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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]

The CuMn/ZSM-5 (CM/Z), CuMn/Beta (CM/B), and CuMn/SSZ-13 (CM/S) catalyst samples were prepared via an excess impregnation method to investigate the metal-support effect. The results show that the activity at 550 °C for NO direct decomposition follows the order of CM/Z (53.4%) > CM/B (49.2%) > CM/S (7.9%). The good activity and stability of CM/Z are attributed to a strong support effect including forming more active copper sites of the (Cu2+-O2--Cu2+)2+ and (Cu+-□-Cu+)2+ dimers, which have higher redox activity, capacity of oxygen mobility, and NO sorption capability. The competitive adsorption between NO and O 2 on the oxygen vacancy of dimers over CM/Z results in the activity decrease from 53.4% to 40.3% at 550 °C after adding 1 vol% O 2. The reaction mechanism over CM/Z was discussed based on the in situ DRIFT and isotopic (18O 2) experiments. Two NO adsorbs firstly on (Cu+-□-Cu+)2+ to form N 2 O, and N 2 O is activated to produce N 2 , followed by the NO adsorption on (Cu2+-O2--Cu2+)2+ to form nitrite and nitrate species and decomposition to NO and O 2. [Display omitted] ● The support effect of ZSM-5, Beta, and SSZ-13 supported CuMn is examined. ● CuMn/ZSM-5 exhibits a high NO to N 2 conversion of 53.4% at 550 °C. ● The intermediate species and competitive adsorption of NO and O 2 are discussed. ● The reaction pathways for NO direct decomposition are proposed. [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]

• Ea of intermediate species is calculated during toluene oxidation. • Relationship between the activation energy of the overall and primitive reaction. • Transient response experiments of isotopically labeled oxygen. • M−K mechanism dominates in the oxidation of toluene. Catalytic properties of multiple metals deposited on TiO 2 nanoparticles were investigated in the oxidation of toluene. Isovolume impregnation method prepared the catalysts containing Cu, Mn, Ni, Co, and Fe deposited on TiO 2 , including CeO 2 and ZrO 2. The effects of loaded metal oxides on the structure and activity of initial catalysts were investigated using various characterization techniques. Toluene's removal efficiency and CO 2 selectivity in the catalyst system were classified as follows: CuCeZr/T > MnCeZr/T > NiCeZr/T > CoCeZr/T > FeCeZr/T. Presence of water vapor exhibits an inhibitory effect on the conversion of toluene, which diminishes at higher temperatures. One contribution of this paper is to obtain the oxidation pathway of toluene and the relationship between the activation energy of all-inclusive and elementary reactions based on the variation of infrared spectrum using Freeman-Carroll method. Another contribution is to clarify the share of Langmuir-Hinshelwood and Mars-van Krevelen mechanisms during the oxidation of toluene over CuCeZr/T catalyst by transient response experiments of isotopically labeled oxygen. These findings provide a feasible method for the design and synthesis of transition metal oxide catalysts for industrial applications. [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]