Transfer Barriers Research Articles

Construction of an interpenetrating manganese residue-derived FeC2O4/CuC2O4 composite with enhanced charge transfer in photo-Fenton reactions via mechanical activation pre-anchoring strategy

The low rates of charge separation and migration and the pronounced photo-corrosion of FeC2O4 significantly limit its environmental applications. Strengthening the charge transfer rate by constructing a tight bimetallic interface is an attractive method. Herein, a novel interpenetrating manganese residue (MR)-derived FeC2O4/CuC2O4 (MAMR-FeCuOx) composite with intimate interface was constructed via mechanical activation (MA) pre-anchoring and liquid-phase deposition-photo-reduction strategy, and was used as a photo-Fenton catalyst for efficient degradation of oxytetracycline (OTC) under visible light irradiation. The Cu2+ was uniformly dispersed and anchored on the surface of MR after MA pretreatment and an interpenetrating structure was formed through the liquid-phase deposition-photo-reduction process. MAMR-FeCuOx displayed excellent photo-Fenton catalytic performance and stability with a 99% OTC removal rate within 10 min, which is 20.87 times higher than that of FeC2O4, and maintained over 96% OTC removal rate even after ten consecutive cycles. These enhanced catalytic performances and stability can be attributed to the formation of an interpenetrating structure with the intimate interface between FeC2O4 and CuC2O4 induced by MA pretreatment, which promoted electronic interactions between Fe and Cu for effectively reducing the charge transfer barriers. This improved the utilization rate of visible light, the interface electron migration, and the separation efficiency of photogenerated charge carriers. This study provides new insights into the valorization of solid waste and the development of stable and efficient FeC2O4-based catalysts.

Thermal suppression of charge disproportionation accelerates interface electron transfer of water electrolysis.

The sluggish electron transfer kinetics in electrode polarization driven oxygen evolution reaction (OER) result in big energy barriers of water electrolysis. Accelerating the electron transfer at the electrolyte/catalytic layer/catalyst bulk interfaces is an efficient way to improve electricity-to-hydrogen efficiency. Herein, the electron transfer at the Sr3Fe2O7@SrFeOOH bulk/catalytic layer interface is accelerated by heating to eliminate charge disproportionation from Fe4+ to Fe3+ and Fe5+ in Sr3Fe2O7, a physical effect to thermally stabilize high-spin Fe4+ (t2g3eg1), providing available orbitals as electron transfer channels without pairing energy. As a result of thermal-induced changes in electronic states via thermal comproportionation, a sudden increase in OER performances was achieved as heating to completely suppress charge disproportionation, breaking a linear Arrhenius relationship. The strategy of regulating electronic states by thermal field opens a broad avenue to overcome the electron transfer barriers in water splitting.

Breaking barriers: Assessing technology transfer for climate-resilient development

The Intergovernmental Panel on Climate Change (IPCC) promotes technology transfer between developed and developing countries as a crucial tool for limiting global temperature rise. This climate change mitigation role of technology transfers has attracted extensive research on the barriers to technology transfer. However, a thematic analysis consolidating the diverse data is lacking. This study aims to fill this gap by conducting a thematic analysis of the barriers to technology transfer, which will consolidate and disseminate information to enhance the chances of successful technology transfer. The study employs a non-time-restricted thematic analysis of the barriers to technology transfer spanning 1990–2023. After analysing a diverse pool of secondary data, 285 codes revealed six primary themes: Organization and knowledge, Government and law, Investment and finance, Consumer and market, Infrastructure and development, and Climate and others. The primary themes of Organization and knowledge (OK) and Government and law (GL), with frequency scores of 108 and 69, respectively, are identified as the top two barriers. Furthermore, within these primary themes of OK and GL, the subbarriers of System and technical and Political issues, with frequency scores of 53 and 26, are the most frequently cited barriers. Addressing the technology transfer barriers identified in this study improves climate resilience and aligns with global climate initiatives such as the Paris Agreement and the "New Global Financing" initiative. Therefore, the study findings can contribute to UN Sustainable Development Goal 12 and the implementation of circular economy practices.

Multipole Expansion of Atomic Electron Density Fluctuation Interactions in the Density-Functional Tight-Binding Method.

The accuracy of the density-functional tight-binding (DFTB) method in describing noncovalent interactions is limited due to its reliance on monopole-based spherical charge densities. In this study, we present a multipole-extended second-order DFTB (mDFTB2) method that takes into account atomic dipole and quadrupole interactions. Furthermore, we combine the multipole expansion with the monopole-based third-order contribution, resulting in the mDFTB3 method. To assess the accuracy of mDFTB2 and mDFTB3, we evaluate their performance in describing noncovalent interactions, proton transfer barriers, and dipole moments. Our benchmark results show promising improvements even when using the existing electronic parameters optimized for the original DFTB3 model. Both mDFTB2 and mDFTB3 outperform their monopole-based counterparts, DFTB2 and DFTB3, in terms of accuracy. While mDFTB2 and mDFTB3 perform comparably for neutral and positively charged systems, mDFTB3 exhibits superior performance over mDFTB2 when dealing with negatively charged systems and proton transfers. Overall, the incorporation of the multipole expansion significantly enhances the accuracy of the DFTB method in describing noncovalent interactions and proton transfers.

“I Thought It Was a Little Risky”: Transfer Barriers for Students with Scholarship Support

ABSTRACT A study of hidden risks, anxieties and barriers to STEM student transfer from community college to a large, comprehensive university is presented. This qualitative study employed a thematic analysis of student responses to a semi-structured interview that asked students about their hesitancy to transfer to a 4-year institution. Participants included students enrolled in a collaborative NSF-sponsored S-STEM scholarship project between three community colleges and a large public university (all in the same large metropolitan area). The project included elements that are well documented in the literature to encourage transfer. These include advising visits by university staff, clear articulation pathways, scholarship support to assist with costs, peer and near peer mentoring opportunities, and cohort-building activities between campuses and on each individual campus. Transfer rates in this group were higher, but still many students with declared interest in transferring did not transfer on time or at all. The authors identified numerous hidden risks and barriers to transfer, in addition to the well-known ones found in the literature. These include additional academic, financial, social, logistical and external/family related barriers. A theme common to many of these barriers was complex bureaucratic processes and events outside of student’s direct control. Many student comments highlighted the importance of in-person connections, mentoring and advising.

Fermi level depinning via insertion of a graphene buffer layer at the gold–2D tin monoxide contact

Two-dimensional (2D) tin monoxide (SnO) has attracted much attention owing to its distinctive electronic and optical properties, which render itself suitable as a channel material in field effect transistors (FETs). However, upon contact with metals for such applications, the Fermi level pinning effect may occur, where states are induced in its band gap by the metal, hindering its intrinsic semiconducting properties. We propose the insertion of graphene at the contact interface to alleviate the metal-induced gap states. By using gold (Au) as the electrode material and monolayer SnO (mSnO) as the channel material, the geometry, bonding strength, charge transfer and tunnel barriers of charges, and electronic properties including the work function, band structure, density of states, and Schottky barriers are thoroughly investigated using first-principles calculations for the structures with and without graphene to reveal the contact behaviours and Fermi level depinning mechanism. It has been demonstrated that strong covalent bonding is formed between gold and mSnO, while the graphene interlayer forms weak van der Waals interaction with both materials, which minimises the perturbance to the band structure of mSnO. The effects of out-of-plane compression are also analysed to assess the performance of the contact under mechanical deformation, and a feasible fabrication route for the heterostructure with graphene is proposed. This work systematically explores the properties of the Au–mSnO contact for applications in FETs and provides thorough guidance for future exploitation of 2D materials in various electronic applications and for selection of buffer layers to improve metal–semiconductor contact.

Li Transport in Defected LiNiO2 from First Principles: Diffusion, Nucleation, and Charge Transfer

Electrochemical intercalation of Li in battery electrodes involves a few types of kinetic processes, including diffusion in inhomogeneous media, phase nucleation/transition, and surface charge transfer. They span several length and time scales and are often coupled with each other, which makes it challenging to identify the rate-limiting step and extract kinetic parameters by fitting an empirical model. Using layered cathode LiNiO2 as an example, I will present how all these processes can be incorporated in one atomistic model without empirical inputs, which reals the kinetic competition between different processes. In this scheme, the energetics of various local environments were calculated by the density functional theory (DFT). And the obtained data were used to train a surrogate Hamiltonian with the cluster expansion method. Then the kinetic Monte Carlo (KMC) simulations were conducted with ion hopping barriers updated on-the-fly based on the Brønsted−Evans−Polanyi (BEP) relation. The charge transfer barriers at the electrode-electrolyte interface were calculated separately using the constant-voltage eNEB method1.The simulation results shown below largely reproduce the experimental voltage profile of LiNiO2 2. Both the hysteresis and the irreversible capacity loss (IRC) at the first discharge are captured. The rate limiting step switches as the Li concentration changes during cycling. Moreover, the layered LiNiO2 is never perfect and there are always some excess Ni in the Li layer, which significantly affects the electrochemical performances. My simulations peek into the atomistic origins of these effects. The excess Ni formed in the bulk during synthesis increase IRC by impeding Li diffusion3; the excess Ni near the surface formed during cycling due to oxygen loss traps Li in the fatigued particles by suppressing Li-poor phase nucleation below certain Li concentration4.

Mechanical characteristics and deformation behavior of Al polycrystal reinforced with SiC particles

Molecular dynamics models are established to investigate the influence of silicon carbide (SiC) particle size and strain rate on the mechanical characteristics and deformation behavior of aluminum (Al)/SiC composite. The results show that the ultimate strength of the Al/SiC composite increases from 0.788 to 0.910 GPa as the SiC reinforcement particle size increases from 10 to 30 Å, due to load transfer effects and barriers to dislocation motion. Plastic deformation of Al/SiC composite decreases with increasing SiC particle size, manifested by a lower proportion of atoms subjected to high shear strain for larger SiC particles. The SiC particle size also influences the change in crystal structure during deformation, as shown by the larger particles better supporting the Al matrix in minimizing the dislocation movement. The study shows that the grain boundary and Al/SiC interface play a significant role in the mechanical properties of the composite by impeding the evolution of dislocation and stacking fault. Moreover, the higher strain rates lead to increased ultimate strength and flow stress due to a greater rate of deformation and energy storage. The distribution of shear strain in the composite shows concentrated deformation at the grain boundary, and the large shear-strain region decreases as the strain rate increases. Additionally, higher strain rate leads to more formation of hexagonal-close-packed and amorphous structures, increased dislocation density, and material failure.

Research trends around open innovation in higher education: advancements and future direction

Open innovation in higher education has emerged as a vital approach, especially in the context of the COVID-19 pandemic, to foster collaboration, knowledge exchange, and address challenges in the academic sector. This study investigates the impact of open innovation on entrepreneurial skills, value co-creation, and technology transfer barriers by examining collaborations between universities and industries in emerging economies and knowledge absorption in SMEs. Additionally, it underscores the significance of open innovation in enhancing teaching and learning quality and aligning with Sustainable Development Goals. To address research gaps, a bibliometric study using VOSviewer software is proposed, aiming to analyze co-occurrence between keywords and explore the relationships between variables. Following the PRISMA statement’s parameters for systematic literature review, the methodology ensures a comprehensive and replicable approach for accurate findings. The study reveals an increasing trend in literary production, with the United Kingdom and Spain leading academic progress. Prominent research trends include technology transfer through open innovation strategies, diversification of business models due to innovation policies, factors influencing collaboration between companies and universities, and the emergence of Education 4.0 with novel educational systems leveraging technology. These findings have implications for supporting the education sector, benefiting students, graduates, and the broader community.

Energy assessment and thermodynamic evolution of a novel semi-clathrate hydrate cold storage system with internally circulating gas bubble disturbance

Low energy storage density, intermittent phase changes, and heat transfer barriers have posed significant challenges in the implementation of hydrate energy storage systems. Based on the heterogeneous nucleation mechanism for tetrabutylammonium bromide (TBAB) hydrate phase change energy storage, a novel cold storage system with internally circulating gas disturbance was constructed for energy evaluation and thermodynamic evolution. The hydrate cold storage efficiency, response time, dynamic driving force, unique force pattern of the coils and guest molecule diffusion were analyzed for the first time. The bubbles generated by gas internal circulation provided numerous nucleation sites for hydrate formation, efficiently promoting the energy storage process. The disturbances caused by the bubbles also rapidly transmitted the energy generated by the phase change. A hydrate storage density of 57.4 kWh/m3 for this system was the maximum among known hydrate storage systems. Notably, a change in solution concentration (from 10 wt% to 40 wt%) resulted in a 2–3-fold increase in the cold charge capacity. Rapid dilution of local solutions and rapid release of cold were the ways to promote the cold discharge. Less damage to the stress structure of the coil was due to the loose accumulation of hydrate particles under gas disturbance. The microbubbles generated by the gas disturbance enabled heterogeneous nucleation and heat-mass transfer in the hydrate cold storage. The gas disturbance-based hydrate energy storage process holds significant guiding value for various applications such as refrigerated transport, building cooling systems, and grid peak shaving.

Assessment of the inhibitory potential of anabolic steroids towards human AKR1D1 by computational methods and in vitro evaluation

Exposure to xenobiotics can adversely affect biochemical reactions, including hepatic bile acid synthesis. Bile acids are essential for dissolving lipophilic compounds in the hydrophilic environment of the gastrointestinal tract. The critical micellar concentration of bile acids depends on the Δ4-reduction stereochemistry, with the 3-oxo-5β-steroid-Δ4-dehydrogenase (AKR1D1) introducing the cis ring A/B conformation. Loss-of-function mutations in AKR1D1 cause hepatic cholestasis, which, if left untreated can progress into steatosis and liver cirrhosis. Furthermore, AKR1D1 is involved in clearing steroids with an A-ring Δ4-double bond. Here, we tested whether anabolic-androgenic steroids (AAS), often taken off-label at high doses, might inhibit AKR1D1, thereby potentially causing hepatotoxicity. A computational molecular model was established and used for virtual screening of the DrugBank database consisting of 2740 molecules, yielding mainly steroidal hits. Fourteen AAS were selected for in vitro evaluation, as such compounds can reach high hepatic concentrations in an abuse situation. Nandrolone, clostebol, methasterone, drostanolone, and methenolone inhibited to various extent the AKR1D1-mediated reduction of testosterone. Molecular modeling suggests that 9 out of 14 investigated AAS are competitive inhibitors. Moreover quantum mechanical calculations show that nadrolone and clostebol are substrates of AKR1D1 with different activation energy barriers for the hydrogen transfer from cofactor to the C5 position affecting their turnover. In this multidisciplinary approach, we established a molecular model of AKR1D1, identified several AAS as inhibitors, and described their binding mode. This approach may be applied to study other classes of inhibitors including non-steroidal compounds.

How Is Substrate Halogenation Triggered by the Vanadium Haloperoxidase from Curvularia inaequalis?

Vanadium haloperoxidases (VHPOs) are unique enzymes in biology that catalyze a challenging halogen transfer reaction and convert a strong aromatic C-H bond into C-X (X = Cl, Br, I) with the use of a vanadium cofactor and H2O2. The VHPO catalytic cycle starts with the conversion of hydrogen peroxide and halide (X = Cl, Br, I) into hypohalide on the vanadate cofactor, and the hypohalide subsequently reacts with a substrate. However, it is unclear whether the hypohalide is released from the enzyme or otherwise trapped within the enzyme structure for the halogenation of organic substrates. A substrate-binding pocket has never been identified for the VHPO enzyme, which questions the role of the protein in the overall reaction mechanism. Probing its role in the halogenation of small molecules will enable further engineering of the enzyme and expand its substrate scope and selectivity further for use in biotechnological applications as an environmentally benign alternative to current organic chemistry synthesis. Using a combined experimental and computational approach, we elucidate the role of the vanadium haloperoxidase protein in substrate halogenation. Activity studies show that binding of the substrate to the enzyme is essential for the reaction of the hypohalide with substrate. Stopped-flow measurements demonstrate that the rate-determining step is not dependent on substrate binding but partially on hypohalide formation. Using a combination of molecular mechanics (MM) and molecular dynamics (MD) simulations, the substrate binding area in the protein is identified and even though the selected substrates (methylphenylindole and 2-phenylindole) have limited hydrogen-bonding abilities, they are found to bind relatively strongly and remain stable in a binding tunnel. A subsequent analysis of the MD snapshots characterizes two small tunnels leading from the vanadate active site to the surface that could fit small molecules such as hypohalide, halide, and hydrogen peroxide. Density functional theory studies using electric field effects show that a polarized environment in a specific direction can substantially lower barriers for halogen transfer. A further analysis of the protein structure indeed shows a large dipole orientation in the substrate-binding pocket that could enable halogen transfer through an applied local electric field. These findings highlight the importance of the enzyme in catalyzing substrate halogenation by providing an optimal environment to lower the energy barrier for this challenging aromatic halide insertion reaction.

An industry survey on approaches, success factors, and barriers for technology transfer in software engineering

AbstractOne central aspect of software engineering research is the transfer of the proposed approaches into industrial practice. In the past, a number of technology transfer approaches and experiences from technology transfer projects in software engineering have already been reported. However, many researchers still struggle to get their research results noticed by practitioners. To investigate what is important to practitioners, we conducted a mixed‐methods study that provides us with reliable quantitative data as well as deeper insights from qualitative data. Our results show that there is a mismatch between industry professionals' needs and commonly proposed technology transfer approaches in the software engineering field. For instance, collaboration between industry and academia as well as participation in empirical evaluations is not deemed important from an industry point of view. In contrast, industry professionals emphasize the use of company‐specific pilot projects conducted by industry and the need for experts to be available in every phase of technology transfer.

Polychromatic atom optics for atom interferometry

Coherent manipulation of atoms with atom-optic light pulses is central to atom interferometry. Achieving high pulse efficiency is essential for enhancing fringe contrast and sensitivity, in particular for large-momentum transfer interferometers which use an increased number of pulses. We perform an investigation of optimizing the frequency domain of pulses by using tailored polychromatic light fields, and demonstrate the possibility to deliver high-efficiency and resilient atom-optic pulses even in the situation of inhomogeneous atomic clouds and laser beams. We find that this approach is able to operate over long interrogation times despite spontaneous emission and to achieve experimentally relevant pulse efficiencies for clouds up to 100~mu text{K}. This overcomes some of the most stringent barriers for large-momentum transfer and has the potential to reduce the complexity of atom interferometers. We show that polychromatic light pulses could enhance single-photon-based large-momentum transfer atom interferometry—achieving 850,hbar k of momentum splitting with experimentally accessible parameters, which represents a significant improvement over the state-of-the art. The benefits of the method extend beyond atom interferometry and could enable groundbreaking advances in quantum state manipulation.

Knowledge transfer and innovation in multinationals: a review of the literature using SCM-TBFO framework

PurposeBusiness research has highlighted the importance of knowledge transfer and innovation in multinational firms for better performance outcomes. However, the existing body of literature is characterized by differentiated theories, antecedents and outcomes. This study aims to address this gap by adopting a systematic approach to analyze knowledge transfer and innovation literature from the perspective of multinational organizations.Design/methodology/approachThis study follows “preferred reporting items for systematic reviews and meta-analyses” (PRISMA) guidelines for conducting a systematic literature review. The study adopts a systematic approach for analyzing the literature using School of thought (S), Contexts (C), Methodologies (M), Triggers (T), Barriers (B), Facilitators (F) and Outcomes (O) framework (SCM-TBFO framework) devised for holistic literature review. The study analyzes 75 articles from reputed journals from 2000 to 2022.FindingsIn general, knowledge transfer and innovation in multinationals is a relatively new area and is evolving rapidly. There are many opportunities to study the various perspectives that are included in the SCM-TBFO framework. The key schools of thought included the evolutionary theory of innovation, institutional theory and internationalization theory. The studies had differing settings or contexts, including China, Europe, the USA and Taiwan. Further, key methodologies that were used included regression, case studies, structural equation modeling (SEM) and theoretical studies. Knowledge transfer and innovation triggers included competitive advantage, competitive pressure, constant requirements for better products and services, foreign direct investment (FDI) and globalization. Knowledge transfer and innovation facilitators were categorized into strategy-related facilitators, organization culture and orientation-related facilitators, and resource-related facilitators. Knowledge transfer and innovation barriers included autonomy, international knowledge dispersion, risk of knowledge leakage, search breadth, ambiguity and institutional voids. Key outcomes of knowledge transfer and innovation in multinationals included financial performance, innovation performance, knowledge flow, transfer effectiveness, patents and new product development.Originality/valueBy synthesizing the literature, the study aims to provide an overview of the current state of research on knowledge transfer and innovation in multinationals. The study develops a holistic model for fostering knowledge transfer and innovation in multinationals. The proposed novel framework can also be applied to perform a holistic assessment of the current literature in various research domains. Further, the study suggests future theory development and research agendas. The study also provides implications for practitioners using the framework to achieve more desirable outcomes.

Pan-Chromosome and Comparative Analysis of Agrobacterium fabrum Reveal Important Traits Concerning the Genetic Diversity, Evolutionary Dynamics, and Niche Adaptation of the Species.

Agrobacterium fabrum has been critical for the development of plant genetic engineering and agricultural biotechnology due to its ability to transform eukaryotic cells. However, the gene composition, evolutionary dynamics, and niche adaptation of this species is still unknown. Therefore, we established a comparative genomic analysis based on a pan-chromosome data set to evaluate the genetic diversity of A. fabrum. Here, 25 A. fabrum genomes were selected for analysis by core genome phylogeny combined with the average nucleotide identity (ANI), amino acid identity (AAI), and in silico DNA-DNA hybridization (DDH) values. An open pan-genome of A. fabrum exhibits genetic diversity with variable accessorial genes as evidenced by a consensus pan-genome of 12 representative genomes. The genomic plasticity of A. fabrum is apparent in its putative sequences for mobile genetic elements (MGEs), limited horizontal gene transfer barriers, and potentially horizontally transferred genes. The evolutionary constraints and functional enrichment in the pan-chromosome were measured by the Clusters of Orthologous Groups (COG) categories using eggNOG-mapper software, and the nonsynonymous/synonymous rate ratio (dN/dS) was determined using HYPHY software. Comparative analysis revealed significant differences in the functional enrichment and the degree of purifying selection between the core genome and non-core genome. We demonstrate that the core gene families undergo stronger purifying selection but have a significant bias to contain one or more positively selected sites. Furthermore, although they shared similar genetic diversity, we observed significant differences between chromosome 1 (Chr I) and the chromid in their functional features and evolutionary constraints. We demonstrate that putative genetic elements responsible for plant infection, ecological adaptation, and speciation represent the core genome, highlighting their importance in the adaptation of A. fabrum to plant-related niches. Our pan-chromosome analysis of A. fabrum provides comprehensive insights into the genetic properties, evolutionary patterns, and niche adaptation of the species. IMPORTANCE Agrobacterium spp. live in diverse plant-associated niches such as soil, the rhizosphere, and vegetation, which are challenged by multiple stressors such as diverse energy sources, plant defenses, and microbial competition. They have evolved the ability to utilize diverse resources, escape plant defenses, and defeat competitors. However, the underlying genetic diversity and evolutionary dynamics of Agrobacterium spp. remain unexplored. We examined the phylogeny and pan-genome of A. fabrum to define intraspecies evolutionary relationships. Our results indicate an open pan-genome and numerous MGEs and horizontally transferred genes among A. fabrum genomes, reflecting the flexibility of the chromosomes and the potential for genetic exchange. Furthermore, we observed significant differences in the functional features and evolutionary constraints between the core and accessory genomes and between Chr I and the chromid, respectively.

Theoretical Insights into the Luminescence and Sensing Mechanisms of N,N′-Bis(salicylidene)-[2-(3′,4′-diaminophenyl)benzthiazole] for Copper(II)

The intramolecular proton transfer (IPT) reaction potential energy surfaces (PESs) of N,N'-bis(salicylidene)-[2-(3',4'-diaminophenyl)benzthiazole] (BTS) in the S0 state and S1 state are constructed. It is found that the IPT reactions in the ground state hardly take place due to the high reaction energy barrier for single-proton (6.3 kcal/mol) and double-proton transfer (14.1 kcal/mol) reactions and low backward reaction energy barriers for single-proton (1.9 kcal/mol) and double-proton transfer (1.2 kcal/mol) reactions. In comparison, an excited-state intramolecular single-proton transfer reaction is a barrierless and exothermic process, and thus, single-proton transfer tautomer T1H contributes most to the fluorescence emission. Based on the analysis of PESs, the experimental absorption and emission spectra are reproduced well by the calculated vertical excitation energies of BTS and its photoisomerization products, and the triple fluorescence emission profile in the experiment is reassigned unequivocally. Furthermore, thermodynamic analysis of the BTS-Cu(II) complex shows that the dinuclear complex (C1) with Cu(II) coordinating with O and N atoms of the hydrogen bonds is the most thermodynamically stable structure, and the intramolecular hydrogen bonding structure in BTS is destroyed due to the chelation of Cu(II) and BTS; as a result, the IPT reaction of C1 in S0 and S1 states is significantly inhibited. The inhibitor of Cu(II) in the IPT reaction plays a major role in fluorescence quenching.

Dopant-induced modulation of lithium-ion conductivity in cubic garnet solid electrolytes: a first-principles study.

Cubic garnet Li7La3Zr2O12 (c-LLZO) is a promising solid electrolyte for all-solid-state batteries, often doped with Ga, Al, and Fe to stabilize the structure and enhance Li-ion conductivity. Despite introducing the same amount of Li vacancies, these dopants with +3 classical charge yield different Li-ion conductivities by around an order of magnitude. In this study, we used density functional theory (DFT) calculations to investigate the impact of Ga, Fe, and Al dopants on Li chemical potential and Li-ion conductivity variations. We identified the energetically favorable dopant location in c-LLZO and determined the optimal U value of 7.5 eV for DFT+U calculations for dopant Fe in c-LLZO. Our calculations showed that Ga or Fe doping enhances the Li chemical potential by 0.05-0.08 eV, reducing Li-ion transfer barriers and increasing Li-ion conductivity, while Al doping lowers the Li chemical potential by 0.08 eV, reducing Li-ion conductivity. To determine the cause of Li chemical potential variations, we performed a combined analysis of the projected density of states, charge density, and Bader charge. The distinct charge distribution from dopant atoms to neighboring O atoms is critical for determining the Li-ion chemical potential. Ga and Fe dopants retain more electrons, which consequently makes the adjacent O atoms acquire a more positive charge that destabilizes Li ions by reducing the restraining force acting on them, thereby enhancing Li-ion conductivity. In contrast, Al doping transfers more electrons to neighboring O atoms, resulting in greater attraction forces to Li ions and reducing Li-ion conductivity. Additionally, Fe-doped LLZO exhibits extra states in the bandgap, potentially causing Fe reduction, as observed in experiments. Our findings provide valuable insights into the design of solid electrolytes and highlight the importance of the local charge distribution around the dopant and Li atoms in determining Li-ion conductivity. This insight could serve as a guiding principle for future materials design and optimization in solid-state electrolyte systems.

Efficient and tunable enhancement of NLO performance for indaceno-based donor moiety in A-π-D-π-D-π-A type first DSSC design by end-capped acceptors

The organic dyes with non-fullerene acceptors (NFAs) have aided in the creation of competitive organic solar cells (OSCs) with long-term sustainability. A series of NFA dyes (IDIC-R1-IDIC-R9) have been designed by varying the end-capped fluorinated moieties (PD1-PD6) at indaceno (IDIC) core. All the calculations were performed by density functional theory (DFT) and time-dependent DFT (TD-DFT)-based approaches. All the geometries were optimized at B3LYP/6-31G + (d,p) of DFT level at their ground state energies. Out of several density functionals, the CAM-B3LYP with 6-31G + (d,p) basis sets was selected after a benchmark study to carry out further calculations. All the dyes had their bandgaps in 0.11-3.12eV while their starting reference dye had a bandgap value of 2.01eV. Their ionization potential (IP) implied that these dyes have strong tendency to lose electrons. The λmax of the dyes was slightly redshifted from the IDIC (476nm) and IDIC-R (479nm) when changing solvent polarity from methanol to DCM and then chloroforms. The natural bond orbital (NBO) analysis showed the (S63)LP → (C61-C62)π* with highest stabilization energy. Their electron injection analysis showed that these dyes can be a good anode material against the aluminum and gold electrodes. The intramolecular charge transfer (ICT) process and stability of the dyes were investigated using frontier molecular orbital (FMO) and natural bond orbital (NBO) analysis. Among all dyes, IDIC-R8 has the highest linear polarizability and second-order hyperpolarizability (βtotal). All the dyes demonstrated promising non-linear optical (NLO) properties due to their low charge transfer barriers. Scientistswould be able to exploit these properties to identify the best NLO materials for existing applications.

Heat-Induced Magnetic Transition for Water Electrolysis on NiFeN@NiFeOOH Core-Shell Assembly.

The overpotentials of electrochemical oxygen evolution reaction (OER) inherently originate from high electron transfer barriers of the redox couple driven water oxidation. Here, we propose a heat-induced magnetic transition strategy to reduce the spin-related electron transfer barriers. Coupling heat into electrochemical OER on a ferro-antiferromagnetic core-shell NiFeN@NiFeOOH, the heat-induced ferro-to-paramagnetic transition for NiFeN core at 55 °C and antiferro-to-paramagnetic transition for NiFeOOH shell at 70 °C significantly accelerate and accordingly achieve a cascaded Ni2+/Ni3+ driven water oxidation reaction. In addition, paramagnetic Niδ+ (δ ≥ 3) in NiFeN@NiFeOOH can thermochemically react with water to produce oxygen. The heat-induced magnetic transition concomitantly triggers the electrochemical redox couple driven water oxidation and the thermochemical water oxidation due to that heat-induced paramagnetic spin reduces the barriers of electricity driving the spin flipping. Our findings offer new insights into constructing the heat-electricity coupling water splitting.