Low Energy Barrier Research Articles

Modulating Built-InElectric Field Strength in Ru/RuO2Interfaces through Ni Doping to Enhance Hydrogen Conversion atAmpere-levelCurrent.

Improving the alkaline hydrogen evolution reaction (HER)efficiency is essential for developing advanced anion exchange membrane water electrolyzers (AEMWEs) that operate at industrial ampere-level currents. Herein, we employ density functional theory (DFT) calculations to identify Ni-RuO2as the leading candidate among various 3d transition metal-doped M-RuO2(where metal M includes Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn). The incorporation of Ni atoms facilitates the partial reduction of RuO2, resulting in the formation of a Ni-Ru/RuO2interface having a significant built-in electric field (BIEF) during electrochemical reactions. The resulted BIEF enhances electron transfer across the interface, which is critical in lowering energy barriers and accelerating the hydrogen evolution reaction(HER)kinetics. As a result, the Ni-RuO2catalyst exhibits an overpotential of 134 mV at 1 A cm-2and a low Tafel slope of 20.85 mV dec-1, with just 0.03 mg cm-2of Ru loading. The highly effective BIEF, therefore, plays a pivotal role in the catalyst's remarkable performance, allowing the Ni-RuO2-based AEMWE to require only 1.71V to maintain stable operation at 1 A cm-2over a 1000-hour period.

Tuning Hydrogen Binding on Ru Sites by Ni Alloying on MoO2 Enables Efficient Alkaline Hydrogen Evolution for Anion Exchange Membrane Water Electrolysis.

Ruthenium (Ru)-based electrocatalysts have shown promise for anion exchange membrane water electrolysis (AEMWE) due to their ability to facilitate water dissociation in the hydrogen evolution reaction (HER). However, their performance is limited by strong hydrogen binding, which hinders hydrogen desorption and water re-adsorption. This study reports the development of RuNi nanoalloys supported on MoO2, which optimize the hydrogen binding strength at Ru sites through modulation by adjacent Ni atoms. Theoretical simulations reveal that substituting Ni atoms for adjacent Ru atoms reduces the high hydrogen adsorption Gibbs free energy on Ru while maintaining a low energy barrier for water dissociation. As a result, the RuNi/MoO₂ catalyst shows excellent HER performance with a low overpotential of 51mV at a current density of 100mAcm⁻2, outperforming commercial Pt/C. Furthermore, RuNi/MoO₂ demonstrates high turnover frequency (7.06s-1), mass activity (13.4Amg-1), and price activity (1030.77Adollar-1). In an AEMWE cell, RuNi/MoO₂ as the cathode catalyst achieves a current density of 1Acm-2 at 60°C with just 1.7V using 1m KOH. This work highlights the potential of RuNi/MoO₂ for ultra-high mass activity in efficient AEMWE applications.

Lattice Strain-Modulated Trifunctional CoMoO4 Polymorph-Based Electrodes for Asymmetric Supercapacitors and Self-Powered Water Splitting.

Developing efficient, multifunctional electrodes for energy storage and conversion devices is crucial. Herein, lattice strains are reported in the β-phase polymorph of CoMoO4 within CoMoO4@Co3O4 heterostructure via phosphorus doping (P-CoMoO4@Co3O4) and used as a high-performance trifunctional electrode for supercapacitors (SCs), hydrogen evolution reaction (HER), and oxygen evolution reaction (OER) in alkaline electrolytes. A tensile strain of +2.42% on the β-phase of CoMoO4 in P-CoMoO4@Co3O4 results in superior electrochemical performance compared to CoMoO4@Co3O4. The optimized P-CoMoO4@Co3O4 achieves a high energy density of 118Wh kg-1 in an asymmetric supercapacitor and low overpotentials of 189mV for the HER and 365mV for the OER at a current density of 500mA cm-2. This results in a low overall water splitting voltage of 1.71V at the same current density making it an effective bifunctional electrode in a 1m KOH freshwater electrolyte. Theoretical analysis shows that the excellent performance of P-CoMoO4@Co3O4 can be attributed to interfacial interactions between CoMoO4 and Co3O4, and the β-phase of CoMoO4, which lead to strong OH- adsorption and low energy barriers for reaction intermediates. Practical application is demonstrated by using P-CoMoO4@Co3O4-based ASCs to self-generate hydrogen (H2) in a P-CoMoO4@Co3O4||P-CoMoO4@Co3O4 alkaline seawater electrolyzer, showcasing its potential for future energy technologies.

Implications of Pyrolytic Gas Dynamic Evolution on Dissolved Black Carbon Formed During Production of Biochar from Nitrogen-Rich Feedstock.

Gases and dissolved black carbon (DBC) formed during pyrolysis of nitrogen-rich feedstock would affect atmospheric and aquatic environments. Yet, the mechanisms driving biomass gas evolution and DBC formation are poorly understood. Using thermogravimetric-Fourier transform infrared spectrometry and two-dimensional correlation spectroscopy, we correlated the temperature-dependent primary noncondensable gas release sequence (H2O → CO2 → HCN, NH3 → CH4 → CO) with specific defunctionalization stages in the order: dehydration, decarboxylation, denitrogenation, demethylation, and decarbonylation. Our results revealed that proteins in feedstock mainly contributed to gas releases, and low-volatile pyrolytic products contributed to DBC. Combining mass difference analysis with Fourier transform ion cyclotron resonance mass spectrometry, we showed that 44-60% of DBC molecular compositions were correlated with primary gas-releasing reactions. Dehydration (-H2O), with lower reaction energy barrier, contributed to DBC formation most at 350 and 450 °C, whereas decarboxylation (-CO2) and deamidization (-HCNO) prevailed in contributing to DBC formation at 550 °C. The aromaticity changes of DBC products formed via gas emissions were deduced. Compared to their precursors, dehydration increased DBC aromaticity, while deamidization reduced the aromaticity of DBC products. These insights on pyrolytic byproducts help predict and tune DBC properties via changing gas formed during biochar production, minimizing their negative environmental impacts.

Temperature-Controlled Gas Hydrate Nucleation in the Heterogeneous Environment.

Nucleation of multicomponent systems is a pervasive phenomenon in nature and is pertinent to a diverse array of scientific and industrial challenges. The nucleation mechanisms of immiscible multicomponent systems remain unclear. Here, gas hydrate is employed as a model system to study the nucleation of multicomponent systems. The effect of gas/liquid and solid/liquid interfaces on hydrate nucleation is examined through molecular dynamics simulations. The results demonstrate that gas hydrates tend to nucleate in the solution phase in the proximity of the gas/liquid interface at lower temperatures, which is controlled by mass transfer. As the temperature increases, the location of hydrate nucleation gradually shifts from the gas/liquid interface to the solid/liquid interface. We anticipate that the nucleation free energy barrier dominates the hydrate nucleation process at these conditions, making the heterogeneous nucleation with a lower free energy barrier more probable. The findings provide molecular insights into the mechanism and pathway underlying interface-induced gas hydrate nucleation. These insights will inform the development of the theory of gas hydrate nucleation, particularly in the context of heterogeneous nucleation.

Fine-Tuning the Anisotropies of Air-Stable Single-Molecule Magnets Based on Macrocycle Ligands.

Air-stable single-molecule magnets (SMMs) can be obtained by confining DyIII ion in a D6h coordination environment; however, most of the current efforts were focused on modifying the rigidity of the macrocycle ligand. Herein, we attempt to assemble air-stable SMMs based on macrocycles with a replaceable coordination site. By using an in situ 1 + 1 Schiff-base reaction of dialdehyde with diamine, three air-stable SMMs have been obtained in which one of the equatorial coordination sites can be varied from -NH- (for Dy-NH), -O- (for Dy-O), and -NMe- (for Dy-NMe). Complex Dy-NH shows a less distorted D6h symmetry and an anisotropy energy barrier of 1270 K. For complex Dy-O, the coordination site of -O- gives a relatively longer coordination bond but a comparable energy barrier in contrast with that of Dy-NH. In the case of complex Dy-NMe, although the -NMe-group gives a very long coordination bond, the large steric effect on the -NMe- group enforces a larger distortion of the D6h coordination geometry, resulting in the fast quantum tunneling of the magnetization that shortcuts the thermal relaxation process; therefore, Dy-NMe shows a lower energy barrier. This study provides a new strategy for modifying the coordinate site on the equatorial plane of D6h symmetry to fine-tune the structure and magnetic anisotropy of SMMs.

Catalytic Deconstruction of Commercial and End‐of‐Life Polyurethane with Heterogeneous Hydrogenation Catalyst

Polyurethane (PU), as a thermoset polymer, is extensively utilized in various applications, such as refrigerator foams, sponges, elastomers, shoes, etc. However, the recycling of post‐consumed PU poses significant challenges due to its intricate and extensive crosslinking structures. Catalytic hydrogenation is one of the most effective methods for recycling PU waste, nevertheless, there is currently a lack for a hydrogenation catalyst that is both high‐performing, recyclable, and cost‐effective for breaking down post‐consumed PU materials. This study first employs a commercial NiMo/Al2O3 catalyst to catalytically break down both model PU and commercial PU into aromatic amines and polyol fractions. Notably, the results indicated that PU waste can be efficiently degraded at a pressure of 5 MPa and at a temperature of 185°C and yielding a significant amount of a valuable chemical monomers. It is speculated that the existence of a catalytic base in the solvent system could trigger glycolysis on the surface of PU particles. Subsequently, with the assistance of hydrogenation catalyst, the process of polymer hydrogenation becomes feasible by breaking C‐N and C‐O bonds with low energy barriers within the polymer. This study demonstrates the capability of fluidized bed hydrogenation process, employing recyclable heterogeneous catalysts for the recycling of PU waste.

Functionalized MXene anodes for high-performance lithium-ion batteries

Investigating the fundamental properties of anode materials is essential for developing lithium-ion batteries (LIBs). Herein, ab initio calculations are used to determine the suitability of MXene M2CTX (M = Sc, Ti, V, Cr, and Mn; TX = Cl, Br, S, Se, O, and Te) sheets as anode materials for LIBs. We revealed that Cr2CSe2 sheet exhibited a Li storage capacity of 391.340mAh/g, surpassing that of graphite (372mAh/g). Furthermore, diffusion barrier analysis revealed considerably lower energy barriers (~0.05eV) for Li-ion diffusion along the C1–A–C2 pathway compared to graphite, demonstrating the potential for enhanced rate and capacity in MXene-based anode materials. These findings provide valuable insights into developing LIBs with enhanced performance.

Constructing dual-atom catalysts by replacing N atoms with heteronuclear transition metals as efficient sulfur host materials for lithium-sulfur batteries: A first-principles study

Dual-atom catalysts (DACs) have shown remarkable electrochemical performance as cathode materials in lithium-sulfur batteries (LSBs), and carbon-nitrogen compounds are highly effective support materials for these catalysts. In previous studies, catalytic atoms were often introduced into the cavities of carbon-nitrogen compounds, but this structure generally lacked stability. This work employs first-principles calculations to investigate the application potential of DACs (TM-TM@g-C3N4) supported on monolayer g-C3N4 through atomic substitution in LSBs. Molecular dynamics simulations and electronic structure analyses indicate that TM-TM@g-C3N4 structures possess good structural stability and exhibit enhanced conductivity. Adsorption studies reveal that, due to the d-electron configuration of heteronuclear dual atoms, the constructed DACs display excellent anchoring performance for LiPSs (with adsorption energies ranging from -1.02 to -5.67eV). Notably, the strong hybridization of Mn and Co d-orbitals in Mn-Co@g-C3N4 at the Fermi level enhances its catalytic performance in the sulfur reduction reaction kinetics, particularly crossing the Fermi level. The reduction of Li2S2 to Li2S, the rate-limiting step, shows a low free energy barrier (-0.09eV). Additionally, weakened Li-S bonds facilitate the decomposition of Li2S on Mn-Co@g-C3N4 (0.77eV). With its suitable adsorption energy and superior catalytic activity in both directions, Mn-Co@g-C3N4 emerges as an optimal support material with strong application potential. This work paves the way for developing high-activity host materials for LiPSs and provides valuable insights for designing homonuclear and heteronuclear DACs in LSBs.

Coexistence of altermagnetism and robust ferroelectricity in a bulk MnO wurtzite structure.

Altermagnetism is a new class of material with zero net magnetization, but having a nonrelativistic spin-split band structure. Here, we investigate the multifunctional properties of the hexagonal wurtzite MnO (w-MnO). w-MnO has a direct band gap of 0.39 eV and the altermagnetic behavior is achieved with a spin splitting of up to 188 meV. The bulk w-MnO has an in-plane magnetic anisotropy energy of -0.17 meV per cell along the [100] direction and temperature-dependent magnetization reveals a Néel temperature of around 180 K. Moreover, a maximum spin Hall conductivity of -285(ℏ/e) S cm-1 is obtained at a chemical potential of -0.24 eV. Along with the altermagnetism, we also find a large out-of-plane spontaneous polarization of 76.25 μC cm-2. w-MnO exhibits a low energy barrier of 0.26 eV per formula unit (f.u.) for polarization switching and this is further decreased to 0.15 eV per f.u. under 5% epitaxial tensile strain. The molecular dynamics simulations suggest that w-MnO retains its ferroelectric order below 2100 K indicating excellent thermal stability. These findings suggest that the hexagonal w-MnO can be a promising candidate for multiferroic applications particularly in spintronic and ferroelectric devices with high thermal stability.

On peptide bond formation from protonated glycine dimers in the gas phase: computational insight into the role of protonation.

Peptide bond formation from the pure protonated glycine dimer, H+(Gly)2, and from the mixed protonated glycine-diglycine dimer, H+Gly2(Gly), was recently found experimentally to occur in gas-phase experiments in the absence of any catalyst and especially under anhydrous conditions [J. Phys. Chem. A, 2023, 127, 775]. In this contribution we further examine the conditions of such unimolecular reactions by means of density-functional theory calculations at the DFT/M06 2X/6-311G++(2df,p) level, focusing in particular on the role played by the protonation site. Two pathways, stepwise and concerted, are identified for the pure protonated dimer, and six pathways are examined for the mixed dimer. The lowest-energy barriers for peptide bond formation are generally found when the reaction occurs precisely at the protonation site. In contrast, the highest barrier is obtained when the dipeptide is protonated away from the reaction site, in which case the peptide bond is formed similarly as with two neutral glycine molecules as the reaction partners. Protonated glycine monomers can also be hydrogen-bonded with the dipeptide, leading to energy barriers that lie inbetween those extreme cases.

Ion Intercalation‐Enabled Reconfigurable Photodetector with Low Programming Voltage and Broadband Response Based on Van Der Waals Tin Disulfide

AbstractArtificial neural networks with integrated sensing and computing capabilities, leveraging reconfigurable optoelectronics, can effectively emulate biological neural networks, thereby enabling rapid and efficient information processing. However, realizing reconfigurable photoresponsivity is often blocked by the requirement for high programming voltages and the limits of the detection spectrum range. This greatly restricts the progress of energy‐efficient and precise neuromorphic vision sensing. Herein, a reconfigurable photodetector with low programming voltage and broadband response is presented via in situ intercalation of Cu+ ions into the van der Waals (vdW) gaps of thermoelectric 2D material SnS2. Interestingly, the vdW gaps provide an ionic transport channel with lower energy barriers compared to oxide‐based memristors, resulting in a low programming voltage (0.5 V). Furthermore, reversible conversion of photo‐detection is achieved from photovoltaic to photo‐thermoelectric (PTE) mode via voltage‐controlled ion distribution, which modulates the phonon scattering rate in the neighboring SnS2 layer. As a result, the response spectrum switches from visible (532 nm) to long‐wave infrared (10 µm) with an on/off ratio as high as 104. Thus, dual‐mode conversion and broadband detection functionality in reconfigurable imaging are realized, suggesting a potential pathway for the development of highly energy‐efficient reconfigurable optoelectronics with a spectrum far beyond human vision.

Unraveling the C-C Coupling Mechanism on Dual-Atom Catalysts for CO2/CO Reduction Reaction: The Critical Role of CO Hydrogenation.

The electrochemical reduction reaction (RR) of CO to high value multicarbon products is highly desirable for carbon utilization. Dual transition metal atoms dispersed by N-doped graphene are able to be highly efficient catalysts for this process due to the synergy of the bimetallic sites for C-C coupling. In this work, we screened homonuclear dual-atom catalysts dispersed by N-doped graphene to investigate the potential in CO reduction to C2+ products by employing density functional theory calculations. We have demonstrated that the two adsorbed CO species on bimetallic sites cannot directly couple unless one of the CO molecules is hydrogenated. All the dual metal atom catalysts prefer a similar coupling mechanism, i.e., the asymmetric coupling of *CO on the bridged site and *CHO on the top site, while the Ni2 and Cu2 catalysts exhibit much better performance with moderate adsorption energies and low energy barriers. The enhanced activities are attributed to the decrease of the energy levels of *CO 2p states that weakens the metal-C bonding and thus facilitates the feasible C-C coupling with both low reaction energies and low barriers. These insights have revealed the significant role of the hydrogenation of CO species prior to the coupling step and may provide a theoretical perspective to understand the generation of C2+ products in the CO2/CORR.

Grain-Boundary-Rich Pt/Co3O4 Nanosheets for Solar-Driven Overall Water Splitting.

Interfacial engineering is considered an effective strategy to improve the electrochemical water-splitting activity of catalysts by modulating the local electronic structure to expose more active sites. Therefore, we report a platinum-cobaltic oxide nanosheets (Pt/Co3O4 NSs) with plentiful grain boundary as the efficient bifunctional electrocatalyst for water splitting. The Pt/Co3O4 NSs exhibit a low overpotential of 55 and 201 mV at a current density of 10 mA cm-2 for the hydrogen evolution reaction and oxygen evolution reaction in 1.0 M potassium hydroxide, respectively. A negligible degradation of 1.52 V at a current density of 10 mA cm-2 after continuous operation for 100 h, demonstrates the long-term stability of the catalyst. Furthermore, the overall water-splitting performance of the Pt/Co3O4 NSs surpasses that of the commercial Pt/C||RuO2. The density functional theory calculation results explain that the improvement of catalyst activity is attributed to the moderate adsorption/desorption energy of *H and the low reaction energy barrier of the rate-determining step. This work presents a novel vision to design bifunctional catalysts for the storage and conversion of hydrogen energy.

Mechanistic insights into carbonate radical-driven reactions: Selectivity and the hydrogen atom abstraction route.

Carbonate radical (CO3•) is inevitably produced in advanced oxidation processes (AOPs) when addressing real-world aqueous environments, yet it often goes unnoticed due to its relatively lower reactivity. In this study, we emphasized the pivotal role of CO3• in targeting the elimination of contaminants by contrasting it with conventional reactive oxygen species (ROSs) and assessing the removal of sulfamethazine (SMT). Similar to singlet oxygen (1O2), CO3• shows a preference for electron-rich organic compounds. In addition, hydrogen atom abstraction (HAA) was determined as the primary pathway in CO3•-driven reactions, with a lower free energy barrier (∆G‡) compared to the addition process, while single electron transfer (SET) was found to be thermodynamically unfavorable in all selected aromatics with varying substituents, using DFT calculations. The H atoms within amino groups (NH2 and NH) were shown to be the most susceptible to abstraction by CO3•, which is more facile than hydroxyl radical (•OH) due to the shorter NH bond cleavage length. Finally, the degradation intermediates of SMT by CO3• were identified, with SO2 extraction, the cleavage of SN and CN bonds, and nitration/nitrosation of NH2 groups being the main degradation pathways. The results from this study are expected to set the stage for the large-scale utilization of CO3• and advance our understanding of its reaction characteristics.

The Network Construction of a New Byproduct-Free XLPE-Based Insulation Using a Click Chemistry-Type Reaction and a Theoretical Study of the Reaction Mechanism.

Cross-linked polyethylene (XLPE) is applied in most advanced high-voltage direct-current (HVDC) power cable insulations, which are produced via dicumyl peroxide (DCP) technology. The electrical conductivity of insulation material can be increased by cross-linking byproducts from the DCP process. Hence, currently much attention is being paid to a new process to produce cross-linking byproduct-free XLPE. The cross-linking in situ between ethylene-glycidyl methacrylate copolymer and 1,5-disubtituted pentane via reactive compounding is a substitute for DCP. The reaction potential energy information of the eighteen reaction channels was obtained at the B3LYP/6-311+G(d,p) level. Results demonstrated that epoxy groups and 1,5-disubtituted reactive groups can react in situ to realize the XLPE-based network structure via covalent linking, and epoxy ring openings yielded ester. 1,5-disubtituted pentane played a cross-linker role. The reactivity of the carboxyl group was stronger than that of the sulfydryl or hydroxyl group. The reaction channel RTS1 was more kinetically favorable due to the lower reaction Gibbs energy barrier height of 1.95 eV. The cross-linking network construction of the new XLPE insulation without byproducts opens up the possibility of DCP substitution, which is beneficial to furthering the design of thermoplastic insulation materials for power cables in the future.

Highly Stable Lanthanide-Organic Frameworks Based on {Ln6O8} Clusters with Photocatalytic Reduction of CO2 to CO.

Metal-organic frameworks (MOFs) with adjustable structures, diverse chemical functionalities, and excellent CO2 capture ability have shown important potential application in the photocatalytic reduction of CO2 to valuable fuel to curb the energy crisis. In this work, a series of new isostructural lanthanide-organic frameworks based on hexanuclear {Ln6O8} clusters, {(DMA)2 [Ln6(μ3-OH)8(H2O)6(SBTC)3]}n (Ln-MOFs, Ln = Eu, Dy, Gd, Tb, Yb; H4SBTC = 5,5'-(ethene-1,2-diyl) di-isophthalic acid; DMA = dimethylamine cation) were synthesized by the solvothermal method. Ln-MOFs were metal-organic frameworks formed by {Ln6(μ3-OH)8} clusters and poly(carboxylic acid) ligands H4SBTC, which exhibited excellent photocatalytic properties for the reduction of CO2 to CO. Among these Ln-MOFs, the production rate of photocatalytic reduction of CO2 to CO by Eu-MOF was 663.00 μmol·h-1·g-1 and the selectivity reached 94.2%, utilizing [Ru(bpy)3]Cl2·6H2O as photosensitizers. Experimental characterizations and density functional theory (DFT) calculations unveiled that the effective charge separation, strong CO2 binding affinity, weak H2O adsorption energy, as well as low reaction energy barriers for the *COOH intermediates over Eu-MOF play an important role in possessing superior photoactivity. This study provides insights into the field of Ln-MOF materials for efficient photocatalytic CO2 reduction and conversion applications.

Enhanced Acidic Oxygen Evolution Reaction Performance by Anchoring Iridium Oxide Nanoparticles on Co3O4.

The sluggish kinetics of the anodic process, known as the oxygen evolution reaction (OER), has posed a significant challenge for the practical application of proton exchange membrane water electrolyzers in industrial settings. This study introduces a high-performance OER catalyst by anchoring iridium oxide nanoparticles (IrO2) onto a cobalt oxide (Co3O4) substrate via a two-step combustion method. The resulting IrO2@Co3O4 catalyst demonstrates a significant enhancement in both catalytic activity and stability in acidic environments. Notably, the overpotential required to attain a current density of 10 mA cm-2, a commonly used benchmark for comparison, is merely 301 mV. Furthermore, stability is maintained over a duration of 80 h, as confirmed by the minimal rise in overpotential. Energy spectrum characterizations and experimental results reveal that the generation of OER-active Ir3+ species on the IrO2@Co3O4 surface is induced by the strong interaction between IrO2 and Co3O4. Theoretical calculations further indicate that IrO2 sites loaded onto Co3O4 have a lower energy barrier for *OOH deprotonation to form desorbed O2. Moreover, this interaction also stabilizes the iridium active sites by maintaining their chemical state, leading to superior long-term stability. These insights could significantly impact the strategies for designing and synthesizing more efficient OER electrocatalysts for broader industrial application.

Electrochemically Stable and Ultrathin Polymer-Based Solid Electrolytes for Dendrite-Free All-Solid-State Lithium-Metal Batteries

Abstract Polymer-based composite solid electrolytes (PCSEs) are increasingly studied in all-solid-state lithium-metal batteries (ASSLMBs) due to the combined advantages of better flexibility of polymer and higher ion conductivity of ceramic electrolytes. However, most reported PCSEs are overly thick, increasing internal resistances. Besides, the poor stability at the Li metal-electrolyte interfaces often leads to severe lithium dendrite formation and reduced cycling stability. Here, we fabricate an ultrathin PCSE with a thickness of 12.4 μm, incorporating polyacrylonitrile (PAN) nanofibers as the structural matrix, and a filler with polyethylene oxide and Li6.5La3Zr1.5Ta0.5O12 (LLZTO). Due to the formation of the LiCN layer on the surface of the lithium metal and the Li-ion transport pathways induced by the dehydrocyanation reaction at the LLZTO/PAN interfaces, the PCSE exhibits a high critical current density of 1.8 mA cm-2 and a low energy barrier of 0.278 eV for Li-ion transfer, accommodating the fast Li-ion migration to avoid Li-dendrite growth. In addition, the stable nitrile groups and the dehydrocyanation reaction ensure the electrochemical stability of the PCSE with a high oxidation voltage of 5.5 V and an exceptional cycling stability (2100 h) in Li||PCSE||Li symmetric cells. Additionally, the Li||PCSE||LiFePO4 full cells demonstrate a high volumetric energy density of 338.3 Wh L-1 at 0.1 C and a robust stability over 100 cycles at 0.5 C. The study offers a new approach for fabricating ultrathin PCSEs and provides insights into the mechanisms of dendrite-free formation, guiding the development of high-performance PCSEs for ASSLMBs.

A Hybrid Photo-Catalytic Approach Utilizing Oleic Acid-Capped ZnO Nanoparticles for the Treatment of Wastewater Containing Reactive Dyes

In pursuit of overcoming Fenton oxidation limitations in wastewater treatment, an introduction of a heterogeneous photocatalyst was developed. In this regard, the current work introduces ZnO nanocrystals that were successfully prepared via a thermal decomposition technique and then capped with oleic acid (OA). The synthesized ZnO-OA and the pristine ZnO were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and field emission scanning electron microscopy (FE-SEM). Then, the study introduces the application of such materials in advanced oxidation processes, i.e., a Fenton reaction to treat dye-containing wastewater. Synthetic wastewater that was prepared using Reactive Blue 4 (RB4) was used as a simulated textile wastewater effluent. Fenton’s oxidation was applied, and the system parameters were assessed using the modified Fenton’s system. The synthesized samples of ZnO were characterized by a recognized wurtzite hexagonal structure. The surface modification of ZnO with oleic acid (OA) resulted in an increase in crystallite size, lattice parameters, and cell volume. These modifications were linked to the efficient capping of ZnO nanoparticles by OA, which further improved the dispersion of the nanoparticles, as demonstrated through SEM imaging. The optimum conditions of ZnO- and ZnO-OA-synthesized modified Fenton composites showed 400 mg/L and 40 mg/L for H2O2 and the catalyst, respectively, at pH 3.0, and within 90 min under UV irradiation the maximal dye oxidation reached 93%. The catalytic performance at its optimal circumstances was in accordance with a pseudo-second-order kinetics model for both ZnO-OA- and the pristine ZnO-based Fenton’s systems. The thermodynamic parameters, including the enthalpy (ΔH′), the entropy (ΔS′), and Gibbs free energy (ΔG′) of activations, were also checked, and their values settled that both ZnO and ZnO-OA Fenton systems are non-spontaneous in nature. Furthermore, the reaction signified for processing at a low energy barrier condition (10.38 and 31.38 kJ/mol for ZnO-OA- and the pristine ZnO-based Fenton reactions, respectively).