Mixed Oxide Research Articles

New MMO coatings for electro-refinery applications: Promoting the production of carboxylates

Within the new circular economy paradigm, this work evaluates the performance of tailored mixed metal oxides (MMO) anodes, based on ruthenium and antimony, for their application into an electrochemically-assisted organic refinery process. This process is designed to transform pollutants into value-added products with minimal mineralization. Oxidation of synthetic wastes consisting of phenol solutions was used to validate the electrochemical conversion of phenolic wastes into carboxylates, which are then considered as bricks to be used for electrosynthesis or to produce fuels. The MMO anodes were manufactured using two synthesis routes (Pechini method and ionic liquid method), each followed by one of three different heating treatments: furnace, microwave, and CO2 laser. The selection of the optimal electrode for the organic electrorefinery was based on a combination of physical and electrochemical properties, degradation performance of phenol to carboxylates, and long-term stability, looking for a truly sustainable solution. Results indicate that anodes synthesized by the ionic liquid (IL) method, regardless of the heating treatment, demonstrated superior performance, with larger active areas (with furnace 82 mC cm−2, microwave 97 mC cm−2, and laser 127 mC cm−2) and higher phenol degradation rates, resulting in a greater generation of carboxylates during electrolysis, yielding primarily oxalate and achieving up to 40% conversion with furnace heating. However, laser-treated anodes exhibited greater stability than furnace-made ones, attributed to the formation of an insulating TiO2 layer. Although the electrode with the longest service life did not show the best catalytic properties for minimizing mineralization, the observed variations in coatings with identical chemical compositions highlight the importance of this research. This study positions itself at the forefront of developing more efficient and sustainable electrochemical technologies for organic waste treatment.

Iron redox states in closed-basin lakes on early Mars: Its sensitivity to water chemistry, hydrology, and atmospheric composition

Mars has experienced drastic environmental evolution in terms of pH, redox, and desiccation. NASA’s Curiosity rover discovered that the sediments of the Pahrump Hills member of the Murray formation in Gale Crater contained different redox states of Fe oxides. To interpret the observations, understanding the factors that control iron redox states within early Gale lakes on Mars is needed. Here, we present the results of a one-dimensional geochemical model of a closed-basin lake that considers the Fe(II) photo-oxidation reaction. Depending on the source of Fe(II) (groundwater vs. river flow), lake pH, advection rate, and atmospheric composition, we defined four types of chemical profiles in the lake; namely, Fe(II) dominated, Fe(III) dominated, carbonate precipitating, and redox-stratified profiles. The Fe(III) dominated profile corresponds to the end member case in which photo-oxidation effectively oxidizes the supplied Fe(II). The redox-stratified profile, interpreted as an intermediate condition between Fe(III) dominated profile and Fe(II) dominated profile, appears in broad parameter set when Fe(II) is supplied from the groundwater, typically with a low to moderate Fe(II) input flux at acidic to alkaline pH (pH 5–9) conditions; however, the low water flux due to the nature of the groundwater may be unable to explain the measured abundance of Fe oxides in the sediments. Another endmember case, the Fe(II) dominated profile, which would also be expected to generate mixed valence Fe oxides, occurs when the pH is acidic (pH 4–5); nevertheless, the acidic pH is inconsistent with the mineral assemblages of the sediments. Carbonate precipitating profiles were limited to the case in which Fe(II) is supplied by groundwater with high Fe input flux and alkaline pH of 8–9. These results may imply either the Fe(II) input flux was high enough for the redox-stratified case or Fe(II) photo-oxidation was suppressed by turbidity or by dusty/cloudy atmosphere, or possibly that Fe(II) oxides found in the Pahrump Hills member are, at least partly, of detrital origin. Although numerous other factors (ex., effect of lake depth, variable pH throughout the lake water, detailed chemical speciation) remain unconsidered, the diverse profiles in Fe redox resulting from Fe(II) photo-oxidation reaction sheds light on interpreting the variety and the evolution of redox condition on early Mars.

Unbounding the Future: Designing NiAl-Based Catalysts for Dry Reforming of Methane.

Dry reforming of methane (DRM), the catalytic conversion of CH4 and CO2 into syngas (H2+CO), is an important process closely correlated to the environment and chemical industry. NiAl-based catalysts have been reported to exhibit excellent activity, low cost, and environmental friendliness. At the same time, the rapid deactivation caused by carbon deposition, Ni sintering, and phase transformation exerts great challenges for its large-scale applications. This review summarizes the recent advances in NiAl-based catalysts for DRM, particularly focusing on the strategies to construct efficient and stable NiAl-based catalysts. Firstly, the thermodynamics and elementary steps of DRM, including the activation of reactants and coke formation and elimination, are summarized. The roles of Al2O3 and its mixed oxides as the support, and the influences of the promoters employed in NiAl-based catalysts over the DRM performance, are then illustrated. Finally, the design of anti-coking and anti-sintering NiAl-based catalysts for DRM is suggested as feasible and promising by tailoring the structure and states of Ni and the modification of Al-based supports including small Ni size, high Ni dispersion, proper basicity, strong metal-support interaction (SMSI), active oxygen species as well as high phase stability.

Super-stable mineralization of arsenic contaminated water using industrialized layered double hydroxides and derivatives

The issue of arsenic contamination, specifically in the form of As(III), is progressively escalating, so presenting a substantial danger to human well-being and security. In this study, commercially industrially produced CaAl-layered double hydroxides (CaAl-LDH) and MgAl-LDH were processed by calcination to produce a series of LDH-based mixed metal oxides (CaAl-x, MgAl-x) at calcination temperatures (x) ranging from 200 to 1000 °C. The resulting CaAl-900 exhibited a remarkable capacity for removing high concentrations of As(III), with a removal capacity of 612.5 mg/g. Besides, MgAl-500 demonstrated effective removal of low levels of As(III) to meet industrial emission standards, specifically below 0.5 mg/L. Furthermore, MgAl-500 was employed to simultaneously stabilize mixed toxic metals (As(III), Pb(II), and Cd(II) ions) in the treatment process of contaminated water, meeting standard levels. The comprehensive analysis of the characterization data indicated that the key determinant for the remarkable capacity of CaAl-900 to remove As(III) was its surface adsorption and memory effect. MgAl-500 also formed complex compounds through formation of As-O-Mg bond. This research showcases the capacity of LDHs produced from the industry for efficient remediation of As(III) ions in water.

Electrolysis of CuCl/HCl aqueous system in Cu–Cl thermochemical cycle for green hydrogen production: Investigations on alternative to platinum anode

The ICT-OEC Cu–Cl cycle is a six-step thermochemical copper-chlorine (Cu–Cl) closed-loop cycle to produce green hydrogen via water splitting. One of the critical steps in this cycle involves the electrolysis of CuCl to generate copper (Cu) and cupric chloride (CuCl2). Using platinum as the anode material in this system is economically disadvantageous and expensive. Consequently, this work investigates the feasibility of alternative anode materials to replace platinum. Mixed Metal Oxide (MMO) coated on Ti mesh (MMO mesh) and Pt coated on Ti mesh (Pt mesh) were evaluated as suitable anode alternatives to pure Pt sheet based on their performance metrics at different voltages. The integration of MMO mesh for a 100-h Time on Stream (TOS) study at a mini-pilot scale demonstrated promising current density and efficiency values. However, performance variations were observed over prolonged operation, potentially due to changes in membrane resistance. After 100 h, the MMO mesh remained undamaged, indicating its durability for extended use. Characterization studies revealed the electrodeposited copper to have a dendritic structure with an FCC phase. The findings suggest that MMO mesh and Pt mesh are viable alternatives to platinum at operating voltages above 0.7 V in this system.

Oestrone removal by anodic oxidation using different mixed metal oxide anodes and graphite cathode

ABSTRACT In this study, the removal of oestrone (E1), one of the endocrine disrupting compounds (EDCs) that strongly affects the life activities of organisms in the receiving water environment and is naturally secreted by many organisms and enters water resources, was investigated by the anodic oxidation (AO) process using titanium (Ti) anode and different metal oxide (MMO) anodes (Ti/Pt, Ti/IrO2, Ti/RuO2, Ti/IrO2-Ta2O5 and Ti/IrO2-RuO2-SnO2) and graphite cathode. Batch experiments showed removal efficiencies between 86.1 and 92.3%. The highest removal efficiency was obtained at the Ti/Pt anode using an applied current of 1.5 A (28 mA/cm2 current density), an initial pH of 8.3, an initial E1 concentration of 20 mg/L, an oxidation time of 160 min and an electrolyte concentration of 0.1 M Na2SO4. Different E1 concentrations (5 mg/L, 10 mg/L, 20 mg/L) were investigated. After 160 min, the removals were 97.9%, 95.5% and 92.4%, with degradation rates (k) of 0.0235, 0.0186 and 0.0158 min−1 and high R2 values. The specific energy consumption was also calculated to be in the range of 396–412 kWh/m3 and the lowest SEC value was obtained at an initial E1 concentration of 20 mg/L.

Preparation of short carbon fiber reinforced photosensitive resin and composite material properties study

AbstractLight‐curing rapid prototyping (SLA) has become an emerging technology in the manufacturing industry because of its high precision, rapid prototyping, and the ability to mold complex parts. To enhance the mechanical properties and thermal stability of its raw material photosensitive resin (PR), carbon fiber (CF) was surface modified by chemical oxidation and grafting of amino silane (KH550) to obtain KH550‐modified carbon fiber (ACF). Then, ACF was composited with photosensitive resin to obtain modified carbon fiber/photosensitive resin (ACF/PR) composites. The viscosities of ACF/PR composites, including the viscosity, curing shrinkage, mechanical properties, and thermal stability of the ACF/PR composites, were characterized. The results showed that KH550 was successfully grafted onto CF. When the addition of ACF in the composites was 0.6%, the tensile strength, elongation at break, and impact strength of ACF/PR reached 39.48 MPa, 20.32%, and 13.62 kJ/m2, which were 120%, 27.15%, and 154% higher than that of the pure resin; the thermal decomposition temperatures and the maximum thermal decomposition temperatures at 50% mass loss of ACF/PR increased to 457.66°C and 442.44°C at 50% mass loss, which is 3.95% and 3.63% higher than that of the pure resin. Currently, the composites have excellent strength, toughness, and thermal stability. This paper gives a cost‐efficient method for improving the functioning of PR.Highlights Mixed acid oxidation and amino silane modification of CFs. Preparation of modified CF/photosensitive resin composites. Composites with excellent mechanical properties and thermal stability.

Promotion of Different Active Phases in MnOX-CeO2 Catalysts for Simultaneous NO Reduction and o-DCB Oxidation

AbstractMnOX-CeO2 catalysts with different Mn and Ce content were prepared to evaluate the effect of metal content on catalytic properties and activity in the simultaneous NO reduction and o-DCB oxidation, in order to elucidate the most active species for the process. Catalytic properties were evaluated by ICP-AES, XRD, skeletal FTIR, STEM-HAADF, XPS, N2-physisorption, H2-TPR, NH3-TPD and pyridine-FTIR. Catalysts with 85%Mn and 15%Ce molar content have been found to be the most active. Their excellent catalytic performance is related to the coexistence of Mn in different phases, i.e., Mn species strongly interacting with Ce and segregated Mn species. The effect of the preparation methods has also been deeply investigated: Co-precipitation method (CP) leads to Mn segregation as Mn2O3, whereas sol-gel preparation method (SG) promotes the formation of an amorphous powder. The synergy between segregated Mn2O3 species and Mn species in high interaction with Ce (resulting in a mixed oxide phase) leads to the presence of Mn with different oxidation states. This effect, together with the high oxygen mobility caused by structural defects, enhances redox, acidic and oxidative properties. The improvement of catalytic properties with Mn content also favors NO reduction side-reactions, with N2O and NO2 being the most important by-products, whereas it limits the production of chlorinated organic by-products in o-DCB oxidation.

Reduced graphene oxide supported Bismuth-Iron mixed oxide nanocomposite: A potent photocatalyst for crystal violet dye degradation and antimicrobial application

The nanocomposites of rGO-[BixFe(1-x)]2O3 (x=0.02, 0.05, 0.10 and 0.20) are successfully synthesized with the help of a cost-effective co-precipitation procedure. Influence of Bi on to the magnetic, optical, microstructural and antimicrobial properties of Fe2O3 are investigated. The presence of pure α-Fe2O3 is being witnessed through the characteristic intensity of XRD peak where phase impurity is not noticed up to 10 % of Bi loading. Presence of various defects have been realized in the sample from PL spectra. The direct band gap of the adsorbent nanocomposite with Bi loading up to 10 % with that of α-Fe2O3 is found to be 2.51 eV and it may be taken as a suitable photocatalyst of choice towards the photodegradation of Crystal Violet with 97.69 % by maintaining the pH-10 and time-60 min as optimum condition. Adsorption capacity (qm) and rate constant (kapp) are found to be 28.50 mg/g and 0.0473 min−1 respectively. The antimicrobial analysis of the synthesized material signifies its antibacterial activity against Staphylococcus aureus (Gram +Ve) and Klebsiella pneumonia (Gram −Ve). On the basis of our finding, the synthesized nano composite may be the materials of choice for the optical device application, memory storage device as well as in the biomedical application.

Effects of MOx modification (M = Mn, Ce, and Fe) on the SCR catalytic properties of the CrOx-WOx mixed oxide catalysts

In this study, a series of MOx-modified (M = Mn, Fe, and Ce) CrOx-WOx mixed oxides were synthesized via the sol-gel technique for the selective catalytic reduction of NOx with NH3. Given the addition of MnOx or CeOx, the availability of the catalyst surface acid sites tended to decline, which negatively affected the proceeding of the deNOx process. Moreover, the retention of oxidative ability by introducing MnOx also favored the over-oxidation of NH3, which accelerated the additional formation of NOx and created a crucial barrier for the increment in the higher-temperature deNOx activity. Apparently, <80 % of the NOx could be effectively eliminated from the working gas within the whole temperature range for the CrCeW and CrMnW samples. By contrast, doping FeOx was able to introduce ample acid sites onto the catalyst surfaces, which was beneficial for the adsorption of NH3 and subsequently the facilitation of the progression of the deNOx process. Furthermore, the weakened oxidizability suppressed the over-oxidation of NH3. Consequently, a broad operating temperature window was obtained for the FeOx-doped catalyst; >90 % NOx conversion efficiency was achieved in the temperature range of 230–450 °C. During the deNOx process, the Eley-Rideal mechanism dominated over the four investigated samples.

Renewable biomass based jet fuel: Aldol condensation of furfural with 3-pentanone over calcium zirconium mixed oxide catalyst

Furfural is a biomass-derived chemical that can be converted into different valuable chemicals using green processes. The current study deals with a highly efficient, robust, and selective solid catalyst for the aldol condensation of furfural and 3-pentanone to synthesize 1-furan-2-yl-2-methylpent-1-en-3-one under environmentally benign conditions. CaZr (different molar ratios of Ca and Zr) mixed oxide (MO) catalysts along with reference CaO and ZrO2 catalysts were prepared by the hydrothermal technique and investigated for the current reaction. Among all, CaZr (1:2) MO catalyst was found to be the best for the conversion of furfural due to its desirable basic strength with good surface area and reusability characteristics. Furfural conversion and 1-furan-2-yl-2-methylpent-1-en-3-one selectivity were found to be 94 % and 98 %, respectively, under optimized reaction conditions. Effect of various reaction parameters was studied carefully to achieve the maximum yield of the required product. Reaction mechanism and kinetics were developed. The reaction aligns with the LHHW mechanism, and the activation energy was determined to be 10.40 kcal/mol.

Sol–gel synthesis of iron titanates for the photocatalytic degradation of cyanide

Iron titanate mixed metal oxides were synthesized by the sol–gel method through four different routes. The effect of (i) the solvent of iron precursor, (ii) the addition of the chelating agent to the titanium or iron solution and (iii) the molar ratio between the chelating agent and the titanium or iron precursor over the overall percentage of obtained iron titanates was evaluated. Fourier-transform infrared spectroscopy (FTIR) and UV–Vis spectroscopy (UV–Vis) performed on the reaction medium evidenced the formation of acetate complexes of titanium (IV) or iron (III) during the different routes. X-ray diffraction (XRD) patterns of the obtained materials showed the formation of ilmenite (FeTiO3), pseudorutile (Fe2Ti3O9) and pseudobrookite (Fe2TiO5) in different proportions, as well as hematite (Fe2O3), rutile [TiO2 (R)] and anatase [TiO2 (A)]. The materials with the highest content of iron titanates obtained in each route were characterized and evaluated in the photocatalytic degradation of cyanide using visible light irradiation. UV–Vis Diffuse Reflectance Spectroscopy (UV–Vis DRS) showed that the samples exhibited energy bandgap values between 2.31 and 2.90 eV, which agrees with the values reported for iron titanates and evidence the possible activation of the materials under visible light. Scanning electron microscopy (SEM) and nitrogen physisorption results showed that the synthesized materials exhibited nanometric particle size and lower surface area (36.7 ± 4.8 m2·g-1) than TiO2 Degussa P-25 (72–155 m2·g-1). The photocatalytic performance of the synthesized materials toward oxidation of CN− exceeded by 56% the activity of pure TiO2. The content of iron titanates in the synthesized materials was found to be the variable with the greatest influence on the photodegradation of cyanide. In addition, an inversely proportional relationship between the pseudorutile content of the materials and their photocatalytic activity was observed.

Enhanced acetone detection performance of mechanically-mixed WO3:ZnO composites

In recent years, the potential use of mixed metal oxide WO3:ZnO is widely sought in photocatalytic application due to its excellent electrical and optical properties, but is less explored for chemiresistive sensor. The heterojunction effect in WO3:ZnO is of particular interest to eradicate common issues suffered by the pristine metal oxide sensors, such as limited sensitivity, poor selectivity, and high operating temperature. In addition, the acetone detection study based on heterostructured WO3:ZnO is quite limited. Herein, we demonstrate that the mechanically-mixed WO3:ZnO sensor exhibits comparable reducing gas sensing performance as other doped WO3:ZnO and relative improvement compared with the undoped composites, without the need of catalyst. In this work, WO3:ZnO thin-film based chemiresistive sensors were fabricated through straightforward methods comprising mechanical mixing and drop casting of sensor materials onto gold interdigitated alumina substrates. Structural and morphological properties of the prepared WO3, ZnO, and WO3:ZnO composites were examined through the X-ray diffraction (XRD), Raman spectroscopy, photoluminescence spectroscopy (PL), field-emission scanning electron microscopy (FESEM), and energy-dispersive X-ray spectroscopy (EDX) analyses, respectively. Sensor performance parameters including operating temperature and response were determined. The sensing properties of WO3:ZnO composites with different weight compositions (1:1, 1:2, and 1:3) were evaluated against the pristine ZnO and WO3. The weight ratio of 1:2 was the optimal composition for the WO3:ZnO composite to achieve the highest sensor response of 53.8 % towards 300 ppm acetone at 200 ºC compared to the pristine ZnO with a response of 23.5 %. The WO3:ZnO (1:2) thin film displayed granular morphology with uniform particle dispersion and porosity, enhancing the gas diffusion. The WO3:ZnO (1:2) thin-film composite sensor exhibited improved sensing performance and good repeatability towards acetone compared with that of ZnO and WO3. The enhanced response to acetone was possibly contributed by the development of n-n heterojunctions, porous morphology, and surface defects in the WO3:ZnO composite. The underlying sensing mechanism of WO3:ZnO composite is also discussed extensively with the aid of energy band diagrams. This study presents a foundation for future development of cost-effective acetone sensors through mechanical mixing with great potential for practical and scalable implementation in various industries.

Selective chlorine evolution reaction using Pt-RuO2 electrocatalysts in brackish water and seawater at circum-neutral pH and its application to seawater desalination

Precious metal-based mixed metal oxides have been widely used as catalysts for the chlorine evolution reaction (CER). However, a concurrent oxygen evolution reaction (OER) leads to insufficient selectivity for CER at circum-neutral pH. Herein, nanoparticulate Pt-RuO2 (PRO) is synthesized with various Pt/Ru ratios at sub-boiling temperatures, followed by post-annealing. The synthetic conditions significantly influence the physicochemical properties (crystalline structures, morphologies, surface areas, double-layer capacitance, and charge transfer resistance) and the electrocatalytic activities of CER in NaCl solutions (0.137 and 0.5 M) and seawater (with a salinity of 3.6 g L–1). Among PRO-x@y samples (where x is the mole fraction of Pt in the mixed Pt and Ru precursor solutions, and y is the annealing temperature [°C]), PRO-0.2@800 and PRO-0.8@500 show remarkable faradaic efficiencies (FEs) for CER (CER-FE). Despite their similar FEs (CER-FEs of approximately 95 % and 99 %, and OER-FEs of 4–6 % and <1 %, for PRO-0.2 and PRO-0.8, respectively), the Pt-rich PRO requires less potential for the same current density (J) and exhibits excellent stability at J = 800 mA cm–2 over 250 h in seawater at circum-neutral pH. The optimized PRO electrode is further used for seawater desalination and simultaneous production of HClO, achieving FEs of ∼100 %. Finally, various electrochemical analyses are conducted to elucidate the CER mechanism.

Hafnium oxide coating to improve the oxidation behavior of Zirconium Diboride

Hafnium dioxide (HfO2) coatings were successfully deposited on zirconium diboride (ZrB2) using reactive magnetron sputtering. After the oxidation at 1500°C or 1600°C, the mutual dissolution of HfO2 and thermally grown ZrO2 was observed which has resulted in the formation of a mixed oxide zone. As the enrichment of the mixed oxide zone by ZrO2 progresses, monoclinic/tetragonal phase transition temperature of ∼1790°C for nominally pure HfO2 moves towards ∼1500 °C. Finally, the inevitable phase transition from monoclinic to tetragonal structure results in the development of cracks, pores, and gaps within the mixed oxide zone. Thickness measurements of the porous ZrO2 scale and the mixed oxide zone of coated specimens revealed an improvent in the oxidation behavior at 1500°C and 1600°C compared to uncoated ZrB2, proving its protective character for short duration oxidation.

Synthesis and characterisation of mixed oxides of Co–Ni catalyst and its application in microwave mediated synthesis of Benzo[b]Pyrans

We present an easy and sustainable procedure for the productive preparation of tetrahydrobenzo[b]pyran derivatives by means of many compounds condensation of dimedon, malononitrile and several aromatic aldehydes utilizing mixed bimetallic oxides of Co–Ni as a catalyst under microwave irradiation. Present protocol involves green synthesis of mixed Co–Ni oxide catalyst using milky latex of Euphorbia neriifolia. The prepared mixed Co and Ni oxide was analyzed by X-ray diffraction (XRD), Scanning electron microscopy (SEM), Transmission electron microscopy (TEM), Fourier Transform Infra-Red Spectroscopy (FT-IR), Energy Dispersive X-ray Analysis (EDAX), X-ray Photoelectron Spectroscopy (XPS) & Brunauer-Emmett- Teller Analysis (BET). This green approach's significance is demonstrated by its one-pot synthesis, convenient without use of solvent shows good isolated yields. Multiple analytical techniques such as Fourier transform infrared spectroscopy (FT-IR), 1H and 13C nuclear magnetic resonance (NMR) spectroscopy are utilized to derive the structural properties. The mixed metal oxides of Co and Ni was found to be catalytically active and can be reused 12 times without significant loss of catalytic activity.

Latent fingerprint imaging using irradiated novel mixed metal oxides (MXOY, M=Ba, Zn, Al, Ce) nanophosphor.

Latent fingerprint developed at the site of crime is considered as crucial physical evidence in forensic investigation. The mixed metal oxides (MXOY, M=Ba, Zn, Al, Ce) nanophosphor was synthesised by irradiating the precursor solution with 60Co gamma radiation followed by solution combustion method. The structural, morphological, optical characteristics and fingerprint imaging were studied using X-ray diffraction (XRD), scanning electron microscopy, UV-visible spectroscopy and powder dusting method, respectively. The XRD results revealed that the average crystallite size is found to be 30nm with the estimated bandgap of 3.18eV. The broadband UV exited luminescence of the phosphors was observed at λMax=330nm. The PL spectrum shows three emission bands at 432, 444 and 460nm that corresponds to blue regions, suggesting that the synthesised nanophosphor is a potential luminous material for latent fingerprinting and luminescent devices.

Benefit of LDH-Derived Mixed Oxides for the Co-Oxidation of Toluene and CO Exhausted from Biomass Combustion

The proposed study is devoted to highlighting the importance of mixed oxides preparation through the layered double hydroxide route for undesirable gas pollutants abatement. Different series of Cu/Al/Ce mixed oxides with similar or different stoichiometrics were prepared and compared for toluene and/or CO oxidation. Catalyst synthesis methods influence material properties and activity for oxidation reactions. The high activity for the oxidation reactions of mixed oxides derived from LDH is explained by the Cu/Ce synergy. The presence of CO in the CO/toluene mixture does not affect the total toluene oxidation, and the toluene does not affect the total oxidation of CO conversion at low temperatures. The most effective catalytic material (Cu6Al1.2Ce0.8) presents a long lifetime stability for total toluene oxidation and resistance to CO poisoning in mixtures.

Revealing the controlling mechanisms of atomic layer etching for high-k dielectrics in conventional inductively coupled plasma etching tool

The possibilities of optimization of the two-step atomic layer etching process for HfO2 in conventional plasma etching tools were studied. The surface modification step was realized in Ar/CF4/H2 plasma, and the reaction between the modified layer and the surface was activated by Ar ion bombardment from the plasma in the second step. Investigation of the effects of activation step duration, DC bias during activation, and Ar plasma density was carried out. The mechanism of the etching process has been shown to involve fluorination of oxide during the modification step and subsequent removal of fluorine-containing particles at the activation step. An increase in parasitic sputtering rate and lower process saturation with the growth of DC bias during activation was demonstrated. The advantage of the ALE process in lower surface roughness over the conventional etching process was shown. Similar etching characteristics of HfO2 and ZrO2 suggest a similarity in the etching process for the mixed hafnium-zirconium oxide material.

Towards an electrochemically-based circular economy: Electro-refinery for valorizing phenolic wastewater

This study introduces an innovative approach to wastewater treatment that combines two electrochemical technologies: electrolysis and electrochemical separation facilitated by anionic exchange membranes. This integrated technology converts pollutants into carboxylates, which are valuable intermediates for further electrosynthesis and fuel production. The efficacy of this approach was demonstrated using synthetic wastewater containing phenol as a model pollutant, chosen for its well-documented characteristics that enable comparative analysis with previous studies. The treatment process utilized mixed metal oxides (MMO) anodes with a composition of Ti/(RuO2)0.8(Sb2O4)0.2 and a boron-doped diamond (BDD) anode. The investigation was structured to evaluate each component of the treatment system individually before examining their collective performance. Through a series of case studies, the research not only confirmed the feasibility of this innovative technology but also highlighted the need for further study on the optimization of operational parameters and electrode materials. Comparative analysis revealed that MMO anodes outperformed BDD anodes, achieving maximum carboxylate transport rates of 138.7 mmol m−2h−1. The efficiency of carboxylate separation from the solution where they were generated reached up to 54.6 mmol kWh−1, while the maximum overall production efficiency was 8.77 mmol kWh−1. The study further determined that current density significantly affects both the production rate and the extent of mineralization, identifying optimal densities of 100 mA cm−2 and 30 mA cm−2 for the electrolyzer and electroseparator units, respectively. This work provides valuable insights for the optimization of this promising wastewater treatment technology, with potential applications in various industries.