Search

CO self-sustaining combustion, induced by a CuCe0.75Zr0.25Oy catalyst, has been confirmed experimentally as an effective strategy to reduce serious environmental pollution and energy waste, which is caused by direct combustion of conventional converter gas in the steelmaking industry. In this paper, the effects of CuCe0.75Zr0.25Oy catalysts prepared by a sol-gel method via three different pore-forming agents (oxalic acid, cellulose and thermal decomposition) were investigated for their catalytic activity of self-sustained CO combustion. Additionally, characterization methods were used to obtain the structural properties of each catalyst. The results obtained show that the CuCe0.75Zr0.25Oy catalyst, as a sol-gel pore-forming agent, prepared from cellulose exhibits the highest activity among the three catalysts. Under the condition of a reaction gas (3% CO+5% O2/N2), the T10 (70°C), T50 (73°C) and T90 (78°C) of the cellulose catalyst are obviously lower than those of the other catalysts, where T10, T50 and T90 denote the reaction temperature corresponding to the CO conversion of 10%, 50% and 90%, respectively. The reason is that the cellulose pore-forming agent promotes the formation of a multistage porous structure, which strengthens the synergistic effect between the Cu and Ce catalysts and changes the redox property of the overall catalyst. On the one hand, the strong synergy between CuO and CeO2 adjusts the dispersion and chemical state of copper nanoparticles. On the other hand, the oxygen vacancies generated locate at the copper-cerium interface enhance the ability of oxygen storage and oxygen release of the catalyst. [ABSTRACT FROM AUTHOR]

Glucose-free and glucose-containing LaCoO3(-G), La0.9Sr0.1CoO3(-G), and La0.9Ce0.1CoO3(-G) perovskite catalysts were synthesized via the sol–gel method, over which the oxidation performance of high-concentration CO was investigated. The experimental results indicate that the catalytic activity can be improved by facilely adding glucose during the preparation where glucose creates a reducing atmosphere and takes away the oxygen atoms of perovskites to form more oxygen vacancies and Co3+. CO self-sustained combustion is favorably achieved and La0.9Ce0.1CoO3-G shows the best catalytic performance. Combining the XPS, H2-TPR, O2-TPD and CO-TPD results, the outstanding performance of La0.9Ce0.1CoO3-G is mainly ascribed to the relatively higher concentrations of Co3+, Ce3+ and oxygen vacancies. The reaction was found to follow the Langmuir–Hinshelwood (L–H) mechanism by in situ IR spectroscopy and kinetic results. Furthermore, La0.9Ce0.1CoO3-G exhibits good high-temperature durability with unchanged CO conversion of 100% at 760 °C. It is suggested that the addition of glucose and the impregnation of Sr or Ce in perovskites is a feasible strategy to design industrial catalysts for CO self-sustained combustion. [ABSTRACT FROM AUTHOR]

The Cu/ZSM-5, Ce/ZSM-5 and Cu-Ce/ZSM-5 catalysts were prepared and characterized in this investigation and the catalytic activity of carbon monoxide (CO) combustion under these catalysts was determined by temperature-programmed oxidation. The activity for the CO combustion follows the decreasing order: Cu-Ce/ZSM-5 > Cu/ZSM-5 > Ce/ZSM-5, indicated by lower ignition, light-off, extinction temperature and broader hysteresis determined via both heating and cooling feeding process. The CO adsorbed on the copper sites to form Cu + –CO complexes, monodentate and bidentate carbonates was considered to be the crucial step for CO catalytic combustion. At the CO concentration ≥5 vol.%, the CO self-sustained combustion was achieved over the Cu-Ce/ZSM-5 catalyst. One reason is due to formation of Cu 2+ ions incorporated into cerium oxides, which are more reducible than the copper clusters, minicrystals and bulk CuO particles. Another reason is attributable to the formation of Ce 4+ /Ce 3+ redox couple, which facilitates oxygen transport on the catalyst surface. [ABSTRACT FROM AUTHOR]

Abstract: Zirconium doped Cu/ZSM-5 catalysts were prepared and characterized in this investigation. Catalytic activity during soot combustion was determined in both O2/He and NO/O2/He atmospheres by temperature-programmed oxidation. The use of zirconium reduces the temperature of maximum soot oxidation rate by 229°C in O2/He atmosphere and 270°C in NO/O2/He atmosphere. The promoting effect of zirconium is discussed in terms of surface dispersion, enrichment of active components, and creation of oxygen vacancies where molecular oxygen or NO x is adsorbed forming basic surface oxygen species active for soot oxidation. The NO2 formed at the copper–zirconium interface sites leads to the ignition temperature being significantly decreased to 93°C, which is inside the exhaust temperature range of diesel engines. To understand the combustion reaction kinetics, the activation energy and reaction order of soot combustion were evaluated. According to the Redhead method, the activation energy for non-catalyzed reaction is 164kJ/mol under the O2/He atmosphere. For the Cu/ZSM-5 and Cu–Zr/ZSM-5, the activation energies under the O2/He atmosphere (134–151kJ/mol) are slightly higher than those under the NO/O2/He atmosphere (128–135kJ/mol). The Freeman–Carroll method is suitable to describe the soot combustion in the NO/O2/He atmosphere, with the activation energies for the catalysts in the range of 97–112kJ/mol and the average value of reaction order equal to 1.36. [Copyright &y& Elsevier]

La 1− x Ce x Mn 1− y Co y O 3 catalysts were prepared by the “glucose method”. The structures and physico-chemical properties for these catalysts were characterized using X-ray diffraction (XRD), nitrogen adsorption, scanning electron microscopy (SEM), Fourier transform infrared spectra (FT-IR), H 2 -temperature-programmed reduction (H 2 -TPR) and O 2 -tempreature-programmed desorption (O 2 -TPD). Results showed that cerium substitution at the A-site in LaMnO 3 produced a CeO 2 phase. The cobalt can be introduced into the B-site in La 0.8 Ce 0.2 MnO 3 at any substitution ratio because of the similar ionic radii between cobalt and manganese. The catalytic activity for soot combustion in air was evaluated using a TG/DTA analyzer. Cerium substitution at A-site enhances the catalytic activity, while cobalt substitution at B-site inhibits the catalytic activity. The activation energy for soot combustion was calculated using the Horowitz method. The activation energy for non-catalytic soot combustion was 164.1 kJ mol − 1 . The addition of catalysts decreased the activation energy by about 26–63 kJ mol − 1 . Among the applied catalysts, Ce20Mn exhibited the lowest activation energy (101.1 kJ mol − 1 ). [ABSTRACT FROM AUTHOR]

Self-sustained catalytic combustion is a sustainable approach to deal with exhaust gas with high concentration CO, and revealing its reaction process is necessary and challenging. Herein, cube (Cu 2 O-C), octahedron (Cu 2 O-O) and dodecahedron (Cu 2 O-D) exposing different crystal planes were used to explore the catalytic combustion mechanism. The catalytic combustion can be self-sustained on the Cu 2 O surface and the activities decrease in the order of Cu 2 O-O > Cu 2 O-D > Cu 2 O-C, contributing to the different exposing planes with (1 1 1), (1 1 0) and (1 0 0), respectively. In-situ DRIFTS results prove that the catalytic combustion of CO to CO 2 on Cu 2 O is prone to follow the MvK mechanism. Comparing with Cu 2 O-D and Cu 2 O-C, the relatively open surface of Cu 2 O-O plane composed of unsaturated copper and oxygen atoms facilitates the CO adsorption on Cu (I) and the mobility of lattice oxygen, leading to the highest low temperature reducibility and catalytic activity. [Display omitted] • CO self-sustained catalytic combustion were achieved on cube, octahedron and dodecahedron Cu 2 O. • Octahedron Cu 2 O with (1 1 1) planes exhibits the best activity for high concentration CO. • Coordination unsaturated Cu and O on the (111) and (110) planes promote CO oxidation. • Catalytic combustion reaction of CO on Cu 2 O mainly follows the MvK mechanism. [ABSTRACT FROM AUTHOR]

Cubic Cu 2 O micro/nanocrystals were successfully synthesized by liquid-phase reduction using copper salt of CuSO 4 or CuCl 2 ·2H 2 O, and glucose or ascorbic acid as reducing agent, respectively. The activity of the catalysts was evaluated by light-off curves of CO self-sustained catalytic combustion via temperature-programmed oxidation of CO (CO-TPO), with the results showing the activity of catalysts following the order of Cu 2 O–Cl-GLU > Cu 2 O– S -GLU > Cu 2 O– S -AA > Cu 2 O–Cl-AA, (Cl denotes CuCl 2 ·2H 2 O, GLU denotes glucose, S denotes CuSO 4 and AA denotes ascorbic acid, respectively), corresponding to the ignition temperature of 109 °C, 122 °C, 137 °C and 186 °C, respectively. The crystal structure, elemental valence, morphology and redox property of the prepared catalysts were analyzed by using various characterization techniques. Combined with in situ infrared spectrum, the CO self-sustained catalytic combustion over Cu 2 O catalysts mainly follows the Mars-van-Krevelen (M-v-K) mechanism: the adsorbed and activated CO reacts with lattice oxygen to yield CO 2 and oxygen vacancy, and then the oxygen vacancy can be replenished by gaseous oxygen. Combined with catalytic performance of high-concentration CO, it is found that the catalysts prepared using glucose as reducing agent are more angular compared with ascorbic acid. The Cu 2 O–Cl-GLU synthesized with glucose and CuCl 2 ·2H 2 O exhibits the best catalytic activity among all the catalysts tested, attributing to its more obvious edge and rough crystal surface. The unique structure of Cu 2 O–Cl-GLU leads to the high exposure rate and coordination unsaturation of atoms on the cubic Cu 2 O micro/nanocrystals that can improve the ability of activating gaseous O 2 and low temperature reducibility, and consequently facilitating the catalytic activity. Cycle path diagram of CO oxidation reaction (a) and schematic diagram of CO oxidation reaction on Cu 2 O (b). [Display omitted] • Effects of reducing agent on catalytic properties is greater than that of copper salt. • High concentration CO can achieve self-sustained catalytic combustion on obtained Cu 2 O. • Glucose enhances unsaturation of Cu atoms contributing to high activity. • Chemically adsorbed oxygen on Cu 2 O surface promotes CO ignition. [ABSTRACT FROM AUTHOR]

A generaland efficient Pd/sulfoxide-phosphine complex-catalyzeddirect asymmetric N-allylic alkylation of indoleshas been developed to allow for the preparation of various N-allylated indoles in generally good yields with excellentenantioselectivities. This catalytic system could also be extendedto other N-containing heterocycles with good results. [ABSTRACT FROM AUTHOR]

The reaction pathways of CO oxidation over the (1 0 0), (1 1 0) and (1 1 1) crystal planes of Cu 2 O. • Morphologies of Cu 2 O micro/nanocrystals were controlled by simply changing precursor concentration. • Increase of precursor concentration results in more exposure of active crystal plane of Cu 2 O. • Activity of CO self-sustained catalytic combustion on Cu 2 O increases with precursor concentration. • Coordination unsaturated Cu and O on the (1 1 1) and (1 1 0) planes promote CO oxidation. The self-sustained catalytic combustion is one of the most effective ways to remove high concentration CO at low temperature. In this paper, Cu 2 O micro/nanocrystals with different morphologies were successfully synthesized by changing the precursor concentration using liquid phase reduction method. The obtained Cu 2 O were characterized using SEM, XRD, XPS, H 2 -TPR and O 2 -TPD, and the relationship between the catalytic performance and morphology was analyzed based on CO-TPD-MS and activity evaluation results. It was found that high precursor concentration leads to more exposure of active crystal planes of Cu 2 O. Compared with Cu 2 O-1 exposing only (1 0 0) crystal planes, Cu 2 O-5, the precursor concentration of which is 5 times of Cu 2 O-1, exposes (1 0 0) and (1 1 0) crystal planes. Cu 2 O-9, with 9 times of precursor concentration of Cu 2 O-1, exposes (1 0 0), (1 1 0) and (1 1 1) crystal planes simultaneously. All the obtained Cu 2 O with different precursor concentrations can achieve self-sustained CO catalytic combustion, and the catalytic activity increases with increasing precursor concentration (Cu 2 O-1 < Cu 2 O-5 < Cu 2 O-9). The results prove that unsaturated coordination of Cu and O on the (1 1 1) and (1 1 0) planes can enhance the corresponding reducibility, adsorption and activation of gaseous oxygen, consequently promoting the CO oxidation to CO 2 over Cu 2 O-9. [ABSTRACT FROM AUTHOR]