mesoporous xerogels was studied by the TEM technique. The micrographs illustrate “wormhole” structure of pores (Fig. 10).
The surface acidity of the calcined xerogels was studied by pyridine adsorption. The IR spectra of the pyridine-treated samples (Fig. 11) display weak absorption bands at 1450, 1492, 1548, 1599, 1625, and 1639 cm−1. The bands corresponding to Lewis acid sites (LPy) are present at 1450 and 1625 cm−1.61,64 Both Lewis and Brønsted acid sites are attributed to a vibrational band at 1492 cm−1. Brønsted acidic sites (BPy) are characterized by the absorption bands at 1548 and 1639 cm−1.64 Pyridine adsorbed by hydrogen bonds (HPy) of Si–OH moieties can be assigned to the vibrational band at 1599 cm−1.61 These findings show that synthesized aluminosilicate xerogels exhibit surface acidity of both Lewis and Brønsted type.
High-temperature powder X-ray diffraction (HT PXRD) was used to determine the crystal phases that arise during calcination (Fig. 12S†). It was found that templated samples remain amorphous up to high temperatures and then crystallize to mullite (PDF 82-1237).65–67 The xerogels SiAlP2 and SiAlF2 are amorphous up to 950 °C before the diffraction lines of mullite are observed at 1000 °C (Fig. 12S†). These findings correspond to exothermic effects in DSC analysis (995 and 985 °C). In the case of xerogels with a lower content of Al, diffraction evidence for mullite appeared at 1050 °C. Besides the mullite phase, crystalline SiO2 (cristobalite PDF 85-0621) at 1100 °C was observed as well. The presence of cristobalite could be explained by the excess of Si(OAc)4 in the starting mixture which results in the phase separation during calcination. Samples synthesized with (AcO)3SiOSi(OAc)3 (SiAlF3-500 and SiAlP3-500) exhibit the mullite phase with crystallization temperature between 950–1000 °C. Crystallization of mullite at ∼980 °C indicates the homogeneity of aluminosilicate gels at the atomic level.26,68,69 These findings show that our mesoporous aluminosilicates can be transformed to homogeneous mullite phase.
Sample | Al mol% (ICP) | n Al in catal. (25 mg) [mmol] | Time [min] | Conversion [%] | Selectivity [%] | TOFa | |
---|---|---|---|---|---|---|---|
Ia | IIa | ||||||
a TOF – apparent turnover frequency [mmol mmol−1 h−1]. | |||||||
SiAlP1-500 | 42.2 | 0.16 | 10 | 46 | 96 | 4 | 86 |
60 | 79 | 95 | 5 | 25 | |||
SiAlF1-500 | 40.6 | 0.15 | 10 | 50 | 97 | 3 | 100 |
60 | 82 | 98 | 2 | 27 | |||
SiAlF2-500 | 58.1 | 0.23 | 10 | 43 | 96 | 4 | 56 |
60 | 69 | 95 | 5 | 15 | |||
SiAlF3-500 | 50.7 | 0.19 | 10 | 50 | 96 | 4 | 79 |
60 | 79 | 96 | 4 | 21 | |||
SiAlP3-500 | 54.1 | 0.21 | 10 | 56 | 96 | 4 | 80 |
60 | 80 | 96 | 4 | 19 |
Sample | Si/Al | Temperature [°C] | Time [h] | m [mg] | Conversion [%] | Selectivity (Ia![]() ![]() |
---|---|---|---|---|---|---|
SiAlF1-500 | 1.5 | 50 | 1 | 25 | 82 | 98![]() ![]() |
SiAlF2-500 | 0.7 | 50 | 1 | 25 | 69 | 95![]() ![]() |
SiAlF3-500 | 1.0 | 50 | 1 | 25 | 80 | 96![]() ![]() |
AS-(14)70 | 14 | r. t. | 6 | 50 | 37 | 95![]() ![]() |
AS-(14)70 | 14 | r. t. | 24 | 50 | 53 | 95![]() ![]() |
AS-(14)70 | 14 | 40 | 6 | 50 | 28 | 95![]() ![]() |
AlKIT-5(10)38 | 10 | r. t. | 0.5 | 50 | 87 | — |
In the case of styrene oxide alcoholysis, our catalysts exhibit a lower efficiency than in aminolysis reactions. Catalytic products confirmed by GC-MS and 1H NMR were (Fig. 15S and 16S†) (1,2-dimethoxyethyl)-benzene (Ib) and phenylacetaldehyde (IIb) (Fig. 14S,†Table 6). Catalyst SiAlF1-500 exhibits 28 and 44% conversion of styrene oxide after 2 and 5 h, respectively. Selectivity for (1,2-dimethoxyethyl)-benzene after 5 h reached 54%.
Sample | Al mol% (ICP) | n Al in catal. [mmol] | Time [h] | Conversion [%] | Selectivity [%] | |
---|---|---|---|---|---|---|
Ib | IIb | |||||
SiAlF1-500 | 40.6 | 0.15 | 2 | 28 | 63 | 37 |
3 | 32 | 59 | 41 | |||
5 | 44 | 54 | 46 |
We also performed a catalytic reaction with the catalyst SiAlF1-500 where no methanol was used. In this case, phenylacetaldehyde was observed as the only product and the catalytic yield after 1 h was 35%. A leaching test confirmed that no Al was released into the solution. Only 0.3% of the total aluminium amount in catalyst was found in the filtrate.
Footnote |
† Electronic supplementary information (ESI) available. CCDC 1437252. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5ra24563j |
This journal is © The Royal Society of Chemistry 2016 |