ISSN 0036 0244, Russian Journal of Physical Chemistry A, 2011, Vol. 85, No. 13, pp. 148154.

Pleiades Publishing, Ltd., 2011.

PHYSICAL CHEMISTRY OF SURFACE PHENOMENA

Effect of the Support and the Reduction Temperature on the Formation of Metallic Nickel Phase in Ni/Silica Gel Precursors of Vegetable Oil Hydrogenation Catalysts1
M. Gabrovskaa, J. Krsti c b, P. Tzvetkovc, K. Tencheva, M. Shopskaa, N. Vukeli c d, and D. Jovanovi c b
a b

Institute of Catalysis, Bulgarian Academy of Sciences, Acad. G. Bonchev str. bl. 11, 1113 Sofia, Bulgaria Institute of Chemistry, Technology and Metallurgy, Department of Catalysis and Chemical Engineering, Njegoeva 12, 11 000 Belgrade, Serbia c Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, Acad. G. Bonchev str., bl 11, 1113 Sofia, Bulgaria d Faculty of Physical Chemistry, University of Belgrade 11000, Serbia e mail: margo@ic.bas.bg
Received December 30, 2010

AbstractNi/SiO2 materials with identical composition (SiO2/Ni = 1.0) have been synthesized by precipi tation of Ni(NO3)2 6H2O solution with Na2CO3 solution on the silica gel, obtained at three different pH values. The present investigation was undertaken in an endeavor to study the effects of the silica gel support type and the reduction temperature on the formation and dispersion of the metallic nickel phase in the reduced Ni/SiO2 precursors of the vegetable oil hydrogenation catalyst. The physicochemical characteriza tion of the unreduced and reduced precursors has been accomplished appropriately by powder X ray diffrac tion, infrared spectroscopy, temperature programmed reduction and H2 chemisorption techniques. It can be stated that the texture peculiarities of the silica gels used as supports influence on the crystalline state and dis tribution of the deposited Ni containing phases during the preparation of the precursors, on the reduction temperature of the investigated solids as well as on the bulk size and surface dispersion of the arising metallic nickel particles. It was shown that two types of Ni2+ species are formed during the synthesis procedure, namely basic nickel carbonate like and Ni phyllosilicate with different extent of presence, location and strength of interaction. The different location of these species is supposed to result in various strength of Ni O and NiOSi interaction, thus determining the overall reducibility of the precursors. It was specified that the Ni2+ species are strongly bonded to the surface of the silica gel obtained at neutral pH value and weakly bonded to the surface of those prepared in acidic and alkaline conditions. It was established that the precur sor, derivates from the silica gel obtained at alkaline conditions, demonstrates both significant reduction of the Ni2+ ions at 430C and finely dispersed metallic nickel particles on its surface. High dispersion of the metallic nickel might be the crucial reason for achieving of high activity in the vegetable oil hydrogenation. Keywords: metalic nickel phase, formation in Ni/silica gel, hydrogenation catalyst, effect of the support and reduction temperature. DOI: 10.1134/S0036024411130073

INTRODUCTION The partial hydrogenation of the vegetable oils continues to be applied as one of the most universal methods in the modern chemical industry, aiming to decrease the un saturation of the high fatty acids, to modify the physical properties of the oils and to enhance the oxidation and thermal stability of the hydrogenated products. The process is widely used in the manufacture of margarines, cooking, frying and salad oils, chocolates, ice creams, shortenings and products of bakery. Currently, the metallic nickel (22
1The article is published in the original.

25 wt % Ni) supported on different natural sources of silica represents the commonly applied commercial catalyst for the process because of the high activity, inert nature of the metal relative to the oil, availability and low cost [13]. Several natural sources of silica as diatomite, ben tonite, clay minerals, as well as different types of zeo lite have been used for a long period of time as supports of the nickel catalysts [4]. However, the natural silica sources have some disadvantages such as the composi tion variation from batch to batch as well as the pres ence of different impurities. Therefore, a number of mechanical, chemical and thermal treatments are

148

EFFECT OF THE SUPPORT AND THE REDUCTION TEMPERATURE

149

necessary to obtain a pure and activated support [5]. These facts lead to the use of synthetic silica, thus the prolonged and expensive procedures for purification of the crude sources can be avoided. Silica gel represents a granular, highly porous and partially hydrated form of silica, made synthetically from sodium silicate. The wide range of silica gel applications like adsorbents for catalytic, biochemical and chromatographic purposes requires the prepara tion of gels of different porosity: microporous, macroporous and various intermediate structures. By strictly controlled conditions of preparation (time, temperature and pH), a range of highly pure silica gels (100% SiO2) with well defined pore system and sur face properties can be produced [6], which makes them appropriate for application as catalyst supports. A good supported metal catalyst is characterized by the presence of highly dispersed metallic particles inside the support that are located in positions easily accessible to the molecules to be catalyzed. It is known that the nature and the organization of the supported phase influence on the behavior of the precursor dur ing the reduction pretreatment and contribute to determine the size and dispersion of the metallic par ticles. In view of this, the aim of the study is to investi gate the conditions of the formation and dispersion of the active metallic nickel phase in the process in hand, that is fundamental for the achievement of good cata lyst performance. The effects of the support and the reduction tem perature on the formation and dispersion of the metal lic nickel phase in reduced Ni/SiO2 systems were stud ied based on the characterization results by the follow ing techniques: powder X ray diffraction (PXRD), infrared (IR) spectroscopy, temperature programmed reduction (TPR) and H2 chemisorption. EXPERIMENTAL Sample Preparation Three types of commercial silica gel (SIG) in a sieve fraction with size of 0.81.0 mm after grinding were applied as supports for the synthesis of the Ni/SIG precursors. The silica gels were prepared at different pH values, namely: acidic (SIG A), neutral (SIG B) and alkaline (SIG C) aiming to obtain the materials with different texture parameters. The precursors were synthesized with identical composition (SiO2/Ni = 1.0) by precipitation on silica gel using aqueous solutions of nickel nitrate Ni(NO3)2 6H2O and Na2CO3 at constant values of both temper ature of 90C and pH 9.0 0.2 under vigorous stirring. A volume of distilled water, containing suspended SIG was placed in a reaction vessel, equipped with a stirrer, thermometer and pH electrode. The suspen sion was heated up to 90C and adjusted with a solu tion of Na2CO3 (0.9 M) to reach a pH level of 9.0.
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A

Then, the nickel nitrate solution (0.5 M) and the pre cipitant were introduced drop wise simultaneously to the reaction vessel controlled by two peristaltic pumps. The resulting slurry was aged for 60 min in the mother liquor under the conditions mentioned above. It was then filtered off, thoroughly washed with hot distilled water (90C) until the pH of the filtrate decreased to 7 and absence of NO 3 ions (testing with solution of diphenylamine in H2SO4) was obtained. The precipi tate was then dried at 120C for 20 h and designated as Ni/SIG X, where X represents the type of used silica gel, for example Ni/SIG A. To get reference sample for the characterization of the Ni/SIG X samples, unsupported basic nickel car bonate denoted as BNC, was prepared according to a preparation procedure described above, however in the absence of the silica support. Sample characterization The chemical composition of the precursors was determined using volumetric and gravimetric tech niques. The as synthesized precursors were treated with an aqueous solution of HCl (1/1) under heating. After separation of the support, the nickel concentra tion was determined by EDTA titration in the pres ence of indicator murexide, while the silica content was achieved by a classical gravimetric method. The phase composition of the supports, unreduced and reduced precursors was established by Powder X ray diffraction (PXRD) technique. PXRD patterns were recorded on a Bruker D8 Advance powder dif fractometer employing CuK radiation, operating at U = 40 kV and I = 40 mA. The phase identification was made by comparison with the Joint Committee on Powder Diffraction Standards (JCPDSs). The mean size of the nickel crystallites was calculated from the metallic nickel reflection (111) at 2 44, according to the Scherrer equation [7]. The infrared (IR) spectra of the supports, unre duced and reduced precursors were recorded within the range 4000400 cm1 at room temperature on a Nicolet 6700 FTIR spectrophotometer (Thermo Elec tron Corporation, USA) with a spectral resolution of 0.4 cm1 and 50 scans, using a KBr pressed disk pellet technique with a sample concentration 0.5 wt %. The temperature programmed reduction (TPR) of the precursors was performed in the measurement cell of a differential scanning calorimeter (DSC) model DSC 111 (SETARAM) directly connected to a gas chromatograph (GC). A quartz reactor was loaded with 0.025 g of the as synthesized samples. Mass flow rates were monitored by Matheson mass flow regulator within 1% accuracy. The temperature was linearly raised from 25 to 700C at a heating rate of 10 K/min. The TPR experiments were accomplished by a gas mix ture H2/Ar (10/90 v/v) with a flow rate of 25 cm3/min. A cooling trap between DSC and GC removed the
Vol. 85 No. 13 2011

150

GABROVSKA et al.

Table 1. Chemical composition of the as synthesized pre cursors Sample Ni/SIG A Ni/SIG B Ni/SIG C Ni, wt % 43.7 45.5 43.5 SiO2, wt % 44.4 42.1 44.6 SiO2/Ni 0.99 0.90 1.00

dispersion (DNi) assuming the adsorption stoichiome tryone hydrogen atom is chemisorbed on one sur face metallic nickel atom. The metallic dispersion is represented by the ratio of surface nickel atoms/total nickel atoms DNi, %. RESULTS AND DISCUSSION The results from the chemical analysis of the as synthesized precursors are summarized in Table 1. Molar ratios of SiO2/Ni about 1.0 are found in all pre cursors that being nearly equal to the SiO2/Ni molar ratio in the synthesis solutions. The obtained data demonstrate that the Ni2+ ions are quantitative precip itated. The PXRD patterns of the supports and the as syn thesized precursors are represented in Fig. 1. The dia grams are vertically displaced and the same scale is used for an easier comparison. The diffraction patterns of the three silica gels show reflections characteristic of amorphous silica (silica halo peak situated at 2 22) better organized in SIG C. It may be noted that the diffractograms of the pre cursors are considerably different from the spectra corresponding to the supports due to the nickel depo sition. On the other hand, the absence of the diffrac tion line at 2 16.5 of the reference BNC sample and the appearance of a reflection at 2 20 in the Ni/SIG precursors presented the main differences between the unsupported and supported Ni contain ing materials. The PXRD patterns of all precursors are weak and broad, denoting poorly crystallized, well dispersed nickel compounds [9]. The observed phenomenon proves that during the synthesis procedure, an interaction occurs between the nickel salt and the silica from the support resulting in obtaining of supported layered Ni phyllosilicate phase (Ni3Si2O5(OH)4 with imperfect antigorite like structure (JCPDS 00 021 0963). Similar PXRD pat terns for Ni/diatomite catalyst precursors have been reported by Echeverria and Andres [9]. The formation of Ni phyllosilicate phase on the support surface has been studied in details by Burattin et al. [10, 11], based on the oxolation type condensation reaction between the Ni2+ complex, containing some water ligands and siliceous species. The latter are arising from the partial dissolution of the silica support in the basic medium. As it has been published, the Ni phyllosilicate com pounds with not clearly defined reflections are always formed during the co precipitation of nickel nitrate and alkali silicate solutions at temperature under 100C [12]. The turbostratic structure of the Ni phyllosilicate phase [12, 13] predetermined the ill organized reflec tions of the Ni/SIG precursors. Moreover, the Ni phyllosilicate phase exhibits different degree of crys tallization, more pronounced in Ni/SIG B sample. It is obvious that the usage of different silica gel types affects the crystallinity of the deposited Ni containing
Vol. 85 No. 13 2011

water obtained during the reduction. The selected conditions were in an agreement with the criteria pro posed by Monti and Baiker [8] to avoid the mass trans fer and temperature control limitations. Bearing in mind, that the activation of the vegeta ble oil hydrogenation catalysts is commonly accom plished by reduction of the precursors in the interval 430550C, the precursors under study were reduced at 430 and 530C for 5 h with a gas mixture of H2/N2 (1/2 v/v at a flow rate of 10 dm3/h and a heating rate of 2 K/min to avoid sintering effect of the reduced metallic nickel) followed by a passivation with a gas mixture of O2/N2 after cooling down to room temper ature. The hydrogen chemisorption measurements were carried out in a volumetric device at room temperature and hydrogen pressure range 0100 Torr (1 Torr = 133.3 Pa). The as synthesized samples were previously submitted to the in situ reduction in the equipment under the conditions described above. The monolayer coverage (capacity for hydrogen adsorption) was determined by extrapolation of the linear part of the isotherm to the zero pressure. The amount of adsorbed hydrogen was used to determine the metallic nickel

Ni/SIG C SIG C

Intensity, a.u.

Ni/SIG B SIG B

Ni/SIG A SIG A BNC

10

30

50

70

90 2, deg

Fig. 1. PXRD patterns of the supports and as synthesized precursors.

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A

EFFECT OF THE SUPPORT AND THE REDUCTION TEMPERATURE

151

phase. Supplementary, the registered high background below 2 15 on the diffractograms of the precursors indicates advanced amorphisation of the observed phase. The interactions of the Ni2+ ions with the silica support are checked by the short rang order infrared spectroscopy. Although the IR spectra of the supports, unreduced and reduced precursors were obtained in 4000400 cm1 region, the comparison was con ducted in the frequency range of 1800400 cm1 because the variations in the absorption profiles char acterizing NiOSi interaction were observed in this region. The spectra of the silica gels (Fig. 2) display vibra tions associated with the silica network, namely: asymmetric SiOSi (~1100 cm1) and symmetric SiOSi stretching vibrations (800 cm1), stretch ing vibration of the free SiOH groups on the surface of the solids (~970 cm1) and SiOSi bending vibra tion (~470 cm1). The bands assigned to the carbonate anions at ~1380 cm1 and to the water molecule defor mation vibrations at ~1630 cm1 are also registered [14, 15]. The IR spectra of the unreduced precursors demonstrate absence of the silica SiOSi stretching vibration bands at ~1100 and ~800 cm1 but instead, a doublet appears at 1050 and 1005 cm1. The split ting and the shift towards lower frequencies, as well as the appearance of a new band at ~660 cm1 are assigned to the formation of Ni phyllosilicate link ages (SiONi), which cover the surface of the support particles [13, 15]. Their generation seems to be most significant in Ni/SiG B. An inspection of the bands evidence apparent dif ferences in the band shape and relative intensity that justify the creation of different Ni2+ species on the sample surfaces. The well expressed band at 1380 cm 1 in the IR spectrum of Ni/SIG A is attributed to the presence of an additional carbonate containing phase most probably located on the surface of the Ni phyllo silicate [16]. Taking into consideration the differences between the precursors documented by PXRD and IR analysis, it is assumed different texture characteristics of the supports, due to the variables in their preparation con ditions. The study based on the low temperature N2 sorption technique performed on the same types of sil ica gels and the corresponding Ni/SIG precursors confirms this supposition [17]. The authors reported that the supports possess different specific surface area (sBET) and average pore diameter (daver), namely SIG A (sBET = 777 m2/g and daver = 2.7 nm), SIG B (sBET = 581 m2/g and daver = 5.7 nm) and SIG C (sBET = 387 m2/g and daver = 9.5 nm). It has been concluded that the usage of the silica gels with different texture parameters provokes diverse location of the Ni2+ spe cies as into the support pores as well as on the support surface. Consequently, the registration of varies prop erties of the resulting catalyst precursors may be
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A

Ni/SIG C SIG C

Transmittance, a.u.

Ni/SIG B SIG B

Ni/SIG A SIG A

BNC

1500

1000

500 , cm1

Fig. 2. IR spectra of the supports and as synthesized pre cursors.

H2 consumption, counts 20
Ni/SIG A

Ni/SIG C

12

BNC 101

Ni/SIG B

4 200 400 600

T, C

Fig. 3. TPR profiles of the as synthesized precursors.

expected, even when the same amount of Ni2+ ions has been introduced. TPR technique is applied in order to elucidate the strength of interaction of the Ni2+ species with the sil ica gels (Fig. 3). The interpretation of the TPR profiles of the precursor is accomplished by comparing them with the profile of the reference BNC sample. The comparison is supposed to clarify the support role in the studied solids. Indeed, the experiments revealed quite different reduction behavior of the formed Ni2+ species. The higher reducibility of the unsupported BNC is attested by the single low temperature peak in the region 220310C that is assumed to represent the full reduction of bulk Ni2+ ions to Ni0. In contrast, multiple reduction peaks with poorly resolved maxima characterize the TPR profiles of the precursors indi
Vol. 85 No. 13 2011

152
Ni0(111) Ni0 Ni0 BNC_R530 0 NiNi0

GABROVSKA et al.

BNC_R430

Ni/SIG C_R530 Ni/SIG C_R430 Ni/SIG B_R530 Ni/SIG B_R430

Ni/SIG A_R530 Ni/SIG A_R430

20

40

60

80

100 2, deg

Fig. 4. PXRD patterns of the reduced precursors; the unre duced Ni phyllosilicate phase is marked with arrows.

cating a complex interaction between the compo nents. The reduction process in both Ni/SIG A and Ni/SIG C samples starts at ~270C that may be asso ciated with the reduction of BNC like species (the peak and shoulder at ~320C). The next step is reduc tion of the Ni2+ ions from the Ni phyllosilicate phase (Tmax ~ 430C). The obtained results suggest that the additional carbonate containing phase registered by IR spectroscopy seems to be BNC like phase, located on the surface of the Ni phyllosilicate in Ni/SIG A precursor. TPR profile of Ni/SIG B solid manifests the beginning of the reduction temperature at 350C and appearance of both a broad peak at ~520 and a shoulder at ~630C.
Table 2. Mean crystallite size and surface dispersion of the metallic nickel Sample Ni/SIG A Ni/SIG B Ni/SIG C BNC
0

L Ni (111) , nm R430 6.0 n.m. 4.2 31.8 R530 6.8 4.9 5.2 32.0

DNi, % R430 1.4 6.7 12.6 R530 0.7 8.0 2.2

Note: L Ni (111) mean metallic nickel crystallite size, calculated from (111) diffraction line; DNisurface dispersion of the metallic nickel, calculated from the amount of adsorbed hydrogen; n.m.not possible to be measured.

This finding can be attributed to reduction of the Ni2+ ions only from the Ni phyllosilicate phase. Hence, the TPR experiments prove the absence of BNC like species in Ni/SIG B precursor. It may be summarized that the TPR profiles of the precursors evidenced a variety of interaction strength, namely: weak (~320430C) and strong (>500C). It may be interpreted based on the above mentioned statements, that the usage of the silica gel supports with different texture characteristics provokes differ ent location of Ni2+ species as into the support pores as well as on the support external surface area namely, Ni phyllosilicate in the pores of the supports or BNC like on the Ni phyllosilicate surface [17]. Such an effect leads to a diverse coordination grade of the Ni2+ ions by the surface oxygen atoms, resulting in dif ferent NiO and NiOSi bond strengths. The stron ger the interactionthe higher temperature TPR peaks. A conclusion may be drawn from the reported TPR results that the Ni2+ species are weakly bonded to the surface of the silica gels obtained at acidic (SIG A) and alkaline (SIG C) pH values and strongly bonded to the surface of silica gel prepared at neutral condi tions (SIG B). Further PXRD study on the reduced precursors at 430 and 530C reveals details in the reduction process and the transformation of the formed Ni2+ species to the metallic nickel state. The patterns of the reduced solids at 430C (Fig. 4) display reflections located at the angles, typical of the metallic nickel phase (JCPDS file 00 004 0850). The differences in the peaks intensity from one sample to another indicate different degree of the metallic nickel crystallization. Applying PXRD data processing, the mean crystallite size (L) of the metallic nickel is eval uated from the diffraction line situated at 2 44. It is clearly shown that this reflection is very broad and badly organized in Ni/SIG B_R430 precursor, sug gesting the existence of small Ni0 particles (high dis persed). The poor crystallinity of the sample prede termines that the evaluation of the mean Ni0 crys tallite size is practically impossible. Contrariwise, the sharper and narrower diffraction lines of Ni/SIG A_R430 precursor and especially in the case of the reference sample BNC_R430 are responsible for the generation of larger Ni0 crystallites (Table 2). The peaks of lower intensity at 2 3240 and 60, documented the presence of Ni phyllosilicate phase in all reduced precursors, however it is better represented in Ni/SIG B_R430. These observations are in agreement with the TPR data about the ham pered reducibility of the Ni/SIG B sample at lower temperatures. The reduction of bulk Ni2+ ions is increased upon treatment with hydrogen at 530C as it is evidenced from the sharpness of the Ni0 reflections. As is represented in the PXRD patterns, the most remarkable changes in the reducibility of the Ni phyl
Vol. 85 No. 13 2011

Intensity, a.u.

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A

EFFECT OF THE SUPPORT AND THE REDUCTION TEMPERATURE

153

losilicate and the crystallization of the Ni0 phase is demonstrated by Ni/SIG B precursor after reduction at 530C. This procedure provokes growing of the metallic nickel particles to value of 4.9 nm, very close to that of Ni/SIG C_R530 (5.2 nm). It is obvious that the reduction procedures, applied to the reference BNC sample do not affect the degree of the metallic nickel crystallization as well as the size of the mean Ni0 particles. It may be marked that the treatment with hydrogen at 530C induces not only significant reduc tion of the Ni2+ species, but causes also slight growth of the nano sized metallic nickel crystallites in all studied samples. The IR spectra of the reduced precursors provide indirect information on the strength of NiOSi interactions. Most notable changes in the spectra are demonstrated of both Ni/SIG A and Ni/SIG C pre cursors after reduction at 430C (Fig. 5). It is seen a backward shift of the doublet to ~1080 cm1 and reap pearance of the band at ~800 cm1, characteristic of the silicate vibrations (bearing of the supports). The presence of the band at 660 cm1 of negligible intensity indicates that significant reduction of the Ni phyllo silicate occurred, particularly for Ni/SIG A R430 solid. In contrast, the IR spectrum of Ni/SIG B_R430 displays well resolved bands at ~1030 and ~660 cm1 thus manifests insufficient extent of the Ni phyllosili cate reduction. It is obvious that the tendency of incomplete reduction of Ni/SIG B is preserved even at temperature of 530C. Contrariwise, an additional shift of the band at ~1080 cm1 up to ~1090 cm1 and an increase in the intensity of the band at ~800 cm1 document considerable reduction of the Ni phyllo silicate in both reduced Ni/SIG A_R530 and Ni/SIG C_R530 solids. The observed phenomenon is better represented in Ni/SIG A_R530 precursor showing complete disappearance of the band at ~660 cm1. The H2 chemisorption data disclose the highest dispersion of the metallic nickel on the surface of Ni/SIG C precursor, after its reduction at 430C (Table 2). Thus, it implies that the sample has the larg est number of active sites on its surface compared to the Ni/SIG A_R430 and Ni/SIG B_R430 precur sors, even though the same amount of Ni2+ ions was precipitated. The lowest dispersion of the metallic nickel is registered on the surface of Ni/SIG A pre cursor after reduction at both studied temperatures. The lowest H2 uptake demonstrated by Ni/SIG A sample is due to the fact, that the main part of Ni2+ species is already reduced at 320C (TPR data). Prolonged thermal treatment at 430 and 530C induces aggregation or sintering of the metallic nickel. In contrast, the main part of Ni2+ ions in Ni/SIG C solid is reduced at 430C. Therefore, this sample chemisorbs the largest amount of H2 and demonstrates the highest Ni0 dispersion after reduction at 430C. Further treatment at 530C leads to the agglomeration
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A

Ni/SIG C_R530

Ni/SIG C_R430

Transmittance, a.u.

Ni/SIG B_R530 Ni/SIG B_R430

Ni/SIG A_R530

Ni/SIG A_R430

1500

1000

500 , cm1

Fig. 5. IR spectra of the reduced precursors.

of the metallic nickel particles. PXRD and TPR experiments performed on Ni/SIG B_R430 precur sor suggest uncompleted reduction of Ni2+ ions at 430C and explain the lower H2 adsorption capacity of the reduced solid. The reduction of Ni2+ species in Ni/SIG B sample increases upon treatment at 530C, the amount of adsorbed H2 increases also and the dis persion of the metallic nickel particles enhances. CONCLUSIONS Based on the characterization studies we can state that the texture peculiarities of the silica gels used as supports influence on the crystalline state and distribution of the deposited Ni containing phases during the course of the precursors preparation; on the reduction temperature of the investigated solids; on the bulk size and surface dispersion of the arising metallic nickel particles. The results show that two types of Ni2+ species are formed during the synthesis procedure, namely basic nickel carbonate like and Ni phyllosilicate with dif ferent extent of presence, location and strength of interaction. The differences in the location of these species in the pores or on the surface of the supports is supposed to result in various strength of NiO and NiOSi interaction, thus determining the overall reductibility of the precursors. The Ni2+ species are strongly bonded to the surface of the silica gel obtained at neutral pH value and weakly bonded to the surface of those prepared in acidic and alkaline conditions.
Vol. 85 No. 13 2011

154

GABROVSKA et al. 4. J. Weldsink, M. Bouma, N. Schn, and A. Beenack ers, Catal. Rev. Sci. Eng. 39, 253 (1997). 5. D. Jovanovi c, R. Radovi c, L. Mares, M. Stankovi c, and Br. Markovi c, Catal. Today 43, 21 (1998). 6. R. Yang, Adsorbents: Fundamentals and Applications (Wiley, 2003). 7. H. Klug and L. Alexander, X Ray Diffraction Proce dures for Polycrystalline and Amorphous Materials (Wiley, 1974). 8. D. Monti and A. Baiker, J. Catal. 83, 323 (1983). 9. S. Echeverria and V. Andres, Appl. Catal. 66, 73 (1990). 10. P. Burattin, M. Che, and C. Louis, J. Phys. Chem. B 101, 7060 (1997). 11. P. Burattin, M. Che, and C. Louis, J. Phys. Chem. B 102, 2722 (1998). 12. J. Van Eijk van Voorthuijsen and P. Franzen, Rec. Trav. Chim. 70, 793 (1951). 13. K. Ghuge, A. Bhat, and G. Babu, Appl. Catal. A: Gen. 103, 183 (1993). 14. R. Lenza and W. Vasconcelos, Mater. Res. 4, 189 (2001). 15. J. Sohn, Catal. Today 73, 197 (2002). 16. O. Solcova, D. C. Uecker, U. Steinike, and K. Jiratova, Appl. Catal. A: Gen. 94, 153 (1993). 17. D. Nikolova, J. Krsti c, L. Spasov, D. Simeonov, D. Loncarevi c, Pl. Stefanov, and D. Jovanovi c, Russ. J. Phys. Chem. 85 (Suppl.) (2011, in press).

The results also documented that similar Ni amount in Ni/SiO2 precursors (43.545.5 wt % Ni) leads to the narrow range of the mean size of the nickel metal particles (4.26.8 nm), when the characteristics of the silica supports and the reduction temperatures change. It was established that the precursor, derivates from the silica gel obtained at alkaline conditions, demon strates both significant reduction of the Ni2+ ions at 430C and finely dispersed Ni0 particles on its surface. High dispersion of the metallic nickel might be the crucial reason for achieving of high activity in the veg etable oil hydrogenation. ACKNOWLEDGMENTS J.K. and D.J. are grateful to the Serbian Ministry of Science (Pr 166001B). The authors are grateful to prof. R. Edreva Kardjieva and prof. G. Kadinov (Institute of Catalysis, BAS) for the useful discussions. REFERENCES
1. M. Balakos and E. Hernandez, Catal. Today 35, 415 (1997). 2. A. Wright, A. Wong, and L. Diosady, Food Res. Int. 36, 1069 (2003). 3. M. Fernndez, G. Tonetto, G. Crapiste, and D. Dami ani, J. Food Eng. 82, 199 (2007).

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A

Vol. 85

No. 13

2011