The kinetics of oxidative cracking of n-hexane to light olefins using the lattice oxygen of VO /SrO-γAl O catalysts has been investigated. Kinetic experiments were conducted in a CREC Riser Simulator (CERC: Chemical Reactor Engineering Center), which mimics fluidized bed reactors. The catalyst's performance is partly attributed to the moderate interaction between active VO species and the SrO-γAl O support. This moderate interaction serves to control the release of lattice oxygen to curtail deep oxidation. The incorporation of basic SrO component in the support also helped to moderate the catalyst's acidity to checkmate excessive cracking. Langmuir-Hinshelwood model was applied to formulate the rate equations. The intrinsic kinetic parameters were obtained by fitting the experimental data to the kinetic model using a nonlinear regression algorithm at a 95% confidence interval, implemented in MATLAB. n-Hexane transforms to olefins at a specific reaction rate of 1.33 mol/gcat.s and activation energy of 119.2 kJ/mol. These values when compared with other duplets (i. e., ki° and E ) for paraffins to olefins, show that indeed olefins are stable products of the oxidative conversion of n-hexane over VO /SrO-γAl O under a fluidized bed condition. Values of activation energy for all CO formation routes indicate that intermediate paraffins are likely to be cracked to form CH than to be converted directly to CO . On the other hand, olefins may transform partly, and directly to CO (E =9.65 kJ/mol) than to form CH (E =89.1 kJ/mol) in the presence of excess lattice oxygen. Overall, olefins appear to be stable to deep oxidation due to the role of SrO in controlling the amount of lattice oxygen of the catalyst at the reaction temperature.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1002/asia.202100209 | DOI Listing |
Sensors (Basel)
January 2025
State Key Laboratory of Materials Processing and Die & Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074, China.
This study has investigated the effects of different annealing temperatures on the microstructure, chemical composition, phase structure, and piezoelectric properties of ZnO films. The analysis focuses on how annealing temperature influences the oxygen content and the preferred c-axis (002) orientation of the films. It was found that annealing significantly increases the grain size and optimizes the columnar crystal structure, though excessive high-temperature annealing leads to structural degradation.
View Article and Find Full Text PDFMolecules
December 2024
Key Laboratory of Ecological Metallurgy of Multi-Metal Intergrown Ores of Ministry of Education, Shenyang 110819, China.
Increasing the concentration of oxygen vacancies in ceria-based materials to solve the bottleneck of their applications in various fields has always been a research hotspot. In this paper, ceria-based cerium-oxygen-sulfur (Ce-O-S) composites that were composed of CeO, CeOS, and Ce(SO) were synthesized by a precipitation method. The compositional, structural, morphological, and light response characteristics of prepared Ce-O-S composites were investigated by various characterization techniques.
View Article and Find Full Text PDFNat Commun
January 2025
Department of Chemistry, University of Zurich, Zurich, Switzerland.
The complexity of the intrinsic oxygen evolution reaction (OER) mechanism, particularly the precise relationships between the local coordination geometry of active metal centers and the resulting OER kinetics, remains to be fully understood. Herein, we construct a series of 3 d transition metal-incorporated cobalt hydroxide-based nanobox architectures for the OER which contain tetrahedrally coordinated Co(II) centers. Combination of bulk- and surface-sensitive operando spectroelectrochemical approaches reveals that tetrahedral Co(II) centers undergo a dynamic transformation into highly active Co(IV) intermediates acting as the true OER active species which activate lattice oxygen during the OER.
View Article and Find Full Text PDFNat Commun
January 2025
Department of Chemistry and Research Institute for Natural Sciences, Korea University, Seoul, Republic of Korea.
The success of proton exchange membrane water electrolysis (PEMWE) depends on active and robust electrocatalysts to facilitate oxygen evolution reaction (OER). Heteroatom-doped-RuO has emerged as a promising electrocatalysts because heteroatoms suppress lattice oxygen participation in the OER, thereby preventing the destabilization of surface Ru and catalyst degradation. However, identifying suitable heteroatoms and achieving their atomic-scale coupling with Ru atoms are nontrivial tasks.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Zhejiang University, Department of Chemistry, CHINA.
Ruthenium dioxide (RuO2) is a benchmark electrocatalyst for proton exchange membrane water electrolyzers (PEMWE), but its stability during the oxygen evolution reaction (OER) is often compromised by lattice oxygen involvement and metal dissolution. Despite that the typical synthesis of RuO2 produces chloride residues, the underlying function of chloride have not well investigated. In this study, we synthesized chlorine-containing RuO2 (RuO2-Cl) and pure RuO2 catalysts with similar morphology and crystallinity.
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!