ISSN 10876596, Glass Physics and Chemistry, 2014, Vol. 40, No. 1, pp. 79–87. © Pleiades Publishing, Ltd., 2014. Original Russian Text © I.V. Ponomarenko, V.A. Parfenov, Yu.N. Zaitseva, S.M. Zharkov, S.D. Kirik, 2014, published in Fizika i Khimiya Stekla.
Template Synthesis of CMK3 Nanostructured Carbon Material and Study of Its Properties1 I. V. Ponomarenkoa, V. A. Parfenova, Yu. N. Zaitsevaa, S. M. Zharkovb, and S. D. Kirika, b a
Institute of Chemistry and Chemical Engineering, Russian Academy of Sciences, Siberian Branch, Akademgorodok 50/24, Krasnoyarsk, 660036 Russia bSiberian Federal University, pr. Svobodnyi 79, Krasnoyarsk, 660049 Russia email:
[email protected]
Abstract—Mesostructured carbon has been obtained by template synthesis. SBA15 mesostructured silicate has been used as a template. The effect of the properties of a template on the ordering of a replica has been studied. It has been shown with the use of Xray diffraction, gas adsorption, and electron microscopy that there are evident correlations of the conditions of synthesis of a template with the ordering of a carbon replica, which can be guided by the synthesis of materials. The ordering of a replica significantly depends on the mesopore volume of the initial template and thickness of the pore wall. One should use templates with the highest possible mesopore volume and minimal wall thickness to obtain highly ordered replicas. These tem plates can be prepared during the treatment of synthesized materials at temperatures close to 100°C. It has been determined that, when there is SBA15, the presence of micropores is a necessary condition for the preparation of carbon replicas that retain the structure of the template. Keywords: mesoporous mesostructured silicates, SBA15, template synthesis, CMK3 mesostructured car bon, Xray diffraction, transmission electron microscopy, adsorption of N2 DOI: 10.1134/S1087659614010180 1
INTRODUCTION
with each other and allows one to obtain threedimen sional nanostructured objects, which are retained through microporous straps [9]. The indicated differ ence is illustrated in Fig. 1. The replica based on MCM41 represents loose rods of identical sizes, while SBA15 provides the preparation of CMK3 carbon material [9], where the orientation of the rods corresponds to the spatial arrangement of the pores in the template.
Templating at the nanometer scale is recognized as an effective approach for the design of nanomaterials with a controlled degree of ordering. Mesoporous mesostructured silicates of the MCM [1, 2] and SBA [3, 4] families represent promising nanosized tem plates. A crystallographically regular structure, cylin drical pore size of 3–4 nm for MCM41 and 7–10 nm for SBA15, relative inertness, and high specific pore volumes and surfaces create unique conditions for supramolecular processes of formation of substance. In the published data, numerous successful examples on the synthesis of secondary nanostructured metal [5], oxide [6], and carbon [7–9] replicas on the men tioned templates were described [10–16]. The repli cas, which were obtained as the initial template, pos sess high specific surface and identical cross sizes of blocks, which are determined by the pores of the initial template. The template based on SBA15 silicate, in contrast to MCM41, has a microporous structure of the sili cate wall [5, 17, 18]. It is considered that this feature provides the relationship of cylindrical mesopores
Thus, as one might state, the presence of micropores is the necessary condition for the design of structured replica. On the other hand, this statement is not completely confirmed in the available published data. For example, the synthesis of structured carbon replicas with the use of SBA15, which does not pos sess microporosity [20, 21], was described in [9, 19]. These examples were also obtained in this work. One can suggest that the described inconsistence is due to the insensitivity of the adsorption measurements to microporosity, when pore size becomes less than 1 nm and the reference to obtained values of microporosity becomes incorrect. For this reason, there is a demand to search for new characteristics of both the template and replicas that are oriented on the synthesis of nano structured replicas.
1 Published
from the Proceedings of the II International Confer ence of the CIS “Sol−Gel Synthesis and Study of Inorganic Compounds, Hybrid Functional Materials, and Disperse Sys tems,” held in Sevastopol’, Ukraine, on September, 18−20, 2012.
The degree of ordering of the mesostructured tem plate and replica is usually characterized by the quality of the obtained diffractograms and the steepness of the 79
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PONOMARENKO et al. (a)
(b)
Fig. 1. Scheme of preparation of nanorods from MCM41 (left) and replica from SBA15 (right).
step of capillary condensation. There are no definite indications on the parameters and their values which enable one to differentiate highordered materials from lowordered. For example, the authors from [22] mention the symbate changes of the number of observed reflexes on the Xray pattern, their intensities and widths, and the relative height of the step of capil lary condensation on the nitrogen adsorption–de sorption isotherm and they suggest that these changes are the consequence of the disordering of carbon material. However, definite values of these parameters as measures of order are not given. The quantitative description of the degree of order ing is considered important for the characterization of the probability of the preparation of the structured replica. In addition, estimation of the degree of order ing enables one to determine the parameters of the template or the conditions that ensure the retention (disordering) of the structure. The aim of this work is to determine the correla tions between the characteristics of the mesostructure of the template and replica. Primary attention was devoted to the values that are available for measure ment, for example, the intensity and width of diffrac tion maxima, the width and height of the step of cap illary condensation in adsorption measurements. In the work, we tried to determine the effect of micropore volume or other structural and texture characteristics of SBA15 material on the ordering of carbon replicas and the conditions of the synthesis of mesoporous templates with the characteristics that are optimal for the preparation of ordered replicas were sought. For this purpose, SBA15 samples were synthesized at var ious temperatures, which have various characteristics; the carbon replicas were synthesized and character ized based on them. Correlation analysis was per formed to establish the parameters that affect the ordering of carbon replicas. EXPERIMENTAL Synthesis of samples. Synthesis of SBA15 was per formed according to the procedure from [3] via the reac tion of tetraethoxysilane (TEOS) with Pluronic P123
(triblockcopolymer, (C2H4O)20(C3H6O)70(C2H4O)20 , Mav = 5800) in 1.6 M HCl at 45°C. At the end of the pri mary precipitation stage (after 24 h), additional treat ment was performed at elevated temperatures for 48 h (see table). After that, the precipitate was filtered, dried in air, and calcined at 550°C. After each step, a portion of the material was taken for recording the Xray pattern. The calcined materials were exposed to adsorption anal ysis. In order to obtain carbon materials, the silicate sample was soaked in a sucrose solution twice [7]. For the first soak, a solution of 5 mL of water, 1.25 g of sucrose, and 0.14 g of sulfuric acid was prepared on a 1 g silicate matrix. For the second soak, 5 mL of water, 0.8 g of sucrose, and 0.09 g of sulfuric acid was pre pared on a 1 g silicate matrix. After each soak, the material was dried at 100°C for 6 h and carbonized at 160°C for 2 h. After the second soak and drying, high temperature carbonization was carried out in a nitro gen flow at 850–900°C. The silicate template was removed by double dissolution in 1 M wateralcohol solution of NaOH. The prepared mesoporous materi als were studied according to Xray diffraction and gas adsorption. Xray analysis. The Xray data were obtained with the use of an X’Pert Pro (Panalytical) Xray diffracto meter with a PIXcel semiconductor detector and graphite monochromator on a secondary beam and CuKα1, 2 emission. Scanning was performed in the range 2θ = 0.4°–7.0°, with a step of 0.026° and expo sure at the 200s point. The lattice parameters and halfwidth of observed reflexes, β, were determined according to the Xray patterns (see table). Gas adsorption. Adsorption was performed on a Micromeritics ASAP (Micromeritics) gas analyzer. Preliminary degassing of the samples was conducted at 300°C under vacuum (p ~ 10–6 Pa) for 6 h. The nitro gen sorptiondesorption isotherms were recorded at 77 K in the range p/p0 0.01–0.99. The specific surface was calculated according to the BET method [23]; the pore size distribution was calculated according to the BJH method [24]; and the specific volume of micro and mesopores was calculated according to the αs
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Temperature of synthesis of silicate templates, structural and texture characteristics of templates and replicas prepared from them Characteristics of materials Temperature Sample of treatment, no. °C 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
95 95 90 90 90 90 90 87 83 83 80 80 80 80 75 75 75 70 70 70 70
template
replica
a, nm
SBET, m2/g
Vmeso, cm3/g
Vμ, cm3/g
D, nm
a, nm
βCARB, deg
11.4 11.4 12 11.5 10.6 10.6 10.6 10.6 10.3 10.3 11.4 11.4 11.4 10.9 10.9 11.6 11.6 10.6 10.6 10.5 10.5
440 440 805 723 730 730 730 729 931 931 947 947 947 852 862 783 783 677 677 493 493
0.95 0.95 1.02 0.51 0.94 0.94 0.94 0.72 0.85 0.85 1 1 1 0.85 0.74 0.85 0.85 0.64 0.64 0.55 0.55
0 0 0.015 0.13 0.04 0.04 0.04 0.07 0.13 0.13 0.1 0.1 0.1 0.1 0.11 0.072 0.072 0.08 0.08 0.03 0.03
9.8 9.8 10.4 8.2 9 9 9 8.5 9.4 9.4 9.8 9.8 9.8 8.3 8.6 9.6 9.6 8.2 8.2 8 9.8
10 10 9.2 8.7 9.1 9.3 9.5 9.2 9.2 9.4 9.1 9 9 9.2 8.9 9.7 9.7 9.3 9.3 8.7 8.7
0.15 0.15 0.15 0.32 0.15 0.13 0.13 0.27 0.15 0.15 0.18 0.22 0.22 0.2 0.22 0.2 0.27 0.29 0.29 0.35 0.35
method [25, 26]. The pore diameter of the silicate materials was calculated via gas adsorption and Xray diffraction data [9] by the following equation:
D = ca
Vmeso . 1 +V meso + Vµ ρ
(1)
Here, c = 1.05 is the ratio of the diameter of the circle to the double side of a hexagon with equivalent areas, a is a lattice parameter, Vmeso is mesopore volume, Vμ is micropore volume, and ρ is the density of the silicate wall (considered 2.2 g/cm3). Transmission electron microscopy. The structure of the samples were studied with the use of a JEOL JEM 2100 transmission electron microscope; and the accel erating voltage was 200 kV. For this purpose, carbon powders were dispersed in isopropyl alcohol with the use of an ultrasound bath. A drop of the obtained slurry was applied on a thin carbon film on the elec tron microscope object grid. GLASS PHYSICS AND CHEMISTRY
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SBET, m2/g 951 1174 1049 1038 1242 987 994 1003 1090 1120 1031 1063 1249 944 950 833 1093 1110 1143 729 945
Vtotal, cm3/g
DBJH, nm
Vstr Vtotal
0.8 1.1 0.85 0.6 1.12 0.81 0.82 0.75 0.87 0.86 0.8 0.79 0.82 0.76 0.58 0.71 0.8 0.79 0.82 0.55 0.58
4.8 4.8 3.2 – 3.7 4 4 3.5 3.7 3.6 3.5 3.4 3.1 3.7 3.1 3.6 3.5 3 3.1 3.6 29
0.78 0.77 0.55 – 0.65 0.77 0.83 0.32 0.51 0.47 0.5 0.38 0.24 0.43 0.45 0.55 0.3 0.1 0.2 0.25 0.05
RESULTS AND DISCUSSION The characteristics of the synthesized SBA15 samples (template) and corresponding carbon replicas are given in table. The obtained data are characterized by nearly 10% dispersion of the values. Although the Xray measurements in a smallangle range and the gas adsorption data are susceptible to various random and systematic errors, their average relative error is better than 2–3%. The analysis of the published data ensures that the observed dispersion is objective and intrinsic for the samples of the considered type. This is presumably because the changes of the experimental conditions of the synthesis were not exposed to suffi cient control. This explains the use in the experimen tal sample of the large amount of experimental data, whose retrieval solved various problems, including the optimization of the synthesis. A typical diffractogram of SBA15 sample is given in Fig. 2. On average, all diffractograms have 3–4 dif fraction peaks and the halfwidth of the reflexes for all samples was 0.13°. The position of the peaks corre sponds to the twodimensional hexagonal packing of 2014
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0.5
Intensity
Intensity
82
1.0
1.5
2.0 2θ, deg
2.5
3.0
0.5
1.0
1.5
2.0 2θ, deg
2.5
3.0
Fig. 2. Xray patterns of SBA15 (left) and replica of various qualities (right).
(а)
50 nm
100 nm (b) Fig. 3. Electron microscopy images of carbon replica of an SBA15 silicate material.
the cylindrical pores. The measurement error of the lattice parameter is less than 0.1 nm (see table). The diffractograms of the obtained carbon replicas (Fig. 2) can be conditionally divided into three groups according to the shape of the peaks: (1) three narrow wellresolved peaks; (2) one wellresolved peak and broad maximum that is obtained due to the overlap of the second and third peaks; and (3) one broad peak. It is evident that the degree of ordering of the material is responsible for this differentiation by the type of reflexes. The parameter was measured on the assump tion of a hexagonal structure of the position of the first
peak. The reason for calculating the parameter was the electron microscopy images of replicas (Fig. 3), which confirm the hexagonal packing of the carbon rods. The disorders that are observed in the shots have vari ous shapes; in particular, there are sections with vari ous carbon packing densities; this results in the loss of the periodical character of the ordering. The reproduction of the template structure by the replica, which is observed by means of electron microscopy, enables one to state the problem on the quantitative estimation of the degree of the reproduc tion. For these purposes, a parameter was introduced
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0.07 0.06 dV/dD, cm3/(g nm)
Amount of adsorbate, cm3/g
700 600 500 400 300
0.05 0.04 0.03 0.02
200 0.01
100 0
0.2
0.4
0.6
0.8
0
1.0
2
6
4
p/p0
8 10 Pore size, nm
12
14
Fig. 4. Adsorption isotherm of SBA15 material (left) and pore size distribution (right).
0.14 0.12 dV/dD, cm3/(g nm)
Amount of adsorbate, cm3/g
1600 1400 1200 1000 800 600
0.10 0.08 0.06 0.04
400 0.02
200 0
0.2
0.4
0.6
0.8
1.0
p/p0
0 2
3
4
5 6 7 8 Pore size, nm
9
10
Fig. 5. Nitrogen sorption isotherms (left) and pore size distribution curves (right) of the carbon replica of various qualities.
which represents the ratio of the reflex half widths (10), βSBA/βCARB, on the diffractograms of the template and carbon replica. At βSBA/βCARB = 1, the widths of the maxima are equivalent and the full recur rence of mesostructure is conditionally considered. The typical adsorption isotherm of SBA15 mate rial is intrinsic for the presence of the step of capillary condensation with hysteresis and narrow poresize distribution that is determined by the BJH method (Fig. 4). The calculated values of the specific surface, meso and micropore volume, and pore diameter are given in the table. GLASS PHYSICS AND CHEMISTRY
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Adsorption isotherms of carbon replicas and dif fractograms are convenient to differentiate into three groups: (1) with a clearcut step of capillary condensa tion, (2) a moderately pronounced step, and (3) a weakly pronounced step. Typical examples of these isotherms are given in Fig. 5. For weakly ordered replicas, during the measure ment of the height of the step of capillary condensa tion, the ambiguity in determining its boundaries arises. At the same time, a clear maximum can be usu ally observed on the pore size of the distribution curve. The area under the maximum corresponds to the vol ume of the pore in the given size range. This volume 2014
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The dependences of (βSBA/βCARB) and (Vstr/Vtotal) to the micropore volume were not established, as is given in Fig. 6. A clear correlation can be observed for the (βSBA/βCARB) and (Vstr/Vtotal) ratios to the meso pore volume of the template; wall thickness, t; and temperature of treatment (Figs. 8–10). The diffractograms of the carbon materials that were synthesized from various templates contain dif fraction maxima with various widths and this half width is greater than that for the initial template. According to the images of electron microscopy (Fig. 3), the ranges of the ordering of the carbon mate rial are sufficiently lengthy. An increase in the width of the diffraction lines for the carbon material can take place due to the microdisturbances that are related to the shear of the replica fiber from the center of the pore, which causes the change of the distance between the fibers. It is obvious that the change of the distance between the fibers also affects Vstr. Thus, the observed correlation of (βSBA/βCARB) and (Vstr/Vtotal) has a phys ical foundation. As was shown in Fig. 7, the (βSBA/βCARB) and (Vstr/Vtotal) values are not correlated to the micropore volume; this, at first sight, contradicts the consider ations on the retention of the carbon fibers due to the carbon straps that appear in the micropores. Despite the large magnification, the obtained electron micros copy images (Fig. 3) do not allow the differentiation of particular straps between fibers. This means that the low number of straps with a small diameter (less than 1 nm) is sufficient to retain the fibers. In fact, the experiments showed that highly organized replicas can be obtained on SBA15 templates with deficient micropores or, as is mentioned by the authors in [9], with the micropores that are underestimated by the αs method.
1.0
Vstr/Vtotal
0.8
R2 = 0.8302
0.6 0.4 0.2
0
0.2
0.4 0.6 βSBA/βCARB
0.8
1.0
Fig. 6. Correlation between the the reproduction parame ter (βSBA/βCARB) and specific volume of the structured component (Vstr /Vtotal).
can be related to the structured part, because it should have narrow size distribution. This value was calcu lated and referred to as Vstr. In the table, the (Vstr/Vtotal) ratio is also given, where Vtotal is the total specific pore volume in the carbon replica. Analysis of the experimental data shows that there is a correlation between the reproduction parameter (βSBA/βCARB) and the specific volume of the structured component (Vstr/Vtotal), which occurs as a linear dependence (Fig. 6). In order to determine the parameters of the tem plate which are correlated to the ordering of the car bon replica, the dependences of the (βSBA/βCARB) and (Vstr/Vtotal) ratios to various characteristics of the tem plate were plotted (Figs. 7–10).
1.0
1.0
0.9
0.9 0.7
0.7
0.6
0.6
0.5 0.4
0.5 0.4
0.3
0.3
0.2
0.2
0.1
0.1
0
R2 = 0.1386
0.8
Vstr/Vtotal
βSBA/βCARB
0.8
R2 = 0.1046
0.02 0.04 0.06 0.08 0.10 0.12 0.14 Vµ
0
0.02 0.04 0.06 0.08 0.10 0.12 0.14 Vµ
Fig. 7. βSBA /βCARB and Vstr /Vtotal vs. micropore volume of initial template. GLASS PHYSICS AND CHEMISTRY
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1.0 R2 = 0.7574
0.9
0.8
0.8
0.7
0.7
0.6
0.6
Vstr/Vtotal
βSBA/βCARB
0.9
0.5 0.4
0.4 0.3
0.2
0.2
0.1
0.1 0.5
0.6
0.7 0.8 Vmeso
0.9
1.0
0 0.4
1.1
R2 = 0.72
0.5
0.3
0 0.4
85
0.5
0.6
0.7 0.8 Vmeso
0.9
1.0
1.1
Fig. 8. (βSBA /βCARB) and (Vstr /Vtotal) vs. mesopore volume.
1.0
1.0 R2
0.9
0.9
= 0.8819
0.8
0.8 Vstr/Vtotal
βSBA/βCARB
0.6 0.5 0.4
0.6 0.5 0.4
0.3
0.3
0.2
0.2
0.1
0.1
0 0.35
R2 = 0.912
0.7
0.7
0.40
0.45
0.50 1/t
0.55
0.60
0 0.35
0.65
0.40
0.45
0.50 1/t
0.55
0.60
0.65
Fig. 9. (βSBA /βCARB) and (Vstr /Vtotal) vs. inverse wall thickness of initial template.
The determined correlation of the specific meso pore volume to the inverse thickness of the pore wall (Figs. 8, 9) is presumably caused by the length of the carbon straps. It is evident that the probability of a break of the carbon strap increases with its length. In addition, the wall thickness determines the length of a micropore and the mesopore volume. The smaller the wall thickness the smaller the length of the carbon strap. For this reason, a decrease in the wall thickness gives an increase of the ordering of the replica. The growth of the ordering with the increase in the period and temperature of the treatment during the synthesis of the template was investigated in this work up to a temperature of 95°C. With an increase in tem perature, the decrease in the thickness of the pore wall GLASS PHYSICS AND CHEMISTRY
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takes place and, accordingly, the ordering of the rep lica increases (see table). Thus, numerous experimental data on the template synthesis of carbon replicas with the use of the SBA15 mesostructured silicate as a template found correla tions of the ordering of the replica with the conditions of the synthesis of the template. The degree of ordering of the carbon replica can be controlled via gas adsorp tion and Xray diffraction. The ordering of the replica depends substantially on the mesopore volume of the initial template and its wall thickness. One should use templates with a possi bly higher mesopore volume and minimum wall thick ness to obtain highly ordered replicas. These templates can be prepared while treating at temperatures close to 2014
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R2 = 0.8472
0.9
0.9
0.8
0.8
0.7
0.7 Vstr/Vtotal
βSBA/βCARB
1.0
0.6 0.5
0.6 0.5
0.4
0.4
0.3
0.3
0.2
0.2
0.1
0.1
0 65
70
75 80 85 90 T of treatment, °C
95
100
R2 = 0.9029
0 65
70
75 80 85 T of treatment, °C
90
95
100
Fig. 10. (βSBA /βCARB) and (Vstr /Vtotal) vs. temperature of treatment.
100°C. The presence of micropores is a condition for prepared carbon replicas that retain the structure of SBA15 template; however, no clear effect of their vol ume on the degree of ordering of the replicas is observed. ACKNOWLEDGMENTS The work was supported by the Russian Founda tion for Basic Research (project nos. 110300610a and 110312161ofim2011) and Program of Funda mental Studies of the Presidium of Russian Academy of Sciences (project no. 24.37). REFERENCES 1. Kresge, C.T., Leonowicz, M.E., Roth, W.J., Vartuli, J.C., and Beck, J.S., Ordered mesoporous molecularsieves synthesized by a liquidcrystal tem plate mechanism, Nature (London), 1992, vol. 359, pp. 710–712. 2. Beck, J.S., Vartuli, J.C., Roth, W.J., Leonowicz, M.E., Kresge, C.T., Schmitt, K.D., Chu, C.T.W., Olson, D.H., Sheppard, E.W., McCullen, S.B., Hig gins, J.B., and Schenker, J.L., A new family of mesopo rous molecularsieves prepared with liquidcrystal tem plates, J. Am. Chem. Soc., 1992, vol. 114, pp. 10834– 10843. 3. Zhao, D., Huo, Q., Feng, J., Chmelka, B.F., and Stucky, G.D., Nonionic triblock and star diblock copolymer and oligomeric surfactant syntheses of highly ordered, hydrothermally stable, mesoporous sil ica structures, J. Am. Chem. Soc., 1998, vol. 120, no. 24, pp. 6024–6036. 4. Zhao, D., Feng, J., Huo, Q., Melosh, N., Fredrickson, G.H., Chmelka, B.F., and Stucky, G.D., Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 angstrom pores, Science (Washing ton), 1998, vol. 548, pp. 279–552.
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23. 24.
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