Activation Energy For Oxidation Research Articles

Operando spectroelectrochemical insights into the selectivity difference of photoelectrocatalytic alcohol oxidation to aldehyde on hematite and titania

Operando spectroelectrochemical spectroscopy is employed to investigate the selectivity of ethanol oxidation on hematite and titania photoanodes. High selectivity of acetaldehyde formation from ethanol oxidation has been identified using the hematite photoanode, whilst modest selectivity and over-oxidation of acetaldehyde are observed using titania photoanodes. This difference in the acetaldehyde selectivity is correlated with the valence band potential. The valence band potential is also associated with the activation energy required for the over-oxidation of acetaldehyde. The activation energy of acetaldehyde oxidation by the photogenerated holes in hematite is 427 meV whilst only 45 meV is required for titania. Kinetic isotope effect shows that the rate-limiting step of ethanol oxidation on hematite and titania involves α-C–H bond breaking, and solvent molecules are important to assist the rehybridization of this α-C. The spectral analyses emphasize the importance of considering the band potential upon the selectivity of alcohol oxidation on a broad scope.

High-temperature oxidation behavior of Mar-M247 and Mar-M247LC for aero-engines at 800–950 °C in air

The isothermal oxidation behavior of Mar-M247 and Mar-M247LC was investigated in air at 800–950 °C for 500 h. The oxidation activation energies of 327.7 kJ/mol and 281.4 kJ/mol were obtained, respectively. The oxidation kinetics and oxide layer evolution indicated that the Cr3+ outward diffusion dominated the oxide film growth. Firstly, NiO replaced Cr2O3 as the outer layer above 900 °C. Next, the formation of the internal Al2O3 was closely related to the γ' phase dissolution. The size of the γ' and the γ/γ' interfacial area may be one of the possible reasons for the minor differences in the Mar-M247 and Mar-M247LC oxidation properties. And finally, it is speculated that the oxide pegs in the oxide layer enhance the adherence of the oxide film to the substrate.

Automated kinetics measurement for homogeneous photocatalytic reactions in continuous microflow

Photocatalytic reactions, achieving chemical synthesis in a more sustainable manner than thermal reactions, have been demonstrated to become more efficient, greener and easier to scale up when combined with continuous microflow technology. Nevertheless, the report on the kinetics measurement for photocatalytic reactions in continuous microflow, especially in a fully automated way, is very rare. In this work, two challenging parameters, i.e., the reaction order with respect to oxygen (2.48) and photoreaction activation energy (-16.83 kJ/mol) of the photocatalytic oxidation of 9,10-diphenylanthracene, were acquired in an automated continuous flow platform using the Steady-state Method. Moreover, the Ramping Method was also successfully implemented in the automated continuous flow photoreaction platform, exhibiting a predictive accuracy of 4.42 %, with 64.3 % less time and 58.0 % less material consumption than the Steady-state Method. And it was found that the improvement in the residence time distribution of the microreactor could improve the accuracy of the Ramping Method. The automated continuous flow process developed in this work could offer an efficient and accurate way to attain the reaction kinetics information for homogeneous photocatalytic reactions.

A facile high-efficiency preparation strategy for Al-containing multi-component boride microcrystals with superior comprehensive performance

Multi-component transition group metal borides (MMB2) have become a research hotspot due to their new composition design concepts and superior properties compared with conventional ceramics. Most of the current methods, however, are complicated and time-consuming, the mass production remains a challenge. Herein, we proposed a new high-efficiency strategy for synthesis of MMB2 using molten aluminum as the medium for the first time. The prepared Al-containing multi-component borides (TiZrHfNbTa)B2 microcrystals had a homogeneous composition with a hexagonal AlB2 structure and ultra-high hardness value of ∼35.3 GPa, which was much higher than data reported in the literature and the rule of mixture estimations. Furthermore, combined with the First-principles calculation results, we found that the Poisson's ratio (v) values exhibit a clearly ascending trend from 0.17 at VEC = 3.5 to 0.18 at VEC = 3.4, then to 0.201 at VEC = 3.2 with the increasing of Al content. This indicates that the intrinsic toughness of multi-component boride microcrystals is obviously enhanced by the trace-doped Al elements. Besides, the fabricated Al-containing multi-component boride microcrystals have superior oxidation activation energy and structural stability. The enhanced oxidation resistance is mainly attributed to the formation of a protective Al2O3 oxide layer and the lattice distortion, both of which lead to sluggish diffusion of O2. These findings propose a new unexplored avenue for the fabrication of MMB2 materials with superior comprehensive performance including ultra-hardness and intrinsically improved thermo-mechanical properties.

The Oxidation Performance of a Carbon Soot Catalyst Based on the Pt-Pd Synergy Effect

Pt-Pd-based noble metal catalysts are widely used in engine exhaust aftertreatment because of their better carbon soot oxidation performance. At present, the synergistic effect of Pt and Pd in CDPFs, which is the most widely used and common doping method, in catalyzing the combustion of carbon smoke has not been reported, and it is not possible to give an optimal doping ratio of Pt and Pd. This paper investigates the carbon soot oxidation performance of different Pt/Pd ratios (Pt/Pd = 1:0, 10:1, 5:1, 1:1) based on physicochemical characterization and particle combustion kinetics calculations, aiming to reveal the Pt-Pd synergistic effect and its carbon soot oxidation law. The results show that Pt-based catalysts doped with Pd can improve the catalyst dispersion, significantly increase the specific surface area, and reduce the activation energy and reaction temperature of carbon soot reactions, but excessive doping of Pd leads to the enhancement of the catalyst agglomeration effect, a decrease in the specific surface area, and an increase in the activation energy and reaction temperature of the carbon soot reaction. The specific surface area and pore capacity of the catalyst are the largest, and the activation energy of particle oxidation and the pre-exponential factor are the smallest (203.44 kJ∙mol−1 and 6.31 × 107, respectively), which are 19.29 kJ∙mol−1 and 4.95 × 108 lower than those of pure carbon soot; meanwhile, the starting and final combustion temperatures of carbon soot (T10 and T90) are the lowest at 585.8 °C and 679.4 °C, respectively, which are 22.1 °C and 20.9 °C lower than those of pure carbon soot.

Effect of silicon on the kinetics and mechanisms of cyclic oxidation of titanium aluminide (Ti45Al5Nb0.5Si) developed by laser direct energy deposition

In this study, titanium aluminides comprising of Ti45Al5Nb0.5Si (TiAl-1), Ti45Al5Nb5Si (TiAl-2) and Ti45Al5Nb10Si (TiAl-3) were developed through laser direct energy deposition (LDED) with Nd-YAG laser under optimized process parameters. The microstructure of TiAl-1 consists of α2+γ phase mixtures. Addition of 5 wt% and 10 wt% Si results in the formation of silicides in addition to γ and α2 phases. A thorough kinetics of cyclic oxidation (from 700°C to 900°C in air) demonstrates that with an increase in Si concentration the activation energy of oxidation increases from 227.99 kJ/mol (TiAl-1) to 337.55 kJ/mol (TiAl-3). The mechanism of oxidation has been established.

Activation energy of heterogeneous catalytic oxidation of methanol in oscillatory regime

Activation energy of heterogeneous catalytic oxidation of methanol in oscillatory regime

Oxidation of Fe35Mn21Ni20Cr12Al12 High Entropy Alloy in Dry Air

The isothermal oxidation of a Fe35Mn21Ni20Cr12Al12 high entropy alloy (HEA) was investigated in dry air for 50 h at 500, 600, and 700 °C after 90% cold rolling. The Fe35Mn21Ni20Cr12Al12 HEA behaves according to the linear oxidation rate with rate constants of 1 × 10−6, 3 × 10−6, and 7 × 10−6 g/(cm2·s) for oxidation at 500 °C, 600 °C, and 700 °C, respectively. The activation energy for oxidation of the HEA was calculated to be 60.866 KJ/mole in the 500–700 °C temperature range. The surface morphology and phase identification of the oxide layers were characterized. The formation of MnO2, Mn2O3, Mn3O4, Cr2O3, and Al2O3 in the oxide layers along with Fe2O3 is the key to the oxidation mechanism. The elemental mapping and line EDX scans were performed to identify the oxidation mechanisms.

Cobalt–Magnesium Oxide Catalysts for Deep Oxidation of Hydrocarbons

Co–Mg catalysts for methane combustion were synthesized and studied, revealing the transformation of MgCo2O4 spinel into a CoO–MgO solid solution with oxygen release from the spinel lattice as the calcination temperature increased. Repeated heat treatment of the calcined solid solution at lower temperatures led to spinel regeneration with segregation of the solid solution phase. A TPR of the samples showed the presence of two characteristic peaks, the first of which relates to the transition of Co3+Oh spinel to the Co2+Oh structure of CoO, and the second to the reduction of CoO to Co°. The second peak was observed at 540–620 °C for samples calcined at temperatures below spinel decomposition, and for high-temperature samples at 900–1100 °C. Taking into account the identity of the structure of phases obtained in both cases, the formation of not a true CoO–MgO solid solution, but rather a mixture of ordered oxides (“pseudo-solid solution”) in the low-temperature region, was postulated. A study of the activity of the samples showed the high activity of the spinel systems and a linear relationship between the activation energy of methane oxidation and the heat treatment temperature.

High-Temperature Oxidation Behaviour of High Entropy Alloys

High-temperature operation, such as in gas turbine engines, is typically limited by the ability of materials to withstand extreme operating conditions. The need for a combination of high-temperature strength and oxidation resistance, as well as microstructural stability, has led to the continued use of nickel-based superalloys as materials for turbine blades, the most critical component in aero gas turbine engines. Due to their limited melting points, materials beyond superalloys are needed to meet increasing fuel efficiency requirements. High entropy alloys have recently been considered as candidates for materials to replace nickel-based superalloys. This paper discusses the microstructures and high-temperature oxidation behavior of Al0.75CoCrCuFeNi high entropy alloy at 900, 1000, and 1100°C. It was found that the oxidation rate constants for Al0.75CoCrCuFeNi oxidized at 900, 1000, and 1100°C are 3.84 x 10-10, 5.99 x 10-10, and 8.97 x 10-10 (mg/cm2.s), respectively, with an activation energy for oxidation of 66.58 kJ/mol.

Kinetic and thermodynamic parameters of curcumin in edible oils with different degrees of unsaturation

The antioxidant activity of curcumin (0.02-0.1%) was evaluated in olive, sesame, and safflower oils at 373, 383, and 393 K. The results were examined in contrast to the effects of tocopherol (0.1%) and BHT (0.02%), so that the inhibitory function of curcumin was evaluated comparatively. The activation energy of oxidation was determined for olive (82.94 kJ·mol-1), sesame (77.39 kJ·mol-1) and safflower oils (74.42 kJ·mol-1). Adding curcumin (0.1%) enhanced the activation energy by 26.26, 26.64, and 38.81% in the case of olive, safflower, and sesame oils, respectively. Based on Gibbs free energy, curcumin functioned more effectively in olive oil at 373 K (growth coefficient: 1.52%), compared to the action of the other two antioxidants, namely tocopherol (1.43%) and BHT (1.39%). The efficiency of curcumin was lower in oils which had a higher degree of polyunsaturation due to the disproportionation of the hydrogen-donating mechanism and the rate of free-radical formation in these oils.

Structure-Function Relationship of Highly Reactive CuOx Clusters on Co3 O4 for Selective Formaldehyde Sensing at Low Temperatures.

Designing reactive surface clusters at the nanoscale on metal-oxide supports enables selective molecular interactions in low-temperature catalysis and chemical sensing. Yet, finding effective material combinations and identifying the reactive site remains challenging and an obstacle for rational catalyst/sensor design. Here, the low-temperature oxidation of formaldehyde with CuOx clusters on Co3 O4 nanoparticles is demonstrated yielding an excellent sensor for this critical air pollutant. When fabricated by flame-aerosol technology, such CuOx clusters are finely dispersed, while some Cu ions are incorporated into the Co3 O4 lattice enhancing thermal stability. Importantly, infrared spectroscopy of adsorbed CO, near edge X-ray absorption fine structure spectroscopy and temperature-programmed reduction in H2 identified Cu+ and Cu2+ species in these clusters as active sites. Remarkably, the Cu+ surface concentration correlated with the apparent activation energy of formaldehyde oxidation (Spearman's coefficient ρ = 0.89) and sensor response (0.96), rendering it a performance descriptor. At optimal composition, such sensors detected even the lowest formaldehyde levels of 3 parts-per-billion (ppb) at 75°C, superior to state-of-the-art sensors. Also, selectivity to other aldehydes, ketones, alcohols, and inorganic compounds, robustness to humidity and stable performance over 4 weeks are achieved, rendering such sensors promising as gas detectors in health monitoring, air and food quality control.

Effect of Silica Nanofiller on Thermal-Oxidative Degradation of Epoxy Composites Synthesized by the Sol-Gel Method

Using the sol-gel method, amine-curing polymer silica composites based on cycloaliphatic epoxy resin were obtained. The content of SiO2 filler in the composites was 0.5–10 wt %. The formed mass fractal of silica nanoparticles during the synthesis of composites has a reinforcing effect on the epoxy polymer matrix. The patterns of non-isothermal destruction of polymers and composites in the presence of atmospheric oxygen have been established. At 5 wt % SiO2, the effective activation energy of the main stage of destruction of composites increases from 165 to 254 kJ mol–1. As a result, the rate of weight loss of the samples decreases (the temperature corresponding to 50% weight loss shifts towards higher values by 30°C). The mechanism of high-temperature oxidation of pure polymer and composite with oxygen has been studied. It has been established that the introduction of SiO2 into the composition of composites increases the activation energy of isothermal oxidation of the substrate.

The response of 316 L steel manufactured by selective laser melting route to high-temperature oxidation behaviour: The role of microstructure modification

The current work examines the effect of 316 L steel's microstructure, which is modified through varying scanning angles with the sample surface (HNS (0°), INS (45°), and VNS (90°)) in the selective laser melting (SLM) method and through surface mechanical attrition treatment (SMAT), on its high-temperature oxidation behaviour (at 600–800 °C) is investigated. We have obtained a deeper understanding of the steel's oxidation behaviour by applying various characterisation techniques. The SMATed steel has a ∼ 1000 μm thick deformed layer containing a gradient microstructure, and its topmost layer contains fine twins and nanograins (∼30 nm). The hardness of this surface is ∼1.65 times the non-treated steel's hardness. All samples follow a parabolic rate law during oxidation. The VNS sample unveils the slowest oxidation rate amid the non-treated samples. SMAT increases the activation energy of oxidation. The distribution of elements across the oxidised samples' cross-section shows discontinuous Cr spreading within the oxide layer on the non-treated samples; however, the deformed samples show uniform distribution. Unlike non-SMATed samples, a minute decline in Cr and Mn content is observed underneath the oxide layer on the SMATed samples, confirming their enhanced outward diffusion. The oxide layer on SMATed samples has more Cr- and Mn-rich oxides. These oxides occupy the grain boundaries of the oxidised non-SMATed surfaces, where the micro-pores and cracks are present. Conversely, oxidised SMATed surfaces display uniform, defect-free Cr- and Mn-rich oxides with finer grains. Moreover, the SMATed layer remains reasonably stable during high-temperature oxidation (hardness drop ranges between ∼9 and ∼ 30%).

Suppressing Oxidation at Perovskite-NiOx Interface for Efficient and Stable Tin Perovskite Solar Cells.

Inorganic nickel oxide (NiOx) is an ideal hole transport material (HTM) for the fabrication of high-efficiency, stable, and large-area perovskite photovoltaic devices because of its low cost, stability, and ease of solution processing. However, it delivers low power conversion efficiency (PCE) in tin perovskite solar cells (TPSCs) compared to other organic HTMs. Here, the origin of hole transport barriers at the perovskite-NiOx interface is identified and a self-assembled monolayer interface modification is developed, through introducing (4-(7H-dibenzo[c,g]carbazol-7-yl)ethyl)phosphonic acid (2PADBC) into the perovskite-NiOx interface. The 2PADBC anchors undercoordinated Ni cations through phosphonic acid groups, suppressing the reaction of highly active Ni≥3+ defects with perovskites, while increasing the electron density and oxidation activation energy of Sn at the perovskite interface, reducing the interface nonradiative recombination caused by tetravalent Sn defects. The devices deliver significantly increased open-circuit voltage from 0.712 to 0.825V, boosting the PCE to 14.19% for the small-area device and 12.05% for the large-area (1 cm2) device. In addition, the 2PADBC modification enhances the operational stability of NiOx-based TPSCs, maintaining more than 93% of their initial efficiency after 1000 h.

Thermally Inducing Viscous Fluids to Generate Co-Based Perovskites Enriched with Active Species for the Removal of VOCs.

Various Co-based perovskites are synthesized through thermally driving viscous fluids. In this process, rare earth salts, cobalt salts, and citric acid do not require homogeneous mixing but only need to be heated until they melt into a molten viscous slurry. The physicochemical properties of cobalt-based perovskites were examined using techniques such as X-ray diffraction (XRD), electron paramagnetic resonance (EPR), scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-Mapping-EDS), X-ray photoelectron spectroscopy (XPS), hydrogen temperature-programmed reduction (H2-TPR), oxygen temperature-programmed desorption (O2-TPD), and N2 adsorption-desorption. The results indicate that the surface-active species can be controlled by altering the A-site elements of cobalt-based perovskites. All catalysts synthesized through the thermal treatment of viscous mixtures exhibited a low activation temperature and a low apparent activation energy for the catalytic oxidation of toluene. Among all cobalt-based perovskites, LaCoO3 demonstrated the most outstanding catalytic activity, primarily attributed to its capacity to expose a larger number of surface-active sites and oxygen species, as well as its superior reducibility. Furthermore, the formation process of optimal LaCoO3 was monitored using thermogravimetric analysis-differential scanning calorimetry (TGA-DSC), and the byproducts of the low-temperature catalytic oxidation of toluene by the catalyst were identified using gas chromatography-mass spectrometry (GC-MS). The possible mechanism of toluene oxidation was inferred by in situ diffuse reflection infrared Fourier transform spectroscopy (DRIFTS). Moreover, LaCoO3 exhibits a predominant resistance to high-temperature hydrothermal conditions. This work provides a scalable and innovative approach to fabricating exceptionally effective catalysts for the efficient purification of VOCs.

Oxidation behavior and kinetics of (Zr, Ti)(C, N)–SiC ceramics with enhanced oxidation resistance at 850 °C–950 °C

The oxidation behavior and kinetics of (Zr, Ti)(C, N)–SiC ceramics subjected to a temperature of 850 °C-950 °C (typical operating temperatures range of Generation-IV nuclear reactors) for 1–4 h are investigated via X-ray diffraction, scanning electron microscopy, and weight gain testing. The results show that the microstructures of the ceramics after oxidation comprises primarily of m-(Zr, Ti)O2, c-(Zr, Ti)O2, and SiO2. After adding Si, the oxidation layer appears as a two-layer structure with both external and internal layers. The oxidation order of (Zr, Ti)(C, N)–SiC ceramics at 850 °C-950 °C is ZrSi > (Zr, Ti)(C, N) > SiC. Unoxidized SiC forms a “core-shell” structure with a dense external layer of SiO2. The dual effect of small SiO2 particles occupying cracks and the “core-shell” structure of SiC–SiO2 withstanding stresses can inhibit the propagation of cracks and reduce the porosity of the oxide layer. The oxidation of Z5T and Z5T5S exhibits linear oxidation kinetics, whereas the oxidation of Z5T10S and Z5T20S results in quasi-parabolic oxidation. By adding Si, the oxidation activation energy of Z5T20S (with the addition of 20 mol% Si) increases by 174 % compared to that of Z5T ceramic, thus improving the oxidation resistance of (Zr, Ti)(C, N)-based ceramics at 850 °C-950 °C.

Oxidation behavior and mechanism of GH4975 superalloy prepared electron beam smelting between 900 °C and 1100 °C in air

In this work, the oxidation behavior and mechanism of GH4975 alloy prepared electron beam smelting were investigated in air at 900–1100 °C. The results show that the oxidation weight gain curve follows a parabolic law, and the oxidation activation energy of GH4975 alloy is 183.465 kJ/mol. The oxide film is mainly composed of NiO in the outer layer, CoCr2O4, TiO2, Cr2O3 and small amount of Al2O3 in the intermediate layer, and Al2O3 in the inner layer. After long-term oxidation, the outward release of internal stresses generated by CoCr2O4 and Cr2O3 will cause flaking of the outer oxide layer and part of the intermediate oxide layer. The formation mechanism and flaking behavior of oxide film were explained, and a growth model and flaking model of oxide film was established, which will provide a reference for the high temperature oxidation behavior of GH4975 alloy.

Water Activation Triggered by Cu-Co Double-Atom Catalyst for Silane Oxidation.

High-performance catalysts sufficient to significantly reduce the energy barrier of water activation are crucial in facilitating reactions that are restricted by water dissociation. Herein we present a Cu-Co double-atom catalyst (CuCo-DAC), which possesses a uniform and well-defined CuCoN6 (OH) structure, and works together to promote water activation in silane oxidation. The catalyst achieves superior catalytic performance far exceeding that of single-atom catalysts (SACs). Various functional silanes are converted into silanols with up to 98 % yield and 99 % selectivity. Kinetic studies show that the activation energy of silane oxidation by CuCo-DAC is significantly lower than that of Cu single-atom catalyst (Cu-SAC) and Co single-atom catalyst (Co-SAC). Theoretical calculations demonstrate two different reaction pathways where water splitting is the rate-determining step and it is accelerated by CuCo-DAC, whereas H2 formation is key for its single-atom counterpart.

Water Activation Triggered by Cu−Co Double‐Atom Catalyst for Silane Oxidation

AbstractHigh‐performance catalysts sufficient to significantly reduce the energy barrier of water activation are crucial in facilitating reactions that are restricted by water dissociation. Herein we present a Cu−Co double‐atom catalyst (CuCo‐DAC), which possesses a uniform and well‐defined CuCoN6(OH) structure, and works together to promote water activation in silane oxidation. The catalyst achieves superior catalytic performance far exceeding that of single‐atom catalysts (SACs). Various functional silanes are converted into silanols with up to 98 % yield and 99 % selectivity. Kinetic studies show that the activation energy of silane oxidation by CuCo‐DAC is significantly lower than that of Cu single‐atom catalyst (Cu‐SAC) and Co single‐atom catalyst (Co‐SAC). Theoretical calculations demonstrate two different reaction pathways where water splitting is the rate‐determining step and it is accelerated by CuCo‐DAC, whereas H2 formation is key for its single‐atom counterpart.