Properties of the surface layer and catalytic activity of Ta<Subscript>2</Subscript>O<Subscript>5</Subscript> with Pt or Pd additives in the oxidation of hydrogen

The catalytic activity in the oxidation of hydrogen (in the gaseous state in the presence of excess oxygen) has been studied for samples of Pt(Pd)/Ta₂O_5−x, formed by reduction with hydrogen. The samples obtained had greater activity than the traditional catalysts Pt(Pd)/Al₂O₃. According to X-ray diffraction analysis and electron microscopic studies, Ta₂O_5−x becomes amorphous with the formation of more reduced non-stoichiometric oxygen-deficient tantalum oxides with a surface layer of catalyst. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 44, No. 3, pp. 180–185, May–June, 2008.     

The influence of hydrogen-containing molybdenum and tungsten bronzes on the catalytic activity of palladium composite catalysts for the oxidation of H<Subscript>2</Subscript>, CO,and CH<Subscript>4</Subscript>

The influence of hydrogen-containing molybdenum and tungsten bronzes on the catalytic activity of palladium composite catalysts for the oxidation of H₂, CO, and CH₄ was studied. It was found that the composite catalysts containing H _x MO₃ phases (M = W or Mo), which were formed by the reduction of MoO₃ and WO₃ oxides with hydrogen in the presence of deposited Pd, showed higher catalytic activity in the oxidation of small molecules (H₂, CO, and CH₄) with excess oxygen than the traditional Pd/Al₂O₃ deposited catalyst with the same content of the deposited metal. It was shown that the thermal stability of the H _x MO₃ phases was the limiting factor influencing the activity of these composite catalysts.     

Effect of Pt and Pd additives on the state of the surface layer and catalytic activity of niobium oxides in the oxidation of hydrogen

Catalysts prepared by the hydrogen reduction of Nb₂O₅ in the presence of Pt or Pd have specific surface much greater than for the starting oxide and their catalytic activity in the oxidation of hydrogen is much greater than the activity of Pt/Al₂O₃ or Pd/Al₂O₃. X-ray phase analysis and X-ray photoelectron spectroscopy were used to establish the existence of Nb₂O_5–x nonstoichiometric oxides in the catalyst, which enhances the catalytic activity of the surface. The kinetic behavior of the oxidation of hydrogen on these catalysts is explained in the framework of the Eley–Riedel mechanism.     

The role of doped Fe on the activity of alumina-supported Pt and Pd diesel exhaust catalysts

Supported Pt and Pd are most commonly used for oxidation catalysts. They have similar and different characteristics for deactivation factors. The catalytic activity of Pt and Pd catalysts supported on ??-Al₂O₃ was studied in the presence and absence of H₂O and SO₂ during CO oxidation under simulated conditions of diesel exhaust gas. Without the addition of H₂O and SO₂ to the feed gas, Pd/Al₂O₃ had a superior catalytic activity compared to Pt/Al₂O₃. The addition of H₂O to the feed gas strongly and negligibly affected the activity of Pd and Pt, respectively, while the addition of SO₂ to the feed gas had a strong poisoning effect on the catalytic activity of both Pt and Pd catalysts. Although being the most active, Pd catalysts exhibited a strong sensitivity to water and sulfur-containing compounds. Fe was added to the Pt and Pd catalysts to introduce sulfur resistance. The addition of Fe enhanced the activity of the catalysts by suppressing the phase transition of Al₂O₃ to Al₂(SO₄)₃ and by hindering metal sintering.     

Platinum electrocatalysts based on oxide supports for hydrogen and methanol fuel cells

Platinum electrocatalysts for fuel cells based on individual oxides Pt/SnO₂ and Pt/TiO₂ and their solid solutions Pt/Ti_1−x M _x O₂ (M = Ru, Nb) and Pt/Sn_1−x M′ _x O_2−δ(M′ = Sb, Ru) were prepared. The influence of the composition of the oxide supports on the activity of the supported platinum catalysts in electrooxidation of methanol and hydrogen in the presence of CO was studied. The prepared platinum catalysts supported on solid solutions of tin dioxide Sn_1−x M _x O_2−δ(M = Sb, Ru; x = 0.4−0.9) and Ti_1−x M _x O₂ (M = Ru, Nb; x = 0.7) exhibited higher tolerance to CO poisoning and higher activities for methanol electrooxidation than commercial Pt,Ru catalysts on carbon support. The use of the proposed oxide supported catalysts in hydrogen and direct methanol fuel cells improved their performances in comparison with that for the fuel cells with traditional Pt,Ru catalysts on carbon support.     

Influence of Pd-Ce interaction and chlorine ion on hydrodesulfurization reaction: The activity and sulfur tolerance of the Pd-Ceo2/Al2O3 catalyst

CeO₂ promoted palladium catalysts supported on Al₂O₃ were prepared using the impregnation (IM) and the deposition-precipitation (DP) methods. The activities and sulfur tolerance of the catalysts for hydrodesulfurization (HDS) were detected with thiophene HDS as probe reaction. H₂ adsorption, XRD, FTIR, NH₃-TPD, XPS were used to characterize the catalysts. The Pd-CeO₂/Al₂O₃ (IM) catalyst was highly active for the HDS reaction, and it had much stronger sulfur tolerance than the Pd/Al₂O₃ catalyst. Pd-CeO₂/Al₂O₃ (DP) showed excellent sulfur tolerance while its initial activity decreased. It was observed that with the chlorine bridge, the interfacial structure of Pd-Cl⁻¹-Ce³⁺ was responsible for the high activity of the Pd-CeO₂/Al₂O₃ (IM) catalyst, at the same time the interaction of Pd with Ce was weakened by Cl₋₁ ions. The enhanced sulfur tolerance over the Pd-CeO₂/Al₂O₃ (IM) catalyst was attributed to the weakened Pd-S bond caused by the competitive adsorption of H₂S on Ce³⁺ ions. As to the Pd-CeO₂/Al₂O₃ (DP) catalyst, a strong interaction of Pd with Ce put Pd at an electron-deficient state, the creation of sulfided palladium was therefore inhibited.     

NO Reduction Over Noble Metal Ionic Catalysts

In last 40 years, catalysis for NO _x removal from exhaust gas has received much attention to achieve pollution free environment. CeO₂ has been found to play a major role in the area of exhaust catalysis due to its unique redox properties. In last several years, we have been exploring an entirely new approach of dispersing noble metal ions in CeO₂ and TiO₂ for redox catalysis. We have extensively studied Ce_1−x M _x O_2−δ (M = Pd, Pt, Rh), Ce_1−x−y A _x M _y O_2−δ (A = Ti, Zr, Sn, Fe; M = Pd, Pt) and Ti_1−x M _x O_2−δ (M = Pd, Pt, Rh, Ru) catalysts for exhaust catalysis especially NO reduction and CO oxidation, structure–property relation and mechanism of catalytic reactions. In these catalysts, lower valent noble metal ion substitution in CeO₂ and TiO₂ creates noble metal ionic sites and oxide ion vacancy. NO gets molecularly adsorbed on noble metal ion site and dissociatively adsorbed on oxide ion vacancy site. Dissociative chemisorption of NO on oxide ion vacancy leads to preferential conversion of NO to N₂ instead of N₂O over these catalysts. It has been demonstrated that these new generation noble metal ionic catalysts (NMIC) are much more catalytically active than conventional nano crystalline noble metal catalysts especially for NO reduction.     

Effect of the nature of the support on the activity of palladium catalysts for oxidation of carbon monoxide

We have studied the catalytic activity of TiN_0.65, TiO₂, Al₂O₃, and palladium catalysts supported on them in the oxidation of carbon monoxide. The order in which the activities of the supported catalysts vary, Pd/Al₂O₃>Pd/TiO₂>Pd/TiN_0.65, is the reverse of the activity series for the supports. This is explained by the effect of transfer of electron density from the palladium to the substrate. Taras Shevchenko Kiev University, 64 Vladimirskaya ul., Kiev 252033, Ukraine, G. V. Kurdyumov Institute of the Physics of Metals, National Academy of Sciences of Ukraine, 36 Akademika Vernadskogo bul’var, Kiev-142 252642, Ukraine. Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 34, No. 2, pp. 118–121, March–April, 1998.     

Catalytic properties of Pt/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalysts in the aqueous-phase reforming of ethylene glycol: Effect of the alumina support

The influence of the alumina support on the catalytic activity of Pt/Al₂O₃ catalysts in aqueous phase reforming of ethylene glycol to hydrogen was studied. The catalysts were prepared by impregnation of γ-, δ-, and α-alumina with H₂PtCl₆. The highest rate of hydrogen production (452 μmol min⁻¹ g⁻¹) obtained with the Pt/α-Al₂O₃ catalyst can be related to the highest extent of dispersion of Pt on α-Al₂O₃. XPS, TEM-EDX and TPR-H₂ measurements showed the absence of chloride-containing surface complexes in the Pt/α-Al₂O₃ catalyst. However, chloride-containing entities were found on the surface of Pt/γ-Al₂O₃ and Pr/δ-Al₂O₃ catalysts. When chloride ions are removed chlorinated Pt species facilitate the sintering of Pt crystallites and in this way affect the extent of Pt dispersion. Moreover, depending upon the particular crystalline form, alumina atoms have different coordination and alumina surfaces contain varying amounts of OH groups of different nature which affect the interaction between Pt and the support.     

Pentacoordinated Al3+‐Stabilized Active Pd Structures on Al2O3‐Coated Palladium Catalysts for Methane Combustion

Supported Pd catalysts are active in catalyzing the highly exothermic methane combustion reaction but tend to be deactivated owing to local hyperthermal environments. Herein we report an effective approach to stabilize Pd/SiO₂ catalysts with porous Al₂O₃ overlayers coated by atomic layer deposition (ALD). ²⁷Al magic angle spinning NMR analysis showed that Al₂O₃ overlayers on Pd particles coated by the ALD method are rich in pentacoordinated Al³⁺ sites capable of strongly interacting with adjacent surface PdO_x phases on supported Pd particles. Consequently, Al₂O₃‐decorated Pd/SiO₂ catalysts exhibit active and stable PdO_x and Pd–PdO_x structures to efficiently catalyze methane combustion between 200 and 850 °C. These results reveal the unique structural characteristics of Al₂O₃ overlayers on metal surfaces coated by the ALD method and provide a practical strategy to explore stable and efficient supported Pd catalysts for methane combustion.     

Hydrogenation of acetone on technetium catalysts

The catalytic properties of supported mono- and bimetallic catalysts of the Tc/support, M/support, and M-Tc/support types (M=Pt, Pd, Rh, Ru, Ni, Re, Co; supports are γ-Al₂O₃, MgO, SiO₂) were investigated in the acetone hydrogenation. The main products of this reaction are isopropyl alcohol and propane. The catalytic activity in the acetone hydrogenation of the metals studied decreases in the consequence Pt>Tc≈Rh>Pd>Ru >Ni≈Re>Co (with γ-Al₂O₃ as the support). The influence of support nature on the catalytic activity was investigated for the Rh−Tc system as an example. A nonadditive increase in the catalytic activity of Rh−Tc/γ-Al₂O₃ in comparison with monometallic catalysts was found. The state of the surface of the catalysts was characterized by the UV-VIS diffuse reflectance spectra. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 414–417, March, 1998.     

Synthesis,characterization, and catalytic activity in the <Emphasis Type="Italic">n</Emphasis>-heptane conversion over Pt/In–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> sol–gel prepared catalysts

Platinum catalysts supported on indium-doped alumina were prepared by the sol–gel method. The method allows the incorporation of In³⁺ in the alumina network. The indium-doped alumina supports showed narrow pore size distribution (5.4–4.0 nm) and high specific surface areas (258–280 m²/g). The ²⁷Al NMR-MAS spectroscopy identified aluminum in tetrahedral, pentahedral, and octahedral coordination; however, the intensity of the signal assigned to aluminum in pentahedral coordination diminishes with the increase of the content of indium. Total acidity determined by ammonia thermodesorption diminishes strongly in Pt/In–Al₂O₃ catalysts, suggesting a selective deposit of platinum over the acid sites of the support. The effect of the support in the platinum catalytic activity was evaluated in the n-heptane dehydrocyclization reaction. The selectivity patterns for such reaction were modified substantially in the doped Pt/In–Al₂O₃ catalysts, in comparison with the Pt-In/Al₂O₃–I coimpregnated reference catalyst. As an important result, the formation of benzene was suppressed totally over the indium-doped alumina sol–gel supports with a high content (3 wt%) of indium.     

A facile synthetic route for the preparation of the Au/Mox/Al2O3 catalysts towards CO oxidation

Summary A new facile single-step synthetic route is reported for the preparation of Au/MO_x/Al₂O₃ catalysts. The preparation method has the merit of facility but leads to not only the simultaneous load of both gold source and MO_x precursor on Al₂O₃ support, but also the formation of Au/MO_x/Al₂O₃ with high gold loading ratio, high dispersion and high activity for CO oxidation.     

Ionic conductivity of sodium silicates with lovozerite-type structure

The ionic conductivity of Na,Zr and Na,Sn silicates of the lovozerite family (Na_{8 − x} H _x ZrSi₆O₁₈ structural type, space group R $ \bar 3 $ \bar 3 m) was studied in the temperature range of 293–800 K using the impedance spectroscopy method (5−5 × 10⁵ Hz). The compositions of the studied compounds were obtained using the method of hydrothermal synthesis in the MO₂-SiO₂-NaOH-H₂O and MO₂-SiO₂-CaO-NaOH-H₂O (M = Zr, Sn) systems at 573–823 K. The samples for electrophysical studies were prepared according to the ceramic technology. It was found that isovalent cation substitutions of Sn⁴⁺ → Zr⁴⁺ in Na₈M⁴⁺Si₆O₁₈ and Na₆CaM⁴⁺Si₆O₁₈ and H⁺ → Na⁺ in Na_{8 − x} H _x ZrSi₆O₁₈ result in an increase in the ionic conductivity by 2–3 orders of magnitude, without affecting the ionic transport activation energy (0.6–0.7 eV). The best electrolytic characteristics are typical for the Na₅H₃ZrSi₆O₁₈ compound, for which the ionic conductivity value is 5 × 10⁻⁴ S/cm at 573 K.     

Platinum nanoparticle size effect on specific catalytic activity in <Emphasis Type="Italic">n</Emphasis>-alkane deep oxidation: Dependence on the chain length of the paraffin

The specific activity of 0.8% Pt/Al₂O₃ catalysts in the deep oxidation of C₁–C₆ n-alkanes increases with an increase in the Pt particle size from 1 to 3–4 nm. Further coarsening of the particles insignificantly changes the specific activity. The size effect was studied for a series of catalysts containing platinum nanoparticles 1 to 11 nm in diameter. The specific catalytic activity variation range depends on the size of the reacting hydrocarbon molecules. As the platinum particle size increases, the specific catalytic activity increases 3–4 times for the oxidation of CH₄ and C₂H₆ and by a factor of 20–30 for the oxidation of n-C₄H₁₀ and n-C₆H₁₄.     

Catalytic partial oxidation of methanol over Au–Pd bimetallic catalysts: a comparative study of SBA-16, SBA-16-CeO<Subscript>2</Subscript>, and CeO<Subscript>2</Subscript> as supports

Au–Pd catalysts supported on SBA-16, SBA-16-CeO₂, and CeO₂ had been studied for partial oxidation of methanol to produce H₂. The physicochemical characteristics of the catalysts prepared by deposition–precipitation using urea hydrolysis were examined by inductively coupled plasma atomic emission spectroscopy (ICP-AES), Brunauer-Emmett-Teller (BET), X-ray powder diffraction (XRD), Temperature-programmed reduction (TPR), and H₂ temperature-programmed desorption (H₂-TPD) analyses. The results show that Au_xPd_y alloys are observed in Au–Pd/SBA-16 and Au–Pd/SBA-16-CeO₂ catalysts. The catalytic results demonstrate that both Au–Pd/SBA-16 and Au–Pd/SBA-16-CeO₂ catalysts exhibit higher activity and lower CO selectivity than the Au–Pd/CeO₂ catalyst. This could be ascribed to the formation of Au_xPd_y alloys. The comparison of the Au–Pd/SBA-16 and Au–Pd/SBA-16-CeO₂ catalysts reveals that the Au–Pd/SBA-16-CeO₂ shows the lower CO selectivity, probably due to the presence of CeO₂.     

Highly Dispersed Ce x Zr1−x O2 Nano-Oxides Over Alumina, Silica and Titania Supports for Catalytic Applications

We have been exploring the utilization of supported ceria and ceria–zirconia nano-oxides for different catalytic applications. In this comprehensive investigation, a series of Ce _x Zr_1−x O₂/Al₂O₃, Ce _x Zr_1−x O₂/SiO₂ and Ce _x Zr_1−x O₂/TiO₂ composite oxide catalysts were synthesized and subjected to thermal treatments from 773 to 1073 K to examine the influence of support on thermal stability, textural properties and catalytic activity of the ceria–zirconia solid solutions. The physicochemical characterization studies were performed using X-ray diffraction (XRD), Raman spectroscopy (RS), X-ray photoelectron spectroscopy (XPS), and high-resolution transmission electron microscopy (HREM), thermogravimetry and BET surface area methods. To evaluate the catalytic properties, oxygen storage/release capacity (OSC) and CO oxidation activity measurements were carried out. The XRD analyses revealed the formation of Ce_0.75Zr_0.25O₂, Ce_0.6Zr_0.4O₂, Ce_0.16Zr_0.84O₂ and Ce_0.5Zr_0.5O₂ phases depending on the nature of support and calcination temperature employed. Raman spectroscopy measurements in corroboration with XRD results suggested enrichment of zirconium in the Ce _x Zr_1−x O₂ solid solutions with increasing calcination temperature thereby resulting in the formation of oxygen vacancies, lattice defects and oxygen ion displacement from the ideal cubic lattice positions. The HREM results indicated a well-dispersed cubic Ce _x Zr_1−x O₂ phase of the size around 5 nm over all supports at 773 K and there was no appreciable increase in the size after treatment at 1073 K. The XPS studies revealed the presence of cerium in both Ce⁴⁺ and Ce³⁺ oxidation states in different proportions depending on the nature of support and the treatment temperature applied. All characterization techniques indicated absence of pure ZrO₂ and crystalline inactive phases between Ce–Al, Ce–Si and Ce–Ti oxides. Among the three supports employed, silica was found to stabilize more effectively the nanosized Ce _x Zr_1−x O₂ oxides by retarding the sintering phenomenon during high temperature treatments, followed by alumina and titania. Interestingly, the alumina supported samples exhibited highest OSC and CO oxidation activity followed by titania and silica. Details of these findings are consolidated in this review.     

Catalytic Activity of WO<Subscript>3</Subscript> and MoO<Subscript>3</Subscript> with Pt and Pd Additives in Oxidation of Hydrogen

We have shown that WO₃ and MoO₃ with Pt or Pd additives exhibit high catalytic activity in the reaction of H₂ oxidation. In the temperature range 313 K to 353 K, we have studied the kinetic behavior of the reaction on 0.1 mass % Pt(Pd)/WO₃ and Pt(Pd)/MoO₃ samples. We have established that the kinetics of H₂ oxidation on these catalysts correspond to an Eley - Rideal mechanism. __________ Translated from Teoreticheskaya i Eksperimental'naya Khimiya, Vol. 41, No. 5, pp. 313–316, September–October, 2005.     

Bimetallic Pd—Pt/γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalysts for complete methane oxidation: the effect of the Pt: Pd ratio

Alumina-supported bimetallic Pt—Pd catalysts proved to be more active in the complete oxidation of methane than monometallic systems (Pt/Al₂O₃, Pd/Al₂O₃). The maximum activity of the bimetallic catalysts was achieved at ~40 at.% Pt in Pd on the catalyst surface. After the oxidation reaction, redistribution of platinum and palladium was observed in the active component of the catalysts with the degree of redistribution depending on the initial Pt: Pd ratio.     

Selective hydrogenation of phenylacetylene on Pd/Al2O3: Effect of the addition of Pt and particle size

Phenylacetylene hydrogenation on Pd, Pt and Pd–Pt/Al₂O₃ catalysts has been studied. In all catalysts activity was found not to depend on particle size. However, selectivity to styrene was found to depend on Pd/Al₂O₃ catalysts. Carbon deposition in both metal and support explains such a behavior. Nevertheless, in small Pd particles a longer residence time of styrene may control the selectivity.