Reduction In Activation Energy Research Articles

Phonon-Lithium Ion Interactions: A Case Study of LiM(SeO3)2 (M = Al, Ga, In, Sc, Y, and La).

Li ion diffusion is fundamentally a thermally activated ion hopping process. Recently, soft lattice, anharmonic phonon, and paddlewheel mechanism have been proposed to potentially benefit the ion transport, while the understanding of vibrational couplings of mobile ions and anions is still very limited but essential. Herein, we accessed the ionic conductivity, stability, and especially, lattice dynamics in LiM(SeO3)2 (M = Al, Ga, In, Sc, Y, and La) with two different types of oxygen anions within a LiO4 polyhedron, namely, edge-shared and corner-shared with MO6 polyhedra, the prototype of which, LiGa(SeO3)2, has been theoretically reported before with the similar structural features to NASICON and later experimentally synthesized with the room temperature conductivity ∼0.11 mS cm-1. It is interesting to note that LiM(SeO3)2 with a higher Li phonon band center shows higher Li conductivity, which is in contradiction to the conventional understanding of the importance for soft lattice to superionic conductors. The anharmonic and harmonic phonon interactions as well as the couplings between the vibration of the edge-bonded or corner-bonded anion in Li polyanions and the Li ion diffusion have been studied in detail. With transition metal M changing from La, Y, In, Ga, Al, and Sc, anharmonic phonons increase with reduced activation energy for Li diffusion. The phonon modes dominated by the edge-bonded oxygen anions contribute more to the migration of the Li ion than those dominated by the corner-bonded oxygen anions because of the greater atomic interaction between the Li ion and the edge-bonded anions. Thus, rather than the overall lattice softness, attention shall be given to reduce the frequency of the critical phonons contributing to Li ion diffusion as well as to increase the anharmonicity, i.e., through asymmetric Li polyhedra, for the design of Li ion superionic conductors for all-solid-state batteries.

Enhanced photocatalytic hydrogen evolution by S-scheme heterojunction and metal phosphide in NiTiO3/Graphdiyne

A key strategy to improve photocatalytic reaction efficiency is to achieve effective separation and migration of photo-generated carriers. Heterojunctions and co-catalysts are essential for boosting charge separation and transfer, reducing activation energy, and providing active sites for surface redox reactions. Herein, we introduce a composite catalytic system based on NiTiO3, enhanced with Graphdiyne (GDY) and NiP, achieving a hydrogen production activity of 8.37 mmol g−1 h−1. This performance is attributed to the combined effects of S-scheme heterojunction formation and NiP nanoparticle generation through phosphorylation. The S-scheme heterojunction effectively separates electron-hole pairs, reducing charge transport distance. Additionally, NiP nanoparticles formed in situ promote faster charge separation from NiTiO3 and act as active sites to accelerate the reduction half-reaction. Consequently, NiTiO3/GDY-P exhibits higher light absorption, faster charge separation, and superior redox capacity compared to NiTiO3. This work presents an efficient, eco-friendly multiphase catalytic system based on an S-scheme heterojunction and metal phosphide.

Debromination of Pyrolytic oil from waste printed circuit boards by catalytic thermo chemical reactions with Ca(OH)2 and ZSM-5

The surge in Waste Electrical and Electronic Equipment (WEEE) volume presents a formidable disposal challenge. This study focused on catalytic pyrolysis of waste printed circuit boards (WPCBs) employing Ca(OH)2 alone and in conjunction with ZSM-5 as catalysts. Kinetic parameters for catalytic and non-catalytic pyrolysis were derived through thermogravimetric analysis (TGA). The Coats-Redfern method for non-catalytic pyrolysis showcased activation energies of 33.52, 405.81, and 67.96 kJ/mol in zones 1, 2, and 3, respectively with corresponding reaction orders of 0.9, 2.8, and 1.2. Introduction of Ca(OH)2 amplified activation energy and reaction order in zones 2 and 3. Subsequent incorporation of ZSM-5 with Ca(OH)2 resulted in reduced activation energy and reaction order in zone 2, while elevating them in zones 1 and 3. Validation through laboratory-scale fixed-bed reactor experiments confirmed TGA findings and unveiled that pyrolysis oil had enhanced phenolic yield because of ZSM-5 where Ca(OH)2 showcased its effectiveness in eliminating halogens.

Simultaneously Boosting Direct and Indirect Urea Oxidation of Nickel Hydroxide via Strategic Yttrium Doping.

Urea electrolysis can address pressing environmental concerns caused by urea-containing wastewater while realizing energy-saving hydrogen production. Highly efficient and affordable electrocatalysts are indispensable for realizing the great potential of this emerging technology. Among the numerous candidates, α-Ni(OH)2 has the merits of good electrocatalytic activity, adjustable heteroelement doping, and low cost; consequently, it has received tremendous attention in the electrolytic fields. Herein, a Y3+-doping strategy is developed to effectively enhance the catalytic performance of nickel hydroxide in the urea oxidation reaction (UOR). Our results show that Y3+ incorporation successfully modulates the electronic structure of α-Ni(OH)2 by inducing Ni3+ formation in the crystal lattice to initiate direct UOR, facilitates the Ni3+/Ni2+ redox transition with higher current responses to promote indirect UOR, and maintains the structural stability of YNi-10 (Ni2+/Y3+ molar ratio = 1:0.1) during long-term UOR operation. Owing to these features, the obtained YNi-10 sample exhibits a higher current density (127 vs 79 mA cm-2 at 1.5 V), a lower Tafel slope (48 vs 75 mV dec-1), a larger potential difference between the UOR and oxygen evolution reaction (OER, 0.26 vs 0.22 V at 80 mA cm-2), a higher reaction rate constant (1.1 × 105 vs 3.1 × 103 cm3 mol-1 s-1), and a reduced activation energy of UOR (2.9 vs 14.8 kJ mol-1) compared with the Y-free counterpart (YNi-0). This study presents a promising strategy to simultaneously boost direct and indirect UORs, providing new insights for further developing high-performance electrocatalysts.

The effects of 1D multi‐wall carbon nanotubes and 2D graphene nanoplatelets on curing behavior of epoxy/vinyl ester interpenetrating polymer network nanocomposites

AbstractThis study meticulously investigated the effect of two carbon allotrope nanofillers, two‐dimensional graphene nanoplatelets (GnPs) and one‐dimensional multi‐wall carbon nanotubes (MWCNTs) individually, at various loadings on the kinetics of curing of the epoxy (EP)/vinyl ester (VE) based interpenetrating polymer network (IPN) system, with a mass ratio of 1:1. The IPN system is including a liquid epoxy resin based on bisphenol A which has been cured by methyltetrahydrophthalic anhydride (MTHPA) in the presence of 1‐methyl imidazole (Mi) as an accelerator and a vinyl ester resin based on bisphenol A which has been cured by methyl ethyl ketone peroxide (MEKP). The curing behavior of all prepared nanocomposites under non‐isothermal conditions was studied using DSC at four heating rates. Two different isoconversional approaches were applied to evaluate the reaction kinetics, that is, the Friedman and the advanced Vyazovkin methods. The obtained activation energy curves for all samples revealed a complex curing behavior involving three stages: early IPN stage, IPN growth stage, and late IPN stage. Then, the activation energy values for each reaction step were determined based on the Friedman method. The presence of GnPs showed no catalytic effect on the reaction of VE with MEKP. In contrast, incorporating MWCNT nanoparticles considerably decreases the activation energy values of the reaction of ring opening of epoxides with MTHPA‐Mi and the reaction of esterification of the hydroxyl groups of VE with MTHPA.Highlights MWCNTs reduce activation energy in curing reactions for EP/MTHPA‐Mi and VE/MTHPA. GnPs do not catalyze VE/MEKP reaction unlike MWCNTs. Combining MWCNTs and GnPs enhances properties of IPN nanocomposites. Curing process includes early, growth, and late IPN stages impacting activation energy. SEM analysis reveals better dispersion of GnPs in IPN nanocomposites with MWCNTs.

CFD-aided enhancement of propylene oxide decomposition in a tubular reactor with a corrugated cooling jacket

_This research delves into the decomposition kinetics of propylene oxide within a novel reactor design characterized by a corrugated inner wall for enhanced cooling. By applying Computational Fluid Dynamics (CFD), this study aims to optimize the reactor's heat transfer capabilities to achieve precise control over the exothermic decomposition process. This approach addresses a previously unexplored area in CFD application, proposing a model that fine-tunes the decomposition efficiency of propylene oxide by considering the interplay of key parameters such as inlet mixture temperature, activation energy, flow rate, and the resulting thermal profile. The primary goal is to advance the development of more efficient and environmentally friendly chemical processing techniques in the propylene oxide industry. The study highlights the critical relationship between activation energy (74–76 kJ/mol), process temperature (29–37 °C), and cooling efficiency in optimizing the decomposition process. Significant findings indicate that higher inlet temperatures (37 °C) and lower activation energies (74 kJ/mol) lead to superior conversion rates. The study presents a clear correlation between temperature elevation, reduced activation energy, and enhanced conversion rates, demonstrating that optimizing these parameters can lead to significantly improved conversion efficiencies, potentially approaching 100 % under ideal conditions.

Scalable 2D Semiconductor‐Based van der Waals Heterostructure Interface with Built‐in Electric Field for Enhanced Electrochemical Water Splitting

Electrochemical water splitting has received tremendous attention as an eco‐friendly approach to produce hydrogen. Noble metals and their oxides are commonly used as electrocatalysts to reduce activation energy barriers for hydrogen and oxygen evolution reactions in high‐performance electrodes, but their cost, scarcity, and limited stability hinder widespread adoption of electrochemical water splitting. Further advancements are therefore needed to reduce reliance on noble metals and improve the long‐term stability. Herein, solution‐processed 2D van der Waals (vdW) p–n heterostructures as an interfacial layer between catalysts and the electrode are introduced to enhance the catalytic performance. These heterostructures are formed by sequentially assembling electrochemically exfoliated black phosphorus and molybdenum disulfide nanosheets into electronic‐grade p‐ and n‐type semiconductor thin films, with the scalability extending across tens‐of‐centimeter scale areas. Benefiting from the charge distribution and built‐in electric field developed upon heterojunction formation, the vdW heterostructure interfacial layer increases both the catalytic activity and stability of commercial Pt/C and Ir/C catalysts compared to when these catalysts are directly loaded onto electrodes. Additionally, the vdW heterostructure also serves as a template for synthesizing nanostructured Pt and Ir catalysts through electrodeposition, further enhancing the catalytic performance in terms of mass activity and stability.

Energy-efficient CO(2) conversion to multicarbon products at high rates on CuGa bimetallic catalyst

Electrocatalytic CO2 reduction to multi-carbon products is a promising approach for achieving carbon-neutral economies. However, the energy efficiency of these processes remains low, particularly at high current densities. Herein, we demonstrate that the low energy efficiencies are, in part, sometimes significantly, attributed to the high concentration overpotential resulting from the instability (i.e., flooding) of catalyst-layer during electrolysis. To tackle this challenge, we develop copper/gallium bimetallic catalysts with reduced activation energies for the formation of multi-carbon products. Consequently, the reduced activation overpotential allows us to achieve practical-relevant current densities for CO2 reduction at low cathodic potentials, ensuring good stability of the catalyst-layer and thereby minimizing the undesired concentration overpotential. The optimized bimetallic catalyst achieves over 50% cathodic energy efficiency for multi-carbon production at a high current density of over 1.0Acm−2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$1.0 \\, {{\\rm{A}}} \\, {{\\rm{cm}}}^{-2}$$\\end{document}. Furthermore, we achieve current densities exceeding 2.0Acm−2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$2.0 \\, {{\\rm{A}}} \\, {{\\rm{cm}}}^{-2}$$\\end{document} in a zero-gap membrane-electrode-assembly reactor, with a full-cell energy efficiency surpassing 30%.

Solid-State Lithium Batteries with in-Situ Polymerized Acrylate-Based Electrolytes Capable of Electrochemically Stable Operation at 100 ℃

In-situ polymerized acrylate-based polymers are very appealing as solid polymer electrolytes (SPEs) in lithium (Li) batteries due to the drop-in compatibility of such in-situ polymerization with conventional battery production, the ease of acrylate polymerization and their inexpensive, facile SPE chemistry. We identified, however, that such SPEs suffer from either a low cationic transference number with dual ion conducting salts (0.12-0.2) or a low ionic conductivity with single Li-ion conducting (SLIC) salts (6·10-6 S cm-1). In this project we overcame these limitations and developed significantly improved SPE with ionic conductivity of up to 2·10-4 Scm-1 and a relatively high Li-ion transference number of 0.4. With a significantly reduced fraction of mobile anions in the hybrid SPE, in-situ polymerized SPE cells with an LiFePO4 (LFP) cathode achieve a stable performance for over 100 cycles at temperatures as high as 100 °C, which is unattainable with conventional Li salts or electrolytes. Furthermore, the motional narrowing observed in the line-shapes of solid-state nuclear magnetic resonance (SS-NMR) spectra provided additional insights of the differences in Li nucleus environments and revealed a reduced activation energy for the hybrid salt SPEs due to their more open structure. This study opens the path for the fabrication of high-performance solid polymer lithium batteries capable of operating at high temperatures using commercial battery fabrication equipment. We expect that further tuning of the acrylate based SPE composition may allow further increases in its conductivity without sacrifices in its electrochemical stability or mechanical properties.

A high-entropy cathode for sodium-ion batteries: Cu/Zn-doping O3-Type Ni/Fe/Mn layer oxides

The O3 layered oxides have been extensively investigated as cathode materials for sodium-ion batteries due to their remarkable theoretical capacity. However, the large radius of Na+ lead to complex phase transitions and tortuous diffusion channels during extraction/insertion, which ultimately restricts the Na+ diffusion kinetics and cyclic stability. In this study, we report a Zn and Cu co-doping strategy to the high entropy layer oxide Na [Ni0·2Fe0·2Mn0·4Cu0·15Zn0.05]O2 (HEO-CuZn) using the sol-gel method to prepare the oxides. Here, Zn is used to stabilize the structure of layer between the transition metal and O atoms, which slows down the adverse phase transition. In the fabricated sample, the element Cu provides additional capacity and inhibits excessive oxidation. The prepared HEO-CuZn used as cathode for Na+ ion battery exhibits better electrochemical performance, delivering a high specific capacity of 148 mA h g−1, and 84 % capacity retention after 100 cycles, which is attributed to the expanded Na+ transfer channels, reduced activation energy and interface side reactions, thus enhancing the Na+ diffusion kinetics. Meanwhile, the high entropy strategy stabilizes the overall structure by reducing the John-Teller distortion and suppressing the Na+/vacancy order, and effectively avoids adverse phase transitions such as O′3 and P′3. This study provides a new insight for the advance of the next generation high specific energy sodium-ion battery.

Mxene-supported NbVH nanoparticles as efficient catalysts for reversible hydrogen storage in magnesium borohydride

Bimetallic niobium vanadium hydride nanoparticles (NbVH NPs) anchored on Ti3C2 were synthesized using a facile ball milling method as an effective catalyst for the dehydrogenation kinetics and reversibility of Mg(BH4)2. It was found that the onset dehydrogenation temperature of the Mg(BH4)2 + 30NbVH NPs@Ti3C2 composite was 105.7 °C and released 9.07 wt% of hydrogen at 330 °C, while undoped Mg(BH4)2 only released 4.2 wt% of H2 from 248 °C to 330 °C. Additionally, the Mg(BH4)2 + 30NbVH NPs@Ti3C2 composite achieved remarkable hydrogen release of over 9.44 wt% at a temperature as low as 230 °C, indicating unexpected dehydrogenation kinetics. In the reversible hydrogen desorption tests, Mg(BH4)2 + 30NbVH NPs@Ti3C2 released 5.98 wt% of H2 in the 2nd cycle at 250 °C and maintained a reversible capacity of 4.35 wt% after 10 cycles, demonstrating a remarkable enhancement in reversibility. The enhancement in the dehydrogenation kinetics of Mg(BH4)2 could be attributed to the greatly reduced activation energies from 343 kJ·mol−1 and 138.3 kJ·mol−1 to 103.7 kJ·mol−1 and 124 kJ·mol−1. Investigations on the evaluation of catalyst and Mg(BH4)2 during reversible hydrogen storage have revealed that NbVH NPs actually acted as a “bidirectional hydrogen pump”, facilitating both the hydrogen release and uptake from Mg(BH4)2. This strategy of multi-component hydrides may show a new way to design effective catalysts for solid-state hydrogen storage materials.

A simple predictive three-step chemical model for gaseous stoichiometric hydrogen–oxygen detonation quenching

Two types of three-step chain-branching kinetics for gaseous hydrogen–oxygen detonation quenching are proposed. The reaction rates dependency on density and pressure, as well as the change in molecular weight are included and fitted to results of detailed chemistry not only along the Hugoniot curve but also behind transverse waves. The trend of induction and reaction times and reduced activation energy of zero-dimensional constant pressure combustion process as well as the induction, reaction lengths, and peak thermicity of the ZND model are focused on in the calibration procedure. One model (3SM-I) is designed to model the ideal detonation whereas the other (3SM-N) focuses on the Dn−κ curve during calibration, i.e. the detonation velocity-mean front curvature curves, aiming to capture the non-idealities. The predictive ability using the proposed models is evaluated in a detonation transmission configuration, a layer of ▪ mixture being confined by N2, in determining the critical height, reactive layer height at which detonation transmission is not possible. Both approaches get closer to the critical height from detailed chemistry. With the present set of model parameters, 3SM-I is better than 3SM-N for prediction of critical height. Moreover, borrowing analytical ignition criteria and wave hierarchy approach, the comparison of various chemical models that are able to recover the critical height suggests that the slope of the Dn−κ curve, linked with the chemical response to losses, is the first key parameter for the critical height determination. In addition, the dynamics of the extinction near criticality such as appearance of transverse detonation and quenching distance from 3SM-I are in very good agreement with that of detailed chemistry due to better estimation of the chemical features along the Hugoniot curve and behind transverse waves. The present study provides a guideline to get simplified chemical models from detailed chemistry for predictive simulations.Novelty and significance statementThe novelty of research is two-fold. The first is to provide general guideline to get simplified models from detailed chemistry for the simulation of detonation extinction with improved predictive ability. The tested configuration was that of a stoichiometric hydrogen–oxygen mixture semi-confined by nitrogen. The evolution of the induction, reaction times, and the maximum thermicity were used as fitting targets for our 3-step model. Furthermore, they were evaluated not only at the post-shock states along the Hugoniot curve, but also behind the transverse waves, keystones of the cellular structure. Second, borrowing analytical ignition criteria and wave hierarchy approach, the comparison of different chemical models that were able to recover the critical height suggested that the slope of the normal velocity–curvature curve was the first key parameter for the critical height determination. Moreover, the dynamics of extinction near criticality, and quenching distance depended on the reaction rate dependency on density and pressure.

Flash Joule Heating: A Promising Method for Preparing Heterostructure Catalysts to Inhibit Polysulfide Shuttling in Li-S Batteries.

The "shuttle effect" issue severely hinders the practical application of lithium-sulfur (Li-S) batteries, which is primarily caused by the significant accumulation of lithium polysulfides in the electrolyte. Designing effective catalysts is highly desired for enhancing polysulfide conversion to address the above issue. Here, the one-step flash-Joule-heating route is employed to synthesize a W-W2C heterostructure on the graphene substrate (W-W2C/G) as a catalytic interlayer for this purpose. Theoretical calculations reveal that the work function difference between W (5.08eV) and W2C (6.31eV) induces an internal electric field at the heterostructure interface, accelerating the movement of electrons and ions, thus promoting the sulfur reduction reaction (SRR) process. The high catalytic activity is also confirmed by the reduced activation energy and suppressed polysulfide shuttling by in situ Raman analyses. With the W-W2C/G interlayer, the Li-S batteries exhibit an outstanding rate performance (665 mAh g-1 at 5.0 C) and cycle steadily with a low decay rate of 0.06% over 1000 cycles at a high rate of 3.0 C. Moreover, a high areal capacity of 10.9 mAh cm-2 (1381.4 mAh g-1) is obtained with a high area sulfur loading of 7.9mg cm-2 but a low electrolyte/sulfur ratio of 9.0 µL mg-1.

S-Block Metal Mg-Mediated Co─N─C as Efficient Oxygen Electrocatalyst for Durable and Temperature-Adapted Zn-Air Batteries.

In the quest to enhance Zn-air batteries (ZABs) for operating across a wide spectrum of temperatures, synthesizing robust oxygen electrocatalysts is paramount. Conventional strategies focusing on orbital hybridization of d-d and p-d aim to moderate the excessive interaction between the d-band of the transition metal active site and oxygen intermediate, yet often yield suboptimal performance. Herein, an innovative s-block metal modulation is reported to refine the electronic structure and catalytic behavior of Co─NC catalysts. Employing density functional theory (DFT) calculations, it is revealed that incorporating Mg markedly depresses the d-band center of Co sites, thereby fine-tuning the adsorption energy of the oxygen reduction reaction (ORR) intermediate. Consequently, the Mg-modified Co─NC catalyst (MgCo─NC) unveils remarkable intrinsic ORR activity with a significantly reduced activation energy (Ea) of 10.0kJmol-1, outstripping the performance of both Co─NC (17.6kJmol-1), benchmark Pt/C (15.9kJmol-1), and many recent reports. Moreover, ZABs outfitted with the finely tuned Mg0.1Co0.9─NC realize a formidable power density of 157.0mWcm-2, paired with an extremely long cycle life of 1700h, and an exceptionally minimal voltage gap decay rate of 0.006mVh-1. Further, the Mg0.1Co0.9─NC-based flexible ZAB presents a mere 2% specific capacity degradation when the temperature fluctuates from 25 to -20°C, underscoring its robustness and suitability for practical deployment in diverse environmental conditions.

Reconstituting the microstructural properties and ionic conductivity of copper - doped yttria-stabilized zirconia via mechanochemical synthesis for intermediate-temperature solid oxide fuel cell applications

The development of highly conductive and thermally stable solid electrolytes is crucial for the next generation of intermediate temperature solid oxide fuel cells (IT-SOFCs). This study investigates the influence of copper (Cu) doping on the microstructure and ionic conductivity of 8 mol. % yttria-stabilized zirconia (8YSZ) when sintered at lower temperatures. The mechanochemical synthesized 1, 3, and 5 wt. % Cu-doped 8YSZ compacts were extensively characterized their properties through a suite of analytical techniques like X-ray diffraction, Raman, X-ray photoelectron, UV–Vis diffused reflectance, particle size analyzer, BET surface area, Emission Scanning Electron Microscopy-Energy Dispersive X-Ray, and AC impedance. The results revealed enhanced ionic conductivity and sinterability, at reduced temperature of 1373 K, with the 5 wt. % Cu-doped 8YSZ demonstrating the highest ionic conductivity of 4.18 × 10−3 S cm−1 at 1023 K, alongside reduced activation energy of 1.14 eV. The lower sintering temperatures and consequential benefits in performance metrics suggest Cu-doping as an effective strategy for optimizing 8YSZ-based electrolytes lowering SOFC manufacturing costs without compromising performance for IT-SOFCs.

Microwave absorbing alkaline catalyst for biodiesel production via MIL-100(Fe): Catalytic optimization, characterizations, kinetics, and distillation simulation

Microwave heating (MW) is known for its efficacy in promoting transesterification for biodiesel production. However, the microwave-induced catalysis, linked to catalyst absorbing capability, remains poorly understood. Herein, a class of alkaline catalysts with strong microwave absorption were synthesized, validating their positive impact on transesterification. Various methods were used to reveal the relationship between microwave absorbing capacity and physicochemical properties of the synthesized catalyst (KF/Mg-MIL). Results indicated the previously recognized basicity’s role for KF/Mg-MIL was surpassed by microwave absorbing capability (permittivity and permeability) in MW (2.45 GHz). KF/Mg-MIL, with εr = 4.94′-j1.09″ and μr = 1.03′-j0.024″, efficiently transformed microwave into thermal energy via the dielectric loss and magnetic loss, saving 50 % energy consumption and reducing 1051.61 kg CO2 for per ton biodiesel compared to water bath heating (WB). Notably, “non-thermal” effect was observed with KF/Mg-MIL in MW, which reduced activation energy by 2.49 kJ/mol and increased the frequency factor by 793.32 min−1 in comparison to WB.

Enhanced ionic conductivity through B-site Zr doping in NaNbO3 solid electrolytes

Oxide ion conductors hold significance in various applications, such as electrolytes in solid oxide fuel cells. This study focuses on synthesizing and systematically investigating the structural, morphological, and electrical properties of NaNb1-xZrxO3-0.5x (0 ≤ x ≤ 0.15) solid electrolyte. X-ray photoelectron spectroscopy (XPS) analysis shows that introducing a small quantity of zirconium into NaNbO3 induces an environment of unbalanced charge neutrality, creating oxygen vacancies. This phenomenon establishes a pathway for the mobility of oxygen ions. Temperature-dependent ac conductivity, analyzed through impedance data, follows Jonscher's power law, with the 's' parameter indicating a correlated barrier hopping mechanism. Enhanced conductivity is observed with Nb5+ substitution by Zr4+. The reduced activation energy value is observed for x = 0.1, which suggests enhanced ion hopping and, hence, enhanced conductivity. NaNb0.9Zr0.1O2.95 exhibits predominantly ionic conduction with a total conductivity of 6.2 × 10−4 S cm−1 and bulk conductivity of 1.72 × 10−3 S cm−1 at 700 °C. This study shows the promising potential of Zr-doped NaNbO3 as a solid electrolyte for various electrochemical applications.

Growth behavior of cristobalite SiO2 coating on 4H–SiC surface via high-temperature oxidation

When SiO2 films undergo oxidation on 4H–SiC, a distinctive crystalline phase, cristobalite, emerges at elevated temperatures. We deeply explored the growth mechanism of the crystallite, focusing on its dependence on the silicon sublimation process (SSO). Activation energy calculations confirmed that the oxidation after SSO above 1350 °C exhibits a lower activation energy. The reduced activation energy suggests the elimination of the solid-phase diffusion process during oxidation. We devised a controllable growth process for the quartz phase to achieve a seamless transition from 0 to 100 % in the area proportion of cristobalite in SiO2. This strategic approach facilitates the precise preparation of oxide layers and holds potential applications in semiconductor device manufacturing.

Enriching Nano-Heterointerfaces in Proton Conducting TiO2-SrTiO3@TiO2 Yolk-Shell Electrolyte for Low-Temperature Solid Oxide Fuel Cells.

A challenging task in solid oxide fuel cells (SOFCs) is seeking for an alternative electrolyte, enabling high ionic conduction at relatively low operating temperatures, i.e., 300-600°C. Proton-conducting candidates, in particular, hold a significant promise due to their low transport activation energy to deliver protons. Here, a unique hierarchical TiO2-SrTiO3@TiO2 structure is developed inside an intercalated TiO2-SrTiO3 core as "yolk" decorating densely packed flake TiO2 as shell, creating plentiful nano-heterointerfaces with a continuous TiO2 and SrTiO3 "in-house" interfaces, as well the interfaces between TiO2-SrTiO3 yolk and TiO2 shell. It exhibits a reduced activation energy, down to 0.225eV, and an unexpectedly high proton conductivity at low temperature, e.g., 0.084 S cm-1 at 550°C, confirmed by experimentally H/D isotope method and proton-filtrating membrane measurement. Raman mapping technique identifies the presence of hydrogenated HO─Sr bonds, providing further evidence for proton conduction. And its interfacial conduction is comparatively analyzed with a directly-mixing TiO2-SrTiO3 composite electrolyte. Consequently, a single fuel cell based on the TiO2-SrTiO3@TiO2 heterogeneous electrolyte delivers a good peak power density of 799.7mW cm-2 at 550°C. These findings highlight a dexterous nano-heterointerface design strategy of highly proton-conductive electrolytes at reduced operating temperatures for SOFC technology.

Study on high-efficiency sulfide removement using sulfate radical-based AOPs and its oxidation mechanism of refractory gold ore

Pyrite enclosure poses a significant challenge in refractory gold ore processing, inhibiting gold leaching. This study explores Sulfate Radical-based Advanced Oxidation Processes (SR-AOPs) as an effective alternative for pretreating such ores. The oxidation pretreatments were performed under heat and ultrasound activation methods, including heat and ultrasound, and the influences of pretreatment time, pH, ultrasound power, pretreatment temperature, and precursor (PDS) concentration were investigated. Both ultrasonic and heat activation effectively mitigate the negative impact of pyrite enclosure on gold leaching. Specifically, the gold leaching rate improved from 21.9 % to 46.1 % and 74.9 % with heat and ultrasound activation, respectively The and generated by PDS dominate the pyrite oxidation according to EPR and quenching tests. Meanwhile, the SR-AOPs treatment also promotes the interactions between pyrite enclosure and leaching agent, reducing the negative influences of pyrite. Kinetic studies indicated that the oxidation processes are different under heat and ultrasound activation. Heat activation is governed by an interfacial chemical reaction, with an activation energy of 25.57 kJ/mol. In contrast, ultrasound-induced cavitation and microjets remove the oxidation layer, disrupt the pyrite crystal structure, and expose encapsulated gold. These effects accelerate pyrite oxidation, shifting the kinetic control step from interfacial chemical reaction to internal diffusion, with a reduced activation energy of 35.06 kJ/mol.