CuFex/CeO2 Catalysts Prepared by Sol-Gel Method for Low-Temperature Catalytic CO Oxidation
Chinese Journal of Rare Metals | Vol.49, Issue 12, 2025 |
pp. 1801-1813
Carbon monoxide (CO) is a colorless, odorless, and highly toxic gas, primarily produced
by vehicle emissions and incomplete fossil fuel combustion. It poses significant environmental
risks and binds to hemoglobin in the bloodstream, leading to hypoxia. Catalytic oxidation
is an efficient and energy-saving method for CO removal. Noble metal catalysts, such
as Pd-based and Pt-based systems, demonstrate excellent activity for CO oxidation,
though their high cost hinders large-scale industrial application. Thus, developing
non-noble metal catalysts that enable complete CO oxidation at low temperatures is
crucial. The sol-gel method, a versatile wet-chemical synthesis technique, allows
precise control over catalyst composition and microstructure, ensuring highly uniform
dispersion of active components on the support. In this work, a series of trimetallic
5%CuFex/CeO2 (x=0~0.1) catalysts with controlled Fe doping were prepared via sol-gel method to elucidate
the promotional effect of Fe on Cu/CeO2 for low-temperature CO oxidation. Comprehensive characterization including X-ray
diffraction (XRD), Raman, Brunauer-Emmett-Teller (BET), scanning electron microscopy
(SEM), and X-ray photoelectron spectroscopy (XPS) was conducted to probe the catalysts'
structural, textural, and electronic properties. H2-temperature-programmed reduction (H2-TPR), O2-temperature-programmed desorption (O2-TPD), and CO-temperature-programmed desorption (CO-TPD) were used to elucidate the
redox capacity of the catalyst and the activation of reactant molecules CO and O2.The catalytic evaluation demonstrated that 5%CuFe0.025/CeO2 catalyst showed optimal performance, achieving 100% CO conversion at 70 ℃, which
represented a significant 40% improvement in low-temperature activity compared to
the Fe-free Cu/CeO2 reference catalyst. Furthermore, the catalyst exhibited excellent stability, maintaining
complete CO conversion throughout a 60 h stability test. XRD patterns confirmed the
preservation of CeO2 fluorite structure in all catalysts, with no detectable CuOx or FeOx crystalline phases, suggesting the high dispersion of both Cu and Fe species on the
catalyst surface. SEM and N2 physisorption analysis revealed that the sol-gel synthesized 5%CuFex/CeO2 catalysts possessed a hierarchical porous architecture. Fe incorporation promoted
the formation of an interconnected network-like morphology with uniform pore distribution,
increasing the specific surface area, which optimized texture and facilitates mass
transport while maximizing active site accessibility, significantly enhancing reaction
kinetics. Raman spectroscopy analysis demonstrated that Fe doping modifies metal-oxygen
bond lengths, creating additional oxygen vacancies. These defect sites facilitated
oxygen activation from ambient air, generating reactive oxygen species for CO oxidation.
Supporting evidence from O2-TPD revealed a distinct low-temperature shift in oxygen desorption peaks after Fe
incorporation, while XPS analysis of O 1s spectra confirmed the increased abundance
of reactive oxygen species-both findings corroborating the enhanced oxygen activation
capacity induced by Fe doping. H2-TPR analysis revealed enhanced α-peak hydrogen consumption with increasing Fe loading,
indicating improved oxygen mobility. Combined CO-TPD and XPS characterizations demonstrated
that optimal Fe doping promotes CuOx dispersion and increases the concentration of active Cu⁺ sites for CO chemisorption.
However, excessive Fe loading (x=0.1) led to attenuated CO desorption intensity in TPD profiles, suggesting iron oxide
over-deposition may block active sites and reduce CO adsorption capacity. In-situDRIFTS
analysis revealed a carbonate-mediated Mars-van Krevelen (MV-K) mechanism for CO oxidation over the catalyst. As the reaction temperature rose,
the abundance of Cu⁺-CO species increased, accompanied by enhanced peaks corresponding
to carbonate intermediates. This suggested that adsorbed CO reacted with surface-active
oxygen species to form carbonate species, which subsequently decomposed into CO2 and desorbed from the catalyst surface. The vacant oxygen sites were then replenished
by adsorbed O2 from the gas phase, generating new active oxygen species. These reactive oxygen species
reacted with adjacent adsorbed CO to produce additional CO2, completing the catalytic cycle. These results indicated that the catalytic performance
of copper-cerium catalysts for complete CO oxidation could be significantly improved
by strategically doping trace metal additives, thereby enabling completed CO conversion
at lower operating temperatures.
DOI: 10.13373/j.cnki.cjrm.XY25050003 Cited: 0 Download: 0
