Search Results (6)

The present study aims to investigate a Pd catalyst on a complex multi-oxide medium-entropy support interlayer La₂O₃-CeO₂-ZrO₂-Al₂O₃ and its possible use as catalysts for methane abatement applications. The low-temperature N₂-adsorption, XRD, TEM, XPS, TPD, and TPR techniques were used to characterize the catalyst. The palladium deposition on the supports leads to the formation of PdO. After the catalytic tests, the metal-Pd phase was observed. The complete oxidation of methane on Pd/La-Ce-Zr-Al catalyst takes place at temperatures above 250 °C, and in the presence of water vapor, the reaction temperature increases to about 70 °C. The careful choice of constituent oxides provides a balance between structural stability and flexibility. The alumina and lanthanum oxide ensure the high specific surface area, while the simultaneous presence of zirconia and ceria leads to the formation of a mixed-oxide phase able to interact with palladium ions by incorporating and de-incorporating them at different conditions. The mechanism of Mars–van Kerevelen was considered as the most probable for the reaction of complete methane oxidation. The possibility of the practical application of Pd-modified La-Ce-Zr-Al catalyst is evaluated. The use of a mix of multiple rare and abundant oxides makes the proposed catalyst a cost-effective alternative. Full article

The present paper reviews original data obtained by the authors from recent separate publications with additional unpublished data, specifically concerning the Lanthanum (La)’s role in the solidification pattern and graphite formation in gray cast irons. Iron melting at 0.018–0.056%S, a 3.7–4.1% carbon equivalent (CE) and less than 0.005%Al_residual are inoculated with La-bearing FeSi alloys at different associations with other inoculating elements. Complex Al-La small inclusions as possible better nucleation sites for (Mn,X)S compounds and La-Ca presence in the body of these sulfides, which possibly provide better nucleation sites for flake graphite, are identified in 0.026%S cast iron. At a lower sulfur content (0.018%S), La,Ca,Al-FeSi alloy still has a high efficiency, but more complex La-bearing alloys are recommended for a higher dendritic austenite amount (LaBaZrTi–FeSi) or for lower eutectic recalescence (LaBaZr–FeSi). La has limited but specific benefits at 0.05–0.06%S irons, including favorable graphitizing factors (a higher amount of graphite precipitated at the end of solidification), lower eutectic recalescence, and a lower value of the first derivative at the end of solidification. When La,Ca,Ba,Al,Zr,S-FeSi treatment (0.035%S base iron) is used, Scanning Electron Microscopy (SEM) analysis finds that the first formed micro-compound is a complex Al-silicate (Zr,La,Ca,Ba presence), which supports the nucleation of the second compound (Mn,Ca,La)S type. At the sulfide-graphite interface, there is a visible thin (nano size) Al-silicate layer (O-Al-Si-Ca-La system), which is more favorable for graphite nucleation (it has better crystallographic compatibility). La is identified in all three important areas of nucleants (the first is formed oxidic nucleus, the second is nucleated Mn-sulfide and the third is a sulfide-graphite interface), thereby increasing the efficiency of graphite nucleation sites. Full article

A catalytic screening was performed to determine the effect of the support on the performance of an Au–Cu based system for the removal of CO from an actual syngas. First, a syngas was obtained from reforming of ethanol. Then, the reformer outlet was connected to a second reactor, where Au–Cu catalysts supported on several single and dual metal oxides (i.e., CeO₂, SiO₂, ZrO₂, Al₂O₃, La₂O₃, Fe₂O₃, CeO₂-SiO₂, CeO₂-ZrO₂, and CeO₂-Al₂O₃) were evaluated. AuCu/CeO₂ was the most active catalyst due to an elevated oxygen mobility over the surface, promoting CO₂ formation from adsorption of C–O* and OH⁻ intermediates on Au⁰ and CuO species. However, its lower capacity to release the surface oxygen contributes to the generation of stable carbon deposits, which lead to its rapid deactivation. On the other hand, AuCu/CeO₂-SiO₂ was more stable due to its high surface area and lower formation of formate and carbonate intermediates, mitigating carbon deposits. Therefore, use of dual supports could be a promising strategy to overcome the low stability of AuCu/CeO₂. The results of this research are a contribution to integrated production and purification of H₂ in a compact system. Full article

Recent studies have shown that the catalytic performance (activity and/or selectivity) of Pt-group metal (PGM) catalysts for the CO and hydrocarbons oxidation as well as for the (CO, HCs or H₂)-SCR of NO_x or N₂O can be remarkably affected through surface-induced promotion by successful application of electropositive promoters, such as alkalis or alkaline earths. Two promotion methodologies were implemented for these studies: the Electrochemical Promotion of Catalysis (EPOC) and the Conventional Catalysts Promotion (CCP). Both methodologies were in general found to achieve similar results. Turnover rate enhancements by up to two orders of magnitude were typically achievable for the reduction of NO_x by hydrocarbons or CO, in the presence or absence of oxygen. Subsequent improvements (ca. 30–60 additional percentage units) in selectivity towards N₂ were also observed. Electropositively promoted PGMs were also found to be significantly more active for CO and hydrocarbons oxidations, either when these reactions occur simultaneously with deNO_x reactions or not. The aforementioned direct (via surface) promotion was also found to act synergistically with support-mediated promotion (structural promotion); the latter is typically implemented in TWCs through the complex (Ce–La–Zr)-modified γ-Al₂O₃ washcoats used. These attractive findings prompt to the development of novel catalyst formulations for a more efficient and cost-effective control of the emissions of automotives and stationary combustion processes. In this report the literature findings in the relevant area are summarized, classified and discussed. The mechanism and the mode of action of the electropositive promoters are consistently interpreted with all the observed promoting phenomena, by means of indirect (kinetics) and direct (spectroscopic) evidences. Full article

Several Ni catalysts of supported (on La₂O₃-αAl₂O₃, CeO₂, and CeO₂-ZrO₂) or bulk types (Ni-La perovskites and NiAl₂O₄ spinel) have been tested in the oxidative steam reforming (OSR) of raw bio-oil, and special attention has been paid to the catalysts’ regenerability by means of studies on reaction-regeneration cycles. The experimental set-up consists of two units in series, for the separation of pyrolytic lignin in the first step (at 500 °C) and the on line OSR of the remaining oxygenates in a fluidized bed reactor at 700 °C. The spent catalysts have been characterized by N₂ adsorption-desorption, X-ray diffraction and temperature programmed reduction, and temperature programmed oxidation (TPO). The results reveal that among the supported catalysts, the best balance between activity-H₂ selectivity-stability corresponds to Ni/La₂O₃-αAl₂O₃, due to its smaller Ni⁰ particle size. Additionally, it is more selective to H₂ than perovskite catalysts and more stable than both perovskites and the spinel catalyst. However, the activity of the bulk NiAl₂O₄ spinel catalyst can be completely recovered after regeneration by coke combustion at 850 °C because the spinel structure is completely recovered, which facilitates the dispersion of Ni in the reduction step prior to reaction. Consequently, this catalyst is suitable for the OSR at a higher scale in reaction-regeneration cycles. Full article

Oxides (such as SiO₂, TiO₂, ZrO₂, Al₂O₃, Fe₂O₃, CeO₂) have often been used to prepare supported Pt catalysts for CO oxidation and other reactions, whereas metal phosphate-supported Pt catalysts for CO oxidation were rarely reported. Metal phosphates are a family of metal salts with high thermal stability and acid-base properties. Hydroxyapatite (Ca₁₀(PO₄)₆(OH)₂, denoted as Ca-P-O here) also has rich hydroxyls. Here we report a series of metal phosphate-supported Pt (Pt/M-P-O, M = Mg, Al, Ca, Fe, Co, Zn, La) catalysts for CO oxidation. Pt/Ca-P-O shows the highest activity. Relevant characterization was conducted using N₂ adsorption-desorption, inductively coupled plasma (ICP) atomic emission spectroscopy, X-ray diffraction (XRD), transmission electron microscopy (TEM), CO₂ temperature-programmed desorption (CO₂-TPD), X-ray photoelectron spectroscopy (XPS), and H₂ temperature-programmed reduction (H₂-TPR). This work furnishes a new catalyst system for CO oxidation and other possible reactions. Full article