Dielectric barrier discharge plasma synthesis of Ag/γ-Al_(2)O_(3) catalysts for catalytic oxidation of CO

In this study,Ag/γ-Al_(2)O_(3)catalysts were synthesized by an Ar dielectric barrier discharge plasma using silver nitrate as the Ag source andγ-alumina(γ-Al_(2)O_(3))as the support.It is revealed that plasma can reduce silver ions to generate crystalline silver nanoparticles(Ag NPs)of good dispersion and uniformity on the alumina surface,leading to the formation of Ag/γ-Al_(2)O_(3)catalysts in a green manner without traditional chemical reductants.Ag/γ-Al_(2)O_(3)exhibited good catalytic activity and stability in CO oxidation reactions,and the activity increased with increase in the Ag content.For catalysts with more than 2 wt%Ag,100%CO conversion can be achieved at 300°C.The catalytic activity of the Ag/γ-Al_(2)O_(3)catalysts is also closely related to the size of theγ-alumina,where Ag/nano-γ-Al_(2)O_(3)catalysts demonstrate better performance than Ag/micro-γ-Al_(2)O_(3)catalysts with the same Ag content.In addition,the catalytic properties of plasma-generated Ag/nano-γ-Al_(2)O_(3)(Ag/γ-Al_(2)O_(3)-P)catalysts were compared with those of Ag/nano-γ-Al_(2)O_(3)catalysts prepared by the traditional calcination approach(Ag/γ-Al_(2)O_(3)-C),with the plasma-generated samples demonstrating better overall performance.This simple,rapid and green plasma process is considered to be applicable for the synthesis of diverse noble metal-based catalysts.

MOLECULAR BEAM STUDIES ON OXIDATION OF CO ON Pd WITH DIFFERENT MIXED RATIOS OF P_(CO) TO P_(O2) ~*

Here some steady-state experiments on oxidation of CO on Pd were performed on a molecular beam apparatus. It is found that the characteristics of the rate of CO_2 formation r versus substrate temperature T are dependent on the ratio P=P_(CO)/P_(O2) in the mixed beam. These characteristics are related to the complicated interactions of co-adsorbed CO and O particles on Pd surface.

Changes in active functional groups during low-temperature oxidation of coal

Using Fourier Transform Infrared (FTIR) combined with an adiabatic oxidation test, temperature-programmed oxidation and gas analysis, we studied the changes of active functional groups during low-temperature oxidation of lignite, gas coal, fat coal and anthracite. During slow low-temperature heat accumulation, aliphatic hydrocarbons, such as methyl and methylene, are attacked by oxygen atoms absorbed by pores on coal surfaces, generating unstable solid intermediate carbon-oxygen complexes, which then decompose into gaseous products (CO, CO2) and stable solid complexes. At the accelerated oxidation stage, the stable complexes begin to decompose in large amounts and provided new active sites for further oxidation, while the aliphatic structures gained energy and fell from the benzene rings to produce CxHy and H2.

Preferential oxidation of CO in excess H_2 over CeO_2/CuO catalyst:Effect of calcination temperature

Different from the classical configuration CuO/CeO2 catalyst,the inverse configuration CeO2 /CuO catalyst （atomic ratio of Ce/Cu=10/100） was prepared by impregnation method.Five calcination temperatures were selected to investigate the interaction between CeO2 and CuO support.It is found that as calcination temperature increased from 500 to 900 C,sintering of CeO2 particles on the support occurred together with the diffusion of a portion of Ce 4＋ ions into CuO crystals,forming solid solution.Formation of interface complex Ce-O-Cu was suggested by TPR measurements.The catalyst calcined at 700 C gives the highest activity for preferential oxidation of CO in excess H2 stream.

Influence of preparation methods on CuO-CeO_2 catalysts in the preferential oxidation of CO in excess hydrogen

Influence of three different preparation methods, i.e. impregnation, coprecipitation, and inverse coprecipitation, on the preferential oxidation of CO in excess hydrogen （PROX） over CuO-CeO2 catalysts has been investigated and CuO-CeO2 catalysts are characterized using BET, XPS, XRD, UV Raman, and TPR techniques. The results show that the catalysts prepared by coprecipitation have smaller particle sizes, well-dispersed CuOx species, more oxygen vacancies, and are more active in the PROX than those prepared by the other methods. However. the inverse coprecipitation depresses the catalytic performance of CuO-CeO2 catalysts and causes the growth of CuO-CeO2 because of different pH value in the precipitation process.

Electro-Oxidation of Concentrated Ce(Ⅲ) at Carbon Felt Anode in Nitric Acid Media

Electro-oxidation of Ce （ Ⅲ ） to Ce （ Ⅳ ） in parallel plate flow type electrolyzer divided with cation exchange membrane was carried out in nitric acid media at carbon felt anode under galvanostatic conditions. Carbon felt was used as an anode for its high specific surface area and high oxygen evolution overpotential. Pt coated Ti plates were used as cathode and anode current feeder. The oxidation of 1 mol· L^-1 Ce（ Ⅲ ） solution in 2 mol· L^- 1 HNO3 was proceeding with a high current efficiency （92%） until about 80% of Ce（ Ⅲ ） was oxidized. Then, oxygen evolution, accompanied by terminal voltage jump, took place, lowering current efficiency. Ce（ Ⅲ ） was oxidized up to 90% with current efficiency of 62%. In this mode, strong carbon felt anode oxidation was observed. The wear out of carbon felt was 46% in six consequent runs （6 h of operation）. After each run, carbon felt surface had to be renewed with slightly alkaline solution to remove carbon oxidation products and ensure regular operational conditions. When anode surface was blocked, oxygen evolution took place from the beginning of electrolysis due to higher actual current density. The wear out of carbon felt anode could be minimized by means of oxygen evolution prevention. In the case when electrolysis had been stopped before oxygen evolution started （at Ce（ Ⅳ ） conversion of about 80% ）, the wear out of anode was less than 2% during 6 consequent runs （4 h of operation）.

Selective Oxidation of CO in Excess H_2 over Ru/Al_2O_3 Catalysts Modified with Metal Oxide

The Ru/Al2O3 catalysts modified with metal oxide （K20 and La2O3） were prepared v/a incipient wetness impregnation method from RuCl3.nH2O mixed with nitrate loading on Al2O3 support. The activity of catalysts was evaluated under simulative conditions for the preferential oxidation of CO （CO-PROX） from the hydrogen-rich gas streams produced by reforming gas, and the performances of catalysts were investigated by XRD and TPR. The results showed that the activity temperature of the modified catalysts Ru-K20/Al2O3 and Ru-La2O3/Al2O3 were lowered approximately 30℃ compared with pure Ru/Al2O3, and the activity temperature range was widened. The conversion of CO on Ru-K20/Al2O3 and Ru-La2O3/Al2O3 was above 99% at 140-160℃, suitable to remove CO in a hydrogen-rich gas and the selectivity of Ru-La2O3/Al2O3 was higher than that of Ru-K2O/Al2O3in the active temperature range. Slight methanation reaction was detected at 220℃ and above.

An experimental study of the effect of ionic liquids on the low temperature oxidation of coal

Fourier transform infrared spectroscopy(FTIR) and constant heating rate experiments were performed to study the low temperature oxidation of coal treated by an ionic liquid,1-allyl-3-methylimidazolium chloride.The inerting effect of the ionic liquid toward the low temperature oxidation process is discussed.The results show that:(1) The hydroxyl content associated with hydrogen bonds,the aliphatic methyl content,the methylene group content,and the ether oxygen bond content are reduced in the treated coal.At the same time the content of aromatic C@C bonds is constant but these chemical bonds weaken and some substituted aromatic hydrocarbon content increases while other types decrease.This demonstrates that(AMIm)Cl dissolves and destroys the coal surface microstructure;(2) The oxygen consumption of the treated coal is less than what is seen in raw coal.The CO,CO 2,C 2 H 4,and C 2 H 6 content from the treated coal is reduced compared to the untreated coal;(3) The apparent activation energy for the oxidizing reaction is different in the treated and raw coals.Micro-structural changes and macroscopic gas production allow us to conclude that(AMIm)Cl can effectively inhibit low temperature oxidation of coal.

Thermal Analysis of Vitamin C Affecting Low.temperature Oxidation of Coal

Simultaneous thermal analysis was used to study the influence of Vitamin C as possible chemical additive inhibiting coal oxidation process at low temperature. Some oxidation characteristics of Vitamin C affecting the coal oxidation were investigated at different heating rates. The TG-DSC data show that the impact of Vitamin C on coal oxidation process can be directly evaluated using ignition temperature and critical temperature. Comparison with the effect of water on coal oxidation shows that Vitamin C is more efficient than water. However, the blank experiment conducted with inert a-Al2O3 also suggests that Vitamin C can decompose at about 200 ℃, which limits the usage of Vitamin C on inhibiting coal oxidation.

Non-isothermal oxidation of coal with Ce(NO3)3 and Cu(NO3)2 additives

Non-isothermal oxidation of brown coal with 5 wt% of Cu(NO3)2, 5 wt% of Ce(NO3)3 and {2.5 wt% Cu(NO3)2 + 2.5 wt% Ce(NO3)3} additives was studied. The introduction of additives was carried out by an incipient wet impregnation method to ensure uniform distribution of cerium and copper nitrates within the structure of coal powdery samples (according to SEM and EDX mapping). The samples reactivity was studied in an isothermal oxidation regime at 200 °C (1 h) and by DSC/TGA at 2.5 °C/min heating rate. The additives implementation was found to reduce significantly the oxidation onset temperature (△Ti = 20-55 °C), the samples oxidation delay time (△ti= 2-22 min) and overall duration of the oxidation process (△tc = 8-16 min). The additives efficiency could be graded in accordance with the activation on the coal oxidation in the following row: Cu(NO3)2 >{Cu(NO3)2 + Ce(NO3)3}> Ce(NO3)3. According to the mass spectroscopy, the obtained row of activation correlates well with the initial temperature of the studied nitrate's decomposition (from 190 to 223 °C). A presence of nitrates was found to change significantly the trend of heat release taking place during the oxidation of coal samples (according to DSC/TGA data). The influence of coal morphology and volatiles concern in initial sample on the parameters of the oxidation process was studied as well. Activation energy (Ea) of the coal oxidation was calculated using Coats-Redfern method. Maximum decrease in Ea from 69 to 58 kJ/mol was observed for the samples with Cu(NO3)2. Graphical abstract.

Oxidation of CO on Nanometer Metal Oxides at Low Temperatures

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Influence of pH values in the preparation of CuO-CeO_2 on its catalytic performance for the preferential oxidation of CO in excess hydrogen

CuO-CeO2 catalyst prepared with co-precipitation showed high catalytic performance for the preferential oxidation of CO in excess hydrogen（PROX）.Influence of pH values in the preparation of CuO-CeO2 on its catalytic performance was investigated in this work.The CuO-CeO2 catalyst prepared at pH = 13.03 had the smallest particle size（5.4 nm）,the largest surface areas（138m 2/g） and the highest activity with CO conversion of 99.6% at 130 ℃.The CuO-CeO2 catalyst was characterized using BET,XRD and TPR techniques.The results showed that when the pH value of the mixed solution containing Cu and Ce species was properly adjusted,both the adsorption layers and diffusion layers of the formed colloidal particles in hydroxide precursor of CuO-CeO2 were modified,resulting in the better catalytic performance for PROX on the final CuO-CeO2 catalyst

High performance CuO-CeO_2 catalysts for selective oxidation of CO in excess hydrogen:Effect of hydrothermal preparation conditions

High performance CuO-CeO2 catalysts for selective oxidation of CO in excess hydrogen were prepared by a hydrothermal method under different preparation conditions and evaluated for catalytic activities and selectivities. By changing the ^nCTAB/^nCe ratio and hydrothermal aging time, the catalytic activity of the CuO-CeO2 catalysts increased and the operating temperature window, in which the CO conversion was higher than 99%, was widened. XRD results showed no peaks of CuOx species and Cu-Ce-O solid solution were observed. On the other hand, Cu＋ species in the CuO-CeO2 catalysts, which was associated with a strong interaction between copper oxide clusters and cerium oxide and could be favorable for improving the selective oxidation performance of CO in excess H2, were detected by H2-TPR and XPS techniques.

Preferential Oxidation of CO in H_2 over CuO/CeO_2 Catalysts

A very active catalyst of CuO/CeO_2 was made by adsorption-impregnation method for preferential oxidation of CO in H_2. The CO conversion is close to 100% and selectivity to CO oxidation is 96% over this catalyst at a low reaction temperature of 95 ℃ and a space velocity of 40000 cm^3·g^(-1)·h^(-1) in the reaction mixture of 1%CO, 1%O_2, and 50%H_2 balanced with N_2. The effect of preparation conditions on catalytic performances was investigated. The catalytic performance of the CuO/CeO_2 catalysts was compared with that of other CO preferential oxidation catalysts reported in literature.

Preferential Oxidation of CO in Excess Hydrogen over CuO-CeO_2 Catalyst Prepared by Chelating Method

The CuO-CeO2 catalyst prepared by chelating method has a superior catalytic performance for the preferential oxidation of CO in rich hydrogen, compared with the CuO-CeO2 catalyst prepared by coprecipitation method. The CO conversions over these catalysts, at 120 ℃ and 120000 ml/（g-h） in the absence of CO2 and H2O, are 99.6% and 88.6%, respectively, and the selectivity of O2 over these catalysts is very close （i.e. 51.3% and 55.8%, respectively）. The influence of certain factors such as hydrogen concentration, carbon monoxide concentration, H2O, O2/CO ratios, and space velocity on the catalytic performance of CuO-CeO2 catalyst prepared by chelating method is also studied. The results show that the addition of hydrogen and H2O has a negative effect on the catalytic performance of CuO-CeO2 catalyst, however, the variation of space velocity and the O2/CO ratio causes a comparatively slight influence.

Synthesis of Mesoporous Cu-Mn-Al_2O_3 Materials and Their Applications to Preferential Catalytic Oxidation of CO in a Hydrogen-rich Stream

A series of mesoporous Cu-Mn-Al2O3（CMA） materials was synthesized at moderate temperature and their structures were characterized by XRD, N2 physical adsorption and TPR techniques. It was found that using metal complex ion[Cu（NH3） 4^2＋-Mn（NH3）6^2＋] as raw materials is easier to form good-structure mesoporous Cu-Mn-Al2O3 materials than using its nitrate salt [Cu（NO3）2-Mn（NO3）2]. The TPR tests results indicate that CuO and MnOx were homogeneously dispersed in the mesoporous materials. Their catalytic application to preferential catalytic oxidation of CO in a hydrogen-rich stream was studied. The activity varies in the order of CMA（1：1, molar ratio）〉 CMA（1：2）〉CMA（2：1）〉CMA（CP）〉CMA（1：0）≈CMA（0：1）. The CMA（1：0） and CMA（0：1） have lower activity compared to other samples, implying that there existed coordination effect between Cu-Mn in the samples. The selectivity varied in the order of CMA（0：1）≥CMA（1：2）〉CMA（1：1）〉CMA（2：1）〉CMA（1：0） at higher temperature （≥ 120 ℃）, indicating that increasing the Cu content enhanced the conversion of H2. The sample CMA（CP） made by coprecipitation method has a lower CO oxidation activity and selectivity than its counter-parts of mesoporous Cu-Mn-Al2O3 materials[CMA（1：2）], this attributed to the lower surface area of the former and poor interaction of CuO with MnOx.

Processing and oxidation of co-deposited Ni-Al coatings

Electrodeposited Ni matrix/Al microparticles or nanoparticles dispersed composite coatings (termed as EMCCs or ENCCs) are developed from a Ni-based electrolyte bath. The Al microparticles are in a size range of 1 -5 μm and the Al nanoparticles in an average size of 75 nm. The Al content in coatings increases with increase in the particle content in the bath. Particle size effect on the degree of codeposition is not significant. However, codeposition of Al nanoparticles instead of microparticles promotes more homogenous growth of Ni deposits on {111}, {200} and {220} planes. The oxidation at 1 050 ℃ of the as-deposited composite coatings shows that at a comparable Al content, ENCC of Ni-Al exhibits a better oxidation resistance than EMCC of Ni-Al due to the fast formation of an alumina scale during the transient stage of oxidation.

Nanosized Au Catalysts Supported on Mg(OH)₂-CeO₂for Preferential Oxidation of CO in Hydrogen Stream

Preferential oxidation of carbon monoxide in the presence of hydrogen (PROX) is a promising method to remove CO from a hydrogen-containing gas mixture. Nanosized gold catalyst supported on CeO2 and modified with Mg(OH)2 was used for preferential oxidation of carbon monoxide in hydrogen-rich stream in this study. Mg(OH)2 was added on CeO2 by incipient-wetness impregnation. Au was loaded on Mg(OH)2-CeO2 by deposition-precipitation method. PROX reaction was carried out in a continuous flow, fixed bed reactor. CO/O2 feed ratio was fixed at 1 to magnify the difference of various catalysts. The catalysts were characterized by N2 sorption, TEM, HR-TEM and XPS. Mg(OH)2 formed a thin layer on the surface of CeO2. CeO2 was in the crystalline phase and Mg(OH)2 was amorphous. Au particles were homogeneously dispersed on the support with a size of 2 - 5 nm. Using CeO2 as a support could increase the dispersion of Mg(OH)2 and thus increase the interaction between Au and Mg(OH)2. Adding Mg(OH)2 on Au/CeO2 could suppress H2 oxidation and therefore increase CO oxidation activity.

Competitive oxidation behavior of Ni-based superalloy GH4738 at extreme temperature

A high thrust-to-weight ratio poses challenges to the high-temperature performance of Ni-based superalloys. The oxidation behavior of GH4738 at extreme temperatures has been investigated by isothermal and non-isothermal experiments. As a result of the competitive diffusion of alloying elements, the oxide scale included an outermost porous oxide layer (OOL), an inner relatively dense oxide layer (IOL), and an internal oxide zone (IOZ), depending on the temperature and time. A high temperature led to the formation of large voids at the IOL/IOZ interface. At 1200℃, the continuity of the Cr-rich oxide layer in the IOL was destroyed, and thus, spallation occurred. Extension of oxidation time contributed to the size of Al-rich oxide particles with the increase in the IOZ. Based on this finding,the oxidation kinetics of GH4738 was discussed, and the corresponding oxidation behavior at 900-1100℃ was predicted.

Role of methoxy and C_(α)-based substituents in electrochemical oxidation mechanisms and bond cleavage selectivity of β-O-4 lignin model compounds

In order to better understand the specific substituent effects on the electrochemical oxidation process of β-O-4 bond, a series of methoxyphenyl type β-O-4 dimer model compounds with different localized methoxyl groups, including 2-(2-methoxyphenoxy)-1-phenylethanone, 2-(2-methoxyphenoxy)-1-phenylethanol, 2-(2-methoxyphenoxy)-1-(4-methoxyphenyl)ethanone, 2-(2-methoxyphenoxy)-1-(4-methoxyphenyl)ethanol, 2-(2,6-dimethoxyphenoxy)-1-(4-methoxyphenyl)ethanone, 2-(2,6-dimethoxyphenoxy)-1-(4-methoxyphenyl)ethanol have been selected and their electrochemical properties have been studied experimentally by cyclic voltammetry, and FT-IR spectroelectrochemistry. Combining with electrolysis products distribution analysis and density functional theory calculations, oxidation mechanisms of all six model dimers have been explored. In particular, a total effect from substituents of both para-methoxy(on the aryl ring closing to Cα) and Cα-OH on the oxidation mechanisms has been clearly observed, showing a significant selectivity on the Cα-Cβbond cleavage induced by electrochemical oxidations.