Mesoporous copper–cerium–oxygen hybrid nanostructures for low temperature catalytic oxidation of carbon monoxide

Mesoporous copper–cerium–oxygen hybrid nanostructures were prepared by one-pot cetyltrimethylammonium bromide surfactant-assisted method, and were characterized by thermogravimetry, X-ray diffraction, transmission electron microscopy, nitrogen adsorption–desorption, X-ray photoelectron spectroscopy and temperature-programmed reduction techniques. Low temperature carbon monoxide oxidation was used as probe reaction to investigate the application of the prepared mesoporous copper–cerium–oxygen hybrid nanostructures in catalysis. The product calcined at 400 °C, with disordered wormlike mesoporous structure, high specific surface area (SSA) of 117.4 m²/g and small catalyst particle size of 8.3 nm, shows high catalytic activity with the 100 % CO conversion at 110 °C, indicating its potential application in catalysis. Catalytic activity results from the samples calcinied at different temperature suggested that high SSA, small catalyst particle size, finely dispersed CuO species and synergistic effect between CuO and CeO₂ were responsible for the high catalytic activity of the catalysts.     

New catalysts based on the heteropoly acid-zeolite system for the synthesis of higher α-olefins by paraffin cracking

Natural zeolites (clinoptilolite) from the Shankanay deposit in Almaty oblast were used to prepare catalysts for the synthesis of higher α-olefins by paraffin cracking. The modification of zeolite with inorganic and organic heteropoly acids resulted in an enhancement of catalytic activity. The olefin yield on the zeolite modified with heteropoly acids was as high as 36.6% after one run in a flow system at atmospheric pressure and temperatures of 500–525°C. The modification of natural zeolite with HPA led to an increase of 22 to 257 m²/g in the total surface area. The increase in catalytic activity after HPA deposition can be attributed to the formation of stable nanostructures with sizes of 1 to 4 nm, resulting in the emergence of stronger Brønsted acid sites. The catalyst works stably in the reaction-regeneration mode.     

Effects of the structure of CeCu catalysts on the catalytic combustion of toluene in air

CeCu composite oxide catalysts were prepared by a hard-template method (CeCu-HT) and a complex method (CeCu-CA). The prepared CeCu composite oxide catalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and Brunauer–Emmett–Teller (BET) analyses. The catalytic properties of the prepared CeCu composite oxide catalysts were also investigated by the catalytic combustion of toluene in air. XRD results showed that the synthesized CeCu composite oxide catalysts had different phase components and crystallinities but similar CeO₂CuO solid solution phases. Low-angle XRD, TEM, and BET results indicated that the prepared CeCu-HT catalyst had a developed ordered mesoporous structure and a large specific surface area of 206.1 m² g^?1. Toluene catalytic combustion results indicated that the CeCu-HT catalyst had higher toluene catalytic combustion activity in air than the CeCu-CA catalyst. The minimum reaction temperature at which toluene conversion exceeded 90% for toluene catalytic combustion on the CeCu-HT catalyst was 225 °C. The toluene catalytic combustion conversion on the CeCu-HT catalyst at 240 °C exceeded 99.3% with decreased toluene concentration in air to below 70 ppm. On the other hand, the toluene catalytic combustion conversion on the CeCu-CA catalyst was only 92% even when the reaction temperature reached 280 °C. The differences between the toluene catalytic combustion performances of the CeCu composite oxide catalysts prepared by different methods can be attributed to their discrepant compositions and structures.     

Optimization of Reaction Conditions and Regeneration Procedure of the PdSb/TiO2 Catalyst for Acetoxylation of Toluene

The catalytic activity of a PdSb/TiO₂ catalyst for the acetoxylation of toluene to produce benzyl acetate was investigated. The reaction was carried out in a fixed bed Hastelloy^® C reactor. The effects of various reaction parameters such as reaction, temperature, space velocity, acetic acid, toluene (Tol), and oxygen concentration in the feed mixture on the catalytic performance were examined and optimized. Interestingly, this catalyst sample displayed reasonably good performance (X-Tol = 54% and S-BA = 91%) with significant decrease in induction period and improved long-term stability compared to previously used catalysts. In addition, regeneration of the catalyst was also carried out at different temperatures in the range from 250 to 400 °C in air. Effective regeneration of the catalyst was achieved at 300 °C; temperatures higher than 300 °C revealed to be not suitable. Furthermore, the duration of regeneration has also been optimized. Doing this, suitable regeneration procedure was established for effective restoration of activity that is lost during the process of deactivation.     

A comparative study on the thermal stability,textural, and structural properties of mesostructured γ-Al2O3 granules in the presence of La,Sn, and B additives

Mesoporous γ-alumina is widely used as catalyst support in various catalytic reactions of industrial interest. However, due to the instability of γ-alumina at elevated temperatures, many efforts have been reported to inhibit the α-alumina phase transition through doping with suitable metalloids, as well as transition, post-transition, or rare-earth elements. In the present study, undoped and La-, Sn-, and B-doped alumina granules were synthesized via sol-gel/oil drop method with the aim to clarify the role of the additives and their content on the porous structure as well as on the chemical, structural, and microstructural behavior of γ-alumina. XRD and DTA/TG results demonstrated that thermal stability of transition aluminas increases more than 100 °C by 3 wt% lanthanum and tin doping; however, boron doping seems to have only negligible effect on the thermal stability. On the other hand, based on nitrogen adsorption-desorption analysis, tin and boron-doped aluminas showed a higher surface area at 750 °C (between 214.74 m²/g to 245.97 m²/g) but higher loss in the surface area after calcination at 1200 °C (between 25.45 m²/g to 8.57 m²/g). On the contrary, the 3 wt% La-doped alumina sample, with a relatively high surface area at 750 °C (227.17 m²/g), exhibited the highest surface area after calcination at 1200 °C (53.07 m²/g). ²⁷Al MAS NMR and HRTEM studies indicated that the presence of 3 wt% La in alumina structure leads to thermal and mesoporous structure stability up to 1200 °C by inhibiting oxygen lattice restructuring. These results provide a comparative perspective of La, B, and Sn additives' behavior in γ-alumina.     

The Synthesis of 1,4-Diazabicyclo (2.2.2) Octane over a Pre-Treated Titanium Silicalite-1 Catalyst

Potassium chloride salt pre-treated titanium silicalite-1 (TS-1) zeolite (K-TS-1) was prepared via an ion-exchange method. XRD, EDX and BET were used to identify the structure of the zeolite. The BET surface area and the adsorption/desorption cumulative pore volume of the K-TS-1 catalyst were about 297 m²/g and 0.213 cm³/g, respectively. The average pore diameter of the K-TS-1 catalyst was 29.49 Å. The catalytic activity of K-TS-1 catalyst was studied in the fixed-bed catalytic reactor. 1,4-Diazabicyclo (2.2.2) octane (DABCO) was prepared from ethylenediamine (EDA) over the K-TS-1 zeolite catalyst. The influences of various reaction parameters such as reaction temperature, space velocity and concentration of EDA were discussed. The conversion of EDA was more than 96% and the selectivity of DABCO and PIP were up to 64 and 30%, respectively, in the temperature of 340 °C and weight hourly space velocity of 1.5 h^?1 in the presence of water.     

Thermally stable ceria–zirconia catalysts for soot oxidation by O2

Ce–Zr mixed oxides calcined at 1000 °C are more active catalysts for soot oxidation than pure CeO₂ calcined at the same temperature, both in loose and tight contact between soot and catalyst. 1000 °C sinterised-CeO₂ presents a very low surface area (2 m²/g), a large crystal size (110 nm) and a lack of surface redox properties. Ce–Zr mixed oxides present higher BET surface areas (typically 17–19 m²/g), smaller crystal sizes and enhanced redox properties. The Zr molar fraction does not affect appreciably the catalytic activity of Ce–Zr mixed oxides in the range studied (Zr molar fraction from 0.11 to 0.51).     

The catalytic activity of Ni/W bimetallic sulfide nanostructured catalysts in the hydrodesulfurization of dibenzothiophene

Two types of catalysts containing NiW bimetallic sulfide nanostructures were prepared by a chemical method employing ammonium thiotungstate and nickel nitrate as metal-sulfide precursors followed by sulfidation in H₂S/H₂ at 400 °C. The nanostructures were grown with excess of Ni, at atomic ratio R = 0.75, 0.85 (R = Ni/Ni + W). High resolution electron microscopy (HRTEM) micrographs revealed the formation of two types of nanostructures, nickel sulfide nanoparticles and long nanorods of tungsten suboxide, both coated by WS₂ layers. The Ni/W catalyst containing mostly nanorods presented twice the catalytic activity (pseudo-zero order constant rate k = 12 × 10⁻⁷ mol/s.g) of the Ni/W catalyst containing nanoparticles (k = 6.3 × 10⁻⁷ mol/s.g) with a low selectivity for tetrahydrodibenzothiophene (THDBT) and high selectivity to cyclohexylbenzene (CHB, 50 mol%). In turn the Ni/W catalyst containing nanoparticles presented a catalytic activity comparable to a Ni/Mo catalyst without inorganic fullerene (IF) nanostructures (k = 7.2 × 10⁻⁷ mol/s.g) but with higher selectivity for hydrogenation to THDBT, (14 mol%) than the sample with nanorods.     

Preparation of a Sulfonated Porous Carbon Catalyst with High Specific Surface Area

A sulfonated (SO₃H-bearing) carbon catalyst with mesoporous structure and high specific surface area is successfully prepared by impregnating the cellulosic precursor (wood powder) with ZnCl₂ prior to activation and sulfonation. The specific surface area of the porous carbon catalyst thus prepared is also found to increase with carbonization temperature to a maximum of 1,560 m² g^?1 at ca. 773 K. Structural analyses reveal that the porous carbon catalysts carbonized at temperatures higher than 723 K contain high densities of micro- and mesopores. The porous carbon catalyst exhibits high catalytic performance for the esterification of acetic acid (343 K), the activity for which is dependent only on the acid density. The porous carbon catalyst also exhibits high catalytic activity for the benzylation of toluene, whereas non-porous sulfonated carbon has very limited activity for this reaction. The activity for the benzylation of toluene is dependent on both the specific surface area and the acid density of the sulfonated porous carbon catalyst.     

Oxidative coupling of methane over Sm-promoted MgO: Influence of composition and preparation conditions

Influences of promoter concentration (or Sm/Mg ratio), precursor for MgO (viz. Mg-acetate, Mg-carbonate and Mg-hydroxide), calcination temperature of Sm-promoted MgO catalyst on the catalytic activity/selectivity in the oxidative coupling of methane (OCM) at different temperatures (650–850°C) and CH₄/O₂ ratios in feed (2·0–8·0) at a high space velocity (51600 cm³ g⁻¹ h⁻¹) have been investigated. The catalytic activity/selectivity of Sm–MgO catalysts in the OCM are found to be strongly influenced by the Sm/Mg ratio, precursor used for MgO and catalyst calcination temperature. The catalyst with Sm/Mg ratio of 0·11, prepared using magnesium acetate and magnesium carbonate as a source of MgO and calcining at 950°C, is found to be highly active and selective in the OCM process. A drastic reduction in catalytic activity/selectivity is observed when the catalyst is supported on low surface area porous catalyst carriers, indicating strong catalyst–support interactions. ©1997 SCI     

Mesoporous aluminosilicate catalysts from FAU precursor under mild acidic conditions and with Al in totally tetrahedral coordination

Al-SBA-15 mesoporous catalyst with strong Brönsted acid sites and Al stabilized in a totally tetrahedral coordination was synthesized from the addition of hydrothermally aged zeolite Y precursor to SBA-15 synthesis mixture under mildly acidic condition of pH 5.5. The materials possessed surface areas between 690 and 850 m²/g, pore sizes ranging from 5.6 to 7.5 nm and pore volumes up to 1.03 cm³, which were comparable to parent SBA-15 synthesized under similar conditions. As much as 2 wt.% Al was present?in the most aluminated sample that was investigated, and the Al remained stable in totally tetrahedral coordination, even after calcination at 550 °C. Calcined Al-SBA-15 showed high hydrothermal stability when treated with steam (20% v/v in nitrogen) at 650 °C for 2 h. Textural characteristics are maintained on steam treatment, and very little or no conversion of Al from tetrahedral to octahedral coordination resulted. The Al-SBA-15 mesoporous catalyst showed significant catalytic activity for cumene dealkylation, and activity increased as the amount of zeolite precursor added to the SBA-15 mixture was increased. The catalyst’s activity was not affected by the aging time of the precursor for up to the 24 h aging time investigated. This method of introducing Al and maintaining it in a total tetrahedral coordination is very effective, in comparison to other direct and post synthesis alumination methods reported.     

Performance characterization of direct formic acid fuel cell using porous carbon-supported palladium anode catalysts

Palladium particles supported on porous carbon of 20 and 50 nm pore diameters were prepared and applied to the direct formic acid fuel cell (DFAFC). Four different anode catalysts with Pd loading of 30 and 50 wt% were synthesized by using impregnation method and the cell performance was investigated with changing experimental variables such as anode catalyst loading, formic acid concentration, operating temperature and oxidation gas. The BET surface areas of 20 nm, 30 wt% and 20 nm, 50 wt% Pd/porous carbon anode catalysts were 135 and 90 m²/g, respectively. The electro-oxidation of formic acid was examined in terms of cell power density. Based on the same amount of palladium loading with 1.2 or 2 mg/cm², the porous carbon-supported palladium catalysts showed higher cell performance than unsupported palladium catalysts. The 20 nm, 50 wt% Pd/porous carbon anode catalyst generated the highest maximum power density of 75.8 mW/cm² at 25 °C. Also, the Pd/porous carbon anode catalyst showed less deactivation at the high formic acid concentrations. When the formic acid concentration was increased from 3 to 9 M, the maximum power density was decreased from 75.8 to 40.7 mW/cm² at 25 °C. Due to the high activity of Pd/porous carbon catalyst, the cell operating temperature has less effect on DFAFC performance.     

Phase structure of V2O5/TiO2 catalyst and catalytic behavior with removal of NO by ammonia

V₂O₅/TiO₂ catalyst with 3% (w/w) V loading has been prepared by sol–gel method. The characterization results of the catalyst structure and catalytic activity show that VO _X state is strongly dependent on the calcination temperature. Little effect is found for phase structure of TiO₂ support on catalytic activity. High catalytic activity in wide temperature range (240–420 °C) is observed for the catalysts calcinated at different temperatures at a space velocity of 50,000 h^?1. Space velocity and alkali metal oxides strongly influence the catalytic activity of the catalyst which was calcinated at 450 °C, furthermore, the one has high tolerance to SO₂ in our test conditions.     

The Preparation of Phosphazene Crosslinked Cyclen Microspheres as Host for Cu<Superscript>2+</Superscript> Ions and Their Utilization as a Support Material for the Preparation of a Copper Nanocatalyst

In this study firstly, phosphazene crosslinked cyclen microspheres were synthesized. Then, supported copper nanoparticles were prepared on these phosphazene crosslinked cyclen microspheres for use as a metal catalyst. The prepared microparticles and microparticle-supported metal catalyst were characterized using FT-IR, SEM-EDX, TEM and XPS analysis. Also, the prepared metal composite was used as a catalyst for the reduction reaction of 4-nitrophenol in the presence of NaBH₄ in aqueous media. The catalytic activity of the Cu-cyclen composite catalyst was investigated using UV–Vis spectroscopy. The reduction studies were completed at four different temperatures (30–60?°C). The activation parameters were calculated from the obtained rate constants at the four different temperatures (30–60?°C). The activation energy, activation enthalpy and activation entropy for the reduction reaction of 4-NP in the presence of Cu-cyclen composite catalyst were calculated as 39.88, 36.56 and ?143.30 kJmol^?1, respectively. The total turnover frequency (TOF) for Cu-cyclen composite catalyst was 0.794 mol 4-NP (mol Cu)^?1 (min)^?1.     

CARBON DIOXIDE METHANATION ON ORDERED MESOPOROUS CO/KIT-6 CATALYST

Mesoporous Co/KIT-6 and Co/SiO₂ catalysts were prepared via hydrogen reduction and were subsequently used in CO₂ catalytic hydrogenation to produce methane. The properties of the prepared Co/KIT-6 catalyst were investigated by low-angle X-ray diffraction, Brunauer-Emmett-Teller analysis, and transmission electron microscopy. The results indicate that the synthesized Co/KIT-6 catalyst has mesoporous structures with well-dispersed Co species, as well as higher CO₂ catalytic hydrogenation activities than that of the Co/SiO₂ catalyst. The Co/KIT-6 catalyst has a large specific surface area (368.9 m² · g^?1) and a highly ordered bicontinuous mesoporous structure. This catalyst exhibits excellent CO₂ catalytic hydrogenation activity and methane product selectivity; the CO₂ conversion and methane selectivity of the Co/KIT-6 catalyst at 280°C are 48.9% and 100%, respectively. The highly ordered, bicontinuous mesoporous structure of the Co/KIT-6 catalyst improves selectivity for the methane product.     

Synthesis and characteristics of lignin-derived solid acid catalysts for microcrystalline cellulose hydrolysis

Three kinds of solid acid catalysts were prepared from alkali lignin in the waste liquor of pulping using carbonation- sulfonation method with different pretreatment. The lignin-derived solid acids (LDSAs) were characterized by FESEM, XRD, FTIR, TGA, BET and acid-base titration, respectively. A comparison study on the catalytic performance of LDSA prepared by different pretreatment method before carbonation in the hydrolysis of microcrystalline cellulose (MCC) was carried out. Results showed that the LDSA prepared by chemical activation with phosphoric acid (LPC-SO₃H) exhibited superior catalytic activity due to its higher densities of -COOH group (1.68 mmol/g) as binding site and -SO₃H group (0.88 mmol/g) as catalytic site as well as its larger specific surface area (488.4 m²/g) than those of the other two LDSAs. A total reducing sugar yield of 50.8% in MCC hydrolysis was obtained under the reaction conditions of temperature of 180 °C, time of 3 h, MCC concentration of 6 mg/mL and mass ratio of catalyst to MCC of 3.3 (w/w). Additionally, the value activation energy for hydrolysis of MCC to reducing sugars using LPC-SO₃H was 83.31 kJ/mol, which was smaller than that using sulfuric acid.     

Synthesis,characteristics, and redox properties of Zr/Sn-doped CeO2 nanoparticles in H2 gas at high temperatures

Metal(M = Zr, Sn)-doped CeO₂ nanoparticles were synthesized by a hydrothermal process to develop PdO@M-doped CeO₂ catalysts. The average particle size of both M-doped CeO₂ nanoparticles was under 10 nm, whereas the particle size reduced as the dopant concentration increased in the M-doped CeO₂ nanoparticles. The largest specific surface area was 226 m²/g in the Zr-doped CeO₂ nanoparticles. The particle morphology showed a spherical shape in both M-doped CeO₂ nanoparticles. The PdO@M-doped CeO₂ catalysts were then prepared by adsorbing Pd(OH)₂ onto the surface of M-doped CeO₂ nanoparticles by a precipitation method and synthesizing the catalysts by calcining at 500 °C for 3 h. The H₂ consumptions of the PdO@M-doped CeO₂ catalysts were characterized as the oxygen storage capacity at various temperatures. The results show that the oxygen storage capacities of the PdO@M-doped CeO₂ catalysts are superior to that of the pure CeO₂ catalyst at temperatures higher than 550 °C. The oxygen storage capacity of the PdO@Sn-doped CeO₂ catalyst is better than that of the PdO@Zr-doped CeO₂ catalyst.     

Hierarchically structured polymer-derived ceramic fibers by electrospinning and catalyst-assisted pyrolysis

Hierarchically structured polymer-derived ceramic fibers were successfully produced by electrospinning a commercially available preceramic polymer to which a cobalt-based catalyst precursor was added, followed by pyrolysis in nitrogen at temperatures ranging from 1250 to 1400 °C. The nanowires formed via the vapor–liquid–solid (VLS) mechanism, involving the reaction of SiO and CO gases, generated from the decomposition of the polymer-derived-ceramic at high temperature, with the heating atmosphere assisted by the presence of nano-sized CoSi droplets. The main crystalline phase for the nanowires was Si₃N₄ below 1350 °C, and Si₂N₂O at 1400 °C, and the amount of nanowires increased with increasing heating temperature. Hierarchically structured fiber mats possessed a higher specific surface area (14.45 m²/g) than that of a sample produced without the cobalt catalyst (4.37 m²/g).     

Preparation of KF/CaO nanocatalyst and its application in biodiesel production from Chinese tallow seed oil

KF/CaO nanocatalyst was prepared by using impregnation method and used to convert Chinese tallow seed oil to biodiesel. The effects of different preparation conditions on biodiesel yield were investigated and the structure of the catalyst was characterized. Transmission electron microscopy (TEM) photograph showed that the catalyst had porous structure with the particle size of 30-100 nm. Brunauer-Emmet-Teller (BET) analysis indicated that the catalyst specific surface area was 109 m² g⁻¹ and average pore size was 97 nm. X-ray diffractometer (XRD) analysis demonstrated that the new crystal KCaF₃ was formed in catalyst, which enhanced catalytic ability. Under the optimal conditions, the biodiesel yield was 96.8% in the presence of as-prepared KF/CaO catalyst, showing potential applications of catalyst in biodiesel industry.     

Changes in the chemical composition of V2O5-loaded CVC-TiO2 materials with calcination temperatures for NH3-SCR of NOx

In this study, the aim was to evaluate the effect of calcinations temperature on the catalytic activity and chemical composition of V₂O₅/TiO₂. We prepared V₂O₅-loaded CVC-TiO₂ catalysts by a combination of chemical vapor condensation (CVC) and impregnation method at different calcination temperatures. These catalysts were analyzed for their ability to catalyze NH₃-based selective catalytic reduction of NO_x. Compared with V₂O₅ loaded P25-TiO₂ (commercial). V₂O₅/CVC-TiO₂ catalysts calcined above 200 °C exhibited better performance towards NO_x conversion than that by a commercial catalyst prepared using P25-TiO₂ (calcined at 500 °C). In addition, the NO_x conversion rate obtained with the sample calcined at 500 °C gave the best result (90 %) at a reaction temperature of 200 °C. From the XPS results, we observed that the V^4+/5+ ratio was well balanced when the V₂O₅ loaded CVC-TiO₂ sample was calcined at 500 ºC.