Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 37

Search results for: CeO2

37 Photocatalytic Activity of Pure and Doped CeO2 Nanoparticles

Authors: Mohamed Khedr, Ahmed Farghali, Waleed El Rouby, Abdelrhman Hamdeldeen


Pure CeO2, Sm and Gd doped CeO2 were successfully prepared via hydrothermal method. The effect of hydrothermal temperature, reaction time and precursors were investigated. The prepared nanoparticles were characterized using X-ray diffraction (XRD), FT-Raman Spectroscopy, transmission electron microscope (TEM) and field emission scanning electron microscope (FESEM). The prepared pure and doped CeO2 nanoparticles were used as photo-catalyst for the degradation of Methylene blue (MB) dye under UV light irradiation. The results showed that Gd doped CeO2 nano-particles have the best catalytic degradation effect for MB under UV irradiation. The degradation pathways of MB were followed using liquid chromatography (LC/MS) and it was found that Gd doped CeO2 was able to oxidize MB dye with a complete mineralization of carbon, nitrogen and sulfur heteroatoms into CO2, NH4+, NO3- and SO42-.

Keywords: CeO2, doped CeO2, photocatalysis, methylene blue

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36 Modification Effect of CeO2 on Pt-Pd Nano Sized Catalysts for Formic Acid Oxidation

Authors: Ateeq Ur Rehman


This article deals with the promotional effects of CeO2 on PtPd/CeO2-OMC electrocatalysts. The synthesized catalysts are characterized using different physicochemical techniques and evaluated in a formic acid oxidation fuel cell. N2 adsorption/desorption analysis shows that CeO2 modification increases the surface area of OMC from 1005 m2/g to 1119 m2/g. SEM, XRD and TEM analysis reveal that the presence of CeO2 enhances the active metal(s) dispersion on the CeO2-OMC surface. The average particle size of the dispersed metal decreases with the increase of Pt/Pd ratio on CeO2-OMC support. Cyclic voltametry measurement of Pd/CeO2-OMC gives 12 % higher anodic current activity with 83 mV negative shift of the peak potential as compared to unmodified Pd/OMC. In bimetallic catalysts, the addition of Pt improves the activity and stability of the catalysts significantly. Among the bimetallic samples, Pd3Pt1/CeO2-OMC displays superior current density (74.6 mA/cm2), which is 28.3 times higher than that of Pt/CeO2-OMC. It also shows higher stability in extended period of runs with least indication of CO poisoning effects.

Keywords: CeO2, ordered mesoporous carbon (OMC), nano particles, formic acid fuel cell

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35 Enhanced Modification Effect of CeO2 on Pt-Pd Binary Catalysts for Formic Acid Oxidation

Authors: Azeem Ur Rehman, Asma Tayyaba


This article deals with the promotional effects of CeO2 on PtPd/CeO2-OMC electro catalysts. The synthesized catalysts are characterized using different physico chemical techniques and evaluated in a formic acid oxidation fuel cell. N2 adsorption/desorption analysis shows that CeO2 modification increases the surface area of OMC from 1005 m2/g to 1119 m2/g. SEM, XRD and TEM analysis reveal that the presence of CeO2 enhances the active metal(s) dispersion on the CeO2-OMC surface. The average particle size of the dispersed metal decreases with the increase of Pt/Pd ratio on CeO2-OMC support. Cyclic voltametry measurement of Pd/CeO2-OMC gives 12 % higher anodic current activity with 83 mV negative shift of the peak potential as compared to unmodified Pd/OMC. In bimetallic catalysts, the addition of Pt improves the activity and stability of the catalysts significantly. Among the bimetallic samples, Pd3Pt1/CeO2-OMC displays superior current density (74.6 mA/cm2), which is 28.3 times higher than that of Pt/CeO2-OMC. It also shows higher stability in extended period of runs with least indication of CO poisoning effects.

Keywords: CeO2, ordered mesoporous carbon (OMC), electro catalyst, formic acid fuel cell

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34 The Effect of Fuel Type on Synthesis of CeO2-MgO Nano-Powder by Combustion Method

Authors: F. Ghafoori-Najafabadi, R. Sarraf-Mamoory, N. Riahi-Noori


In this study, nanocrystalline CeO2-MgO powders were synthesized by combustion reactions using citric acid, ethylene glycol, and glycine as different fuels and nitrate as an oxidant. The powders obtained with different kinds of fuels are characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The size and morphology of the particles and the extent of agglomeration in the powders were studied using SEM analysis. It is observed that the variation of fuel has an intense influence on the particle size and morphology of the resulting powder. X-ray diffraction revealed that any combined phases were observed, and that MgO and CeO2 phases were formed, separately.

Keywords: nanoparticle, combustion synthesis, CeO2-MgO, nano-powder

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33 Disposable PANI-CeO2 Sensor for the Electrocatalytic Simultaneous Quantification of Amlodipine and Nebivolol

Authors: Nimisha Jadon, Rajeev Jain, Swati Sharma


A chemically modified carbon paste sensor has been developed for the simultaneous determination of amlodipine (AML) and nebivolol (NBV). Carbon paste electrode (CPE) was fabricated by the addition of Gr/PANI-CeO2. Gr/PANI-CeO2/CPE has achieved excellent electrocatalytic activity and sensitivity. AML and NBV exhibited oxidation peaks at 0.70 and 0.90 V respectively on Gr/ PANI-CeO2/CPE. The linearity range of AML and NBV was 0.1 to 1.6 μgmL-1 in BR buffer (pH 8.0). The Limit of detection (LOD) was 20.0 ngmL-1 for AML and 30.0 ngmL-1 for NBV and limit of quantification (LOQ) was 80.0 ngmL-1 for AML and 100 ngmL-1 for NBV respectively. These analyses were also determined in pharmaceutical formulation and human serum and good recovery was obtained for the developed method.

Keywords: amlodipine, nebivolol, square wave voltammetry, carbon paste electrode, simultaneous quantification

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32 Investigation of Physical Properties of W-Doped CeO₂ and Mo-Doped CeO₂: A Density Functional Theory Study

Authors: Aicha Bouhlala, Sabah Chettibi


A systematic investigation on structural, electronic, and magnetic properties of Ce₀.₇₅A₀.₂₅O₂ (A = W, Mo) is performed using first-principles calculations within the framework Full-Potential Linear Augmented Plane Wave (FP-LAPW) method based on the Density Functional Theory (DFT). The exchange-correlation potential has been treated using the generalized gradient approximation (WC-GGA) developed by Wu-Cohen. The host compound CeO2 was doped with transition metal atoms W and Mo in the doping concentration of 25% to replace the Ce atom. In structural properties, the equilibrium lattice constant is observed for the W-doped CeO₂ compound which exists within the value of 5.314 A° and the value of 5.317 A° for Mo-doped CeO2. The present results show that Ce₀.₇₅A₀.₂₅O₂ (A=W, Mo) systems exhibit semiconducting behavior in both spin channels. Although undoped CeO₂ is a non-magnetic semiconductor. The band structure of these doped compounds was plotted and they exhibit direct band gap at the Fermi level (EF) in the majority and minority spin channels. In the magnetic properties, the doped atoms W and Mo play a vital role in increasing the magnetic moments of the supercell and the values of the total magnetic moment are found to be 1.998 μB for Ce₀.₇₅W₀.₂₅O₂ and to be 2.002 μB for Ce₀.₇₅Mo₀.₂₅O₂ compounds. Calculated results indicate that the magneto-electronic properties of the Ce₁₋ₓAₓO₂(A= W, Mo) oxides supply a new way to the experimentalist for the potential applications in spintronics devices.

Keywords: FP-LAPW, DFT, CeO₂, properties

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31 Water Gas Shift Activity of PtBi/CeO₂ Catalysts for Hydrogen Production

Authors: N. Laosiripojana, P. Tepamatr


The influence of bismuth on the water gas shift activities of Pt on ceria was studied. The flow reactor was used to study the activity of the catalysts in temperature range 100-400°C. The feed gas composition contains 5%CO, 10% H₂O and balance N₂. The total flow rate was 100 mL/min. The outlet gas was analyzed by on-line gas chromatography with thermal conductivity detector. The catalytic activities of bimetallic 1%Pt1%Bi/CeO₂ catalyst were greatly enhanced when compared with the activities of monometallic 2%Pt/CeO₂ catalyst. The catalysts were characterized by X-ray diffraction (XRD), Temperature-Programmed Reduction (TPR) and surface area analysis. X-ray diffraction pattern of Pt/CeO₂ and PtBi/CeO₂ indicated slightly shift of diffraction angle when compared with pure ceria. This result was due to strong metal-support interaction between platinum and ceria solid solution, causing conversion of Ce⁴⁺ to larger Ce³⁺. The distortions inside ceria lattice structure generated strain into the oxide lattice and facilitated the formation of oxygen vacancies which help to increase water gas shift performance. The H₂-Temperature Programmed Reduction indicated that the reduction peak of surface oxygen of 1%Pt1%Bi/CeO₂ shifts to lower temperature than that of 2%Pt/CeO₂ causing the enhancement of the water gas shift activity of this catalyst. Pt played an important role in catalyzing the surface reduction of ceria and addition of Bi alter the reduction temperature of surface ceria resulting in the improvement of the water gas shift activity of Pt catalyst.

Keywords: bismuth, platinum, water gas shift, ceria

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30 Effect of Aging Time on CeO2 Nanoparticle Size Distribution Synthesized via Sol-Gel Method

Authors: Navid Zanganeh, Hafez Balavi, Farbod Sharif, Mahla Zabet, Marzieh Bakhtiary Noodeh


Cerium oxide (CeO2) also known as cerium dioxide or ceria is a pale yellow-white powder with various applications in the industry from wood coating to cosmetics, filtration, fuel cell electrolytes, gas sensors, hybrid solar cells and catalysts. In this research, attempts were made to synthesize and characterization of CeO2 nano-particles via sol-gel method. In addition, the effect of aging time on the size of particles was investigated. For this purpose, the aging times adjusted 48, 56, 64, and 72 min. The obtained particles were characterized by x-ray diffraction spectroscopy (XRD), scanning electron microscopy (SEM), transmitted electron microscopy (TEM), and Brunauer–Emmett–Teller (BET). As a result, XRD patterns confirmed the formation of CeO2 nanoparticles. SEM and TEM images illustrated the nano-particles with cluster shape, spherical and a nano-size range which was in agreement with XRD results. The finest particles (7.3 nm) was obtained at the optimum condition which was aging time of 48 min, calcination temperature at 400 ⁰C, and cerium concentration of 0.004 mol. Average specific surface area of the particles at optimum condition was measured by BET analysis and recorded as 47.57 m2/g.

Keywords: aging time, CeO2 nanoparticles, size distribution, sol-gel

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29 A Novel CeO2-WOx-TiO2 Catalyst for Oxidative Desulfurization of Model Fuel Oil

Authors: Corazon Virtudazo-Ligaray, Mark Daniel G. de Luna, Meng-Wei Wan, Ming-Chun Lu


A series of ternary compound catalyst with nanocomposites of ceria, tungsten trioxide and titania (CeO2-WOx-TiO2) with different WOx mole fraction (10, 20, 30, 40) have been synthesized by sol-gel method. These nanocomposite catalysts were used for oxidative extractive desulfurization of model fuel oil, which were composed of dibenzothiophene (DBT) dissolved in toluene. The 30% hydrogen peroxide, H2O2 was used as oxidant and acetonitrile as extractant. These catalysts were characterized by SEM-EDS to determine the morphology. Catalytic oxidation results show that the catalysts have high selectivity in refractory fuel oil with organo sulfur contents. The oxidative removal of DBT increases as the HPW content increases. The nanocomposites CeO2-WOx-TiO2 also shows high selectivity for DBT oxidation in the DBT–toluene acetonitrile system. The catalytic oxidative desulfurization ratio of model fuel reached to 100% with nanocomposites CeO2-WOx-TiO2 (35-30-35) mol percent catalyst nanocomposition under 333 K in 30 minutes.

Keywords: ceria, oxidative desulfurization, titania, phosphotungstic acid

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28 Development of an Inexpensive Electrocatalytic Energy Material: Cu-Ni-CeO2 for High Performance Alcoholic Fuel Cell

Authors: Sujit Kumar Guchhait, Subir Paul


One of the major research areas is to find an alternative source of energy to fulfill the energy crisis and environmental problems. The Fuel cell is such kind of energy producing unit. Use of fuel cell to produce renewable energy for commercial purpose is limited by the high cost of Pt based electrode material. Development of high energetic, as well as inexpensive fuel cell electrode materials, is needs of hour to produce clean energy using derive bio-fuel. In this present investigation, inexpensive Cu-Ni-CeO2 electrode material has been synthesized by using pulse current. The surface morphology of the electrode materials is controlled by several deposition parameters to increase the rate of electrochemical oxidation of alcoholic fuel, ethanol. The electrochemical characterization of the developed material was done by Cyclic Voltammetry (CV) and Chronoamperometry (CA) and Electrochemical Impedance Spectroscopy test. It is interesting to find that both these materials have shown high electrocatalytic properties in terms of high exchange current density (I0), low polarization resistance (Rp) and low impedance. It is seen that the addition of CeO2 to Ni-Cu has outperformed Pt as far as high electrocatalytic properties are concerned. The exchange current density on the Cu-Ni-CeO2 electrode surface for ethanol oxidation is about eight times higher than the same on the Pt surface with much lower polarization resistance than the later. The surface morphology of the electrode materials has been revealed by Field Effect Scanning Electron Microscope (FESEM). It is seen that grains are narrow and subspherical with 3D surface containing pores in between two elongated grains. XRD study exhibits the presence of Ni and CeO2 on the Cu surface.

Keywords: electro-catalyst, alcoholic fuel, cyclic voltammetry, potentiodynamic polarization, EIS, XRD, SEM

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27 Adsorption of Bovine Serum Albumine on CeO2

Authors: Roman Marsalek


Preparation of nano-particles of cerium oxide and adsorption of bovine serum albumine on them were studied. Particle size distribution and influence of pH on zeta potential of prepared CeO2 were determined. Average size of prepared cerium oxide nano-particles was 9 nm. The simultaneous measurements of the bovine serum albumine adsorption and zeta potential determination of the (adsorption) suspensions were carried out. The adsorption isotherms were found to be of typical Langmuir type; values of the bovine serum albumin adsorption capacities were calculated. Increasing of pH led to decrease of zeta potential and decrease of adsorption capacity of cerium oxide nano-particles. The maximum adsorption capacity was found for strongly acid suspension (am=118 mg/g). The samples of nanoceria with positive zeta potential adsorbed more bovine serum albumine on the other hand, the samples with negative zeta potential showed little or no protein adsorption. Surface charge or better say zeta potential of CeO2 nano-particles plays the key role in adsorption of proteins on such type of materials.

Keywords: adsorption, BSA, cerium oxide nanoparticles, zeta potential, albumin

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26 Hierarchical Porous Carbon Composite Electrode for High Performance Supercapacitor Application

Authors: Chia-Chia Chang, Jhen-Ting Huang, Hu-Cheng Weng, An-Ya Lo


This study developed a simple hierarchical porous carbon (HPC) synthesis process and used for supercapacitor application. In which, mesopore provides huge specific surface area, meanwhile, macropore provides excellent mass transfer. Thus the hierarchical porous electrode improves the charge-discharge performance. On the other hand, cerium oxide (CeO2) have also got a lot research attention owing to its rich in content, low in price, environmentally friendly, good catalytic properties, and easy preparation. Besides, a rapid redox reaction occurs between trivalent cerium and tetravalent cerium releases oxygen atom and increase the conductivity. In order to prevent CeO2 from disintegration under long-term charge-discharge operation, the CeO2 carbon porous materials were was integrated as composite material in this study. For in the ex-situ analysis, scanning electron microscope (SEM), X-ray diffraction (XRD), transmission electron microscope (TEM) analysis were adopted to identify the surface morphology, crystal structure, and microstructure of the composite. 77K Nitrogen adsorption-desorption analysis was used to analyze the porosity of each specimen. For the in-situ test, cyclic voltammetry (CV) and chronopotentiometry (CP) were conducted by potentiostat to understand the charge and discharge properties. Ragone plot was drawn to further analyze the resistance properties. Based on above analyses, the effect of macropores/mespores and the CeO2/HPC ratios on charge-discharge performance were investigated. As a result, the capacitance can be greatly enhanced by 2.6 times higher than pristine mesoporous carbon electrode.

Keywords: hierarchical porous carbon, cerium oxide, supercapacitor

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25 Computational Determination of the Magneto Electronic Properties of Ce₁₋ₓCuₓO₂ (x=12.5%): Emerging Material for Spintronic Devices

Authors: Aicha Bouhlala, Sabah Chettibi


Doping CeO₂ with transition metals is an effective way of tuning its properties. In the present work, we have performed self-consistent ab-initio calculation using the full-potential linearized augmented plane-wave method (FP-LAPW), based on the density functional theory (DFT) as implemented in the Wien2k simulation code to study the structural, electronic, and magnetic properties of the compound Ce₁₋ₓCuₓO₂ (x=12.5%) fluorite type oxide and to explore the effects of dopant Cu in ceria. The exchange correlation potential has been treated using the Perdew-Burke-Eenzerhof revised of solid (PBEsol). In structural properties, the equilibrium lattice constant is observed for the compound, which exists within the value of 5.382 A°. In electronic properties, the spin-polarized electronic bandstructure elucidates the semiconductor nature of the material in both spin channels, with the compound was observed to have a narrow bandgap on the spin-down configuration (0.162 EV) and bandgap on the spin-up (2.067 EV). Hence, the doped atom Cu plays a vital role in increasing the magnetic moments of the supercell, and the value of the total magnetic moment is found to be 2.99438 μB. Therefore, the compound Cu-doped CeO₂ shows a strong ferromagnetic behavior. The predicted results propose the compound could be a good candidate for spintronics applications.

Keywords: Cu-doped CeO₂, DFT, Wien2k, properties

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24 CO2 Methanation over Ru-Ni/CeO2 Catalysts

Authors: Nathalie Elia, Samer Aouad, Jane Estephane, Christophe Poupin, Bilal Nsouli, Edmond Abi Aad


Carbon dioxide is one of the main contributors to greenhouse effect and hence to climate change. As a result, the methanation reaction CO2(g) + 4H2(g) →CH4(g) + 2H2O (ΔH°298 = -165 kJ/mol), also known as Sabatier reaction, has received great interest as a process for the valorization of the greenhouse gas CO2 into methane which is a hydrogen-carrier gas. The methanation of CO2 is an exothermic reaction favored at low temperature and high pressure. However, this reaction requires a high energy input to activate the very stable CO2 molecule, and exhibits serious kinetic limitations. Consequently, the development of active and stable catalysts is essential to overcome these difficulties. Catalytic methanation of CO2 has been studied using catalysts containing Rh, Pd, Ru, Co and Ni on various supports. Among them, the Ni-based catalysts have been extensively investigated under various conditions for their comparable methanation activity with highly improved cost-efficiency. The addition of promoters are common strategies to increase the performance and stability of Ni catalysts. In this work, a small amount of Ru was used as a promoter for Ni catalysts supported on ceria and tested in the CO2 methanation reaction. The nickel loading was 5 wt. % and ruthenium loading is 0.5wt. %. The catalysts were prepared by successive impregnation method using Ni(NO3)2.6H2O and Ru(NO)(NO3)3 as precursors. The calcined support was impregnated with Ni(NO3)2.6H2O, dried, calcined at 600°C for 4h, and afterward, was impregnated with Ru(NO)(NO3)3. The resulting solid was dried and calcined at 600°C for 4 h. Supported monometallic catalysts were prepared likewise. The prepared solids Ru(0.5%)/CeO2, Ni(5%)/CeO2 and Ru(0.5%)-Ni(5%)/CeO2 were then reduced prior to the catalytic test under a flow of 50% H2/Ar (50 ml/min) for 4h at 500°C. Finally, their catalytic performances were evaluated in the CO2 methanation reaction, in the temperature range of 100–350°C by using a gaseous mixture of CO2 (10%) and H2 (40%) in Ar balanced at a total flow rate of 100 mL/min. The effect of pressure on the CO2 methanation was studied by varying the pressure between 1 and 10 bar. The various catalysts showed negligible CO2 conversion at temperatures lower than 250°C. The conversion of CO2 increases with increasing reaction temperature. The addition of Ru as promoter to Ni/CeO2 improved the CO2 methanation. It was shown that the CO2 conversion increases from 15 to 70% at 350°C and 1 bar. The effect of pressure on CO2 conversion was also studied. Increasing the pressure from 1 to 5 bar increases the CO2 conversion from 70% to 87%, while increasing the pressure from 5 to 10 bar increases the CO2 conversion from 87% to 91%. Ru–Ni catalysts showed excellent catalytic performance in the methanation of carbon dioxide with respect to Ni catalysts. Therefore the addition of Ru onto Ni catalysts improved remarkably the catalytic activity of Ni catalysts. It was also found that the pressure plays an important role in improving the CO2 methanation.

Keywords: CO2, methanation, nickel, ruthenium

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23 Evaluation of Toxicity of Cerium Oxide on Zebrafish Developmental Stages

Authors: Roberta Pecoraro, Elena Maria Scalisi


Engineered Nanoparticles (ENPs) and Nanomaterials (ENMs) concern an active research area and a sector in full expansion. They have physical-chemical characteristics and small size that improve their performance compared to common materials. Due to the increase in their production and their subsequent release into the environment, new strategies are emerging to assess risk of nanomaterials. NPs can be released into the environment through aquatic systems by human activities and exert toxicity on living organisms. We evaluated the potential toxic effect of cerium oxide (CeO2) nanoparticles because it’s used in different fields due to its peculiar properties. In order to assess nanoparticles toxicity, Fish Embryo Toxicity (FET) test was performed. Powders of CeO2 NPs supplied by the CNR-IMM of Catania are indicated as CeO2 type 1 (as-prepared) and CeO2 type 2 (modified), while CeO2 type 3 (commercial) is supplied by Sigma-Aldrich. Starting from a stock solution (0.001g/10 ml dilution water) of each type of CeO2 NPs, the other concentration solutions were obtained adding 1 ml of the stock solution to 9 ml of dilution water, leading to three different solutions of concentration (10-4, 10-5, 10-6 g/ml). All the solutions have been sonicated to avoid natural tendency of NPs to aggregate and sediment. FET test was performed according to the OECD guidelines for testing chemicals using our internal protocol procedure. A number of eight selected fertilized eggs were placed in each becher filled with 5 ml of each concentration of the three types of CeO2 NPs; control samples were incubated only with dilution water. Replication was performed for each concentration. During the exposure period, we observed four endpoints (embryo coagulation, lack of formation of somites, failure to lift the yolk bag, no heartbeat) by a stereomicroscope every 24 hours. Immunohistochemical analysis on treated larvae was performed to evaluate the expression of metallothioneins (MTs), Heat Shock Proteins 70 (HSP70) and 7-ethoxyresorufin-O-diethylase (EROD). Our results have not shown evident alterations on embryonic development because all embryos completed the development and the hatching of the eggs, started around the 48th hour after exposure, took place within the last observation at 72 hours. A good reactivity, both in the embryos and in the newly hatched larvae, was found. The presence of heartbeat has also been observed in embryos with reduced mobility confirming their viability. A higher expression of EROD biomarker was observed in the larvae exposed to the three types of CeO2, showing a clear difference with the control. A weak positivity was found for MTs biomarker in treated larvae as well as in the control. HSP70 are expressed homogeneously in all the type of nanoparticles tested but not too much greater than control. Our results are in agreement with other studies in the literature, in which the exposure of Danio rerio larvae to other metal oxide nanoparticles does not show adverse effects on survival and hatching time. Further studies are necessary to clarify the role of these NPs and also to solve conflicting opinions.

Keywords: Danio rerio, endpoints, fish embryo toxicity test, metallic nanoparticles

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22 Electrochemical Biosensor for Rutin Detection with Multiwall Carbon Nanotubes and Cerium Dioxide Nanoparticles

Authors: Stephen Rathinaraj Benjamin, Flavio Colmati Junior, Maria Izabel Florindo Guedes, Rosa Amalia Fireman Dutra


A new enzymatic electrochemical biosensor based on multiwall carbon nanotubes and cerium oxide nanoparticles for the detection of rutin has been developed. The cerium oxide nanoparticles /HRP/ multiwall carbon nanotubes/ carbon paste electrode (HRP/ CeO2/MWCNTs/CPE) was prepared by ensuing addition of MWCNTs and HRP on the CPE, followed by the mixing with cerium oxide nanoparticles. Surface physical characteristics of the modified electrode and the electrochemical properties of the composite were investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), cylic voltammetry (CV), differential pulse voltammetry (DPV) and square wave voltammetry (SWV). The HRP/ CeO2/MWCNTs/CPE showed good selectivity, stability and reproducibility, which was further applied to detect rutin tablet and capsule samples with satisfactory results.

Keywords: cerium dioxide nanoparticles, horseradish peroxidase, multiwall carbon nanotubes, rutin

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21 Iridium-Based Bimetallic Catalysts for Hydrogen Production through Glycerol Aqueous-Phase Reforming

Authors: Francisco Espinosa, Juan Chavarría


Glycerol is a byproduct of biodiesel production that can be used for aqueous-phase reforming to obtain hydrogen. Iridium is a material that has high activity and hydrogen selectivity for steam phase reforming. Nevertheless, a drawback for the use of iridium in aqueous-phase reforming is the low activity in water-gas shift reaction. Therefore, in this work, it is proposed the use of nickel and copper as a second metal in the catalyst to reach a synergetic effect. Iridium, iridium-nickel and iridium-copper catalysts were prepared by incipient wetness impregnation and evaluated in the aqueous-phase reforming of glycerol using CeO₂ or La₂O₃ as support. The catalysts were characterized by XRD, XPS, and EDX. The reactions were carried out in a fixed bed reactor feeding a solution of glycerol 10 wt% in water at 270°C, and reaction products were analyzed by gas chromatography. It was found that IrNi/CeO₂ reached highest glycerol conversion and hydrogen production, slightly above 70% and 43 vol% respectively. In terms of conversion, iridium is a promising metal, and its activity for hydrogen production can be enhanced when adding a second metal.

Keywords: aqueous-phase reforming, glycerol, hydrogen production, iridium

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20 Radiation Stability of Pigment ZnO Modified by Nanopowders

Authors: Chundong Li, V. V. Neshchimenko, M. M. Mikhailov


The effect of the modification of ZnO powders by ZrO2, Al2O3, TiO2, SiO2, CeO2 and Y2O3 nanoparticles with a concentration of 1-30 wt % is investigated by diffuse reflectance spectra within the wavelength range 200 to 2500 nm before and after 100 keV proton and electron irradiation. It has been established that the introduction of nanoparticles ZrO2, Al2O3 enhances the optical stability of the pigments under proton irradiation, but reduces it under electron irradiation. Modifying with TiO2, SiO2, CeO2, Y2O3 nanopowders leads to decrease radiation stability in both types of irradiation. Samples modified by 5 wt. % of ZrO2 nanoparticles have the highest stability of optical properties after proton exposure. The degradation of optical properties under electron irradiation is not high for this concentration of nanoparticles. A decrease in the absorption of pigments modified with nanoparticles proton exposure is determined by a decrease in the intensity of bands located in the UV and visible regions. After electron exposure the absorption bands have in the whole spectrum range.

Keywords: irradiation, nanopowders, radiation stability, zinc oxide

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19 NiO-CeO2 Nano-Catalyst for the Removal of Priority Organic Pollutants from Wastewater through Catalytic Wet Air Oxidation at Mild Conditions

Authors: Anushree, Chhaya Sharma, Satish Kumar


Catalytic wet air oxidation (CWAO) is normally carried out at elevated temperature and pressure. This work investigates the potential of NiO-CeO2 nano-catalyst in CWAO of paper industry wastewater under milder operating conditions of 90 °C and 1 atm. The NiO-CeO2 nano-catalysts were synthesized by a simple co-precipitation method and characterized by X-ray diffraction (XRD), before and after use, in order to study any crystallographic change during experiment. The extent of metal-leaching from the catalyst was determined using the inductively coupled plasma optical emission spectrometry (ICP-OES). The catalytic activity of nano-catalysts was studied in terms of total organic carbon (TOC), adsorbable organic halides (AOX) and chlorophenolics (CHPs) removal. Interestingly, mixed oxide catalysts exhibited higher activity than the corresponding single-metal oxides. The maximum removal efficiency was achieved with Ce40Ni60 catalyst. The results indicate that the CWAO process is efficient in removing the priority organic pollutants from wastewater, as it exhibited up to 59% TOC, 55% AOX, and 54 % CHPs removal.

Keywords: catalysis, nano-materials, NiO-CeO2, paper mill, wastewater, wet air oxidation

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18 Effect of Graphene on the Structural and Optical Properties of Ceria:Graphene Nanocomposites

Authors: R. Udayabhaskar, R. V. Mangalaraja, V. T. Perarasu, Saeed Farhang Sahlevani, B. Karthikeyan, David Contreras


Bandgap engineering of CeO₂ nanocrystals is of high interest for many research groups to meet the requirement of desired applications. The band gap of CeO₂ nanostructures can be modified by varying the particle size, morphology and dopants. Anchoring the metal oxide nanostructures on graphene sheets will result in composites with improved properties than the parent materials. The presence of graphene sheets will acts a support for the growth, influences the morphology and provides external paths for electronic transitions. Thus, the controllable synthesis of ceria:graphene composites with various morphologies and the understanding of the optical properties is highly important for the usage of these materials in various applications. The development of ceria and ceria:graphene composites with low cost, rapid synthesis with tunable optical properties is still desirable. By this work, we discuss the synthesis of pure ceria (nanospheres) and ceria:graphene composites (nano-rice like morphology) by using commercial microwave oven as a cost effective and environmentally friendly approach. The influence of the graphene on the crystallinity, morphology, band gap and luminescence of the synthesized samples were analyzed. The average crystallite size obtained by using Scherrer formula of the CeO₂ nanostructures showed a decreasing trend with increasing the graphene loading. The higher graphene loaded ceria composite clearly depicted morphology of nano-rice like in shape with the diameter below 10 nm and the length over 50 nm. The presence of graphene and ceria related vibrational modes (100-4000 cm⁻¹) confirmed the successful formation of composites. We observed an increase in band gap (blue shift) with increasing loading amount of graphene. Further, the luminescence related to various F-centers was quenched in the composites. The authors gratefully acknowledge the FONDECYT Project No.: 3160142 and BECA Conicyt National Doctorado2017 No. 21170851 Government of Chile, Santiago, for the financial assistance.

Keywords: ceria, graphene, luminescence, blue shift, band gap widening

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17 Catalytic Combustion of Methane over Pd-Meox-CeO₂/Al₂O₃ (Me= Co or Ni) Catalysts

Authors: Silviya Todorova, Anton Naydenov, Ralitsa Velinova, Alexander Larin


Catalytic combustion of methane has been extensively investigated for emission control and power generation during the last decades. The alumina-supported palladium catalyst is widely accepted as the most active catalysts for catalytic combustion of methane. The activity of Pd/Al₂O₃ decreases during the time on stream, especially underwater vapor. The following order of activity in the reaction of complete oxidation of methane was established: Co₃O₄> CuO>NiO> Mn₂O₃> Cr₂O₃. It may be expected that the combination between Pd and these oxides could lead to the promising catalysts in the reaction of complete methane. In the present work, we investigate the activity of Pd/Al₂O₃ catalysts promoted with other metal oxides (MOx; M= Ni, Co, Ce). The Pd-based catalysts modified by metal oxide were prepared by sequential impregnation of Al₂O₃ with aqueous solutions of Me(NO₃)₂.6H₂O and Pd(NO₃)₂H₂O. All samples were characterized by X-ray diffraction (XRD), temperature-programmed reduction (TPR), and X-ray photoelectron spectroscopy (XPS). An improvement of activity was observed after modification with different oxides. The results demonstrate that the Pd/Al₂O₃ catalysts modified with Co and Ce by impregnation with a common solution of respective salts, exhibit the most promising catalytic activity for methane oxidation. Most probably, the presence of Co₃O₄ and CeO₂ on catalytic surface increases surface oxygen and therefore leads to the better reactivity in methane combustion.

Keywords: methane combustion, palladium, Co-Ce, Ni-Ce

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16 Effect of Water Addition on Catalytic Activity for CO2 Purification from Oxyfuel Combustion

Authors: Joudia Akil, Stephane Siffert, Laurence Pirault-Roy, Renaud Cousin, Christophe Poupin


Oxyfuel combustion is a promising method that enables to obtain a CO2 rich stream, with water vapor ( ̴10%), unburned components such as CO and NO, which must be cleaned before the use of CO2. Our objective is then the final treatment of CO and NO by catalysis. Three-way catalysts are well-developed material for simultaneous conversion of NO, CO and hydrocarbons. Pt and/or Rh ensure a quasi-complete removal of NOx, CO and HC and there is also a growing interest in partly replacing Pt with less-expensive Pd. The use of alumina and ceria as support ensures, respectively, the stabilization of such species in active state and discharging or storing oxygen to control the oxidation of CO and HC and the reduction of NOx. In this work, we will compare different metals (Pd, Rh and Pt) supported on Al2O3 and CeO2, for CO2 purification from oxyfuel combustion. The catalyst must reduce NO by CO in an oxidizing environment, in the presence of CO2 rich stream and resistant to water. In this study, Al2O3 and CeO2 were used as support materials of the catalysts. 1wt% M/Support where M = Pd, Rh or Pt catalysts were obtained by wet impregnation on supports with a precursor of palladium [Pd(acac)2], rhodium [Rh(NO3)3] and platinum [Pt(NO2)2(NO3)2]. Materials were characterized by BET surface area, H2 chemisorption, and TEM. Catalytic activity was evaluated in CO2 purification which is carried out in a fixed-bed flow reactor containing 150 mg of catalyst at atmospheric pressure. The flow of the reactant gases is composed of: 20% CO2, 10% O2, 0.5% CO, 0.02% NO and 8.2% H2O (He as eluent gas) with a total flow of 200 mL.min−1, with same GHSV (2.24x104 h-1). The catalytic performances of the samples were investigated with and without water. It shows that the total oxidation of CO occurred over the different materials. This study evidenced an important effect of the nature of the metals, supports and the presence or absence of H2O during the reduction of NO by CO in oxyfuel combustions conditions. Rh based catalysts show that the addition of water has a very positive influence especially on the Rh catalyst on CeO2. Pt based catalysts keep a good activity despite the addition of water on the both supports studied. For the NO reduction, addition of water act as a poison with Pd catalysts. The interesting results of Rh based catalysts with water can be explained by a production of hydrogen through the water gas shift reaction. The produced hydrogen acts as a more effective reductant than CO for NO removal. Furthermore, in TWCs, Rh is the main component responsible for NOx reduction due to its especially high activity for NO dissociation. Moreover, cerium oxide is a promotor for WGSR.

Keywords: carbon dioxide, environmental chemistry, heterogeneous catalysis

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15 Apatite-Forming Ability of Doped-Ceria Coatings for Orthopedic Implants

Authors: Ayda Khosravanihaghighi, Pramod Koshy, Bill Walsh, Vedran Lovric, Charles Christopher Sorrell


There is an increasing demand for orthopedic implants owing to the increasing numbers of the aging population. Titanium alloy (Ti6Al4V) is a common material used for orthopedic implants owing to its advantageous properties in terms of good corrosion resistance, minimal elastic modulus mismatch with bone, bio-inertness, and high mechanical strength. However, it is important to improve the bioactivity and osseointegration of the titanium alloy and this can be achieved by coating the implant surface with suitable ceramic materials. In the present work, pure and doped-ceria (CeO₂) coatings were deposited by spin coating on the titanium alloy surface in order to enhance the biological interactions between the surface of the implant and the surrounding tissue. In order to examine the bone-binding ability of an implant, simulated body fluid (SBF) tests were conducted in order to assess the capability of apatite layer formation on the surface and thus predict in vivo bone bioactivity. Characterization was done using scanning electron microscopy (SEM) and X-ray diffraction (XRD) analyses to determine the extent of apatite formation. Preliminary tests showed that the CeO₂ coatings were biocompatible and that the extent of apatite formation and its characteristics can be enhanced by doping with suitable metal ions.

Keywords: apatite layer, biocompatibility, ceria, orthopaedic implant, SBF, spin coater, Ti-implant

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14 Abatement of NO by CO on Pd Catalysts: Influence of the Support in Oxyfuel Combustion Conditions

Authors: Joudia Akil, Stephane Siffert, Laurence Pirault-Roy, Renaud Cousin, Christophe Poupin


The CO2 emitted from anthropic activities is perceived as a constraint in industrial activity due to taxes, stringent environmental regulations, impact on global warming… To limit these CO2 emissions, reuse of CO2 represents a promising alternative, with important applications in chemical industry and for power generation. However, CO2 valorization process requires a gas as pure as possible Oxyfuel-combustion that enables obtaining a CO2 rich stream, with water vapor (10%) is then interesting. Nevertheless to decrease the amount of the by-products found with the CO2 (especially CO and NOx which are harmful to the environment) a catalytic treatment must be applied. Nowadays three-way catalysts are well-developed material for simultaneous conversion of unburned hydrocarbons, carbon monoxide (CO) and nitrogen oxides (NOx). The use of Pd attracted considerable attention on the basis of economic factors (the high cost and scarcity of Pt and Rh). This explains the large number of studies concerning the CO-NO reaction on Pd in the recent years. In the present study, we will compare a series of Pd materials supported on different oxides for CO2 purification from the oxyfuel combustion system, by reducing NO with CO in an oxidizing environment containing CO2 rich stream and presence of 8.2% of water. Al2O3, CeO2, MgO, SiO2 and TiO2 were used as support materials of the catalysts. 1wt% Pd/Support catalysts were obtained by wet impregnation on supports with a precursor of palladium [Pd(acac)2]. The obtained samples were subsequently characterized by H2 chemisorption, BET surface area and TEM. Finally, their catalytic performances were evaluated in CO2 purification which is carried out in a fixed-bed flow reactor containing 150 mg of catalyst at atmospheric pressure. The flow of the reactant gases is composed of: 20% CO2, 10% O2, 0.5% CO, 0.02% NO and 8.2% H2O (He as eluent gas) with a total flow of 200mL.min−1, in the same GHSV. The catalytic performance of the Pd catalysts for CO2 purification revealed that: -The support material has a strong influence on the catalytic activity of 1wt.% Pd supported catalysts. depending of the nature of support, the Pd-based catalysts activity changes. -The highest reduction of NO with CO is obtained in the following ranking: TiO2>CeO2>Al2O3. -The supports SiO2 and MgO should be avoided for this reaction, -Total oxidation of CO occurred over different materials, -CO2 purification can reach 97%, -The presence of H2O has a positive effect on the NO reduction due to the production of the reductant H2 from WGS reaction H2O+CO → H2+CO2

Keywords: carbon dioxide, environmental chemistry, heterogeneous catalysis, oxyfuel combustion

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13 Transport Properties of Alkali Nitrites

Authors: Y. Mateyshina, A.Ulihin, N.Uvarov


Electrolytes with different type of charge carrier can find widely application in different using, e.g. sensors, electrochemical equipments, batteries and others. One of important components ensuring stable functioning of the equipment is electrolyte. Electrolyte has to be characterized by high conductivity, thermal stability, and wide electrochemical window. In addition to many advantageous characteristic for liquid electrolytes, the solid state electrolytes have good mechanical stability, wide working range of temperature range. Thus search of new system of solid electrolytes with high conductivity is an actual task of solid state chemistry. Families of alkali perchlorates and nitrates have been investigated by us earlier. In literature data about transport properties of alkali nitrites are absent. Nevertheless, alkali nitrites MeNO2 (Me= Li+, Na+, K+, Rb+ and Cs+), except for the lithium salt, have high-temperature phases with crystal structure of the NaCl-type. High-temperature phases of nitrites are orientationally disordered, i.e. non-spherical anions are reoriented over several equivalents directions in the crystal lattice. Pure lithium nitrite LiNO2 is characterized by ionic conductivity near 10-4 S/cm at 180°C and more stable as compared with lithium nitrate and can be used as a component for synthesis of composite electrolytes. In this work composite solid electrolytes in the binary system LiNO2 - A (A= MgO, -Al2O3, Fe2O3, CeO2, SnO2, SiO2) were synthesized and their structural, thermodynamic and electrical properties investigated. Alkali nitrite was obtained by exchange reaction from water solutions of barium nitrite and alkali sulfate. The synthesized salt was characterized by X-ray powder diffraction technique using D8 Advance X-Ray Diffractometer with Cu K radiation. Using thermal analysis, the temperatures of dehydration and thermal decomposition of salt were determined.. The conductivity was measured using a two electrode scheme in a forevacuum (6.7 Pa) with an HP 4284A (Precision LCR meter) in a frequency range 20 Hz < ν < 1 MHz. Solid composite electrolytes LiNO2 - A A (A= MgO, -Al2O3, Fe2O3, CeO2, SnO2, SiO2) have been synthesized by mixing of preliminary dehydrated components followed by sintering at 250°C. In the series of nitrite of alkaline metals Li+-Cs+, the conductivity varies not monotonically with increasing radius of cation. The minimum conductivity is observed for KNO2; however, with further increase in the radius of cation in the series, the conductivity tends to increase. The work was supported by the Russian Foundation for Basic research, grant #14-03-31442.

Keywords: conductivity, alkali nitrites, composite electrolytes, transport properties

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12 Effect of Al Particles on Corrosion Resistance of Electrodeposited Ni-Al Composite Coatings

Authors: M. Adabi, A. Amadeh


Electrodeposition is known as a relatively economical and simple technique commonly used for preparation of metallic and composite coatings. Electrodeposited composite coatings produced by dispersion of particles into the metal matrix show better properties than pure metallic coatings. In recent years, many researches were carried out on Ni matrix coatings reinforced by ceramic particles such as Ni-SiC, Ni-Al2O3, Ni-WC, Ni-CeO2, Ni-ZrO2, Ni-TiO2 to improve their corrosion and wear resistance. However, little effort has been made on incorporation of metal particles into Ni matrix. Therefore, the aim of this work was to produce Ni–Al composite coating on 6061 aluminum alloy by pulse plating and to investigate the effects of electrodeposition parameters, e.g. concentration Al particles in the electrolyte and current density, on composition and corrosion resistance of the composite coatings. The morphology and corrosion behavior of the coated 6061 Al alloys were studied by means of scanning electron microscope (SEM) equipped with energy dispersive X-ray spectrometer (EDS) and potentiodynamic polarization method, respectively. The results indicated that the addition of Al particles up to 50 g L-1 increased the amount of co-deposited Al particles in nickel matrix. It is also observed that the incorporation of Al particles decreased with increasing current density. Meanwhile, the corrosion resistance of the coatings shows an increment by increasing the content of Al particles into nickel matrix.

Keywords: Ni-Al composite coating, current density, corrosion resistance

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11 Development of Rh/Ce-Zr-La/Al2O3 TWCs’ Wash Coat: Effect of Reactor on Catalytic and Thermal Stability

Authors: Su-Ning Wang, Yao-Qiang Chen


The CeO2-ZrO2-La2O3-Al2O3 composite oxides are synthesized using co-precipitation method by two different reactors (i.e. continuous stirred-tank reactor and batch reactor), and the corresponding Rh-only three-way catalysts are obtained by wet-impregnation approach. The textural, structural, morphology and redox properties of the support materials, as well as the catalytic performance of the Rh-only catalyst are investigated systematically. The results reveal that the materials (CZLA-C) synthesized by continuous stirred-tank reactor have a better physic-chemical properties than the counterpart material (CZLA-B) prepared by batch reactor. After aging treatment at 1000 ℃ for 5 h, the BET surface area and pore volume of S1 reach up to 76 m2 g-1 and 0.36 mL/g, respectively, which is higher than that of S2. The XRD and Raman results demonstrate that a high structural stability is obtained by S1 because of the negligible lattice variation and the slight grain growth after aging treatment. The SEM and TEM images display that the morphology of S1 is assembled by many homogeneous primary nanoparticles (about 6.12 nm) that are connected to form mesoporous structure The TPR measurement shows that S1 possesses a higher reduction ability than S2. Compared with the catalyst supported on the CZLA-B, the as-prepared CZLA-C demonstrates an improved three-way catalytic activity both before and after aging treatment.

Keywords: composite oxides, reactor, catalysis, catalytic performance

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10 Production, Quality Control, and Biodistribution Studies of 141ce-Edtmp as a Potential Bone Pain Palliation Agent

Authors: Fatemeh Soltani, Simindokht Shirvani Arani, Ali Bahrami Samani, Mahdi Sadeghi, Kamal Yavari


Cerium-141 [T1/2 = 32.501 days, Eβ (max) = 0.580 (29.8%) and 0.435(70.2%) MeV, Eγ=145.44 (48.2%) keV] possesses radionuclidic properties suitable for use in palliative therapy of bone metastases. 141Ce also has gamma energy of 145.44 keV, which resembles that of 99mTc. Therefore, the energy window is adjustable on the Tc-99m energy because of imaging studies. 141Ce can be produced through a relatively easy route that involves thermal neutron bombardment on natural CeO2 in medium flux research reactors (4–5×1013 neutrons/cm2•s). The requirement for an enriched target does not arise. Ethylenediamine tetramethylene phosphonic acid (EDTMP) was synthesized and radiolabeled with 141Ce. Complexation parameters were optimized to achieve maximum yields (>99%). The radiochemical purity of 141Ce-EDTMP was evaluated by radio-thin layer chromatography. The stability of the prepared formulation was monitored for one week at room temperature, and results showed that the preparation was stable during this period (>99%). Biodistribution studies of the complexes carried out in wild-type rats exhibited significant bone uptake with rapid clearance from blood. The properties of produced 141Ce-EDTMP suggest applying a new efficient bone pain palliative therapeutic agent to overcome metastatic bone pains.

Keywords: bone pain palliative, cerium-141, EDTMP, radiopharmaceutical

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9 Production and Characterization of Ce3+: Si2N2O Phosphors for White Light-Emitting Diodes

Authors: Alparslan A. Balta, Hilmi Yurdakul, Orkun Tunckan, Servet Turan, Arife Yurdakul


Si2N2O (Sinoite) is an inorganic-based oxynitride material that reveals promising phosphor candidates for white light-emitting diodes (WLEDs). However, there is now limited knowledge to explain the synthesis of Si2N2O for this purpose. Here, to the best of authors’ knowledge, we report the first time the production of Si2N2O based phosphors by CeO2, SiO2, Si3N4 from main starting powders, and Li2O sintering additive through spark plasma sintering (SPS) route. The processing parameters, e.g., pressure, temperature, and sintering time, were optimized to reach the monophase Si2N2O containing samples. The lattice parameter, crystallite size, and amount of formation phases were characterized in detail by X-ray diffraction (XRD). Grain morphology, particle size, and distribution were analyzed by scanning and transmission electron microscopes (SEM and TEM). Cathodoluminescence (CL) in SEM and photoluminescence (PL) analyses were conducted on the samples to determine the excitation, and emission characteristics of Ce3+ activated Si2N2O. Results showed that the Si2N2O phase in a maximum 90% ratio was obtained by sintering for 15 minutes at 1650oC under 30 MPa pressure. Based on the SEM-CL and PL measurements, Ce3+: Si2N2O phosphor shows a broad emission summit between 400-700 nm that corresponds to white light. The present research was supported by TUBITAK under project number 217M667.

Keywords: cerium, oxynitride, phosphors, sinoite, Si₂N₂O

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8 Effect of Catalyst Preparation Method on Dry Reforming of Methane with Supported and Promoted Catalysts

Authors: Sanjay P. Gandhi, Sanjay S. Patel


Dry (CO2) reforming of methane (DRM) is both scientific and industrial importance. In recent decades, CO2 utilization has become increasingly important in view of the escalating global warming phenomenon. This reaction produces syngas that can be used to produce a wide range of products, such as higher alkanes and oxygenates by means of Fischer–Tropsch synthesis. DRM is inevitably accompanied by deactivation due to carbon deposition. DRM is also a highly endothermic reaction and requires operating temperatures of 800–1000 °C to attain high equilibrium conversion of CH4 and CO2 to H2 and CO and to minimize the thermodynamic driving force for carbon deposition. The catalysts used are often composed of transition Methods like Nickel, supported on metallic and non-metallic oxides such as alumina and silica. However, many of these catalysts undergo severe deactivation due to carbon deposition. Noble metals have also been studied and are typically found to be much more resistant to carbon deposition than Ni catalysts, but are generally uneconomical. Noble metals can also be used to promote the Ni catalysts in order to increase their resistance to deactivation. In order to design catalysts that minimize deactivation, it is necessary to understand the elementary steps involved in the activation and conversion of CH4 and CO2. CO2 reforming methane over promoted catalyst was studied. The influence of ZrO2, CeO2 and the behavior of Ni-Al2O3 Catalyst, prepare by wet-impregnation and Co-precipitated method was studied. XRD, BET Analysis for different promoted and unprompted Catalyst was studied.

Keywords: CO2 reforming of methane, Ni catalyst, promoted and unprompted catalyst, effect of catalyst preparation

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