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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]

This study focuses on the variation in activity-controlling factors during CO catalytic ignition over a CuO–CeO 2 catalyst. The activity for CO combustion follows the decreasing order of CuO–CeO 2 > CuO > CeO 2. Except for inactive CeO 2 , increasing temperature induces CO ignition to achieve self-sustained combustion over CuO and CuO–CeO 2. However, CuO provides enough copper sites to adsorb CO, and abundant active lattice oxygen, thus obtaining a higher hot zone temperature (208.3°C) than that of CuO–CeO 2 (197.3 °C). Catalytic ignition triggers a kinetic transition from the low-rate steady-state regime to a high-rate steady-state regime. During the induction process, Raman, X-ray photoelectron spectroscopy (XPS), CO temperature-programmed desorption (CO-TPD) and infrared (IR) spectroscopy results suggested that CO is preferentially adsorbed on oxygen vacancies (Cu+-[O v ]-Ce3+) to yield Cu+-[C O]-Ce3+ complexes. Because of the self-poisoning of CO, the adsorbed CO and traces of adsorbed oxygen react at a relative rate, which is entirely governed by the kinetics on the CO-covered surface and the heat transport until the pre-ignition regime. Nonetheless, the Cu+-[C O]-Ce3+ complex is a major contributor to CO ignition. The step-response runs and kinetic models testified that after ignition, a kinetic phase transition occurs from a CO-covered surface to an active lattice oxygen-covered surface. During CO self-sustained combustion, the rapid gas diffusivity and mass transfer is beneficial for handling the low coverage of CO. The active lattice oxygen of CuO takes part in CO oxidation. [ABSTRACT FROM AUTHOR]

Abstract The self-sustained combustion of carbon monoxide (CO) has been studied over the CuCe 0.75 Zr 0.25 O δ catalyst by sol–gel method, and compared with the CuCe 0.75 Zr 0.25 O δ (H) and Ce 0.75 Zr 0.25 O δ to investigate sensitivity of different active sites, such as dispersed CuO, Cu–Ce and Ce–Zr solid solution. The CuCe 0.75 Zr 0.25 O δ (H) is obtained via CuCe 0.75 Zr 0.25 O δ sonicated in nitric acid to remove surficial CuO species, and the Ce 0.75 Zr 0.25 O δ is prepared as the reference catalyst. Using the temperature programmed oxidation of CO together with an infrared camera (CO-TPO + FLIR), the catalytic activity for CO self-sustained combustion is determined not only by the ignition temperatures, following the decreasing order CuCe 0.75 Zr 0.25 O δ (81 °C) > CuCe 0.75 Zr 0.25 O δ (H) (131 °C) > Ce 0.75 Zr 0.25 O δ (167 °C) at the flow rate of 200 mL/min, but also by corresponding limits of lean combustion (equivalence ratio Φ) of 0.06–0.09, 0.10–0.13, 0.24–0.37, respectively, under the flow rate of 100–1000 mL/min. The M-K mechanism, in which adsorbed CO reacts with lattice oxygen, is crucial for all the catalysts via temperature programmed surficial reaction and in situ infrared analysis (TPSR + DRIFT). The sensitivity of active sites as follows: well-dispersed CuO > Cu–Ce solid solution > Ce–Zr solid solution. As rate-determining step for CO self-sustained combustion, CO is preferentially adsorbed on surficial dispersed CuO to yield carbonyls, and then the carbonyls interact with lattice oxygen to form CO 2 release. CO is secondly adsorbed on the surficial oxygen of copper and cerium sites in solid solution to yield carbonates. The carbonates formed are more stable and thus CO 2 is produced at the lower rate than carbonyls, indicating that the solid solution is less active than dispersed CuO. Exposed Ce3+ favors to form vacancies on the Cu–Ce solid solution surface, which is beneficial to adsorbing both CO and O 2 , thus presenting the higher activity than Ce–Zr solid solution. [ABSTRACT FROM AUTHOR]

The self-sustained combustion of CO was studied over a series of CuCe1–xZrxOy/ZSM-5 catalysts with different Ce/Zr molar ratios to evaluate the correlation of their structural characteristics with catalytic performance. The obtained results demonstrated that the activity of the cerium-containing catalysts was much higher than that of the CuZr1/Z, with the activity of CO combustion following the order: CuZr1/Z < CuCe0.25Zr0.75/Z < CuCe0.5Zr0.5/Z < CuCe1/Z < CuCe0.75Zr0.25Z. After cerium addition, the cerium-zirconium mixed oxides formed promoted the copper species well dispersed on the catalyst surface. The high activities of cerium-containing catalysts were closely related to the synergetic effects among the copper, cerium, and zirconium species, as the surface copper species provided sites for CO adsorption and the cerium-zirconium mixed oxides promote the activation of oxygen. The activities were probably also attributed to some copper species present as substitutional defects in the ceria lattice, which were more reducible than the copper clusters, minicrystals, and bulk CuO particles. The CuCe0.75Zr0.25/Z possessed excellent redox capacity, adsorption/activation properties for O and CO species, and therefore induced a self-sustained combustion of CO at the lowest temperature than that of other CuCe1-xZrxOy/ZSM-5 catalysts. [ABSTRACT FROM PUBLISHER]

This paper presents the results of a study of self-sustained catalytic combustion of CO ignited by dielectric barrier discharge (DBD) using Ce 0.5 Zr 0.5 O y /TiO 2 (CeZr/Ti), CuZr 0.25 O y /TiO 2 (CuZr/Ti), and CuCe 0.75 Zr 0.25 O y /TiO 2 (CuCeZr/Ti) catalysts. DBD excites and dissociates some of the reactant molecules in the gas phase. These are more easily adsorbed on the catalyst surface than are ground-state species, therefore induction begins at a lower background temperature than in thermal catalysis. CO is adsorbed on copper sites, therefore CeZr/Ti is inactive in CO ignition, but CuZr/Ti and CuCeZr/Ti achieve DBD ignition at 34 and 44 s, respectively, at a specific energy density (SED) of 1500 J/L. CO catalytic ignition by DBD involves two steps. The induction process is dominated by plasma catalysis. At the same SEDs, induction with CuCeZr/Ti begins earlier than those with CuZr/Ti, in good agreement with the reducibilities and oxygen-transfer properties of these catalysts. The ignition process is governed by thermal catalysis because the enhancement of external diffusion induced by increasing the temperature improves the reaction rate. CuZr/Ti provided more CO adsorption sites than did CuCeZr/Ti, contributing to shortening of the ignition delay. [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]

Self-sustained catalytic combustion is a promising strategy to remove CO from the off-gas produced during steelmaking, where the potential catalysts are bulk copper-cerium-zirconium mixed oxides or those supported on TiO 2 or ZSM-5 substrates. In this study, the effects of the catalyst support on the CO catalytic ignition performance and reaction pathways were investigated by FTIR coupled with a novel in-situ cell, together with the state-of-the-art characterization techniques. The Infrared (IR) transmission cell equipped with a magnetically driven system, could effectively prevent overlaps between active intermediate peaks (Cu+-CO and Cu+(CO) 2) and gaseous CO peaks. The Cu+ cations located at the phase interface are the main active sites. The Cu and Ce interactions lead to the formation of solid solutions of CuCe 0.75 Zr 0.25 O δ (CuCeZr). The monocarbonyls [Cu+-CO] are the dominant species during CO oxidation, and the vacancies in the solid solutions are occupied by oxygen, accelerating the oxygen cycle. The TiO 2 or ZSM-5 supports promote copper dispersion over CuCe 0.75 Zr 0.25 O δ /TiO 2 (CuCeZr/T) and CuCe 0.75 Zr 0.25 O δ /ZSM-5 (CuCeZr/Z) catalysts, which can be attributed to their high surface areas (168.2 and 346.3 m2/g, respectively), while the Cu-Ce interactions are less relevant. Hence, CO oxidation mainly occurs at the phase interface between copper oxide and TiO 2 /ZSM-5. Dicarbonyls [Cu+(CO) 2 ] are the main intermediates for the CuCeZr/T and CuCeZr/Z catalysts, and the Cu2+ species are reduced to form dicarbonyls that also take part in the oxidation process. Although a well copper dispersion enhances the activity of individual copper sites on the CuCeZr/T and CuCeZr/Z catalysts, considering the redshift of the carbonyl bands and the increase in CO adsorption, the close interactions and high contents of Cu and Ce favor the local accumulation of heat and mass transfer over bulk CuCeZr, leading to the ignition of CO at low temperatures. [Display omitted] • CuCe 0.75 Zr 0.25 O δ and CuCe 0.75 Zr 0.25 O δ /TiO 2 and CuCe 0.75 Zr 0.25 O δ /ZSM-5 catalysts were designed. • The structure-activity relationship was obtained. • The self-sustained combustion and stability limit of CO were carried out. • The in-situ IR with a novel magnetically driven IR cell was designed and performed. • The intermediate species and reaction pathways over different catalysts were evidenced. [ABSTRACT FROM AUTHOR]

Catalytic oxidation technology is a promising strategy to eliminate carbon monoxide (CO), volatile organic compounds (VOC) and other emissions from industrial boilers and to address ammonia (NH 3) escape. Herein, we demonstrate the potential of copper-cerium-zirconium mixed oxides or those supported on TiO 2 or ZSM-5 substrates for the simultaneous catalytic removal of CO, toluene and NH 3. Among them, CuCeZr/ZSM-5 exhibits the best co-processing ability for mixed gases. In situ infrared spectroscopy analyses suggest that there is a competitive adsorption among CO, toluene and NH 3 , and the inhibition is in descending order of toluene＞CO＞NH 3. Based on the physical-chemical characterizations, the Cu-Ce interfacial structure plays an important role in CO ignition at low temperatures. More importantly, the abundant acidic sites on the ZSM-5 support can improve the stability of adsorbed NH 3 at high temperatures, resulting in the best NH 3 catalytic oxidation performance of CuCeZr/ZSM-5 with no secondary pollutants of NO x. This study provides a strategy for the catalyst design to eliminate multiple pollutants targeting the properties of pollutants. [Display omitted] • Simultaneous removal of CO, toluene and NH 3 was achieved by CuCeZr based catalyst. • The best mixed gas treatment was observed for CuCeZr/ZSM-5 catalyst. • Cu-Ce interfacial structure allows preferential ignition of CO at low temperature. • The acidic sites on the ZSM-5 promoted the adsorption and oxidation of NH 3. [ABSTRACT FROM AUTHOR]

CO self-sustaining catalytic combustion tends to be one of potential means to achieve efficient conversion of off-gases from steelmaking. Building model catalysts to investigate the reaction process academically is essential to design optimized catalysts and Cu 2 O exposing (1 0 0), (1 1 1) and (1 1 0) planes are excellent materials. Herein, morphological CeO 2 /Cu 2 O inverse model catalysts were synthesized to reveal the synergistic effect and reaction mechanism. It is demonstrated that the ignition temperature is lowered on the interface by synergistic effect, which dominates the ignition, while the combustion after ignition is controlled by Cu 2 O planes providing abundant lattice oxygen to react with CO. Additionally, exposure of different planes plays a significant role in the reaction since O-termination on (1 0 0) inhibits the interaction, whereas Cu-termination on (1 1 0) surface structure and coordinately unsaturated Cu+ on open (1 1 1) surface respectively contribute to their superior catalytic performance. [Display omitted] ● Inverse model CeO 2 /Cu 2 O catalysts with regular morphology were successfully prepared. ● Synergistic effect on Cu-Ce interface lowered ignition temperature, dominating the ignition. ● The catalytic activity and synergistic effect vary among planes with (1 1 1) performing the best. ● Exposure of crystal planes with higher activity assists in designing optimized catalysts. [ABSTRACT FROM AUTHOR]

Chemical looping combustion (CLC) and catalytic combustion (CC), which are potential technologies to promote CO→CO 2 efficient conversion and energy conservation for the steelmaking off-gas, are investigated in reaction activity, structure evolution catalysts/oxygen carriers (OCs) and energy recovery using Cu/CeO 2 materials. Activity results suggest that the rod-shaped samples with well-defined (100) crystal faces exhibit higher activity than the sphere-shaped samples with (111) crystal faces, obtaining the optimized copper content of 3 wt%. IR spectra confirmed the proposed reaction pathway that the CO adsorbed on copper sites (Cu+–CO) at the Cu–Ce interface reacts with adjacent surface lattice oxygen. The gaseous oxygen continuously migrates to the external surface of materials, thus resulting in strongly exothermic CO self-sustained combustion during CC. Such a violent reaction does not cause obvious evolution of chemical composition, crystalline phase and structure. Since the active lattice oxygen is gradually consumed but not replenished by external gaseous O 2 in time, CO combustion is not self-sustained during CLC. Therefore, the reduction cycle is no longer confined to the surface of the material but penetrates deep into its body, which accelerates Cu+ enrichment at the surface and leads to irreversible sintering and agglomeration of the material. • The activity of nanorod and nanosphere Cu/CeO 2 was compared. • CLC reaction is more exergy efficiency when burning. • The reason of catalyst deactivation in CLC was investigated. • The migration of active oxygen species in CC and CLC was compared. [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]

• The LMO-W, LMO-SW, LCMO-W, LCMO-SW, LSMO-W and LSMO-SW catalysts were well designed by precursors. • The Binary search was used to determine the lean-combustion limits for the self-sustained combustion of CO. • The stability of the LCMO-SW catalyst was evaluated under CO oxidation at the furnace temperature of 535 °C. • The influence mechanism of self-sustaining combustion stability of CO catalyst was investigated and put forward. • The L-H mechanisms were performed for SCR reaction over the catalysts via in situ IR experiments. The LaMnO 3 , La 0.9 Ce 0.1 MnO 3 and La 0.9 Sr 0.1 MnO 3 catalysts are synthesized using sugar agent, and the CO self-sustained combustion is investigated, where the catalytic performance is decided by temperature with CO conversions of 10% (T 10), 50% (T 50), and 90% (T 90). The results show that self-sustaining combustion is successfully realized on the catalyst, and the order of activity decrease is as follows: La 0.9 Ce 0.1 MnO 3 (with sugar) > La 0.9 Sr 0.1 MnO 3 (with sugar) > LaMnO 3 (with sugar) > LaMnO 3 (without sugar) > La 0.9 Sr 0.1 MnO 3 (without sugar) > La 0.9 Ce 0.1 MnO 3 (without sugar). Combined with the results of XPS, H 2 -TPR, O 2 -TPD and CO-TPD techniques, the excellent activity of La 0.9 Ce 0.1 MnO 3 (with sugar) can be attributed to the high content of Mn4+ ions and reactive oxygen vacancies enriched on the catalyst surface, sound low-temperature reduction, and uniform dispersion. Besides, in situ IR spectroscopy results indicate that the catalytic combustion of CO over manganese-based perovskite catalysts follows the L-H mechanism: the chemisorption of CO and O 2 takes place to produce monodentate carbonates and bicarbonate species, which then decompose to yield CO 2 release. The high-temperature stability test provides evidence that the La 0.9 Ce 0.1 MnO 3 (with sugar) gives 100% CO conversion and that the activities remain almost unchanged after reaction for 12 h, where the temperature of catalyst bed reaches about 717 °C. The results obtained are helpful to accept this technology on efficient and clean energy utilization in iron and steel industry. [ABSTRACT FROM AUTHOR]

• The powder sample is well designed and coated on the HC tube to form CuCe 0.75 Zr 0.25 O δ /HC catalyst. • The transient changes and two-dimensional temperature region are obtained for CO self-combustion via CO-TPO + FLIR. • The various intermediate species and competitive adsorption of reactants on different active sites are evidenced. • The different pathways and roles of M-K and L-H mechanisms are proposed using in situ IR. A CuCe 0.75 Zr 0.25 O δ catalyst was prepared by the sol-gel method and successfully coated on honeycomb ceramic (HC) carrier. The activity of CuCe 0.75 Zr 0.25 O δ /HC was determined by the CO-TPO + FLIR, with the results performing that the critical condition for CO self-sustained combustion is 3 vol% CO + 3 vol% O 2 /N 2 at 0.5 L/min. As the CO concentration increases from 1 vol% CO to 3 vol% CO, the induction process (T 15) shifts to rapid ignition with a transient change for the CO oxidation reaction. The furnace temperature for CO self-sustained combustion decreases with increasing the CO and O 2 concentrations. Upon increasing the CO 2 concentration, however, furnace temperature is needed to increase and realize CO complete conversion. The thermal stability test combined with SEM + EDX results indicate that the CuCe 0.75 Zr 0.25 O δ /HC retains an excellent thermal stability after a 200 h, and the high-temperature region remains at 225 ± 1 °C during the CO self-combustion reaction. The activity of catalyst is reduced slightly after the 200 h test because of the carbon deposition on the catalyst surface, but such a slight deactivation can be eliminated by the air oxidation method. In situ IR results show a competitive adsorption of CO/O 2 and CO 2 on the Cu-Ce active sites, indicating that the addition of gaseous CO 2 performs an inhibition of CO oxidation. CO preferentially adsorbs linearly at Cu+ sites to form carbonyls that react with lattice oxygen to produce CO 2 to release, which can be ascribed to M-K mechanism. The L-H mechanism is less important, which involves the relatively weak reaction of adsorbed CO and adsorbed oxygen on the Cu-Ce active sites to form carbonate species. [ABSTRACT FROM AUTHOR]