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1.
Precious-metal catalysts (e.g., Au, Rh, Ag, Ru, Pt, and Pd) supported on transition-metal oxides (e.g., Al2O3, Fe2O3, CeO2, ZrO2, Co3O4, MnO2, TiO2, and NiO) can effectively oxidize volatile organic compounds. In this study, porous platinum-supported zirconia materials have been prepared by a “surface-casting” method. The synthesized catalysts present an ordered nanotube structure and exhibited excellent performance toward the catalytic oxidation of formaldehyde. A facile method, utilizing a boiling water bath, was used to fabricate graphene aerogel (GA), and the macroscopic 3D Pt/ZrO2-GA was modified by introducing an adjustable MOF coating by a surface step-by-step method. The unblocked mesoporous structure of the graphene aerogel facilitates the ingress and egress of reactants and product molecules. The selected 7 wt.% Pt/ZrO2-GA-MOF-5 composite demonstrated excellent performance for HCHO adsorption. Additionally, this catalyst achieved around 90 % conversion when subjected to a reaction temperature of 70 °C (T90 %=70 °C). The Pt/ZrO2-GA-MOF-5 composite induces a catalytic cycle, increasing the conversion by simultaneously adsorbing and oxidizing HCHO. This work provides a simple approach to increasing reactant concentration on the catalyst to increase the rate of reaction.  相似文献   

2.
The catalytic activity of the CuO/ZrO2, CoO/ZrO2, Fe2O3/ZrO2, and CuO/(CoO, Fe2O3)/ZrO2 systems in the reaction of selective CO oxidation in the presence of hydrogen was studied at 20–450°C over the oxide concentration range of 2.5–10 wt % on the surface of ZrO2. The conversion of CO on the CoO/ZrO2 systems was almost independent of the concentration of CoO: 88 or 90% for 2.5 or 10% CoO, respectively. TPR data allowed us to relate the catalytic activity of CoO/ZrO2 to Co-O-Zr clusters, the amount of which was almost constant over the test range of CoO concentrations. The conversion of CO on 2.5% CuO/ZrO2 was 32% (190°C) or 62–66% on 5–10% CuO/ZrO2 (170°C). According to TPR data, clusters like Cu-O-Zr occurred on the surface of ZrO2, and the amount of these clusters reached a maximum upon supporting 5% CuO. The catalytic properties of 5% CuO/5% CoO/ZrO2 and 5% CoO/5% CuO/ZrO2 samples were identical to those of 5% CuO/ZrO2 samples. It is likely that the formation of active reaction sites upon consecutively supporting the oxides occurred on the same surface sites of ZrO2. In this case, Co and Cu oxides competed for cluster formation, and the copper cation can displace the cobalt cation from the formed clusters. The Fe2O3 samples were inactive; a maximum conversion of 34% (290°C) was observed on 10% Fe2O3/ZrO2. The catalytic properties of CuO/Fe2O3/ZrO2 were also identical to those of CuO/ZrO2, and they depended on the presence of Cu-O-Zr clusters on the surface.  相似文献   

3.
This paper reports an investigation regarding the influence of the cation M(II) (M = Zn, Ni, Mg) on the formation of MCr2O4 by thermal decomposition of the corresponding M(II),Cr(III)-carboxylates (precursors) obtained by redox reaction between the corresponding metal nitrates and 1,3-propanediol. The decomposition products at different temperatures have been characterized by FT-IR spectroscopy and thermal analysis. Thus, we have evidenced that by thermal decomposition of the studied precursors in the range 250–300 °C, different amorphous oxidic phases mixtures form depending on the nature of metalic cation: (Cr2O3+x + ZnO) (Cr2O3+x + Ni/NiO) and (Cr2O3+x+MgO). In case of M = Zn, around 400 °C when the transition Cr2O3+x to Cr2O3 takes place, zinc chromite nuclei form by the interaction ZnO with Cr2O3. In case of M = Ni, due to the partial reduction of Ni(II) at Ni(0) during the thermal decomposition of the precursor the formation of nickel chromite by the reaction NiO + Cr2O3 is shifted toward 500 °C, when Ni is oxidized at NiO. The thermal evolution of the mixture (MgO + CrO3) is different due to the formation as intermediary phase of MgCrO4, which decomposes to MgCr2O4 around 560 °C. In order to investigate the chromites formation mechanism, we have studied the mechanical mixtures of single oxides obtained from the corresponding carboxylates. These mixtures (MO + Cr2O3) have been annealed at 400, 500, and 600 °C to study the evolution of the crystalline phases. It results in the prepared mixture behaving different from the mixtures obtained by thermal decomposition of the binary M(II),Cr(III)-carboxylates, recommending our synthesis method for obtaining binary oxides.  相似文献   

4.
A series of cobalt-containing granulated and structured catalysts based on zirconium and aluminum oxides has been studied. The optimum composition of binary oxide samples (80% ZrO2 − 20% Al2O3) for the selective reduction of nitrogen monoxide with methane (84% conversion of NO achieved at 320 °C) has been determined. The activity of the structured catalysts depends on both the composition of the secondary carrier (ZrO2, Al2O3, and their mixture) and on the nature of the skeleton of the cellular structure (cordierite, kaolin-aerosil). __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 43, No. 4, pp. 237–241, July–August, 2007.  相似文献   

5.
The dependence of the activity of СuO/ZrO2 catalysts in the CO oxidation reaction with oxygen in the presence of an excess of hydrogen and adsorption of СО over them on the CuO content (0.5 to 15%) and the structure of the support ZrO2, monoclinic (М), tetragonal (Т), or mixed (М + Т) has been studied. It has been found that the activity of CuO/ZrO2 is associated with the adsorption capacity of the samples for СО at 20°С. Thus, 5%CuO/ZrO2(Т + М) and 5% CuO/ZrO2(Т) samples, which exhibit the maximum activity (the СО conversion over them is 80–85% at 160°С), also possess a high chemisorption capacity towards CO (~2.2 × 1020 molecules/g). At the same time, CuO/ZrO2(М) samples with the CuO contents of 1 and 5% do not chemisorb СО and are inactive in the reaction at 160°С. The СО conversion over them does not exceed 32–36% at 250°С. On the basis of the data obtained by X-ray phase analysis, temperature-programmed reduction with Н2, temperature-programmed СО desorption, and electron paramagnetic resonance, a conclusion has been made that at low temperatures СО oxidation proceeds over CunOm clusters that are located on ZrO2(Т) crystallites. With the increase in the copper oxide content from 0.5 to 5%, the activity of the clusters increases, while the reaction temperature decreases. CuOm oxo complexes and particles of the СuO phase do not exhibit catalytic activity. The reasons for the low activity of the CuO/ZrO2(М) samples with the CuO contents of 1 and 5% in the СО oxidation and adsorption processes are discussed. The mechanism of the low-temperature СО oxidation with oxygen in an excess of hydrogen over a 5% CuO/ZrO2(Т + М) catalyst is considered.  相似文献   

6.
It has been established that oxides of the rare-earth elements with moderate redox potentials (La2O3, CeO2) increased the activity and working stability of Ni-Al2O3/cordierite catalysts in the reactions of deep and partial oxidation of methane. In the presence of the (NiO + La2O3 + Al2O3)/cordierite catalyst the process of carbon dioxide conversion of methane can be intensified by introduction of oxygen into the reaction gas mixture which decreases the temperature to achieve high conversion to 75–100 °C and has practically no effect on selectivity with respect to H2. Translated from Teoreticheskaya i éksperimental'naya Khimiya, Vol. 44, No. 6, pp. 359–364, November–December, 2008.  相似文献   

7.
Non‐oxidative methane dehydroaromatization is a promising reaction to directly convert natural gas into aromatic hydrocarbons and hydrogen. Commercialization of this technology is hampered by rapid catalyst deactivation because of coking. A novel approach is presented involving selective oxidation of coke during methane dehydroaromatization at 700 °C. Periodic pulsing of oxygen into the methane feed results in substantially higher cumulative product yield with synthesis gas; a H2/CO ratio close to two is the main side‐product of coke combustion. Using 13C isotope labeling of methane it is demonstrated that oxygen predominantly reacts with molybdenum carbide species. The resulting molybdenum oxides catalyze coke oxidation. Less than one‐fifth of the available oxygen reacts with gaseous methane. Combined with periodic regeneration at 550 °C, this strategy is a significant step forward, towards a process for converting methane into liquid hydrocarbons.  相似文献   

8.
Catalysts based on uranium oxides were systematically studied for the first time. Catalysts containing various amounts of uranium oxides (5 and 15%) supported on alumina and mixed Ni-U/Al2O3 catalysts were synthesized. The uranium oxide catalysts were characterized using the thermal desorption of argon, the low-temperature adsorption of nitrogen, X-ray diffraction analysis, and temperature-programmed reduction with hydrogen and CO. The effects of composition, preparation conditions, and thermal treatment on physicochemical properties and catalytic activity in the reactions of methane and butane oxidation, the steam and carbon dioxide reforming of methane, and the partial oxidation of methane were studied. It was found that a catalyst containing 5% U on alumina calcined at 1000°C was most active in the reaction of high-temperature methane oxidation. For the Ni-U/Al2O3 catalysts containing various uranium amounts (from 0 to 30%), the introduction of uranium as a catalyst constituent considerably increased the catalytic activity in methane steam reforming and partial oxidation.  相似文献   

9.
The chemical compatibility of perovskite-type Ba0.5Sr0.5Co0.8Fe0.2O3?δ (BSCF) oxides with Cr2O3 has been examined between room temperature and 1,100 °C. Differential thermal analysis and thermogravimetric analysis were used to analyze the thermal behavior of BSCF–Cr2O3 binary mixtures in all composition ranges (0–100 mass% BSCF). The reaction products were identified by X-ray analysis after heating at 700–1,100 °C. As we expected, it was found that perovskite-type BSCF oxide had a poor chemical compatibility with the Cr2O3 oxide. In particular, the decomposition process of the BSCF–Cr2O3 binary mixture is quite complex and it starts at about 700–750 °C. The mixtures of BSCF and Cr2O3 oxides reacted forming mixed complex oxides based on (Ba/Sr)FeO3, (Co/Fe)CrO4, and (Ba/Sr)CrO4 mixtures.  相似文献   

10.
This paper presents a study regarding the obtaining of NiCr2O4 by two new unconventional synthesis methods: (i) the first method is based on the formation of Cr(III) and Ni(II) carboxylate-type precursors in the redox reaction between the nitrate ion and 1,3-propanediol. The thermal decomposition of these complex combinations, at ~300 °C, leads to an oxide mixture of Cr2O3+x and NiO, with advanced homogeneity, small particles and high reactivity. On heating this mixture at 500 °C, Cr2O3 reacts with NiO to form NiCr2O4, which was evidenced by FT-IR and X-ray diffractometry (XRD) analysis; (ii) the second method starts from a mechanical mixture of (NH4)2Cr2O7 and Ni(NO3)2·6H2O. On heating this mixture, a violent decomposition at 240 °C with formation of an oxides mixture (Cr2O3 + CrO3) and NiO takes place. On thermal treatment up to 500 °C, an intermediary phase NiCrO4 is formed, which by decomposition at ~700 °C leads to NiCr2O4, evidenced by FT-IR and XRD analysis. NiCr2O4 is formed, in both cases, starting with a temperature higher than 400 °C, when the non-stoichiometric chromium oxide (Cr2O3+x ) loses the oxygen excess and turns to stoichiometric chromium oxide (Cr2O3), which further reacts with NiO.  相似文献   

11.
The isothermal oxidation behavior of Ni–45.16%Ti (composition in atomic percent) alloy was investigated by thermogravimetric analysis, and differential scanning calorimeter (DSC) methods. It was found that Ni-rich NiTi alloy exhibits a different oxidation behavior at temperatures above 400 °C in oxygen atmosphere. The alloy was exposed to oxygen atmosphere isothermally, i.e., between 400 and 800 °C, for 1 h. A gravimetric method was used to determine the oxidation kinetics and it was seen that the oxidation constant increases significantly with isothermal temperature. The activation energy of oxidation reaction for NiTi alloy was determined to be 65.47 kJ mol?1. According to DSC measurements, the transformation temperature of alloy (M s, M f, A s and A f) was increased and also R phase disappeared above 500 °C. The formal oxides were determined by means of SEM–EDX measurements and obtained oxides are TiO and TiO2 oxides.  相似文献   

12.
In order to generate synthesis gas or hydrogen free from nitrogen by partial oxidation of methane using air as an oxidant, gas?Csolid reactions of methane and a metal oxide and/or mixed metal oxides were carried out. The background of the gas?Csolid reaction was briefly reviewed and then a series of the present author??s studies was described. As metal oxides Fe2O3 and NiO were active, but the reaction with methane and these oxides afforded complete oxidation to give H2O and CO2. To both oxides, addition of Cr- and Mg- oxides promoted the following reaction to give synthesis gas. $$ {\text{CH}}_{ 4} + {\text{ MM}}'{\text{O}}_{\text{x}} \to {\text{CO }} + {\text{ 2H}}_{ 2} + {\text{ MM}}^{\prime}{\text{O}}_{{{\text{x}} - 1}} $$ After the reaction with methane, mixed oxides were reduced to lower valence state oxides and they were regenerated by the oxidation with air. $$ {\text{MM}}^{\prime}{\text{O}}_{{{\text{x}} - 1}} + {\text{ Air}} \to {\text{MM}}'{\text{O}}_{\text{x}} + {\text{ N}}_{ 2} $$ Up to 10 repeated reaction and regeneration cycles did not or only slightly decreased the activity of the mixed oxides. By switching two or more reactors, the reaction and the regeneration were carried out to give synthesis gas continuously.  相似文献   

13.
Cobalt ferrite (CoFe2O4) was used as a catalyst for direct methane cracking. The reaction was accomplished in a fixed bed reactor at normal atmospheric pressure, while gas flow rate (20–50 mL/min) and reaction temperature (800–900 °C) were varied. The fresh CoFe2O4 morphology is sponge-like particle with inverse spinel structure as revealed from SEM and XRD results. The methane conversions and hydrogen formation rate were increased with reaction temperature, while catalyst stability and induction period decreased. Increases of gas flow rate > 20 mL/min led to a decrease the overall catalytic activity of CoFe2O4 for methane cracking. The XRD results of spent catalysts revealed that CoFe alloy was the active phase of methane cracking. TGA analysis showed that the largest amount of deposited carbon was 70.46 % at (20 mL/min, 900 °C), where it was 34.40 % at (50 mL/min, 800 °C). The deposited carbon has the shape of spherical carbon nanostructures and/or nano sprouts as observed with SEM. Raman data confirmed the graphitization type of the deposited carbon.  相似文献   

14.
Samples of a precursor for an aluminum oxide ceramics reinforced with zirconium oxide were synthesized by hydrolysis of various aluminum salts in the presence of a ZrO2 sol under conditions of urea decomposition at 90°C and pH < 4 maintained, with hydrolysis products deposited onto the surface of ZrO2 sol particles. It was found that the nature of a salt anion affects the interaction of hydrolysis products of the aluminum cation with the surface of ZrO2 sol particles. The structure of products formed in thermal treatment of samples of a precursor for Al2O3-ZrO2 (T = 1250°C) was characterized by X-ray phase analysis and scanning electron microscopy. The phase transition temperatures of the oxides Al2O3 and ZrO2 contained in the precursor were estimated using the results of thermal analysis of the samples in the temperature range 20–1300°C.  相似文献   

15.
Miniaturization of microelectronic devices has reached a fundamental scaling limit; parasitic electron tunneling through the ultrathin gate dielectric has become a major obstacle to continued device performance. One method for overcoming this limitation is to replace SiO2 gate dielectrics with thicker high-κ metal oxides. La2O3 and ZrO2 are two such materials that have received significant interest, but low stability to post-anneal water absorption and low-crystallization temperatures, respectively, have limited their widespread use. We recently reported an aqueous, all-inorganic route to high-κ lanthanum zirconium oxide dielectric films (1/1 La/Zr), which mitigates the disadvantages of the binary oxides but maintains their high-κ properties. In this contribution, we vary the La/Zr ratio of the aqueous precursor to optimize the properties of the resulting films. We find that the La0.20Zr0.80Oy composition is optimal for providing a high dielectric constant (∼18.2 at 600 °C) while maintaining excellent film morphology and stability. 20% La was necessary to prevent crystallization up to 600 °C, but films with higher La content displayed diminished dielectric constants and decreased stability towards post-anneal water absorption.  相似文献   

16.
The catalysts of silver supported on mesoporous silica modified with Co3O4, CeO2, and ZrO2 were prepared by an impregnation method; characterized by X-ray diffraction analysis, temperature-programmed reduction, and low-temperature nitrogen adsorption; and studied in a model reaction of CO oxidation. It was found that the Ag/SiO2 system exhibited high activity in the reaction of CO oxidation, and the addition of transition metal oxides led to reduction of the temperature of 50% CO conversion by 40°C. The modification of Ag/SiO2 with cerium dioxide was found most effective because of the interaction of silver particles and CeO2 on the surface of silica gel.  相似文献   

17.
The decrease in the polarization resistance of the anode of solid-oxide fuel cells (SOFCs) due to the formation of an additional NiO/(ZrO2 + 10 mol % Y2O3) (YSZ) functional layer was studied. NiO/YSZ films with different NiO contents were deposited by reactive magnetron sputtering of Ni and Zr–Y targets. The elemental and phase composition of the films was adjusted by regulating oxygen flow rate during the sputtering. The resulting films were studied by scanning electron microscopy and X-ray diffractometry. Comparative tests of planar SOFCs with a NiO/YSZ anode support, NiO/YSZ functional nanostructured anode layer, YSZ electrolyte, and La0.6Sr0.4Co0.2Fe0.8O3/Ce0.9Gd0.1O2 (LSCF/CGO) cathode were performed. It was shown that the formation of a NiO/YSZ functional nanostructured anode leads to a 15–25% increase in the maximum power density of fuel cells in the working temperature range 500–800°C. The NiO/YSZ nanostructured anode layers lead not only to a reduction of the polarization resistance of the anode, but also to the formation of denser electrolyte films during subsequent magnetron sputtering of electrolyte.  相似文献   

18.
The catalytic activity of the CoO/CeO2 and CuO/CoO/CeO2 systems in selective CO oxidation in the presence of hydrogen at 20–450°C ([CuO] = 1.0–2.5%, [CoO] = 1.0–7.0%) is reported. The maximum CO conversion (X) decreases in the following order: CuO/CoO/CeO2 (X = 98–99%, T = 140–170°C) > CoO/CeO2 (X = 67–84%, T = 230–240°C) > CeO2 (X = 34%, T = 350°C). TPD, TPR, and EPR experiments have demonstrated that the high activity of CuO/CoO/CeO2 is due to the strong interaction of the supported copper and cobalt oxides with cerium dioxide, which yields Cu-Co-Ce-O clusters on the surface. The carbonyl group in the complexes Coδ+-CO and Cu+-CO is oxidized by oxygen of the Cu-Co-Ce-O clusters at 140–160°C and by oxygen of the Co-Ce-O clusters at 240°C. The decrease in the activity of the catalysts at high temperatures is due to the fact that hydrogen reduces the clusters on which CO oxidation takes place, yielding Co0 and Cu0 particles, which are inactive in CO oxidation. The hydrogenation of CO into methane at high temperatures is due to the appearance of Co0 particles in the catalysts.  相似文献   

19.
In this study, we demonstrated a highly sensitive electrochemical sensor for the determination of glucose in alkaline aqueous solution by using nickel oxide single-walled carbon nanotube hybrid nanobelts (NiO–SWCNTs) modified glassy carbon electrode (GCE). The hybrid nanobelts were prepared by the deposition of SWCNTs onto the Ni(SO4)0.3(OH)1.4 nanobelt surface, followed by heat treatment at different temperatures ranging from 400 °C to 600 °C. The NiO–SWCNTs hybrid nanobelts modified electrode prepared at 500 °C displays enhanced electrocatalytic activity towards glucose oxidation, revealing a synergistic effect between the NiO and the deposited SWCNTs. The as-fabricated nonenzymatic glucose sensor exhibits excellent glucose sensitivity (2,980 μA cm?2 mM?1), lower detection limit (0.056 μM, signal/noise [S/N] ratio?=?3), and wider linear range (0.5–1,300 μM). Moreover, the sensor has been successfully used for the assay of glucose in serum samples with good recovery, ranging from 96.4 % to 102.4 %.  相似文献   

20.
Carbon dioxide reforming (CDR) of methane to synthesis gas over supported nickel catalysts has been reviewed. The present review mainly focuses on the advantage of ceria based nickel catalysts for the CDR of methane. Nickel catalysts supported on ceria–zirconia showed the highest activity for CDR than nickel supported on other oxides such as zirconia, ceria and alumina. The addition of zirconia to ceria enhances the catalytic activity as well as the catalyst stability. The catalytic performance also depends on the crystal structure of Ni–Ce–ZrO2. For example, nickel catalysts co-precipitated with Ce0.8Zr0.2O2 having cubic phase gave synthesis gas with CH4 conversion more than 97% at 800 °C and the activity was maintained for 100 h during the reaction. On the contrary, Ni–Ce–ZrO2 having tetragonal phase (Ce0.8Zr0.2O2) or mixed oxide phase (Ce0.5Zr0.5O2) deactivated during the reaction due to carbon formation. The enhanced catalytic performance of co-precipitated catalyst is attributed to a combination effect of nano-crystalline nature of cubic Ce0.8Zr0.2O2 support and the finely dispersed nano size NiO x crystallites, resulting in the intimate contact between Ni and Ce0.8Zr0.2O2 particles. The Ni/Ce–ZrO2/θ–Al2O3 also exhibited high catalytic activity during CDR with a synthesis gas conversion more than 97% at 800 °C without significant deactivation for more than 40 h. The high stability of the catalyst is mainly ascribed to the beneficial pre-coating of Ce–ZrO2 resulting in the existence of stable NiO x species, a strong interaction between Ni and the support, and an abundance of mobile oxygen species in itself. TPR results further confirmed that NiO x formation was more favorable than NiO or NiAl2O4 formation and further results suggested the existence of strong metal-support interaction (SMSI) between Ni and the support. Some of the important factors to optimize the CDR of methane such as reaction temperature, space velocity, feed CO2/CH4 ratio and H2O and/or O2 addition were also examined.  相似文献   

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