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Article
Differences in Catalytic Activity of Poly(vinylamine) Introduced
on Surface of Mesoporous SBA-15 by Grafting From and
Grafting Onto Methods in Knoevenagel Condensation
Anna Wach, Marek Drozdek, Barbara Dudek, Marta Biazik, Piotr Latka, Marek Michalik, and Piotr Kustrowski
J. Phys. Chem. C, Just Accepted Manuscript DOI: 10.1021/acs.jpcc.5b05868 Publication Date (Web): 11 Aug 2015
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The Journal of Physical Chemistry C is published by the American Chemical Society.


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3 Differences in Catalytic Activity of Poly(vinylamine) Introduced on Surface of
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5 Mesoporous SBA-15 by Grafting From and Grafting Onto Methods in Knoevenagel
6
7 Condensation
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10 Anna Wach1, Marek Drozdek1, Barbara Dudek1, Marta Biazik1, Piotr tka1,
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12 Marek Michalik2, Piotr Kutrowski1,*
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1
14 Department of Chemical Technology, Faculty of Chemistry, Jagiellonian University,
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16 Ingardena 3, 30-060 Krakw, Poland
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18 2
Institute of Geological Sciences, Jagiellonian University, Oleandry 2a, 30-063 Krakw,
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21 Poland
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23
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25 Abstract
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27 Various amounts of poly(vinylamine) (PVAm) were deposited on the surface of SBA-15
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30 mesoporous silicas, pre-functionalized with suitable organosilanes, by two different grafting
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32 techniques grafting form and grafting onto. In the grafting from route, the radical
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34 copolymerization between the vinyl-modified SBA-15 and N-vinylformamide, followed by
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36 acid hydrolysis and neutralization, was performed. The grafting onto pathway consisted in
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38
the reaction of pre-prepared PVAm chains with epoxide functionalities present on the silica
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41 surface. DRIFT spectroscopy confirmed the formation of covalent and hydrogen bonds
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43 between PVAm and the pre-functionalized SBA-15 surface. Low-temperature N2 adsorption
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45 and XPS allowed to observe differences in the distribution of formed PVAm in the pore
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47 system of SBA-15. A higher efficiency of polymer deposition and its higher dispersion were
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50 achieved using the grafting from method. Furthermore, XRD and TEM confirmed the
51
52 *
53 Corresponding author at: Department of Chemical Technology, Faculty of Chemistry,
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55 Jagiellonian University, Ingardena 3, 30-060 Krakw, Poland.
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57 Tel.: +48-12-6632006; fax: +48-12-6450515. E-mail address: kustrows@chemia.uj.edu.pl.
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3 stability of hexagonal SBA-15 structure during all modification steps. A number of accessible
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5 NH2 surface species, considered as active sites, appeared to be a crucial parameter influencing
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7 the catalytic activity of the synthesized hybrid materials in the Knoevenagel condensation of
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10 benzaldehyde and ethyl cyanoacetate.
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12
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14 Keywords: mesoporous silica, amine-containing polymer, anchoring, basic catalysts,
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16 benzaldehyde, ethyl cyanoacetate
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21 1. Introduction
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23 The discovery of ordered mesoporous silicas (OMS), synthesized using ionic or nonionic
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25 structure directing agents, has opened up a new field of research in material science 1-4. A lot
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27 of effort has been put into the development of OMS with various tunable size and
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30 arrangement of pores combined with an extremely high surface area 5-10. Although OMS offer
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32 many advantages compared to microporous zeolites with respect to their pore diameters
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34 (typically in the range of 3-30 nm), important shortcomings (such as non-crystalline,
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36 amorphous walls as well as low strength and concentration of acid sites) limit severely their
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potential applications 11,12. In most cases, an appropriate modification is required to form
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41 active surface sites and improve desired properties (e.g. hydrophobicity/hydrophilicity,
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43 acidity/basicity) of OMS. Various organic functional groups (e.g. thiol, amine, epoxide,
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45 nitrile) are often incorporated within a silica framework in order to modify the physical and
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47 chemical properties of OMS 13-15. Until now, such organic-inorganic hybrid materials have
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50 been synthesized mostly by an addition of organosilane agent during the silica synthesis (in-
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52 situ co-condensation) 15,16, or by a postsynthetic reaction of organosilane with surface silanols
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54 (grafting) 1,15,17. The main advantage of the former method is homogeneous distribution of
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56 functional groups in the modified OMS, while the grafted materials retain a greater
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3 hydrothermal stability and enhanced mesopore ordering. Furthermore, the functionalization of
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5 silica particles by grafting of polymer chains is expected to play an important role in the
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7 designing novel organic-inorganic hybrid materials due to a variety of polymers and
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10 polymerization techniques available (e.g. radical, cationic, anionic, ring-opening and
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12 controlled radical polymerization) 18-22. Two general routes are used to attach covalently
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14 polymer chains to an inorganic surface: grafting from and grafting onto 23-27. The
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16 grafting from technique involves copolymerization of monomer and active compounds
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18
covalently bonded to the SiO2 surface. In contrast, the grafting onto method utilizes a
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21 reaction between end-groups of pre-prepared polymer molecules and complementary
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23 functional groups present on the inorganic surface (e.g. -OH, -NH2, -COOH).
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25 The silica-based mesoporous organic-inorganic hybrid materials have been recognized as
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27 active catalysts of many reactions including the base-catalyzed processes, which provide
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30 clean and sustainable routes for the synthesis of fine chemicals (like pharmaceuticals,
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32 cosmetics and polymers) 28-31. The base-catalyzed carbon-carbon forming reactions, such as
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34 aldol condensation 32,33, Michael addition 33,34, Knoevenagel condensation 32,35,36 and Henry
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36 reaction 37, are typically performed in the presence of large amounts of alkali metal
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38
hydroxides and alkoxides or liquid organic bases (e.g. piperidine) under homogenous
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41 conditions. The application of properly active heterogeneous basic catalysts allows obtaining
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43 a high yield and selectivity of product along with waste reduction and an easier catalyst
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45 separation. OMS modified by immobilization of nitrogen-containing species (e.g. primary,
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47 secondary and tertiary amines 38,39, diamines 40, ammonium hydroxide 41, guanidines 42 and
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50 proton sponges 43) showed high catalytic activity in the base-catalyzed processes. Macquarrie
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52 et al. 44 investigated the role of the distribution of aminopropyl groups on the catalytic activity
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54 in nitroaldol condensation and Michael addition. They have found that the MCM-41-based
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56 catalysts prepared by grafting exhibited higher activity than those obtained by direct synthesis
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3 due to higher accessibility of active sites on the catalyst surface. It is noteworthy that the
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5 amine content as well as their nature and strength have a significant effect on the activity in
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7 base-catalyzed reactions. In particular, the Knoevenagel condensation between benzaldehyde
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10 and molecules containing activated methylene groups with different pKa values, such as ethyl
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12 cyanoacetate (pKa = 9.0), ethyl acetoacetate (pKa = 10.7) and diethyl malonate (pKa = 13.3)
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14 are very good model reactions for probing the basic strength of a catalyst 45. Recently, we
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16 have reported the catalytic activity of poly(vinylamine)/SBA-15 hybrid materials in the
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Knoevenagel condensation 46. Poly(vinylamine) (PVAm) was selected as a modifier with the
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21 highest density of reactive primary amine groups of any polymers including poly(ethylene
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23 imine) and poly(allylamine) 47. The PVAm/SBA-15 catalysts were synthesized by the
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25 deposition of poly(N-vinylformamide) (PNVF) on the surface of unmodified mesoporous
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27 silica by in-situ polymerization. The subsequent acid hydrolysis and neutralization with
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30 NaOH (pH=7.010.0) allowed obtaining the PVAm/SBA-15 hybrid materials with various
31
32 distributions of N-containing species (amide, non-protonated and protonated amino groups).
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34 We showed that the conditions of neutralization step strongly influenced the catalytic activity.
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36 The treatment of hybrid material at higher pH caused the deprotonation of positively charged
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ammonium species and the appearance of additional NH2 groups being active centers of the
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41 Knoevenagel condensation.
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43 In the present paper we discuss an influence of various parameters on the catalytic
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45 activity of amino-functionalized polymer-mesoporous silica hybrid materials in the
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47 Knoevenagel condensation between benzaldehyde and ethyl cyanoacetate. Two novel
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50 methods of synthesis of PVAm/SBA-15 materials, based on grafting from and grafting
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52 onto (Scheme 1), have been developed. Both techniques required pre-functionalization of
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54 silica particles with a suitable silane coupling agent. In the first approach, the polymer growth
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56 was initiated from the SiO2 surface by the radical copolymerization between the vinyl-
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3 modified SBA-15 particles (functionalized with vinyltriethoxysilane, VTS) and N-
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5 vinylformamide (NVF). Finally, poly(N-vinylformamide) covalently attached to the silica
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7 surface was converted to PVAm by acid hydrolysis followed by neutralization. In the second
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10 method, 3-glycidoxypropyltrimethoxysilane (GPTMS) was used to irreversibly attach the
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12 polymer chains. The highly reactive epoxide functionalities present on the silica surface
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14 readily reacted with amino groups from pre-prepared PVAm chains during the ring opening
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16 reaction.
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21 2. Experimental Section
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23 2.1. Synthesis
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25 Synthesis of mesoporous SBA-15 silica. The SBA-15 material was synthesized using a
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27 nonionic surfactant as a structure-directing agent according to the method reported
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30 previously 48. Briefly, 8.0 g of Pluronic P123 (Aldrich) was dissolved in a solution containing
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32 60 g of distilled H2O and 120.0 g of 2M HCl. Afterward, 17.0 g of tetraethyl orthosilicate
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34 (99,0%, Aldrich) was added dropwise and the resultant mixture was stirred at 35C for 20 h.
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36 The homogenous gel was aged at 100C for 24 h under static conditions. The white solid
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38
product was filtered and calcined in air at 550C for 10 h to completely remove the organic
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41 template.
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43 Grafting from method. An amount of 12.0 g of SBA-15 (dried at 200C overnight) was
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45 dispersed in 300 ml of anhydrous toluene. Then, 24.0 g of vinyltriethoxysilane (VTS, 97.0%,
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47 Aldrich) was added under stirring 15. The obtained mixture was refluxed for 6 h under an inert
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50 atmosphere. After filtration, the resulting SBA-15_VTS material was washed with toluene
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52 and methanol and dried under vacuum at 50C.
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54 An amount of 4.2 g of SBA-15_VTS was introduced into 200 ml of aqueous solution of
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56 freshly distilled N-vinylformamide (NVF, 98.0%, Aldrich) at the intended NVF/SiO2 mass
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3 ratio of 0.10, 0.25, 0.50, 1.00, 1.50 or 2.50. The solution was stirred at room temperature for
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5 0.5 h under an inert atmosphere, subsequently was heated to 60C and the appropriate amount
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7 of initiator 2,2-azobis(2-methylpropionamidine) dihydrochloride (AAPH, 97.0%, Aldrich)
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10 was added (AAPH/NVF = 0.01). The polymerization was performed at 65C for 6 h. The
11
12 resulting solid was isolated by filtration, washed with distilled H2O and dried under vacuum at
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14 50C.
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16 In the next step, the synthesized material was dispersed in 100 ml of hydrochloric acid
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solution (18%) and kept at 60C for 24 h under stirring. Subsequently, the obtained solid was
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21 filtered, carefully washed with water and dried under vacuum at 50C. For neutralization, the
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23 modified material (1.5 g) was suspended in 75 ml of distilled water under stirring. Then, an
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25 aqueous solution of NaOH (1 M) was added dropwise until pH = 9.0 was reached. After
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27 filtration, the final poly(vinylamine)/SBA-15 material (SBA-15_VTS_PVAm_x, where
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30 x = 0.10, 0.25, 0.50, 1.00, 1.50 or 2.50) was dried at 50C.
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32 Grafting onto method. 3-glycidoxypropyltrimethoxysilane (GPTMS, 98%, Aldrich) was
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34 chemically grafted on the SBA-15 surface (SBA-15_GPTMS) at the intended GPTMS/SiO2
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36 mass ratio of 2.0 using the same procedure as previously described for the vinyl-modified
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silica (SBA-15_VTS).
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41 PVAm was produced independently using the method described in the literature 49. 25 g
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43 of NVF and 475 g of distilled H2O were mixed and degassed in a 1000 ml flask under stirring.
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45 The solution was heated up to 60C and 0.954 g of AAPH was added. The polymerization
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47 was performed at 65 C for 4 h under argon atmosphere. Subsequently, the formed PNVF
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50 (with Mw = 14500, determined using the Mark-Houwink equation 50) was converted to PVAm
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52 by hydrolysis in basic aqueous solution. For this purpose, 500 ml of 4 M NaOH was added.
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54 The reaction mixture was maintained at 60C for 4 h to assure the complete conversion of
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3 amide groups into amino ones. After purification by dialysis, the polymer was dried under
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5 vacuum at 50C.
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7 The synthesis of SBA-15_GPTMS_PVAm_x (where x = 0.10, 0.25, 0.50, 1.00, 1.50 or
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10 2.50) started from premixing of 2.15 g of the GPTMS-modified silica particles, an appropriate
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12 amount of PVAm and 250 ml of distilled water. The mixture was stirred at room temperature
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14 for 30 min, then the solution was heated to 60C to react for another 6 h. The resulting solid
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16 was cooled, filtered, washed with distilled water and dried under vacuum at 50C.
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2.2. Characterization
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21 The powder X-ray diffraction (XRD) measurements were performed using Bruker D2 Phaser
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23 with a LYNXEYE detector. The diffraction patterns were collected using Cu K radiation
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25 ( = 1.54184 ) in a 2 angle range of 0.75-5.00 with a step of 0.02. Nitrogen sorption
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27 analysis was measured at -196C using a Micromeritics ASAP 2020 instrument. The samples
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30 were preliminary outgassed at 120C for 10 h. The specific surface area were calculated using
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32 the BrunauerEmmettTeller (BET) equation. The micro- and mesopore volumes as well as
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34 pore size distributions of the native and functionalized SBA-15 materials were determined
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36 basing on the equilibrium model of nonlocal density functional theory (NLDFT) 51.
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38
Thermogravimetric analysis (TG) was carried out in an oxidizing atmosphere with an SDT
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41 Q600 thermobalance (TA Instruments). The measurements were performed in an alumina pan
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43 using about 10.0 mg of a sample. The decomposition of organic part was monitored in an air
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45 flow (100 ml/min), while the temperature was increased from 30C to 1000C at a rate of
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47 20C/min. Elemental analysis (EA) of C, H and N was carried out with using a EURO EA
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50 3000 elemental analyzer (EuroVector). Transmission electron microscopy (TEM) images
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52 were obtained on a Tecnai G2 F20 transmission electron microscope equipped with a field
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54 emission gun operating at 200 kV. Samples in a powder form were placed on a copper grid
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56 and then coated by carbon. A Hitachi S-4700 scanning electron microscope equipped with a
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3 Noran Vantage analyzer was used to collect SEM images under accelerating voltage of 15 kV.
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5 Diffuse reflectance infrared Fourier transform (DRIFT) spectra were recorded with a Thermo
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7 Scientific Nicolet 6700 FT-IR spectrometer equipped with a DRIFT device and a MCT-A
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10 detector. Typically, 200 scans were acquired for each spectrum in the range 650-4000 cm-1
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12 with a resolution of 4 cm-1. Prior to the DRIFT measurements, the samples were diluted to
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14 4 wt.% in potassium bromide and softly milled in an agate mortar. The X-ray photoelectron
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16 spectra (XPS) were acquired using a Prevac photoelectron spectrometer equipped with a
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hemispherical VG SCIENTA R3000 analyzer. The spectra were taken using a
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21 monochromatized aluminum source AlK (E = 1486.6 eV) and a low-energy electron flood
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23 gun (FS40A-PS) to compensate for the charge accumulation on the surface of nonconductive
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25 samples. Spectra were processed and deconvoluted using the CasaXPS software. The binding
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27 energy values of measured regions were referenced to the Si 2p core level (103.6 eV). The
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30 surface composition was studied based on the areas and binding energies of C 1s, N 1s, O 1s,
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32 Cl 2p and Si 2p core levels.
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36 2.3. Catalytic tests
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The synthesized PVAm/SBA-15 hybrid materials were tested as catalysts in a liquid phase
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41 Knoevenagel condensation of benzaldehyde with ethyl cyanoacetate. In a typical experiment,
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43 40 ml of ethanol as a solvent was stirred under nitrogen atmosphere and preheated to 40C.
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45 Subsequently, 20 mmol of benzaldehyde, 20 mmol of ethyl cyanoacetate and 0.5 g of catalyst
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47 were added to a batch reactor, to begin the reaction. The progress of the reaction was
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50 monitored by gas chromatography (GC). Samples were taken periodically using a syringe
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52 with a septum and analyzed using a gas chromatograph (CP-3800) equipped with a flame
53
54 ionization detector and a capillary column (5% diphenyl - 95% dimethylpolysiloxane). N-
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56 dodecane was used as an internal standard. The conversion of reactants was calculated based
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3 on the percentage of consumed substrates, in reference to the internal standard. After 6 h, the
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5 reaction mixture was filtered and the solid catalyst was washed with ethanol and dried. The
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7 products of the condensation isolated from the filtrate by a rotary evaporation of the solvent
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9
10 were analyzed by 1H and 13C NMR spectroscopy (Bruker 500 MHz AVANCE II).
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12 3. Results and discussion
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14 3.1. Pre-functionalization of SBA-15 surface
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16 In order to stabilize the structure of hybrid polymer-silica material, the polymer chains need to
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be chemically attached to the inorganic surface. In this work, we decided to use the selected
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21 silane coupling agents (namely VTS and GPTMS), which introduced on the SBA-15 surface
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23 facilitate the formation of strong covalent bonds between the inorganic support and polymer
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25 molecules. To achieve desired high concentration of functional groups on the surface of the
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27 modified silica, the deposition of VTS and GPTMS was performed using 2-3 times more of
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30 the appropriate silylating agent than it would be implied by the number of silanols available
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32 on the SBA-15 surface. The concentration of surface OH groups was expected to be about 3.5
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34 mmol/g, according to the results of IR and NMR measurements reported by Ide et al. 52.
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36 Therefore, the amount of organosilane used in the grafting process was 10.5 mmol of VTS or
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8.5 mmol of GPTMS per 1 g of the silica support.
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41 The amount of vinyl and epoxy groups introduced onto the surface of pre-functionalized
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43 SBA-15 was determined by TG analysis (TG and DTG curves are shown in Supporting
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45 Information, Figure S1). Two well-resolved regions of mass loss can be distinguished: (i)
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47 below 150C and (ii) between 150 and 450C. The low-temperature DTG peak is associated
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50 with the evaporation of physically adsorbed water. On the other hand, desorption and
51
52 oxidation of functional organic groups begins above 150C. At higher temperatures (>500C)
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54 the mass loss attributed to dehydroxylation by condensation of silanols becomes noticeable 53.
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56 Consequently, to determine the amount of organic molecules grafted to the silica surface, the
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3 mass loss measured in the range 150-450C was corrected taking into account the effect
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5 related to the elimination of silanols from the silica surface. The calculated loadings of the
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7 silylating agents were found to be 4.25 and 7.07 wt.% for SBA-15_VTS and SBA-
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10 15_GPTMS, respectively.
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12 The successful grafting of silane coupling agents was verified by DRIFT spectroscopy.
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14 Figure 1A shows the spectra of the unmodified SBA-15 support and both silane-
15
16 functionalized silicas. The presence of silica network is manifested by the presence of strong
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18
band in the 1000-1250 cm-1 region and the peak centered at 815 cm-1, which correspond to the
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21 asymmetric stretching and bending modes of siloxane groups, respectively 54. Moreover, the
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23 absorption band at 975 cm-1 is assigned to the stretching vibrations of Si-O-H groups in the
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25 silica framework, whereas the sharp band at 3745 cm-1 is ascribed to the stretching vibrations
26
27 of isolated surface silanol groups 55. After the silane grafting, the intensity of peak at 3745 cm-
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29 1
30 is attenuated due to the interaction with organosilane molecules. It is noteworthy that the
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32 grafting process did not lead to the complete disappearance of the absorption band attributed
33
34 to isolated hydroxyl groups. It can therefore be assumed that some of silanol groups were
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36 inaccessible to the silylating agent molecules. The similar phenomenon was reported by Ide et
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38
al. 52, who established that up to 50% of silanols in the SBA-15 type materials are unreachable
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41 for small molecules. This is mainly due to the microporosity and surface roughness of SBA-
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43 15 as well as steric hindrance effects. Nevertheless, new bands characteristic of VTS and
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45 GPTMS are observed in the vinyl- and epoxy-functionalized SBA-15, indicating that the
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47 organic groups appeared on the silica surface. In the case of the SBA-15_VTS hybrid
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49
50 material, the infrared absorption band at 1603 cm-1 (overlapped with the band at 1635 cm-1
51
52 corresponding to the bending vibrations of O-H in adsorbed water molecules) is ascribed to
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54 the C=C stretching vibrations, while the peaks at 3070, 2960 and 1413 cm-1 correspond to the
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56 asymmetrical and symmetrical stretching vibrations as well as in-plane bending deformation
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3 of the vinyl group 56. For SBA-15_GPTMS, the very weak peaks at 3055, 2990 and 905 cm-1
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5 are assigned to the stretching vibrations and ring deformations of the epoxy group, whereas
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7 the band at 1445 cm-1 corresponds to the CH2 scissoring of glycidoxy groups 57. Furthermore,
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10 the asymmetric and symmetric stretching modes of alkyl groups as well as unreacted alkoxy
11
12 (ethoxy or methoxy) groups present in the organosilanes result in the appearance of typical
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14 bands in the regions of 2850-2900 and 2930-2980 cm-1 58,59.
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3.2. Composition and structure of poly(vinylamine)/SBA-15 hybrid materials
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21 DRIFT spectroscopy was also used to study the structure of PVAm/SBA-15 hybrid materials
22
23 synthesized by the grafting from and grafting onto routes. The spectra collected for SBA-
24
25 15_VTS_PVAm_2.5 and SBA-15_GPTMS_PVAm_2.5 are shown in Figure 1B. After the
26
27 modification, the appearance of new absorption bands characteristic of PVAm is observed in
28
29
30 the ranges of 2800-3400 and 1300-1700 cm-1 60,61. The peaks at 3290 and 3350 cm-1 are
31
32 assigned to the asymmetric and symmetric N-H stretching modes of -NH2 groups, whereas the
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34 band at 1595 cm-1 appears due to the -NH2 bending mode. Additionally, the stretching (2820-
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36 2980 cm-1) and deforming (1350-1460 cm-1) vibrations of C-H in the polymer backbone are
37
38
noticeable. Lastly, the bands related to other N-containing species, like residual formamido
39
40
41 groups (1670 cm-1) and protonated amino groups (1520 cm-1), appear in the low frequency
42
43 region. It should also be noticed that the presence of very strong and broad band in the range
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45 3100-3500 cm-1 and the disappearance of the band corresponding to the isolated silanol
46
47 groups suggests the strong interaction of the deposited polymer with the surface of SBA-15
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50 by hydrogen bonds 62.
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52 The efficiency of poly(vinylamine) deposition on the pre-functionalized silica was
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54 investigated by thermogravimetric and elemental analysis. The carbon and nitrogen contents
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56 obtained by elemental analysis are reported in Table 1. The similar amounts of carbon are
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3 observed for the poly(vinylamine)/SBA-15 materials prepared by the grafting from and
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5 grafting onto techniques. However, it should be kept in mind that the carbon content
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7 measured is influenced by carbon originating from the silane coupling agents. Fortunately,
8
9
10 analysis of the nitrogen content comes to the rescue. Taking into account additional analysis
11
12 we may ascertain that slightly higher grafting yields are achieved using the grafting from
13
14 method compared to the grafting onto one. Only for the SBA-15_PVAm_2.5 materials, a
15
16 similar efficiency of deposition (around 5 wt.% of nitrogen) is observed. In order to get a
17
18
further insight in the polymer loading, Figure 2 is drawn based on the TG measurements
19
20
21 (compare an example TD/DTG in Figure S2). The polymer content was determined from total
22
23 mass loss, excluding the effects related to VTS, GPTMS and silanol decomposition as well as
24
25 desorption of surface moisture. Nevertheless, it should be kept in mind that PVAm exists
26
27 partially in the form of hydrochloride salt, and the presence of Cl causes slight differences
28
29
30 between the TG and EA results. To sum up, the obtained results reveal the higher efficiency
31
32 of PVAm deposition in the case of the grafting from method.
33
34 The mesoporous structure of the pristine and polymer-functionalized SBA-15 was
35
36 examined by XRD and TEM. Low angle XRD patterns (Figure 3) show the intense diffraction
37
38
line in the range of 2 = 0.9-1.1 and two weak diffraction lines at higher 2 angles. These
39
40
41 well-defined peaks are indexed as (100), (110) and (200) Bragg reflections, which are typical
42
43 of the p6mm honeycomb structure, as expected for SBA-15 type ordered mesoporous
44
45 silicas 63. The observed characteristic patterns imply that the two-dimensional hexagonal
46
47 porous framework of SBA-15 is preserved after functionalization with polymers. As can be
48
49
50 seen, the introduction of polymer species into the mesoporous materials provokes a significant
51
52 increase in the intensity of the (100) reflection. This probably originates from an increased X-
53
54 ray scattering contrast between the walls and the pores of the material due to filling of the
55
56 complementary pores present in the walls of SBA-15 with the polymer chains 64. The values
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3 of hexagonal unit cell parameter (a0), calculated based on the position of (100) diffraction
4
5 peaks (a0 = 2d1003), are presented in Table 1. The d100 interplanar spacing value reported for
6
7 both pre-functionalized silica materials is similar to the value found for the pristine SBA-15,
8
9
10 indicating that the lattice size is retained after grafting of silane coupling agents. In contrast, a
11
12 noticeable decrease of the unit cell size is observed after the PVAm introduction. It is
13
14 noteworthy that the calculated unit cell parameter does not change significantly with
15
16 increasing amount of introduced polymer species. This result suggests that the stepwise
17
18
modification of silica may cause somewhat densification of silica walls 65,66.
19
20
21 The TEM images of SBA-15, SBA-15_VTS_PVAm_2.5 and SBA-
22
23 15_GPTMS_PVAm_2.5 are presented in Figure 4. All TEM pictures clearly show the p6mm
24
25 hexagonal morphology with well-ordered 1D arrays, typically representing the SBA-15
26
27 materials. The preservation of the cylindrical shape of the pores and their hexagonal
28
29
30 mesostructure indicates that the channel structure of parent SBA-15 is not destroyed during
31
32 the polymer grafting. The SEM images taken for these samples (Figure 5) additionally
33
34 confirm the stability of the fibrous-like morphology consisting of long rod-like particles of
35
36 SBA-15.
37
38
39
40
41 3.3. Distribution of poly(vinylamine) in hybrid materials
42
43 The low-temperature nitrogen physisorption and X-ray photoelectron spectroscopy provide
44
45 information on differences in the polymer distribution in the PVAm-silica hybrid materials.
46
47 The nitrogen adsorption-desorption isotherms of selected poly(vinylamine)/SBA-15 materials
48
49
50 prepared by grafting from and grafting onto methods are shown in Figure 6. The isotherm
51
52 for the pristine SBA-15 is of type IV according to the IUPAC classification, which is typical
53
54 for mesoporous materials with a well-ordered pore structure. Additionally, the presence of
55
56 well-defined hysteresis loop with very steep, parallel adsorption and desorption branches
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3 (type H1), indicates formation of uniform open-ended cylindrical mesopores 64,67. The
4
5 grafting of PVAm on the SBA-15 surface resulted in a gradual decrease in the amount of
6
7 adsorbed nitrogen. Nevertheless, the IV type isotherm typical for SBA-15 is maintained after
8
9
10 the polymer functionalization. A slight broadening and tailing of the hysteresis loop with the
11
12 increasing polymer content is observed. This effect can be attributed to the reduction in both
13
14 pore diameter and uniformity of pore size along the channels due to the random deposition of
15
16 polymeric species inside mesopores. The phenomenon of plugging silica mesochannels
17
18
with formed polymer was reported earlier by several authors 64,68. The textural parameters
19
20
21 calculated for the pristine SBA-15 and the PVAm/SBA-15 materials are collected in Table 1.
22
23 As shown, in the case of both modification methods, functionalization of SBA-15 surface
24
25 with polymer species results in a gradual decrease in the BET surface area (SBET) as well as
26
27 the total pore volume (Vtotal). A similar trend is found for the micropore volume (Vmicro),
28
29
30 which can be interpreted as penetration of micropores present in the mesopore walls of silica
31
32 support by the polymer chains. It should be emphasized that no preferential location of PVAm
33
34 in the intrawall pores of SBA-15 is observed, which was previously found for a polymer
35
36 deposited by grafting polymerization of N-isopropylacrylamide on SBA-15 functionalized
37
38
with 1-(trichlorosilyl)-2-(m/p-(chloromethylphenyl)ethane 69. In order to understand the
39
40
41 influence of the modification method on the polymer distribution, specific surface areas was
42
43 calculated in relation to the SiO2 content. Figure 7 shows the correlation between the obtained
44
45 SBET values and the real polymer content (determined by TG). The impact of modification
46
47 method on the distribution of formed PVAm is evident. Assuming the non-porous nature of
48
49
50 poly(vinylamine) we can conclude that in the case of SBA-15_VTS_PVAm materials a
51
52 relatively quick saturation of pore volume by PVAm occurs. For SBA-15_GPTMS_PVAm,
53
54 filling of pore volume with polymer species takes place gradually. This indicates that a part of
55
56 polymer is deposited on the outer surface. In order to get better insight in the distribution of
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3 polymer species, the pore wall thickness, twall, was estimated on the basis of geometrical
4
5 models for cylindrical pores in hexagonal arrangement proposed by Kruk, Jaroniec and Sayari
6
7 (KJS method) 63,70. The wall thickness was calculated from the difference between the cell
8
9
10 parameter a0 and pore size wd in a honeycomb structure:  = 
and
=
11
 
12
   , where c is a constant dependent on the pore geometry (1.213 for
13 
14
15 hexagonal structure), is density of silica framework (2.2 g/cm3) and Vmeso is the mesopore
16
17 volume. The aforementioned calculations show that the wall thickness increased
18
19
20 systematically from 2.0 nm to 2.9 nm (for grafting from) or 2.7 nm (for grafting onto)
21
22 after the deposition of polymer species, which gives evidence that the polymer layers are
23
24 formed on the mesopore walls.
25
26 The XPS analysis was carried out to characterize the PVAm grafting on the SBA-15
27
28
surface as well as to gain information on the elemental composition of the outermost few
29
30
31 atomic layers of external surface of hybrid materials. The presence of C 1s and N 1s peaks in
32
33 all modified materials clearly confirms the introduction of polymer chains onto the SBA-15
34
35 surface. The surface atomic concentration and core-level binding energy values of surface
36
37 species are summarized in Table 2 and 3 for the samples synthesized by grafting from and
38
39
40 grafting onto method, respectively. The high-resolution N 1s spectra collected for SBA-
41
42 15_VTS_PVAm_2.5 as well as SBA-15_GPTMS_PVAm_2.5 are displayed in Figure 8. The
43
44 N 1s core level spectra were fitted with three components 71,72. The main peak at a binding
45
46 energy of 399.7 eV is attributed to non-protonated, primary amino groups (-NH2). The peak at
47
48
401.6 0.1 eV points out the presence of hydrogen bonded or protonated amino species (---
49
50
51 NH2/NH3+), while the third component at 400.3 0.1 eV originates from nitrogen in residual
52
53 formamide groups. The corresponding high-resolution C 1s spectra are comparatively shown
54
55 in Figure S3. For both series of polymer-functionalized silica hybrid materials, we observe an
56
57 increase in the carbon and nitrogen atomic percentage with rising amount of the polymer.
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3 However, depending on the grafting method chosen, there are significant differences in the
4
5 surface polymer content and distribution of N-containing species. Interestingly, after using the
6
7 grafting onto method we discover much more nitrogen on the surface as compared to the
8
9
10 "grafting from" method. The observed effect can be caused by an enhanced amount of
11
12 polymer present on the surface due the ring opening reaction undergoing preferentially on the
13
14 outer surface of silica support. Moreover, we observe different ratios between non-protonated
15
16 and protonated amino groups, which may originate from the different synthesis protocols used
17
18
during the polymer deposition. The quantitative results demonstrate that the SBA-
19
20
21 15_GPTMS_PVAm samples have higher amount of accessible and non-protonated amino
22
23 groups in comparison with the SBA-15_VTS_PVAm materials. For example, in the case of
24
25 SBA-15_VTS_PVAm_2.5 the contribution of the primary amino groups is estimated to be
26
27 69.2%, whereas for SBA-15_GPTMS_PVAm_2.5 the number of accessible and non-
28
29
30 protonated amino groups is 81.3%.
31
32
33
34 3.4. Catalytic activity of poly(vinylamine)/SBA-15 hybrid materials
35
36 Activity of the synthesized PVAm/SBA-15 hybrid materials was tested in the base-catalyzed
37
38
the Knoevenagel condensation between benzaldehyde and ethyl cyanoacetate (Scheme 2).
39
40
41 The conversions of benzaldehyde measured during the reaction in the presence of the catalysts
42
43 prepared by grafting from and grafting onto methods are demonstrated in Figure 9A and
44
45 9b, respectively. It was proved that all of the synthesized materials exhibit enhanced catalytic
46
47 activity. Nevertheless, achieved conversions depend on both the polymer content and the
48
49
50 modification method used for the PVAm introduction. Increase of the PVAm loading results
51
52 in a gradual increase of the catalytic activity. However, the hybrid materials produced by the
53
54 grafting from method appeared to be more efficient catalysts compared to the SBA-
55
56 15_GPTMS_PVAm samples. Furthermore, the SBA-15_VTS_PVAm hybrid materials
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3 showed a significantly higher selectivity to ethyl trans--cyanocinnamate which is the
4
5 desirable reaction product. In the case of these catalysts, selectivity of 100% was detected for
6
7 the samples with a lower PVAm content, and only for SBA-15_VTS_PVAm_1.5 and SBA-
8
9
10 15_VTS_PVAm_2.5 it dropped to 98% and 95%, respectively. Such high selectivity was
11
12 observed earlier for the most active amino-functionalized SBA-15 catalysts 73-76. The opposite
13
14 tendency was observed for the materials prepared by the grafting onto method. At a low
15
16 PVAm content, the selectivity about 90% was achieved, and it increased to 100% for the
17
18
SBA-15_GPTMS_PVAm_1.0, SBA-15_GPTMS_PVAm_1.5 and SBA-
19
20
21 15_GPTMS_PVAm_2.5 catalysts.
22
23 To facilitate the comparison of the catalytic activity for the studied samples the initial
24
25 reaction rate was calculated. In Figure 10 the correlation between the rate of the Knoevenagel
26
27 condensation and the content of amine groups, determined by XPS, is shown. The presented
28
29
30 relationship evidences that the catalytic activity strongly depends on the surface concentration
31
32 of amine species, which can be considered as active sites in the studied reaction. It should
33
34 however be noticed that the efficiency of amine functionalities on PVAm introduced by
35
36 grafting from method is considerably higher compared to the SBA-15_GPTMS-PVAm
37
38
series. At least two factors influence the lower activity of the materials modified by the
39
40
41 grafting onto technique. During grafting onto, the PVAm chains react with the pre-
42
43 functionalized silica surface via amine groups, which causing them to lose their catalytic
44
45 activity. Additionally, in the case of these samples low-temperature N2 adsorption and XPS
46
47 revealed that the polymer was preferentially deposited on the external surface of SBA-15,
48
49
50 probably in a coiled form with a large number of inaccessible NH2 groups. As was shown by
51
52 Marcoux et al. 73 too deeply embedded amine groups distributed onto the SBA-15 surface
53
54 cannot be reached by reactants and remain inactive in the Knoevenagel condensation. On the
55
56
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3 other hand, Guillet-Nicolas et al. 74 revealed that uniformity of NH2-containing polymer on
4
5 the SBA-15 surface is a prerequisite for higher catalytic activity.
6
7 A direct comparison of the catalytic results collected for the synthesized PVAm/SBA-15
8
9
10 hybrid materials with data discussed in the literature is very difficult due to various conditions
11
12 (e.g. temperature, a type and amount of solvent, a content of catalyst) used in the catalytic
13
14 studies. Nevertheless, the productivity of the most active SBA-15_VTS_PVAm_2.5, defined
15
16 as the amount of ethyl trans--cyanocinnamate produced per mass of a catalyst as a function
17
18
of time, is 35 mmol gcat-1 h-1. This parameter is higher compared to that achieved under the
19
20
21 same conditions for the most active PVAm/SBA-15 catalyst (31 mmol gcat-1 h-1) synthesized
22
23 by the in situ polymerization method 46. Furthermore, it surpasses the productivity of the
24
25 amino-functionalized SBA-15 obtained by co-condensation of tetraethyl orthosilicate (TEOS)
26
27 and 2-(aminoethyl)aminopropyl trimethoxysilane (ATMS) (30 mmol gcat-1 h-1) 73. Marcoux et
28
29
30 al. 73 also exhibited more active amine-containing SBA-15 catalysts: (i) with ethylenediamine
31
32 introduced onto SBA-15 functionalized with cross-linked poly(chloromethylstyrene) by
33
34 nucleophilic substitution (38 mmol gcat-1 h-1) and (ii) obtained by post-grafting of ATMS on
35
36 SBA-15 (44 mmol gcat-1 h-1). However, it should be kept in mind that these results were
37
38
achieved at higher temperature (80C) in the presence of environmentally unfriendly toluene
39
40
41 as a solvent. Additionally, the grafted PVAm/SBA-15 catalysts show high stability during the
42
43 catalytic tests, as was previously confirmed for the samples produced by in situ
44
45 polymerization as well 46, and can be re-use in recycling cycles after washing by ethanol
46
47 without a significant activity loss.
48
49
50
51
52 4. Conclusions
53
54 The novel solid base catalysts based on poly(vinylamine) deposited on the surface of SBA-15
55
56 mesoporous silica were obtained using two grafting techniques grafting from and
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3 grafting onto. The PVAm chains were chemically attached to vinyl and epoxy functional
4
5 groups, which were introduced on the silica surface during pre-functionalization with a
6
7 suitable silane agent. DRIFT spectroscopy confirmed that the stability of polymer was
8
9
10 additionally improved by hydrogen bonds formed between PVAm and surface silanols. XRD
11
12 and TEM revealed that the hexagonal structure of mesoporous silica was preserved during the
13
14 PVAm deposition. Nevertheless, the grafting method influenced on the distribution of NH2-
15
16 containing polymer on the inorganic support. Grafting from was a more effective method in
17
18
the homogeneous dispersion of PVAm on the entire SBA-15 surface, whereas grafting onto
19
20
21 resulted in the enrichment of external surface in the deposited polymer, as was shown by low-
22
23 temperature N2 adsorption and XPS. The dispersion of PVAm affected the catalytic activity of
24
25 the hybrid materials in the Knoevenagel condensation of benzaldehyde and ethyl
26
27 cyanoacetate. The samples prepared by the grafting from technique appeared to be
28
29
30 significantly more active catalysts possessing a higher number of amine groups considered as
31
32 active sites of the studied reaction.
33
34
35
36 Acknowledgment
37
38
This work was supported by the National Science Centre under the grant no.
39
40
41 2012/07/B/ST5/00917. Anna Wach wishes to thank Lesser Poland Scholarship Fund for PhD
42
43 students Doctus co-financed by European Social Fund for the financial support. The
44
45 research was carried out with the equipment purchased thanks to the financial support of the
46
47 European Regional Development Fund in the framework of the Polish Innovation Economy
48
49
50 Operational Program (contract No. POIG.02.01.00-12-023/08).
51
52
53
54 Supporting Information Available: TG/DTG curves and high-resolution C 1s photoelectron
55
56 spectra collected for vinyl-functionalized SBA-15, epoxy-functionalized SBA-15 as well as
57
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3 PVAm/SBA-15 hybrid materials synthesized by grafting from and grafting onto methods
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5 are shown. This material is available free of charge via the Internet at http://pubs.acs.org.
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7
8
9
10 References
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12 (1) Beck, J. S.; Vartuli, J. C.; Roth, W. J.; Leonowicz, M. E.; Kresge, C. T.; Schmitt, K. D.;
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12 Base Catalysts for Aldol Reaction by Optimizing the Density and Type of Organoamine
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14 Groups on Nanoporous Silica. J. Catal. 2009, 265, 131-140.
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Catalyst and Adsorbent. Appl. Catal. A 2012, 421-422, 14-37.
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23 A. Knoevenagel and Aldol Condensations Catalysed by a New Diamino-functionalised
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25 Mesoporous Material. J. Mol. Catal. A 1999, 142, 361-365.
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36 Silicates as Base Catalyst for Transesterification. Stud. Surf. Sci. Catal. 1998, 117, 445-452.
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5 Functionality Distribution in Polyvinylamine/SBA-15 Hybrid Catalysts for Knoevenagel
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7 Condensation. Catal. Commun. 2015, 64, 52-57.
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56 Propane Selective Oxidation. Ind. Eng. Chem. Res. 2010, 49, 6790-6802.
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23 Reflection IR Spectroscopy Shows that Surface Hydroxyls Play Only a Minor Role in
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25 Alkylsilane Monolayer Formation on Silica. J. Phys. Chem. Lett. 2013, 4, 2745-2751.
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41 Polymers and Silica Particles by Nucleophilic Substitution Reaction of Poly(vinyl amine).
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43 Beilstein J. Org. Chem. 2010, 6, 1-13.
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5 Polymerization in Mesoporous Silica toward the Design of Organic-Inorganic Composite
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45 W. E. S. XPS and NEXAFS Studies of Aliphatic and Aromatic Amine Species on
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47 Functionalized Surfaces. Surface Science 2009, 603, 2849-2860.
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50 (72) Seifert, S.; Hhne, S.; Simon, F.; Hanzelmann, C.; Winkler, R.; Schmidt, T.; Frenzel, R.;
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52 Uhlmann, P.; Spange, S. Adsorption of Poly(vinylformamide-co-vinylamine) Polymers
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5 ofamino-functionalized mesoporous polymer-SBA-15 nanocomposites. Appl. Catal. A 2014,
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12 mesoporous polymer-silica composites: introduction of reactive amines. New J. Chem. 2010,
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14 34, 355-366.
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16 (75) Wang, X.; Lin, K. S. K.; Chan, J. C. C.; Cheng, S. Direct Synthesis and Catalytic
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21 Materials. J. Phys. Chem. B 2005, 109, 1763-1769.
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23 (76) Wang, X.; Chan, J. C. C.; Tseng, Y.-H.; Cheng, S. Synthesis, characterization and
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25 catalytic activity of ordered SBA-15 materials containing high loading of diamine functional
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27 groups. Microporous Mesoporous Mater. 2006, 95, 57-65.
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8 SBET Vtotal Vmicro DDFT a0 twall C N
9 Sample
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[m2/g] [cm3/g] [cm3/g] [nm] [nm] [nm] [wt.%] [wt.%]
11 SBA-15 925 1.00 0.32 7.2 10.8 2.0 0.06 -
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13 SBA-15_VTS 812 0.89 0.28 7.1 10.9 2.2 3.00 -
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15 SBA-15_VTS_PVAm_0.1 543 0.80 0.19 7.4 10.1 2.1 3.62 1.33
16 SBA-15_VTS_PVAm_0.25 423 0.66 0.15 7.3 10.0 2.4 6.68 2.80
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18 SBA-15_VTS_PVAm_0.5 395 0.60 0.14 7.1 10.2 2.6 8.07 3.52
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20 SBA-15_VTS_PVAm_1.0 389 0.60 0.13 6.8 10.3 2.6 9.22 4.08
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SBA-15_VTS_PVAm_1.5 346 0.51 0.12 6.4 10.1 2.9 10.51 4.86
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23 SBA-15_VTS_PVAm_2.5 343 0.50 0.11 6.3 10.1 2.9 10.83 5.00
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25 SBA-15_GPTMS 718 0.80 0.24 7.0 10.9 2.4 3.83 -
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27 SBA-15_GPTMS_PVAm_0.1 576 0.78 0.21 7.3 10.3 2.2 5.35 0.94
28 SBA-15_GPTMS_PVAm_0.25 515 0.74 0.18 7.3 10.3 2.3 6.17 1.89
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30 SBA-15_GPTMS_PVAm_0.5 472 0.70 0.17 7.3 10.4 2.4 7.16 2.44
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32 SBA-15_GPTMS_PVAm_1.0 389 0.61 0.14 7.2 10.2 2.6 8.55 3.32
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SBA-15_GPTMS_PVAm_1.5 377 0.59 0.13 7.2 10.3 2.6 9.88 4.01
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35 SBA-15_GPTMS_PVAm_2.5 340 0.52 0.11 6.6 10.3 2.7 11.60 5.00
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37 SBET - surface area (BET method); Vtotal and Vmicro - total and micropore volume (NLDFT method); DDFT average pore diameter (NLDFT method, adsorption branch of isotherm); a0 - unit
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11 C 1s N 1s O 1s Si 2p Cl 2p
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Sample O=C-NH
14 C=C C-C, C-H C-O, C-N O=C-NH -NH2 O=C-NH -NH3+ SiO2 H2O SiO2 Cl-
(284.5) (285.40.1) (286.50.1) (288.30.1) (399.7) (400.30.1) (401.60.1)
Si-O-C (533.00.1) (534.8) (103.6) (198.10.1)
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18 SBA-15 - - - - - - - - 65.20 - 34.80 -
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20 SBA-15_VTS 2.40 2.54 2.54 - - - - 2.54 58.16 - 31.83 -
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SBA-
22 0.99 4.97 3.18 0.40 1.89 0.40 0.49 0.80 55.42 1.19 30.04 0.24
23 15_VTS_PVAm_0.1
24 SBA-
25 15_VTS_PVAm_0.2 0.45 7.91 5.52 0.52 3.51 0.52 1.05 0.96 49.61 1.45 28.07 0.43
26 5
27 SBA-
0.24 9.32 6.28 0.54 3.99 0.54 1.28 1.01 48.51 0.84 26.98 0.48
28 15_VTS_PVAm_0.5
29 SBA-
- 10.20 7.36 0.60 4.71 0.60 1.53 1.12 45.25 2.07 25.84 0.73
30 15_VTS_PVAm_1.0
31 SBA-
- 10.70 8.43 0.64 5.51 0.64 1.70 1.22 44.52 0.91 25.08 0.64
32 15_VTS_PVAm_1.5
33 SBA-
- 11.01 8.78 0.67 5.65 0.67 1.85 1.29 43.50 0.82 24.59 1.17
34 15_VTS_PVAm_2.5
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11 C 1s N 1s O 1s Si 2p Cl 2p
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13 O=C-NH SiO2 Cl-
Sample C-C, C-H C-O, C-N C-O-C O=C-NH -NH2 O=C-NH -NH3+ H2O SiO2
14 Si-O-C C-O-C (198.0
15 (285.30.1) (286.40.1) (287.3) (288.30.1) (399.7) (400.30.1) (401.60.1) (535.00.2) (103.6)
(531.80.2) (532.90.1) 0.1)
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18 SBA-15 - - - - - - - - 65.20 - 34.80 -
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20 SBA-15_GPTMS 1.98 2.78 1.85 - - - - 0.93 60.47 - 31.99 -
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23 15_GPTMS_PVAm_0.1 7.31 7.76 1.11 0.33 4.10 0.33 0.92 1.14 48.81 0.53 27.37 0.28
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25 SBA-
2615_GPTMS_PVAm_0.25 8.91 9.71 0.77 0.37 6.00 0.37 1.19 1.20 45.35 0.45 25.29 0.37
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28 SBA-
29 15_GPTMS_PVAm_0.5 9.48 10.25 0.69 0.41 6.57 0.41 1.22 1.24 44.35 0.36 24.63 0.39
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31 SBA-
32 15_GPTMS_PVAm_1.0 10.32 11.04 - 0.47 7.22 0.47 1.29 1.31 43.30 0.12 24.15 0.31
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34 SBA-
35 10.90 11.65 - 0.49 7.92 0.49 1.37 1.35 41.74 0.14 23.51 0.44
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37 SBA-
38 11.70 12.27 - 0/54 8.49 0.54 1.41 1.43 40.16 0.41 2.65 0.41
39 15_GPTMS_PVAm_2.5
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46 Figure 1. DRIFT spectra collected for (A) pristine SBA-15 (a), vinyl-functionalized SBA-15
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31 Figure 8. Distribution of N-containing species in the poly(vinylamine)/SBA-15 hybrid
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51 Figure 9. Conversion of benzaldehyde achieved over the PVAm/SBA-15 catalysts synthesized
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