J. Chem. Chem. Eng.

7 (2013) 1111-1116

DAVID

PUBLISHING

Physico-Chemical Studies of Platinum-Ruthenium Catalysts of Oxidative Conversion of Methane to Synthesis-Gas

Tungatarova Svetlana*, Baizhumanova Tolkyn, Shlygina Irina, Shapovalov Anatolii, Zhumabek Manapkhan and Kassymkan Kaisar
D.V. Sokolsky Institute of Organic Catalyst and Electrochemistry, Almaty 050010, Kazakhstan Received: August 07, 2013 / Accepted: September 18, 2013 / Published: December 25, 2013. Abstract: The results of studying the interaction of H2 and O2 with Pt-, Ru- and Pt-Ru catalysts supported on 2% Ce/(+)-Al2O3, at varying the ratios and concentrations of supported elements by using the temperature-programmed desorption method are presented. It has been shown that H2 is adsorbed as four forms, differing in the structure, temperature, order and activation energy of desorption: 2ads, 2+ads, ads, at (des > 873 K). The relationship of activity and selectivity of Pt-Ru catalysts with the presence of active centers able to adsorb atomic hydrogen with desorption energy (Edes) = 60-70 kJ/mol in the catalytic oxidation of methane was determined. It was found that the O2 adsorbed as two forms differing in the structure, temperature and activation energy of desorption. It has been determined that changing the atomic ratio of elements in the catalysts significantly affect on the adsorption of O2. The introduction of ruthenium into the platinum catalyst increases the oxygen adsorption; and the surface is stabilized in a homogeneous state. Quantum chemical calculations of the activation of C-H bonds in a molecule of methane on RumPtn (m + n = 4) clusters have been carried out. Key words: Pt-Ru catalysts, selective catalytic oxidation of methane, adsorption.

1. Introduction
Information on the use of 1.0%-3.0% Pt-Ru catalysts on Al2O3 and TiO2 in the process of dehydrogenation of cyclohexane and propane [1], complex gas cleaning of vehicles from CO, CHx and NO [2], and in SCO (selective catalytic oxidation) of CH4 [3-5] available in the literature. It is known about the use of metal grids of Pt, Pt/5% Rh, Pt/10% Rh, Pt/10% Ir and Pd in the reaction SCO of methane. Experiments were conducted at atmospheric pressure, temperature 973-1373 K and contact time 0.21-0.33 ms. It was shown that at 20% conversion of methane selectivity of CO was 90%, and the selectivity for H2 varied in the range of 30%-50%. Number of O2 on Pt catalyst
Corresponding author: Tungatarova Svetlana, Ph.D., research field: oxidative catalysis. E-mail: tungatarova58@mail.ru.
*

reduced with formation of synthesis gas, and on Pt-Rh catalyst, it increased with increasing of CH4:O2 ratio [6]. Refs. [7-9] have been investigated catalysts containing 0.5 wt.% Ru/SiO2, 0.5 wt.% Ru/-Al2O3, 0.5 wt.% Ru/YSZ, 0.5 wt.% Ru/TiO2, 0.5 wt.% Ru/Y2O3, 0.5 wt.% Pt/CeO2, and 0.5 wt.% Pt/Al2O3 in the SO reaction of methane into synthesis gas. Experiments were conducted at atmospheric pressure and temperature 673-1023 K. 0.5 wt.% Ru/SiO2, 0.5 wt.% Ru/-Al2O3, 0.5 wt.% Ru/YSZ, 0.5 wt.% Ru/TiO2 catalysts provide conversion of methane up to 65%, maximum 82% selectivity to CO at 1,023 K. 0.5 wt.% Ru/Y2O3 catalyst provides methane conversion to 27.5%, the selectivity by carbon monoxide-78.9%, and by hydrogen-79.2% at 873 K. Conversion of methane on 0.5 wt.% Pt/CeO2 and 0.5 wt.% Pt/Al2O3 catalysts was 53% and 39%, and the selectivity for CO and H2 72% and 42%, and 64% and 57%,

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Physico-Chemical Studies of Platinum-Ruthenium Catalysts of Oxidative Conversion of Methane to Synthesis-Gas

respectively, at a reaction temperature of 873 K using 10 mg sample of catalyst. It was investigated Pt-, Ru- and Pt-Ru/2% Ce/(+)-Al2O3 catalysts with different ratios of Pt to Ru in the SCO of methane to synthesis gas at short contact times [10-12]. Optimum conditions of preparation of catalysts for conducting the process were found. It was found that the conversion of methane varied from 96% to 100%, the selectivity for hydrogen100%, CO95%-100% at 1,173 K and contact time 3.0-4.0 ms. 100% conversion of methane to synthesis gas by direct mechanism at 100% selectivity by H2 and CO are observed at the atomic ratio of Pt:Ru 2:1 or 1:1 (32.4 and 45.3 at.% Ru in the mixed Pt-Ru catalysts) and contact time () = 4.0 ms. Determining the nature of the adsorption of hydrogen and oxygen on Pt-, Ru- and Pt-Ru catalysts on 2% Ce/(+)-Al2O3, at varying the adsorption temperature, ratios of elements, concentration of metals on carrier using the TPD (temperature programmed desorption) method is the purpose of research. The data of quantum chemical calculations are presented for the study of structure and catalytic activity of platinum-ruthenium clusters.

prior to the adsorption of hydrogen. Desorption of adsorbed hydrogen was conducted at increase of temperature with rate 15o/min from 290 K to 1,373 K at Ar flow rate 60 mL/min with analysis of forming H2 on a chromatograph with thermal conductivity detector (detector temperature323 K, I70 mA, sensitivity 1:4). The activation energy of desorption of adsorbed hydrogen and oxygen (Edes) was calculated by the transformed Polanyi-Wigner equation which relates the change in concentration of hydrogen with temperature [13]. The calculation was performed on a specially developed computer program. Amount of the isolated hydrogen is calculated on the areas of the desorption curves as a result of tangent to a well defined peaks in the regions I and II and lowering the perpendicular to the abscissa at the inflection points of curves of the beginning and end of IV desorption region [13]. Quantum chemical calculations were performed using the software package G-09 (C01 version, the license of 07/02/2012). Calculations were carried out in the framework of DFT with the exchange-correlation functional B3LYP.

Two-exponential basis set LanL2DZ with effective spanning potential was used in the calculation of clusters. Mixed basis is used in the calculation of cluster complexes with a molecule of methane: 6-31G(d,p)for C and H atoms; LanL2DZfor Ru and Pt atoms.

2. Experiments
2.1 Catalysts Series of Pt-, Ru- and Pt-Ru catalyst supported on 2% Ce/(+)-Al2O3 was prepared for study. Catalysts were prepared by sequentially supporting of elements on the (+)-Al2O3 (100-200 microns, specific surface 57.7 m2/g) from aqueous solutions of metal salts Ce(NO3)3 6H2O, Ru(OH)Cl3, and H2PtCl6 6H2O by capillary impregnation of incipient wetness followed by heating in air at 873 K 3 h. 2.2 Methods The adsorption properties of catalysts were studied on the installation produced by Setaram (France). 0.25 g of catalyst was evacuated at P = 10-5 mm Hg for 0.5 h and then heated in Ar for 1 h at T = 573 K

3. Results and Discussion

Fig. 1 shows the TPD of hydrogen from 0.25 g of 1% Pt-, Ru- and Pt-Ru catalysts on 2% Ce/ (+)-Al2O3 after reduction in H2 at 773 K for 1 h. 2 peak at 273-373 K with Tmax = 333-336 K and 373-773 K with T max = 473 K, as well as less pronounced peak in the region from 873 K to 1,173 K with Tmax = 1,000-1,073 K are available in desorption curves. It has been determined that the total amount of adsorbed hydrogen in the range 28.4-32.2 10-5 mol/g in Pt- and Pt-Ru catalysts with 0.32 and 0.45 at.% Ru,

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Fig. 1 Temperature-programmed desorption of H2 from 0.25 g of 1.0% Pt-, Ru- and Pt-Ru catalysts on 2% Ce/(+)-Al2O3 with different concentrations of active components after reduction in H2. 11.0 at.% Pt; 20.82 at.% Pt + 0.18 at.% Ru; 30.68 at.% Pt + 0.32 at.% Ru; 40.55 at.% Pt + 0.45 at.% Ru; 50.34 at.% Pt + 0.66 at.% Ru; 60.11 at.% Pt + 0.89 at.% Ru; 71.0 at.% Ru.

high temperature region (> 873 K)100 times as compared with Pt catalyst. The calculation of orders and Edes of hydrogen in all areas for all catalyst samples were carried out. The calculation showed that the hydrogen of the I and II forms is desorbed by the first order with Edes = 28.0-30.0 kJ/mol and 35.5-51.8 kJ/mol, and in the III-IV regionby the second order with Edes = 58.5-76.6 kJ/mol and 92.4-118.3 kJ/mol, due to the separation of molecular and recombination of two adsorbed hydrogen atoms, respectively. Thus, the study of the interaction of hydrogen with reduced Pt-, Ru- and Pt-Ru catalysts supported on 2% Ce/(+)-Al2O3, by temperature-programmed desorption method indicates on hydrogen adsorption as four forms, differing in the structure, temperature, order and activation energy of desorption: 2ads, 2+ads, ads, at (des > 873 K). It was determined that the active centers capable to adsorb the hydrogen atoms with Edes = 60-70 kJ/mol, are active in the selective oxidation of CH4 to synthesis gas on Pt-Ru contacts. The results of studying the interaction of O2 with Pt-, Ru- and Pt-Ru catalysts on 2% Ce/(+)-Al2O3 by varying the ratios and concentrations of supported elements using temperature-programmed desorption method is presented. Fig. 2 shows that O2 is adsorbed as two forms differing in the structure, temperature and desorption activation energy. The relationship of activity and selectivity of Pt-Ru catalysts in the selective catalytic oxidation of methane with the presence of active centers able to adsorb atomic oxygen was determined. Two peaks in the region 273-573 K with Tmax = 413-453 K, and at 573-1,173 K with Tmax = 943-973 K are available on the curves of temperatureprogrammed desorption. The total amount of adsorbed oxygen is in the range 4.4-8.5 10 -4 mol/g. Desorption of oxygen in the form of the I peak is 2.0-5.0 10-4 mol/g. Desorption in the II region varies slightly from 2.1 to 4.1 10-4 mol/g. Effect of the catalyst composition on the content of strongly bound oxygen in the II region is more prominent. It can be

then decreases slightly to 21.0-21.7 on catalysts containing Ru > 0.45 at.%, and is only 14.8 10-5 mol/g on 1% Ru. The main amount of hydrogen is desorbed from all contacts in the II (32%-40%) and III regions (40%-46%). The hydrogen content on Pt-catalyst in the IV region is 15%-30%, and decreases with increasing concentration of Ru in bimetallic catalysts. On 1.0 at.% Ru, the hydrogen content is reduced to 0.3%. Desorption of hydrogen in the I region is very low0.2-1.0 10-5 mol/g, in the II region it is slightly changed from 8 to 12 10-5 mol/g. Effect of catalysts composition on the content of strongly bound hydrogen in the III and IV regions is more prominent. When the concentration of Ru in Pt-Ru catalysts above 0.45 at.%, the amount of desorbed hydrogen generated in the III temperature region is reduced on 30%-50% or more, and in the IV

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Physico-Chemical Studies of Platinum-Ruthenium Catalysts of Oxidative Conversion of Methane to Synthesis-Gas

atoms. The calculated binding energy in the cluster (kcal/mol) per atom increases in the series: Pt4(58) < RuPt3(66) < Ru2Pt2(70) < Ru3Pt(77) < Ru4(82). It can be seen that 4-atomic model clusters of ruthenium are the most stable. The increase of platinum content leads to a slight decrease in stability (about 25% for the platinum clusters compared with the ruthenium cluster). Value of the binding energy per atom in cluster can be correlated with the size of clusters formed during formation of the real catalysts. The most stable complexes were obtained for clusters with the composition Ru2Pt2 (I) and Ru2Pt2 (II) with intermolecular Ru-H bond (Fig. 3). In this case, the
Fig. 2 Temperature-programmed desorption of O2 from 0.3 g 1.0 wt.% Pt-, Ru- and Pt-Ru catalysts on 2% Ce/(+)-Al2O3 after oxidation by O2 at 573 K, 1 h. 11.0% Pt; 20.68% Pt-0.32% Ru; 30.55% Pt-0.45% Ru; 40.11% Pt-0.89% Ru; 51.0% Ru.

formation

of

intermolecular

complexes

is

accompanied by increase the positive charge on the methane molecule and elongation of one of the C-H bonds. RuPt3 complex (source geometry C(Ru)-H(Pt)) is formed with binding energy -6.06 kcal/mol. Length of the activated C-H bond = 1.128 . Transfer of electron density on the cluster is +0.146 share of the charge of electron. This complex follows the models (I) and (II) in strength and magnitude of activation of the C-H bond. The formation of intermolecular H-Pt bond is a feature of the Ru2Pt2, Ru2Pt2, Pt4 complexes. The most significant transfer from methane molecule to the cluster is observed for these complexes. The change in length of the C-H bond and transfer of electron density from methane molecules on cluster in Ru and Ru3Pt complexes are comparable in magnitude and significantly less than in complexes with clusters containing from 50% to 100% platinum. Performed analysis shows that the interaction of CH4 with Ru-Pt clusters has a complicated character, since there is no unambiguous correlation between the energy of interaction, the transfer of electron density from methane molecules on cluster and the lengthening of the C-H bond. At the same time the Ru2Pt2 clusters (I and II) are the most stable; considerable transfer of electron density and elongation

seen that the amount of desorbed oxygen that is released in the II temperature region, decreases at concentration of Ru 0.45 at.% and higher in the Pt-Ru catalysts. Thus there were established the adsorption and energy characteristics of Pt-, Ru- and Pt-Ru catalysts with different atomic proportions of active components by temperature-programmed desorption of oxygen. Change of atomic ratios in catalysts significantly affects on adsorption of oxygen. Data on quantum chemical calculations of activation of the C-H bond in methane molecule on RumPtn clusters (m + n = 4) are also presented. The initial geometry of the cluster was defined as a regular tetrahedron with edge 1.57 . Structures in the form of distorted tetrahedrons were obtained by optimization. The positive charge in the mixed clusters is focused on the ruthenium atoms, the negativeon the platinum atoms. The increase of the platinum content in the mixed clusters corresponds to increase of the positive charge on the ruthenium

Physico-Chemical Studies of Platinum-Ruthenium Catalysts of Oxidative Conversion of Methane to Synthesis-Gas

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the most promising catalysts in accordance with the quantum chemical calculations which are consistent with the previously obtained experimental results. It is assumed that the SCO of CH4 occurs by direct mechanism with the participation of reduced Pt-Ru clusters having the highest adsorption capacity for hydrogen atoms on Pt:Ru (2:1, 1:1) catalysts. The obtained data can be used to explain the mechanism of SCO of CH4 and other alkanes on investigated contacts.
(a) (b)

References
[1] Efimov, M. N.; Zemtsov, L. M.; Karpacheva, G. P.; Ermilova, M. M.; Orehova, N. V.; Dzidziguri, E. L.; et al. In New Nanostructured Catalyst for Dehydrogenation of Hydrocarbons on the Basis of Pt-Ru Alloys, Proceedings of XVIII Mendeleev Congress on General and Applied Chemistry, Moscow, Russia, Sept. 23-28, 2007. Popova, N. .; Antonova, N. A.; Moroz, E. . Ruthenium-Containing Catalysts for Gas Purification from CO, NO and C3H6: II. Effect of the Composition and the Method of Preparation of Platinum-Ruthenium Catalysts on Their Activity. Kinetics and Catalysis 1997, 38, 692-696. Kipnis, . .; Volnina, E. .; Neluba, . Y.; Rozovskyi, A. Y. In Low-temperature Partial Oxidation of Methane on Ru and Pt Catalysts, Proceedings of XVIII Mendeleev Congress on General and Applied Chemistry, Moscow, Russia, Sept. 23-28, 2007. Dossumov, K.; Salakhova, R. K.; Popova, N. M.; Tungatarova, S. A.; Grigorieva, V. P.; Komashko, L. V.; et al. In Nanostructured Polyoxide and Pt-Ru Metal Clusters over CeO2 Promoted Alumina for Methane Conversion to Synthesis-Gas, Proceedings of III Intern. Conf. Catalysis: Fundamentals and Application Dedicated to the 100th Anniversary of Acad. G. K. Boreskov, Novosibirsk, Russia, Jul. 04-08, 2007. Popova, N. .; Dossumov, K. Catalysts of Selective Oxidation and Decomposition of Methane and Other Alkanes; Gylym: Almaty, 2007; pp 99-164. Fathi, M.; Heitnes, H. K.; Sperle, T.; Rokstad, O. A.; Holmen, A. Partial Oxidation of Methane to Synthesis-Gas at Very Short Contact Times. Catalysis Today 1998, 42, 205-209. Boucouvalas, J.; Efstathiou, A. M.; Verykios, X. E. Partial Oxidation of Methane to Synthesis-gas over Supported Ruthenium Catalysts. Studies in Surface Science and Catalysis 1997, 107, 435-440.

[2]

[3] (a) (b) Fig. 3 The geometry of initial and optimized structures including Ru-Pt cluster and CH4 molecule. IRu2Pt2 (1:1) [C(Ru)-H(Ru)], (a)initial, (b)optimized; IIPt2Ru2 (1:1) [C(Ru)-H(Pt)], (a)initial, (b)optimized.

[4]

of C-H bond are characteristic for them. Complexes of Ru2Pt2 clusters and Pt4 are characterized by lower energy of the intermolecular interaction, but their formation is accompanied by the largest transfer of electron density to cluster and significant lengthening of the C-H bond.

[5]

4. Conclusions
Thus, it was found that the introduction of ruthenium into platinum catalyst with the ratio of Pt:Ru = 2:1 (0.68 Pt:0.32 Ru, wt.%) increases the adsorption of oxygen in the second temperature region; and the surface is stabilized in a homogeneous state. It was found that Pt:Ru catalysts at the ratio of 1:1 are
[6]

[7]

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Physico-Chemical Studies of Platinum-Ruthenium Catalysts of Oxidative Conversion of Methane to Synthesis-Gas Platinum-Ruthenium Catalysts. Petroleum Chemistry 2010, 50, 455-461. [12] Tungatarova, S. A.; Dossumov, K.; Popova, N. M.; Baizhumanova, T. S. Nanostructured Supported Pt, Ru and Pt-Ru Catalysts for Oxidation of Methane into Synthesis-Gas. Journal of Alloys and Compounds 2010, 504, S349-S352. [13] Popova, N. M.; Antonova, N. A.; Sass, A. S.; Moroz, E. .; Ushakov, V. A.; Kochubei, D. I.; et al. Ruthenium-Containing Catalysts for Gas Purification from CO, NO, and C3H6: I. Synthesis and Characterization of Platinum-Ruthenium Catalysts. Kinetics and Catalysis 1997, 38, 685-691.

Nishimoto, H.; Ikenaga, N.; Suzuki, T. Partial Oxidation of Methane to Synthesis-Gas over Ru-loaded Y2O3 Catalyst. Catalysis Letters 2002, 82, 161-167. [9] Pantu, P.; Gavalas, G. R. Methane Partial Oxidation on Pt/CeO2 and Pt/Al2O3 Catalysts. Appl. Catal. A: General 2002, 223, 253-260. [10] Tungatarova, S. A.; Dossumov, K.; Baizhumanova, T. S. Production of Synthesis-Gas on Low-Percentage Pt-, Ruand Pt-Ru Catalysts. Topics in Catalysis 2010, 53, 1285-1288. [11] Dossumov, K.; Popova, N. M.; Baizhumanova, T. S.; Tungatarova, S. A. Selective Oxidation of Methane into Synthesis-Gas at Short Contact Times on Low-Loading