Low Barrier Research Articles

In situ Triggered Rich‐LiF/Mg Multifunctional Passivation Layer for Modifying the Anode Interface of All‐Solid‐State Lithium Metal Batteries

AbstractLithium (Li) is a promising anode material for all‐solid‐state Li metal batteries (ASSLMBs) due to its high energy density. However, the interface incompatibility of Li/solid electrolyte and uneven Li deposition induces the penetration of Li dendrites. Herein, a multifunctional rich‐LiF/Mg artificial solid electrolyte interphase (SEI) layer is constructed from a MgF2‐PVDF‐HFP film to passivate the Li anode and achieve effective inhibition of Li dendrites. Notably, the triggered LixMg alloys rivet the Li6PS5Cl (LPSCl) electrolyte and Li anode together well, producing satisfactory interface contact and reducing overpotential. The mechanism of LiF and LixMg alloys to enhance the stability of the Li/LPSCl interface is further elucidated by density functional theory (DFT). Moreover, the synergistic interaction of LiF with high interfacial energy and LixMg alloys with low diffusion barrier promotes uniform deposition of Li during plating/stripping and structural stability. Therefore, the modified Li‐symmetric cell exhibits ultra‐high critical current density (2.0 mA cm−2) and considerable cyclic stability (more than 1000 h at 0.5 mA cm−2). Remarkably, NCM//LPSCl//3% MgF2‐PVDF‐HFP@Li ASSLMBs exhibit considerable long‐term cycle stability (86.9% capacity retention after 100 cycles at 0.2 C). This work highlights the critical role of the intermediate passivating layer in mitigating side reactions and preventing Li penetration.

Light-Induced Polaronic Crystals in Single-Layer Transition Metal Dichalcogenides.

Light-induced ordered states can emerge in materials after irradiation with ultrafast laser pulses. However, their prediction is challenging because the inverted band occupation confounds our chemical intuition. Hence, we use a recently developed constrained density functional perturbation theory approach to systematically screen single-layer transition metal dichalcogenides (TMDs) for light-induced ordered states. We demonstrate that all examined single-layer TMDs reveal similar light-induced charge orderings. The corresponding reconstructions are periodic arrangements of polarons (polaronic crystals), characterized by triangular metal clusters and having no equivalent at equilibrium conditions. The polarons are accompanied by localized midgap states in the electronic band structure, detectable by experimental methods. We assess the selenides as the most promising candidates for potential photoexcitation experiments because they transition at low critical fluences, have low transition barriers, and maintain an open band gap under photoexcitation. Our work paves the way for innovative material design approaches targeting light-induced phases.

High and temperature-stable electrostrain in lead-free environmentally friendly BiFeO3-BaTiO3 piezoelectric ceramics

Currently, environmental pollution and industrial effluents are depleting soil, water, and aquatic life and pose serious concerns to climate change. Environmentally friendly piezoelectric materials are considered potential agents for industrial applications, as they can generate clean energy by applying mechanical forces. High and temperature-insensitive piezoelectric strain is an ever-increasing demand in lead-free ceramics. In this work, a lead-free La-doped BiFeO3-BaTiO3 composition is designed at the crossover boundary of normal-relaxor ferroelectrics. The properties are optimized as a function of sintering temperature (Ts) from 960 to 1000 °C. An enhanced and thermally stable converse piezoelectric constant (d33∗) of 760 ± 23 pm/V over a wide range of 25–150 °C is achieved at an optimized TS of 980 °C. This high electrostrain response is mainly attributed to the low energy barrier for domain switching due to multiple-point crystal structure morphotropic phase boundary. Additionally, the high Curie temperature (TC) of 355 °C with excellent piezoelectric strain performance of our work are promising results for high-temperature piezoelectric actuators. The framework of chemical composition design and phase engineering of this work could inspire further development of lead-free ceramics for industrial applications.

Fabrication of boron modified bi-functional air diffusion electrode for ciprofloxacin degradation: In-situ H2O2 generation and self-activation

In order to improve H2O2 in-situ generation in electrochemical system, a boron (B) modified air diffusion electrode (B@ADE) was fabricated in the present study. Carbon black (CB) doped by B was deposited on ADE surface as catalytic layer. Performance of B@ADE with different B/C mass ratios has been investigated and 0.3 was identified as the optimal one·H2O2 yield can be achieved 204.85 mg L-1 within 45 min at 0.3-B@ADE, which was 1.51 times for that of ADE. Meanwhile, H2O2 self-activation on B@ADE surface was observed and effects of different operating parameters on •OH formation have been analyzed. XPS analyzation demonstrated that BC2O, BC2O and C=O/O-C=O were related to H2O2 generation. DFT calculation revealed that BCO2 was benefit for O2 adsorption, while BC2O promoted *OOH desorption with lower free energy barriers for H2O2 and •OH generation. Quenching experiments for ciprofloxacin (CIP) demonstrated that •OH, O2•- and 1O2 were co-existed in the system with their contribution quantified. Four possible degradation pathways were proposed through active sites identification by DFT calculation and intermediates detection by HPLC-MS/MS. Bio-toxicity analyzation results showed that the toxicity of most intermediates was lowered than CIP. These results proved that electrochemical oxidation system with B@ADE enhanced in-situ H2O2 generation and self-activation, with great potential for practical application.

Deciphering the Morphological Difference of Amyloid-β Fibrils in Familial and Sporadic Alzheimer's Diseases.

The aggregation of amyloid-β (Aβ) into amyloid fibrils is the major pathological hallmark of Alzheimer's disease (AD). Aβ fibrils can adopt a variety of morphologies, the relative populations of which are recently found to be associated with different AD subtypes such as familial and sporadic AD (fAD and sAD, respectively). The two AD subtypes differ in their ages of onset, AD-related genetic predispositions, and dominant Aβ fibril morphologies. We postulate that these disease subtype-dependent fibril morphology differences can be attributed to the intrinsic fibril properties and interacting molecules in the environment. Using atomistic discrete molecular dynamics simulations, we demonstrated that the fAD-dominant morphology exhibited a lower free-energy barrier for fibril growth but also a lower stability compared with the sAD-dominant fibril morphology, resulting in the time-dependent population change consistent with experimental observations. Additionally, we studied the effect of the Bri2 BRICHOS domain, an endogenous protein that has been reported to inhibit Aβ aggregation by preferential binding to fibrils, as one of the possible environmental factors. The Bri2 BRICHOS domain showed stronger binding to the fAD-dominant fibril than the sAD-dominant fibril in silico, suggesting a more effective suppression of fAD-dominant fibril formation. This result explains the high population of the sAD-dominant fibril morphology in sporadic cases with normal Bri2 functions. Genetic predisposition in fAD, on the other hand, might impair or overwhelm Bri2 functions, leading to a high population of fAD-associated fibril morphology. Together, our computational findings provide a theoretical framework for elucidating the AD subtypes entailed by distinct dominant amyloid fibril morphologies.

‘Invisible’ Molecular Dynamics Revealed for a Conformationally Chiral π‐Stacked Perylene Bisimide Foldamer

Whilst energetic and kinetic aspects of folding processes are meanwhile well understood for natural biomacromolecules, the folding dynamics in so far studied artificial foldamer counterparts remain largely unexplored. This is due to the low energy barriers between their conformational isomers that make the dynamic processes undetectable with conventional methods such as UV/vis absorption, fluorescence, and NMR spectroscopy, making such processes ‘invisible’. Here we present an asymmetric perylene bisimide dimer (bis‐PBI 1) that possesses conformational chirality in its folded state. Owing to the large interconversion barrier (≥ 116 kJ mol–1), four stereoisomers could be separated and isolated. Since the interconversion between these stereoisomers requires the foldamer to first open and then to re‐fold, the transformation of one stereoisomer into others allowed us to ‘visualize’ the dynamics of folding with time and determine its lifetimes and the energetic barriers associated with the folding process. Supported by quantum chemical calculations, we identified the open structure to be only a fleeting metastable state of higher energy. Our experimental observation of the kinetics associated with the molecular dynamics in the PBI foldamer advances the fundamental understanding of folding in synthetic foldamers and paves the way for the design of smart functional materials.

'Invisible' Molecular Dynamics Revealed for a Conformationally Chiral π-Stacked Perylene Bisimide Foldamer.

Whilst energetic and kinetic aspects of folding processes are meanwhile well understood for natural biomacromolecules, the folding dynamics in so far studied artificial foldamer counterparts remain largely unexplored. This is due to the low energy barriers between their conformational isomers that make the dynamic processes undetectable with conventional methods such as UV/vis absorption, fluorescence, and NMR spectroscopy, making such processes 'invisible'. Here we present an asymmetric perylene bisimide dimer (bis-PBI 1) that possesses conformational chirality in its folded state. Owing to the large interconversion barrier (≥ 116 kJ mol-1), four stereoisomers could be separated and isolated. Since the interconversion between these stereoisomers requires the foldamer to first open and then to re-fold, the transformation of one stereoisomer into others allowed us to 'visualize' the dynamics of folding with time and determine its lifetimes and the energetic barriers associated with the folding process. Supported by quantum chemical calculations, we identified the open structure to be only a fleeting metastable state of higher energy. Our experimental observation of the kinetics associated with the molecular dynamics in the PBI foldamer advances the fundamental understanding of folding in synthetic foldamers and paves the way for the design of smart functional materials.

Diffusion of Ge Donors in β‐Ga2O3

Diffusion of Ge donors in β‐Ga2O3 is studied using a combination of secondary‐ion mass spectrometry, diffusion simulations, and first‐principles calculations, and compared to previous studies on Sn diffusion. Ge is implanted into (01)‐oriented samples and annealed at temperatures from 900 to 1050 °C for a total of 8 h. From previous first‐principles calculations, Sn is predicted to diffuse via the formation of a mobile complex with VGa that migrates through a sequence of exchange and rotation jumps. Herein, it is similarly predicted that Ge diffusion is mediated by VGa. However, the microscopic mechanism differs, as Ge can diffuse more easily through exchange combined with complex dissociation, rather than rotational jumps. This is explained by the difference in Ga‐site preference of Ge compared to Sn, and the three‐split mechanism that enables low migration barriers for VGa. The dissociation mechanism leads to a considerably faster transport for Ge as compared to Sn. The experimentally obtained Ge diffusion profiles are successfully fitted using a reaction–diffusion model based on the predicted diffusion mechanism, yielding a migration barrier of 2.5 ± 0.2 eV for the complex. The 2.72 eV obtained from first‐principles calculations is in good agreement with this value.

Experimental and DFT studies of mercury adsorption and oxidation on CuCo2O4(110) surface

Elemental mercury (Hg0) is a typical toxic pollutant in flue gas from coal-fired power plants. The specific role of oxygen transfer on Hg0 oxidation over CuCo2O4 oxygen carrier and the involved reaction mechanisms were systematically studied by experimental and theoretical methods. In this study, the CuCo2O4 oxygen carrier with spinel-structure was prepared with salt-assisted combustion method. To reduce the grain size and increase the specific surface area of the oxygen carrier, the optimal KCl: CuCo2O4 ratio of 1:1 was obtained. Oxygen uncoupling ability of CuCo2O4 oxygen carrier was very strong, and the oxygen-releasing performance was slightly decreased after ten cyclic processes. Simulation based on density functional theory (DFT) shows that CuCo2O4 has relative low oxygen vacancy formation energy and oxygen transport energy barrier, and the oxygen vacancy is the preferred O2 adsorption site. Hg0 removal experiments show that CuCo2O4 has a strong ability to remove Hg0. The proportion of Hg2+ increases with the temperature, and the proportion of HgP decreases accordingly. Simulation shows that the 3-Co site on the surface of the CuCo2O4 oxygen carrier is the optimum Hg0 adsorption site. CuCo2O4 is found as a strong oxygen-releasing oxygen carrier, which can effectively promote the oxidation of Hg0.

Constrained nuclear-electronic orbital QM/MM approach for simulating complex systems with quantum nuclear delocalization effects incorporated

The hybrid quantum mechanics/molecular mechanics (QM/MM) approach, which combines the accuracy of QM methods with the efficiency of MM methods, is widely used in the study of complex systems. However, past QM/MM implementations often neglect or face challenges in addressing nuclear quantum effects, despite their crucial role in many key chemical and biological processes. Recently, our group developed the constrained nuclear-electronic orbital (CNEO) theory, a cost-efficient approach that accurately addresses nuclear quantum effects, especially quantum nuclear delocalization effects. In this work, we integrate CNEO with the QM/MM approach through the electrostatic embedding scheme and apply the resulting CNEO QM/MM to two hydrogen-bonded complexes. We find that both solvation effects and nuclear quantum effects significantly impact hydrogen bond structures and dynamics. Notably, in the glutamic acid–glutamate complex, which mimics a common low barrier hydrogen bond in biological systems, CNEO QM/MM accurately predicts nearly equal proton sharing between the two residues. With an accurate description of both quantum nuclear delocalization effects and environmental effects, CNEO QM/MM is a promising new approach for simulating complex chemical and biological systems.

AB–stacked bilayer β12–borophene as a promising anode material for alkali metal-ion batteries

As the lightest 2D material, monolayer borophene exhibits a specific charge capacity of 1860 mA h g−1 for Li-ion batteries, which is four times higher than that of graphite and is one of the highest specific charge capacities ever reported for 2D anode materials. Additionally, it showed high mechanical strength and a low diffusion barrier. However, monolayer borophene suffers from stability issues in its free-standing form, which restricts its real-life applications. Inspired by the recent experimental investigations, which proved the higher stability of bilayer borophene polymorphs (BBPs) over their monolayer counterparts, in this work, we investigated the dynamical and thermodynamical stabilities of both AA– and AB–stacked BBPs in their β12 phase using first-principles calculations. Between the two stacking patterns, we found that only the AB–stacked β12–BBP is both energetically and dynamically stable, and we further investigated its potential as a high-performance anode material for alkali metal-ion batteries. Our investigations show that AB–stacked β12–BBP exhibits good electrical conductivity before and after metal atom (Li/Na/K) adsorption onto it. Further, AB–stacked β12–BBP adsorbs the metal atoms strongly with adsorption energies ranging between −0.89 to −1.44 eV, indicating that there is a lesser possibility of forming dendrites on this anode. Similarly, it has a low diffusion energy barrier (~ 0.13–0.49 eV) for metal atoms, meeting the fast charge/discharge rate requirements. Moreover, it exhibits a reasonably low average metal-insertion voltage (0.43 to 0.65 V) and a specific charge capacity of 330–413 mA h g−1 that is comparable to graphite. All the above findings suggest that the AB–stacked bilayer β12– borophene can be a potentially favorable anode material.

Reversible Local Protonation-Deprotonation: Tuning Stimuli-Responsive Circularly Polarized Luminescence in Chiral Hybrid Zinc Halides for Anti-Counterfeiting and Encryption.

Precise control over the organic composition is crucial for tailoring the distinctive structures and properties of hybrid metal halides. However, this approach is seldom utilized to develop materials that exhibit stimuli-responsive circularly polarized luminescence (CPL). Herein, we present the synthesis and characterization of enantiomeric hybrid zinc bromides: biprotonated ((R/S)-C12H16N2)ZnBr4 ((R/S-LH2)ZnBr4) and monoprotonated ((R/S)-C12H15N2)2ZnBr4 ((R/S-LH1)2ZnBr4), derived from the chiral organic amine (R/S)-2,3,4,9-Tetrahydro-1H-carbazol-3-amine ((R/S)-C12H14N2). These compounds showcase luminescent properties; the zero-dimensional biprotonated form emits green light at 505 nm, while the monoprotonated form, with a pseudo-layered structure, displays red luminescence at 599 and 649 nm. Remarkably, the reversible local protonation-deprotonation behavior of the organic cations allows for exposure to polar solvents and heating to induce reversible structural and luminescent transformations between the two forms. Theoretical calculations reveal that the lower energy barrier associated with the deprotonation process within the pyrrole ring is responsible for the local protonation-deprotonation behavior observed. These enantiomorphic hybrid zinc bromides also exhibit switchable circular dichroism (CD) and CPL properties. Furthermore, their chloride counterparts were successfully obtained by adjusting the halogen ions. Importantly, the unique stimuli-responsive CPL characteristics position these hybrid zinc halides as promising candidates for applications in information storage, anti-counterfeiting, and information encryption.

In Situ Unraveling Surface Reconstruction of Ni‐CoP Nanowire for Excellent Alkaline Water Electrolysis

The surface reconstruction behavior of transition metal phosphides precursors is considered as an important method to prepare efficient oxygen evolution catalysts, but there are still significant challenges in guiding catalyst design at the atomic scale. Here, the CoP nanowire with excellent water splitting performance and stability is used as a catalytic model to study the reconstruction process. Obvious double redox signals and valence evolution behavior of the Co site are observed, corresponding to Co2+/Co3+ and Co3+/Co4+ caused by auto‐oxidation process. Importantly, the in situ Raman spectrum exhibits the vibration signal of Co–OH in the non‐Faradaic potential interval for oxygen evolution reaction, which is considered the initial step in reconstruction process. Density functional theory and ab initio molecular dynamics are used to elucidate this process at the atomic scale: First, OH− exhibits a lower adsorption energy barrier and proton desorption energy barrier at the configuration surface, which proposes the formation of a single oxygen (–O) group. Under a higher –O group coverage, the Co–P bond is destroyed along with the POx groups. Subsequently, lower P vacancy formation energy confirm that the Ni‐CoP configuration can fast transform into a highly active phase. Based on the optimized reconstruction behavior and rate‐limiting barrier, the Ni‐CoP nanowire exhibit an excellent overpotential of 1.59 V at 10 mA cm−2 for overall water splitting, which demonstrates low degradation (2.62%) during the 100 mA cm−2 for 100 h. This work provide systematic insights into the atomic‐level reconstruction mechanism of transition metal phosphides, which benefit further design of water splitting catalysts.

Reversible Local Protonation‐Deprotonation: Tuning Stimuli‐Responsive Circularly Polarized Luminescence in Chiral Hybrid Zinc Halides for Anti‐Counterfeiting and Encryption

AbstractPrecise control over the organic composition is crucial for tailoring the distinctive structures and properties of hybrid metal halides. However, this approach is seldom utilized to develop materials that exhibit stimuli‐responsive circularly polarized luminescence (CPL). Herein, we present the synthesis and characterization of enantiomeric hybrid zinc bromides: biprotonated ((R/S)‐C12H16N2)ZnBr4 ((R/S‐LH2)ZnBr4) and monoprotonated ((R/S)‐C12H15N2)2ZnBr4 ((R/S‐LH1)2ZnBr4), derived from the chiral organic amine (R/S)‐2,3,4,9‐Tetrahydro‐1H‐carbazol‐3‐amine ((R/S)‐C12H14N2). These compounds showcase luminescent properties; the zero‐dimensional biprotonated form emits green light at 505 nm, while the monoprotonated form, with a pseudo‐layered structure, displays red luminescence at 599 and 649 nm. Remarkably, the reversible local protonation‐deprotonation behavior of the organic cations allows for exposure to polar solvents and heating to induce reversible structural and luminescent transformations between the two forms. Theoretical calculations reveal that the lower energy barrier associated with the deprotonation process within the pyrrole ring is responsible for the local protonation‐deprotonation behavior observed. These enantiomorphic hybrid zinc bromides also exhibit switchable circular dichroism (CD) and CPL properties. Furthermore, their chloride counterparts were successfully obtained by adjusting the halogen ions. Importantly, the unique stimuli‐responsive CPL characteristics position these hybrid zinc halides as promising candidates for applications in information storage, anti‐counterfeiting, and information encryption.

Meso/Microporous Single‐Atom Catalysts with Curved Fe‐N4 sites Boost the Oxygen Reduction Reaction Activity

Zeolitic‐imidazolate frameworks (ZIFs) are among the most efficient precursors for the synthesis of atomically dispersed Fe‐N/C materials, which are promising catalysts for enhancing the performance of Zn‐air batteries (ZABs) and proton exchange fuel cells (PEMFCs). However, existing ZIF‐derived Fe‐N/C electrocatalysts mostly consist of microporous materials, leading to insufficient mass transport and inadequate battery/cell performance. In this study, we synthesize an atomically dispersed meso/microporous Fe‐N/C material with curved Fe‐N4 active sites, denoted as FeSA‐N/TC, through the pyrolysis of hemin‐modified ZIF films on ZnO nanorods, obtained from the self‐assembly reaction between Zn2+ from ZnO hydrolysis and 2‐methylimidazole. Density functional theory calculations demonstrate that the curved Fe‐N4 active sites can weaken the intermediate adsorptions, resulting in lower free energy barriers and enhanced performance during oxygen reduction reaction (ORR). Specifically, FeSA‐N/TC exhibits exceptional ORR performance with half‐wave potentials of 0.925 V in alkaline media and 0.825 V in acidic media. When used as the cathodic catalyst in PEMFCs and ZABs, FeSA‐N/TC achieves high peak power densities (H2‐O2 PEMFC: 1100 mW cm–2; H2‐Air PEMFC: 715 mW cm–2; liquid‐state ZAB: 228 mW cm–2; solid‐state ZAB: 112 mW cm–2), demonstrating its feasibility and efficiency in practical applications.

Meso/Microporous Single-Atom Catalysts with Curved Fe-N4 sites Boost the Oxygen Reduction Reaction Activity.

Zeolitic-imidazolate frameworks (ZIFs) are among the most efficient precursors for the synthesis of atomically dispersed Fe-N/C materials, which are promising catalysts for enhancing the performance of Zn-air batteries (ZABs) and proton exchange fuel cells (PEMFCs). However, existing ZIF-derived Fe-N/C electrocatalysts mostly consist of microporous materials, leading to insufficient mass transport and inadequate battery/cell performance. In this study, we synthesize an atomically dispersed meso/microporous Fe-N/C material with curved Fe-N4 active sites, denoted as FeSA-N/TC, through the pyrolysis of hemin-modified ZIF films on ZnO nanorods, obtained from the self-assembly reaction between Zn2+ from ZnO hydrolysis and 2-methylimidazole. Density functional theory calculations demonstrate that the curved Fe-N4 active sites can weaken the intermediate adsorptions, resulting in lower free energy barriers and enhanced performance during oxygen reduction reaction (ORR). Specifically, FeSA-N/TC exhibits exceptional ORR performance with half-wave potentials of 0.925 V in alkaline media and 0.825 V in acidic media. When used as the cathodic catalyst in PEMFCs and ZABs, FeSA-N/TC achieves high peak power densities (H2-O2 PEMFC: 1100 mW cm-2; H2-Air PEMFC: 715 mW cm-2; liquid-state ZAB: 228 mW cm-2; solid-state ZAB: 112 mW cm-2), demonstrating its feasibility and efficiency in practical applications.

Exploring the factors influencing the ketoenamine-enolimine tautomeric equilibrium of pyridoxal 5′-phosphate in branched-chain aminotransferases

Pyridoxal 5′-phosphate (PLP), the active form of vitamin B6, is a critical coenzyme for various enzymes. It generates a Schiff base with the substrate and exhibits ketoenamine and enolimine tautomeric forms due to intramolecular proton transfer. This study aims to ascertain the predominant tautomeric form of the PLP Schiff base in MtIlvE and analyze its influencing factors. Molecular dynamics simulations indicate that the ketoenamine tautomer has higher binding free energy than the enolimine tautomer. Density functional theory calculations suggest that, despite their ability to interconvert at a relatively low energy barrier, the ketoenamine tautomer is thermodynamically more stable. Factors affecting the keto-enol tautomeric equilibrium were investigated by constructing various QM-cluster models. Our results demonstrate that both the protonation of the pyridine nitrogen and the presence of Tyr209, which stabilizes the O3 anion, shift the tautomeric equilibrium toward the ketoenamine configuration. These findings provide a theoretical basis for investigating enzyme catalytic mechanisms.

StaffsVerse: Building a Metaverse Campus Utilising the Unreal Editor for Fortnite

In pursuit of redefining the conventional campus introductory experience, this paper presents the development and implementation of the StaffsVerse project - a virtual campus immersion tool. Designed as a Metaverse representation, the StaffsVerse project intends to transform the physical campus of Staffordshire University into an interactive digital environment. Its purpose extends to serving as a versatile tool for remote education delivery, virtual campus tours, public science outreach, and facilitating a seamless transition for students into the university community. Through immersive digital engagement, the StaffsVerse project seeks to bridge the gap between remote learners and the campus environment while facilitating a smooth integration into academic and social aspects of university life. In contrast to previous implementations of virtual campuses, the StaffsVerse project is unique in leveraging the capabilities of Unreal Editor in Fortnite (UEFN). This approach enables the development of highly detailed, interactive, and engaging environments within the expansive Fortnite ecosystem. The project's primary objective is to harness the infrastructure and extensive user base of one of the world's most widely played multi-platform games, thereby ensuring a low barrier to access. Therefore, this paper will explore how the UEFN system's adaptability can effectively create an accurate virtual replica of the physical Staffordshire University campus. The key contribution of this paper includes an overview of the design and developmental journey of the StaffsVerse project. The evolution of the project will be outlined by discussing the two pivotal iterations of the game-based implementation and explaining the decision-making process that led to the resulting version. The examination extends to the unique features of the UEFN build, addressing the inherent challenges and opportunities specific to the platform. Furthermore, specific game-based decisions are discussed, such as replicating essential campus locations, integrating interactive features, and incorporating elements unique to the virtual environment. The paper will discuss the specific educational opportunities UEFN offers, including the potential for enhancing student engagement through gamified campus experiences, insights into creating a Metaverse university campus, and contributions to the growing discourse on the intersection of game-based virtual environments in learning.

Every reaction Detail Matters: An in silico driven Step-by-Step Guide to understand the B2O3-Catalyzed CO2 to cyclic carbonates conversion

The catalytic conversion of carbon dioxide (CO2) to cyclic organic carbonates (COCs) via cycloaddition with epoxides offers a dual benefit of reducing CO2 emissions while producing valuable chemical products. In this detailed in silico study, we employ density functional theory (DFT) to meticulously investigate the mechanisms underlying the B2O3/n-NBu4Br-catalyzed cycloaddition of CO2 and epoxides, following a step-by-step approach according to the reaction details. We provide a comprehensive comparison of the non-catalyzed, n-NBu4Br alone, and B2O3/n-NBu4Br-catalyzed pathways, emphasizing two distinct active sites within the B2O3 framework: Site 1 (six-membered boroxol ring) and Site 2 (open chain configuration). Our computational analysis highlights that the Site 1-catalyzed reaction pathway is more favorable, featuring a lower overall energy barrier of 26.8 kcal/mol, compared to 32.5 kcal/mol for the Site 2-catalyzed pathway. Detailed intrinsic bond orbital (IBO), natural adaptive orbital (NAdO) and distortion-interaction analysis (DIA) reveal significant differences in bonding properties and energy interactions, elucidating why Site 1 exhibits superior catalytic activity over Site 2. These findings are corroborated by experimental observations, which indicate that ball milling B2O3 increases defect sites, thereby enhancing exposure of active sites Site 1 and improving catalytic performance. This study provides an in-depth understanding of how the intrinsic properties of boron active sites influence the catalytic efficiency of B2O3, offering valuable insights for the design and optimization of metal-free catalysts for CO2 conversion.

A Multifunctional NaxBi/NaCl Flexible Interface Layer for Solid‐State Na Metal Batteries

AbstractNa3Zr2Si2PO12 (NZSP) electrolyte with excellent air stability and acceptable ionic conductivity demonstrates a significant potential for application in solid‐state Na metal batteries. However, the poor interfacial contact between NZSP and Na anode has severely hindered its practical application. Herein, a BiCl3/polytetrafluoroethylene flexible interface layer is constructed between NZSP and Na metal anode. BiCl3 can react with Na metal to form a multifunctional NaxBi/NaCl‐rich flexible interface layer during the cycling process, which can effectively enhance the interfacial contact, avoid the formation of voids and reduce the interfacial resistance. NaxBi with low energy barrier can provide fast Na+ diffusion path, and NaCl with a wide band gap can inhibit electron injection and suppress Na dendrite growth. Owing to the multifunctional NaxBi/NaCl flexible interface layer, the Na/BiCl3@NZSP/Na symmetric cell exhibits a reduced interfacial resistance from 1252.1 to 67.6 Ω and achieves a high critical current density of 2 mA cm⁻2 at 25 °C. At 0.1 mA cm⁻2/0.1 mAh cm⁻2 and 0.3 mA cm⁻2/0.3 mAh cm⁻2, the symmetric cell can stably cycle for 3000 and 1100 h. Additionally, the Na3V2(PO4)3/BiCl3@NZSP/Na full cell can retain 96.7% of initial capacity (≈111 mAh g−1) after 300 cycles at 0.5 C and excellent rate capability.