Local Electron Density Research Articles

Two-dimensional QDs-Co-CuS1-x/Ti3C2/TiO2 heterojunction with synergistic unsaturated bimetal sites and sulfur vacancies for highly selective photocatalytic CO2 reduction

The primary factors that determine the efficiency and selectivity of multi-electron photoreduction of CO2 include the chemical properties of the active sites, as well as the kinetics of charge separation and transfer. Herein, a novel two-dimensional QDs-Co-CuS1-x/Ti3C2/TiO2 heterojunction is developed, with Co-CuS1-x quantum dots serving as cocatalysts and Ti3C2 MXene as an effective electron transfer channel. The anchoring effect of Ti3C2 facilitates the formation of robust TiS bonds with Co-CuS1-x, thereby promoting efficient separation and transfer of photoelectrons to the Co-Cu bimetallic active sites. This process enhances the local electron density at these sites and accelerates the kinetics of electron transfer to absorbed CO2. The recyclability of the Co-Cu sites is also significantly enhanced by continuous photoelectron injection. Importantly, DFT calculations indicate that the synergistic dual sites involving highly exposed Co-Cu and S vacancies promote rate-determining step from COO* to COOH*, which may account for the highly selective photoreduction of CO2-to-CO. Benefitting from the synergic effects of the active sites and efficient separation of carriers, the optimized Co-CuS1-x/Ti3C2/TiO2 exhibits a satisfactory CO photoreduction rate of 30.8 µmol∙g−1∙h−1, with an excellent selectivity of 87.9 % and apparent quantum yield of 0.61 % in the absence of any sacrificial reagents, which is 6.5 times higher than Co-CuS1-x, 54.0 times than Ti3C2Tx/TiO2.

X-Ray Spectra of Black Hole X-Ray Binaries with Returning Radiation

In the disk–corona model, the X-ray spectrum of a stellar-mass black hole in an X-ray binary is characterized by three components: a thermal component from a thin and cold accretion disk, a Comptonized component from a hot corona, and a reflection component produced by illumination of the cold disk by the hot corona. In this paper, we assume a lamppost corona, and we improve previous calculations of the X-ray spectrum of black hole X-ray binaries. The reflection spectrum is produced by the direct radiation from the corona as well as by the returning radiation of the thermal and reflection components and is calculated considering the actual spectrum illuminating the disk. If we turn the corona off, the reflection spectrum is completely generated by the returning radiation of the thermal component, as it may happen for some sources in soft spectral states. After choosing the radial density profile of the accretion disk, the ionization parameter is calculated self-consistently at any radial coordinate of the disk from the illuminating X-ray flux and the local electron density. We show the predictions of our model in different regimes, and we discuss its current limitations as well as the next steps to improve it.

Gold nanostars and nanourchins for enhanced photothermal therapy, bioimaging, and theranostics.

Photothermal therapy (PTT), a recently emerging method for eradicating tumors, utilizes hyperthermia induced by photo-absorbing materials to generate heat within cancer cells. Gold nanoparticles (AuNPs) have gained reliability for in vitro and in vivo applications in PTT due to their strong light absorbance, stability, and biocompatibility. Yet, their potential is limited by their spherical shape, impacting their size capabilities, electromagnetic enhancement effects, and localized surface plasmon resonance (LSPR). Anisotropic shapes have been tested and implemented in this treatment to overcome the limitations of spherical AuNPs. Nanostars (AuNSs) and nanourchins (AuNUs) offer unique properties, such as increased local electron density, improved catalytic activity, and an enhanced electromagnetic field, which have proven to be effective in PTT. Additionally, these shapes can easily reach the NIR-I and NIR-II window while exhibiting improved biological properties, including low cytotoxicity and high cellular uptake. This work covers the critical characteristics of AuNS and AuNUs, highlighting rough surface photothermal conversion enhancement, significantly impacting recent PTT and its synergy with other treatments. Additionally, the bioimaging and theranostic applications of these nanomaterials are discussed, highlighting their multifaceted utility in advanced cancer therapies.

Mn-Rich Induced Alteration on Band Gap and Cycling Stability Properties of LiMnxFe1-xPO4 Cathode Materials.

Olivine-type LiMnxFe1-xPO4 (LMFP) has inherited the excellent heat-stable structure of LiFePO4 (LFP) and the high-voltage property of LiMnPO4 (LMP), which shows great promise as a high-safety, high-energy-density cathode material. In order to combine the high energy density and excellent electrochemical performance, it is essential to consider the Mn/Fe ratio. This paper presents a theoretical investigation of the lattice structure parameters, embedded lithium voltage, local electron density, migration barrier, and lithium ion delithiation and lithiation mechanism of different LiMnxFe1-xPO4 (0.5 ≤ x ≤ 0.8) compounds. In situ-coated LiMnxFe1-xPO4 (0.5 ≤ x ≤ 0.8) composite cathode materials with a size of 100-200 nm were prepared by a hydrothermal method to verify the theoretical study. LiMn0.6Fe0.4PO4/C exhibited a specific capacity of 140.2 and 97.58 mA h·g-1 at 1 and 5C, respectively, and a remarkable capacity retention rate of 88.5% after 200 cycles at 1C. When LiMn0.6Fe0.4PO4/C was assembled into a flexible pouch battery and subjected to long cycle tests at different rates and squeeze and extrusion tests, it demonstrated a capacity retention rate of 99.35% for 100 cycles at 0.2C and 93.2% for 200 cycles at 0.5C. Moreover, the structural evolution of LiMn0.6Fe0.4PO4/C were analyzed in situ XRD, indicating a high stability and the resulted as obtine electrochemical performance, paving the way for optimization of high-energy-density LMFP cathode materials.

Localized Electron Redistribution in Methanol Molecules over the Sea Urchin-like Tricobalt Tetroxide/Copper Oxide Nanostructures for Fast Hydrogen Release.

Catalytic methanolysis of ammonia borane (NH3BH3) is a prospective technology in the field of hydrogen energy in which hydrogen production and hydrogen storage can be integrated together. The splitting of the O-H bond is identified as the rate-determining step (RDS) in this reaction. Thus, a deep understanding of the relationship between the electronic structure of the catalyst, especially the localized electron density of active sites, and the breaking behaviors of the O-H bond is of extreme importance for the rational design of robust catalysts for the reaction. In this work, sea urchin-like tricobalt tetroxide/copper oxide (Co3O4/CuO) nanostructures with rich oxygen vacancies (Ov) were fabricated by a simple synthetic route. In NH3BH3 methanolysis, the optimal Co3O4/CuO sample exhibited ultrahigh catalytic activity with a turnover frequency (TOF) of 87.5 min-1. Interestingly, when NH3BH3 methanolysis was carried out under visible-light illumination, the TOF further increased to 116.4 min-1, which is the highest TOF value among those of the noble-metal-free catalysts ever documented in the literature. Theoretical calculation results evidenced that the Cu site in the Co3O4/CuO sample was in charge of the adsorption and activation of methanol molecules. Both the Ov and visible-light illumination can help electrons on the Cu site flow to the adsorbed methanol molecule, thus leading to localized electron redistribution of the methanol molecule and the extension of the O-H bond. The cooperation of Ov and visible light makes splitting of the O-H bond easier, which is favorable for fast hydrogen release from NH3BH3 methanolysis. This study helps us to gain an insight into the influence of localized electron redistribution of methanol molecules on the RDS, which conduces to the rational design of highly effective nanocatalysts. Moreover, the coinduction strategy for localized electron redistribution with oxygen vacancy engineering and visible-light illumination opens up a route to boost catalytic activity in NH3BH3 methanolysis.

Theoretical and experimental insights of two surfactants’ effects on SnIn electrodeposited coatings from ethaline

This work uses computational methodologies to investigate the behavior of Sn2+ and In3+ ions in deep eutectic solvent (DES) based on choline chloride and ethylene glycol (1ChCl:2EG, ethaline), under different conditions, such as different temperatures, ion ratios, and in the presence and absence of hexadecyltrimethylammonium bromide (CTAB) and sodium dodecyl sulfate (SDS) surfactants. Furthermore, SnIn alloys were electrodeposited on Cu surfaces to analyze the effect of the investigated different conditions on the surface morphology and chemical composition of the electrodeposited coatings. Morphology and composition were analyzed using Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray (EDS). For computational approach, twelve Molecular Dynamics (MD) simulations were conducted using the GROMACS software. After MD simulations, Quantum Theory of Atoms in Molecules (QTAIM) properties were obtained. The results presented that In3+ showed a stronger affinity for Cl− than Sn2+ but it presents weaker and less stable interactions with OA (OA = oxygen of ethylene glycol-EG), particularly at higher temperatures. Electron Density and Electron Localization Function analysis indicated that In-Cl interactions are stronger and more polarized than other interactions. The Laplacian of Electron Density suggested an intermolecular nature for all interactions. The surfactant addition altered these interactions slightly, with CTAB reducing the density of Cl− around In3+ and SDS positively interacting with In3+ at 297 K and in a Sn2+:In3+ 1:1. As SDS interacted more with In3+ ions, the electrodeposition times varied between 4965 s and 75,541 s. SEM images revealed temperature- and potential-dependent changes in film morphology, changing from globular to smooth. CTAB and SDS additions led to uniform coating in Sn2+: In3+ solutions. For the 1:1 ratio at −1.4 V, there were no significant changes (between 75 and 77 %) in the percentage of Sn deposited with the use of surfactants at 297 K. At 343 K, the surfactant-free coating exhibited 69 % Sn, CTAB facilitated the Sn deposition, increasing the percentage to 92 %. At the same time, the presence of the SDS resulted in 79 % Sn. Similar behavior was obtained for −1.0 V. For 1:4 at −1.0 V at 297 K, 35 % of Sn was observed without surfactant, 29 % with CTAB, and 33 % with SDS. At 343 K, there was an increase in Sn content for 42 %, 49 % and 60 %, indicating the positive influence of the temperature, respectively. At −1.4 V, however, there was no observed influence on the Sn percentages without surfactant. With CTAB (between 29 and 34 %) at 297 and 343 K. At these temperatures, the addition of SDS promoted a higher content of Sn, increasing to 56 % and 43 %, respectively.

Dynamical control of nanoscale electron density in atomically thin n-type semiconductors via nano-electric pulse generator.

Controlling electron density in two-dimensional semiconductors is crucial for both comprehensive understanding of fundamental material properties and their technological applications. However, conventional electrostatic doping methods exhibit limitations, particularly in addressing electric field-induced drift and subsequent diffusion of electrons, which restrict nanoscale doping. Here, we present a tip-induced nanospectroscopic electric pulse modulator to dynamically control nanoscale electron density, thereby facilitating precise measurement of nano-optoelectronic behaviors within a MoS2 monolayer. The tip-induced electric pulse enables nanoscale modulation of electron distribution as a function of electric pulse width. We simultaneously investigate spatially altering photoluminescence quantum yield at the nanoscale region. We model the extent of electron depletion region, confirming a minimum doping region with a radius of ∼265 nanometers for a 30-nanosecond pulse width. Our approach paves the way for engineering local electron density and in situ nano-optical characterization in two-dimensional materials, enabling an in-depth understanding of doping-dependent nano-optoelectronic phenomena.

Visible-Light-Induced Rapid Elimination of Antibiotic Resistance Contaminations Using Graphitic Carbon Nitride Tailored with Carrier Confinement Domains.

Solar water disinfection facilitated by photocatalyst has been considered a viable point-of-use (POU) method for mitigating antibiotic resistance contaminations at the household or community levels. Here, density functional theory calculations are used to guide the fabrication of a carrier confinement domains (CCD)-decorated graphitic carbon nitride (CN) photocatalyst. The CCD integration effectively disrupts the electron distribution symmetry of CN, amplifies its local electron density, and facilitates the formation of long-range ordered structure, thereby enhancing charge separation efficiency. Importantly, the CCD directs the migration of photogenerated carriers to specific regions upon light illumination, effectively minimizing their spatial proximity. As a result, the overall reactive oxygen species level of the photocatalytic system is markedly elevated, with a twelvefold increase in H2O2 concentration, alongside a nearly two-order-of-magnitude rise in •O2 - and •OH steady-state concentrations. Remarkably, a record-high disinfection efficiency is attained, successfully inactivating 7 log of antibiotic-resistant bacteria within 30min. Additionally, the photocatalyst can be integrated into a continuous-flow fixed-bed reactor, facilitating clean water production for up to 60h at a rate of 121Lm-2day-1, highlighting its significant potential for POU applications.

Unraveling the promotive mechanism of nitrogen-doped porous carbon from wasted lignin for Cr (VI) removal

Persistent environmental pollution by heavy metals, particularly Cr (VI), poses significant risks to ecosystems and human health due to its high toxicity and bioaccumulation potential. The development of high-performance, cost-effective adsorbents from sustainable materials remains a critical challenge in the field of Cr (VI) remediation. This study investigates the influence of pyrrolic-N (N-5) within nitrogen-doped hierarchical porous carbon (N-HPC) on its adsorption capacity. Results indicate that N-HPC variants with a higher N-5 content exhibit superior adsorption abilities. The optimal sample demonstrated an exceptional adsorption capacity of 386.2 mg/g for Cr (VI). Even after seven regeneration cycles, this N-HPC variant maintained a remarkable 77.8 % removal efficiency for Cr (VI), highlighting its robust stability and selectivity. The relationship between the physicochemical properties of N-5 and N-HPC was thoroughly examined, revealing that N-5 plays a crucial role in the adsorption process. Due to its high electronegativity, nitrogen-doping into the carbon framework generates a dipole moment, enhancing the electronegativity of N-HPC, altering its local electron density and polarity, increasing specific surface area, carbon defect density, and ion exchange capacity. These factors collectively contribute to significant improvements in pore filling, ion exchange efficiency, and electrostatic adsorption by N-HPC. The reduction complexation mechanism emerges as the dominant factor in the adsorption process. N-5 not only provides reducing electrons as an electron donor, facilitating the continuous conversion of Cr (VI) to Cr (III), but also acts as an adsorption active site, complexing Cr to the surface of N-HPC. This synergistic effect strengthens the reduction complexation, enhances adsorption performance, and improves the regeneration cycle and adsorption selectivity for Cr.

First-principles calculations concerning ferromagnetism in Q-carbon

Spin-constrained first-principles calculations were performed to assess amorphous carbon systems having a density of 5.24, 5.46 or 5.63 g/cm3. The liquid quenching method was employed to produce suitable amorphous structures, and analyses of radial distribution functions, distributions of local magnetic moments and partial electronic densities of states were carried out. The system with a magnetic moment of 0.4 μB/atom and density of 5.63 g/cm3 was found to possess a high proportion (approximately 72.1 %) of sp3 hybridized carbon atoms. This result was in good agreement with recent experimental evaluations of ferromagnetic Q‑carbon. The simulations also indicated that unpaired electrons will be present in two types of sp2 hybridized carbon atoms and that these electrons are largely responsible for ferromagnetism in Q‑carbon. The present work provides an important starting point that will assist in understanding the nature of this material and promote the study of high-density Q‑carbon materials with novel physical properties.

A “pre-constrained bimetallic” strategy for the preparation of efficient synergistic electrocatalytic hydrogen evolution catalysts

A micro-sized bimetallic nanoparticles (NPs) catalyst that anchors a mixture of Co and Pd atoms onto a porous nitrogen-doped carbon (NC) framework for electrocatalysis of hydrogen evolution reaction (HER). Programmable metal-porphyrin ligands serve as building blocks for attaching bimetallic sites (consisting of Co and Pd) in metal-organic frameworks for decentralized anchoring before pyrolysis. Experimental studies have shown the interaction between Pd and Co in Co20/Pd20-NC results in electron depletion near Co and electron accumulation near Pd, respectively. Therefore, there is an asymmetric local electron density distribution on the bimetallic site of Co20/Pd20-NC, which improves the activity of the catalyst. To achieve a current density of 10mA·cm-2 in both acidic and alkaline conditions, the Co20/Pd20-NC exhibits noteworthy HER characteristics with overpotentials of 23 and 52mV, respectively. The Co20/Pd20-NC prepares in this study which shows good characteristics in the process of electrocatalytic hydrogen evolution, and has a good application prospect.

Population of excited levels of Fe+, Ni+, and Cr+ in exocomets’ gaseous tails

The star β Pictoris is widely known for harbouring a large population of exocomets, which create variable absorption signatures in the stellar spectrum as they transit the star. Although the physical and chemical properties of these objects have long been elusive, the recently developed exocomet curve of growth technique has, for the first time, enabled estimates of exocometary column densities and excitation temperatures, based on absorption measurements in mutliple spectral lines. Using this new tool, we present a refined study of a β Pic exocomet observed on December 6, 1997 with the Hubble Space Telescope. We first show that the comet’s signature in Fe II lines is well explained by the transit of two gaseous components, with different covering factors and opacities. Then, we show that the studied comet is detected in the lines of other species, such as Ni II and Cr II. These species are shown to experience similar physical conditions as Fe II (same radial velocity profiles and same excitation temperatures), hinting that they are well mixed. Finally, using almost 100 Fe II lines rising from energy levels between 0 and 33 000 cm–1, we derive the complete excitation diagram of Fe+ in the comet. The transiting gas is found to be populated at an excitation temperature of 8190 ± 160 K, very close to the stellar effective temperature (8052 K). Using a model of radiative and collisional excitation, we show that the observed excitation diagram is compatible with a radiative regime, associated with a close transit distance (≤60 R⋆ ∼ 0.43 au) and a low electronic density (≤107 cm–3). In this regime, the excitation of Fe+ is controlled by the stellar flux, and does not depend on the local electronic temperature or density. These results allow us to derive the Ni+/Fe+ and Cr+/Fe+ ratios in the December 6, 1997 comet, at 8.5 ± 0.8 ⋅ 10–2 and 1.04 ± 0.15 ⋅10–2, respectively, close to solar abundances.

Chirality and Local Electron Density of States in a Two-Dimensional Molecular Crystal Self-Assembled by Prochiral Radical Molecules.

Creating and unveiling chiral systems is important to the development of new materials and devices. In this study, after depositing prochiral radical molecule 3-carbamoyl-2,2,5,5-tetramethyl pyrroline-1-oxyl (CTPO) on a Au(111) substrate, 2D molecular crystals with two chiralities of CTPO molecules have been discovered. A single CTPO molecule is an achiral molecule in three-dimensional space, and it can form chiral configurations after adsorbing on the substrate. The chiralities of 2D molecular crystals originate from the chiral properties of adsorbed CTPO molecules and their assembling. Molecules with different chiralities are connected with molecular recognition through hydrogen bond interactions. Through density functional theory simulations, the hydrogen bond networks and molecular structures of this system were explored. To gain a further understanding of this system, the electronic property of CTPO/Au(111) was studied with a local density of states (LDOS) characterization. A peculiar LDOS distribution related to the vibrational excitation of the molecules was mapped at the submolecular scale. These results are useful for understanding the nature of chirality formation, 2D molecular crystal construction, and radical molecule applications.

Does Aromaticity Play a Role in Electronic and Structural Properties of YBn (n=2-14) Clusters?

Nanoclusters exhibit electronic, optical, and magnetic properties that differ significantly from those of extended and molecular systems with comparable stoichiometries. In this work, we examined the structural, energetic, and electronic characteristics of yttrium-doped boron clusters (YBn, where n ranges from 2 to 14) with the aid of robust wavefunction analysis tools. Special emphasis is placed on the elucidation of the potential aromatic character exhibited by the resultant molecules and how it can affect their chemical bonding and stability. Our results revealed that the YBn stability is governed by the maximization of the ionic Y-B interactions. This circumstance is evidenced from the lowest-energy conformations, which manifest as half-sandwich structures wherein the majority of boron atoms are bonded to yttrium. The stabilization of such chemical contacts comes at the expense of a notorious depletion of the Y local electron density, crystallizing in a considerable ionic character, close to Y2++ . Such a prominent charge transfer is coupled to the enhancement of the electron delocalization within the Bn lattice, resulting in quite remarkable local and global aromatic characters. Altogether, this study shows how the toolkit of real space chemical bonding descriptors can offer valuable insights into the structural and electronic properties, along with the chemical bonding, of YBn clusters, contributing to a more comprehensive understanding of their behavior.

Structural modulation of Na4Fe3(PO4)2P2O7 via cation engineering towards high-rate and long-cycling sodium-ion batteries

Mixed iron-based phosphate Na4Fe3(PO4)2P2O7/C (NFPP) has gradually emerged as a promising cathode material for sodium-ion batteries (SIBs) owing to its affordability and convenient preparation. However, poor electrical conductivity and inadequate sodium-ion diffusion limit the exertion of its electrochemical properties. Herein, a structural modulation strategy based on Cd doping is applied to NFPP to address the above limitations. In situ X-ray diffraction analysis reveals that Cd-doped NFPP (NFCPP) undergoes an incomplete solid-solution reaction driven by Fe2+/Fe3+ redox. Cd doping effectively stabilises the crystal structure, resulting in a minimal 1 % change in unit cell volume during cycling. Density of state calculations indicate that Cd doping reduces the band gap, increases the local electron density and significantly improves electron conductivity. Benefitting from the enhanced electrochemical kinetics and intercalation pseudocapacitance, the optimised Na4Fe2.91Cd0.09(PO4)2P2O7/C (NFCPP@3%) exhibits exceptional rate performance (capacity of 62 mAh/g at 20 C) and ultra-long cycling life (82.7 % after 6000 cycles at 20 C). A full SIB prepared using NFCPP@3% and hard carbon, display a 91 % capacity retention rate at a current density of 130 mA g−1 over 200 cycles. This work demonstrates that doping can effectively enhance electrochemical performance and offers insights into future development of SIBs.

Ultrahigh Transparent Safety Film for Spectrally Selective Photo/Electrothermal Conversion via Surface-Enhanced Plasma Resonance Dynamics.

Traditional deicing methods are increasingly insufficient for modern technologies like 5G infrastructure, photovoltaic systems, nearspace aerocraft, and terrestrial observatories. To address the challenge of combining anti-icing efficiency with operational performance, an innovative, spectrally selective, photo/electrothermic, ice-phobic film was prepared through a cost-effective mist deposition method. By manipulating the diameter ratio and density of nanowires, the local density of free electrons within this film is controlled to precisely dictate the position and intensity of surface plasmon resonance to achieve spectrally selective photo/electrothermal conversion. Additionally, the synthesized hydrophobic N-Boroxine-PDMS/SiO2 layer improves thermal stability and accelerates the deicing process. It achieves rapid deicing within 86 s under photothermal conditions and 65 s with Joule heating while maintaining high optical transmittance. The film improves the operational efficiency and thermal safety of equipment while preserving aesthetics and stability, thereby underscoring its broad suitability for advanced outdoor installations in cold environments.

Localized Electron Density Engineering for Bright and Stable Near-Infrared Electroluminescence from All-Inorganic Lead-Free Tin Halides

Localized Electron Density Engineering for Bright and Stable Near-Infrared Electroluminescence from All-Inorganic Lead-Free Tin Halides

Control for selective sorption of heavy metals cations with anion exchanger AB-17-8 by modifying the surface with citrate groups

The citric acid modification produces an intermediate layer on the AB-17-8:C6H8O7 surface; the layer, on one hand, is firmly secured to the surface owing to the electrostatic coupling between the citrate anion and the positively charged trimethylammonium centers of the anion exchanger surface; on the other hand, it has carbonyl groups with a local negative electron density. The sorption of heavy metals cations occurs through coordination interactions via electrostatic mechanism with local centers of negative electron density, in particular, with the carbonylic oxygen atom.

WS2@FeBC assisted Fe(III)-activated percarbonate for roxarsone and tetracycline simultaneous removal: Interfacial fenton-like process enhanced by oxygen vacancies and tungsten redox

Sodium percarbonate (SPC) has garnered significant interest for its application in water decontamination via advanced oxidation processes (AOPs), however, SPC Fenton-like processes are always hindered by slow iron cyclic conversion and the production of ferric sludge, which limit their efficiency and practicality. Herein, a novel strategy was proposed to greatly improves the Fe(II)/Fe(III) cycling by utilizing oxygen vacancies (OV) in conjunction with W(IV)/W(VI) redox couples synergistically. In the optimized WS2@FeBC/Fe3+/SPC system, over 97 % removal efficiencies were achieved for both tetracycline (TC) and roxarsone (ROX) within just 10 min. Furthermore, the WS2@FeBC/Fe3+/SPC system exhibits robust performance across a broad pH range (3 to 11) and maintains high removal efficiencies above 90 % even after seven reuse cycles. Quenching experiments combined with electron paramagnetic resonance (EPR) and open-circuit potential measurements indicate that surface-adsorbed hydroxyl radicals (•OHads) and direct electron transfer are crucial for TC/ROX degradation. Density functional theory (DFT) calculations and X-ray photoelectron spectroscopy (XPS) analyses reveal that oxygen vacancies enhance H2O2 activation to produce •OHads, while sulfur vacancies accelerate the W(IV)/W(VI) redox process by mediating localized electron density around tungsten, thereby promoting the Fe(III)/Fe(II) cycling. This study provides a novel perspective on the surface interfacial reactions between reactive oxygen species (ROS) and organic pollutants, offering significant advancements in understanding and improving AOPs for water treatment.

Enhancing Zn2+/H+ Joint Charge Storage in MnO2: Concurrently Tailoring Mn's Local Electron Density and O's p-Band Center.

Enhancing proton storage in the zinc-ion battery cathode material of MnO2 holds promise in promoting its electrochemical performance by mitigating the intense Coulombic interaction between divalent zinc ions and the host structure. However, challenges persist in addressing the structural instability caused by Jahn-Teller effects and accurately modulating H+ intercalation in MnO2. Herein, the doping of high-electronegativity Sb with fully occupied d-orbital in MnO2 is reported. The Sb doping strategy engenders the formation of Mn-O-Sb path in the structure with a strong dipole polarization field, which facilitates the delocalization of eg orbital electron in Mn and thus mitigates the Jahn-Teller effects. Simultaneously, adjusting the level of Sb doping in MnO2 leads to modulation of the p-band center of O, optimizing its interaction with hydrogen and thereby enhancing proton storage. Consequently, MnO2 doped with 6% Sb exhibits commendable performance in both rate capability and cycling endurance, delivering 113 mAh g-1 at 2 A g-1 after 2000 cycles. This investigation underscores the crucial role of electronic structural engineering in elevating the electrochemical performance of cathode materials for zinc-ion batteries.