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CuO/CeO2 catalysts were widely studied as an alternative to precious metal catalysts, and the Cu–Ce synergy was essential to improve the catalytic performance. In this paper, the effects of CuO loading on Cu–Ce synergy in CuO/CeO2 nanorod catalysts and their performance in toluene combustion were systematically investigated. It was found that non-equilibrium plasma facilitated the dispersion of CuO active species on the CeO2 surface. With the increase of the CuO loading from 1 wt% to 4 wt%, the Cu–Ce synergistic effect was gradually improved, which generated Cu+/Cu2+ and Ce3+/Ce4+ redox electron pairs. The highest oxygen vacancy concentration and Cu+ content of CuCe-4 (4 wt%) resulting from strong Cu–Ce synergy accelerated the activation of chemisorbed oxygen and consequently improved the efficiency of toluene catalytic combustion. [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]

Graphical abstract Highlights • The catalytic self-sustained combustion of toluene was successfully developed. • CuCeZr/TiO 2 catalyst showed the excellent performance in self-sustained combustion. • TPO in N 2 atmosphere was used to investigate the role of lattice oxygen in toluene combustion. Abstract The catalytic self-sustained combustion of toluene over Cu x Mn 1-x Ce 0.75 Zr 0.25 /TiO 2 catalysts (x = 1, 0.5, 0) was studied in a microscale combustor. The catalytic activity is determined not only by the temperature with toluene conversion of 90% (T co), but also by the corresponding lean-combustion limits. It was found that the self-sustained combustion was achieved successfully over the catalysts, with the toluene concentrations of 0.35 con.%, 0.50 con.% and 1.00 con.%. According to T co, the activity decreased in the order of CuCe 0.75 Zr 0.25 /TiO 2 (234 °C)＞Cu 0.5 Mn 0.5 Ce 0.75 Zr 0.25 /TiO 2 (238 °C) ＞MnCe 0.75 Zr 0.25 /TiO 2 (284 °C). The excellent activity of CuCe 0.75 Zr 0.25 /TiO 2 catalyst could be ascribed to the high content of active lattice oxygen, good low-temperature reducibility and homogeneous dispersion, combined with the results of H 2 -TPR, O 2 -TPD and XPS. Furthermore, the results of in-situ DRIFT and temperature-programmed oxidation (TPO) of toluene in N 2 atmosphere suggested that toluene was adsorbed on the catalyst surface by removing α-H from methyl and combining with active oxygen specie to form benzyl group, which was finally oxidized into CO 2 and H 2 O with lattice oxygen. [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]