ABSTRACT Nowadays, fast‐charging capability in battery materials is intensively pursued in both academia and industry, yet the crystallographic factors that fundamentally determine rapid Li + transport remain unclear. Here, we identify the theoretical structural capacity for collective Li + transport, defined by the availability of crystallographically accessible Li diffusion sites, as a decisive but previously underappreciated structural origin governing interfacial Li + transport, and introduce Li‐site density (ρ Li‐site ) as a quantitative descriptor to guide surface architecture design for accelerated Li + migration. Guided by this principle, we construct a coherent and fluorinated 1T‐Li 1 + x CoO 2 − y F y surface structure on LiCoO 2 , which simultaneously preserves crystallographic compatibility with the O3 matrix and provides an exceptionally high ρ Li‐site (∼48 sites·nm −3 ), substantially exceeding those of commonly employed frameworks (≤ 31 sites·nm −3 ). The modified cathode delivers unprecedented rate capability, achieving 183 and 175 mAh g −1 at 10C and 20C, respectively. In‐situ synchrotron x‐ray and neutron diffraction results further reveal that the 1T phase effectively suppressed O3 to H1‐3 phase transitions and stabilized oxygen frameworks, enabling outstanding cycling stability with 87% capacity retention after 500 cycles. This work establishes Li site density‐guided surface engineering as a general structural principle for simultaneously improving interfacial reaction kinetics and structural durability in high‐voltage layered oxide cathodes.

Dissolved organic matter (DOM) sequestration is critical to soil formation of bauxite residue (BR) in which BR undergoes mineral weathering and neutralization / acidification driven by microbial and/or plant root-derived organic acids (OA). The present study aimed to understand the molecular fractionation and adsorption of DOM in BR minerals during key stages of mineral weathering and neutralization, using mixed organic acids to simulate the mineral weathering process in the ecological engineering context. Selective adsorption and molecular fractionation of DOM derived from microbial decomposition of plant mulch were characterized using the highresolution electrospray ionization Orbitrap mass spectrometry (Orbitrap-MS). The OA-treatments progressively weathered sodalite-like alkaline minerals to form amorphous Al/Si/Fe phases and lowered pH, increasing surface reactive sites in mineral phases. The slightly weathered (pH 9-7) and highly weathered and acidified BR minerals (pH 5-4), preferentially adsorbed high-molecular-weight organics rich in aromatic and/or polyphenolic domains. Synchrotron-based Al, Si, and Fe K-edge X ray absorption spectroscopic analyses (XAS) and Fourier transform infrared (FTIR) mapping, revealed strong associations of secondary Al/Si/Fe phases with protein-, carboxylic-, aromatic-, and oxygenated lipid-like compounds. These findings highlight the critical role of mineral weathering in BR for controlling the stabilization of DOM during eco-engineered soil formation processes.

Understanding the mechanisms determining soil organic carbon (SOC) persistence along environmental gradients is central for climate change mitigation and carbon stewardship, but much remains unknown in this regard. This study investigated SOC accumulation, partitioning, and molecular composition along a toposequence (300 to 1100 m above sea level) within the Gondwanan subtropical rainforest of Australia. We assessed how climatic, mineralogical, and pedogenic factors regulate the distribution of particulate (POM) and mineral-associated organic matter (MAOM) and influence SOC functional composition. It was found that SOC concentrations increased by 77% with elevation, predominantly accumulating as MAOM which increased from 26.5 to 73.2 g C kg-1 soil, reaching 81% of the theoretical mineral saturation capacity. This increase in OC in the stable MAOM fraction was associated with an increase in 1:1 clays and highly reactive, weathered soil minerals at higher elevation (Fe-and Al-oxyhydroxides), which increased from 18% of the total mineral content at 300 m to 87% at 1100 m. Despite there being a 77% increase in SOC with elevation, SOC functional group composition remained consistent. These findings indicate that SOC persistence along the toposequence is driven primarily by soil mineralogy and physicochemical protection rather than selective preservation or molecular recalcitrance.

Cathode-solid electrolyte (SE) interfacial instability poses a major challenge for achieving stable and high-power operations in all-solid-state batteries, which promise superior energy density, thermal stability, and safety over the current Li-ion technology. For technologically important Ni-rich NMCs (LiNixMnyCozO2 or NMCxyz; x/y/z: Ni/Mn/Co stoichiometry) paired with sulfide SEs, redox-mediated instability of the SE is often blamed for rapid cathode deterioration. Here, in-depth spectroscopic and electrochemical analyses of Ni-rich NMCs with a promising sulfide SE reveal hitherto unrecognized electrochemical isolation of active NMC particles driven by rapid interfacial degradations, sparking accelerated capacity fading and poor thermal stability. Introducing a functionalized conductive carbon into the cathode suppresses sulfide SE degradation into reactive polysulfides that drive NMC deterioration. Consequently, NMC622 and NMC811-based cells display high active material utilization, enhanced stability, attractive rate capability and thermal resilience - illustrated by 1C (1C: 160 mA g-1) capacity of ∼150 mAh g-1, 5C rate retention of 95% after 500 cycles with high active loading (≥12 mg cm-2), and an average Coulombic efficiency of 99.8% even for high-temperature cycling. This study uncovers a critical performance degradation pathway in a key cathode-SE pairing and presents a scalable strategy for its in situ regulation, enabling significant performance gains.

This study reveals how the morphology of organic mixed ionic-electronic conductors (OMIECs) controls the mixed ionic-electronic transport of organic electrochemical transistors (OECTs). Two p-type OMIECs with oligoethylene glycol (OEG) side chains, namely P3MEEET and P3MEEMT, are blended with polystyrene (PS) to produce laterally phase-separated morphologies. By varying the ratio between OMIEC and PS, distinct morphologies are created via nucleation and growth and via spinodal decomposition. Furthermore, porous films are fabricated through the selective dissolution of PS, providing a direct comparison between blend and porous structures on OECT performance. In blends, the reduced ion injection area significantly enhances the mobility (μ) and figure of merit (μC*). Due to the hydrophilic nature of the OMIECs, adding pores to the films does not have a positive effect on signal amplification but improves ion storage via side injection and increases the effective volumetric capacitance (C*). Comparing the two OMIECs studied, porous samples based on P3MEEMT experience a greater benefit from electrolyte side injection. Both blend and porous samples are characterized using a range of techniques, including spectroelectrochemistry (SEC), atomic force microscopy (AFM), scanning transmission X-ray microscopy (STXM), quartz crystal microbalance (QCM), along with ex situ and in situ grazing-incidence wide-angle X-ray scattering (GIWAXS) to unravel the mechanism of the mixed ionic-electronic transport from both an ionic and electronic perspective.

The sulfur K-edge near-edge X-ray absorption fine-structure (NEXAFS) spectra of the common conjugated polymers P3HT and PBTTT are studied from both experimental and theoretical perspectives. Experimental angle-resolved spectra are measured to characterize both the dominant peaks and the dichroism of the polymers. First-principles calculations using the density functional theory-based many-body X-ray absorption spectroscopy (MBXAS) method are performed for the two polymers as well as for the thiophene and thienothiophene units that make up the conjugated backbones of these polymers. Through this combined approach, we are able to confidently assign the observed peaks to specific molecular orbitals and identify the orientation of their transition dipole moments (TDMs) with respect to the coordinate frame of the polymer backbone. In particular, we are able to establish the character and orthogonal nature of the three main low-energy peaks at: (i) 2473.5 eV, 1s -> (S-C)pi* with TDM along the pi-stacking direction; (ii) 2474.1 eV, 1s -> (S-C)sigma* with TDM along the backbone; and (iii) 2475.4 eV, 1s -> (S-C)sigma* with TDM perpendicular to the first two. By performing both gas-phase and solid-state simulations, and with reference to the NEXAFS spectra of thiophene and thienothiophene building blocks, the influences of polymerization and molecular packing are also explored.

Hexagonal boron nitride (h-BN) exhibits high selectivity toward olefins in oxidative dehydrogenation of propane (ODHP), however, the active sites (BOx species) for ODHP are easily leached under high-temperature and water-containing conditions, leading to catalyst deactivation. In this work, we developed a molten Mg strain engineering strategy to treat h-BN via a compression-expansion process to induce lattice distortion, which resulted in significant electron enrichment across the BOx surface. Experiments combined with density functional theory calculations revealed that this electron enrichment surface not only enhanced activity for ODHP but also prevented the leaching of BOx by H2O during the ODHP. As a result, the Mg-induced lattice-distored h-BN exhibited enhanced ODHP activity and hydrothermal stability, with a 17.2% higher propane conversion than the as-synthesized BN and a stable propane conversion above 50% for 35 h without decline. This work tailors the h-BN structure to adjust electron distribution and prevent active-site leaching in high-temperature and water-containing environments, enhancing its industrial applicability.

Seawater electrolysis faces several significant obstacles, including low energy efficiency and anode corrosion due to chlorine chemistry, which limit its practical potential. To overcome this, we developed a catalyst composed of boron‐doped CoS2 protected by metal–organic framework sheets (MOFs) (B‐CoS2/MOF heterostructures). Introducing B atoms into the CoS2 layer tunes the surface chemistry to promote adhesion of Ni–MOF. Density functional theory calculations indicate a strong interaction at the heterointerface, with a binding energy of −4.13 eV, where the MOF anchors onto the B‐CoS2 surface through a NiS bond measuring 2.08 Å, confirming the presence of an ionic bond. This strong heterointerface promotes OH− adsorption while repelling Cl− ions due to the presence of SO42‐, effectively mitigating chlorine‐induced degradation. Therefore, the B‐CoS2/MOF catalyst achieves an industrial‐scale current density of 1.0 A cm−2 at an overpotential of 542 mV in alkaline seawater and operates stably for 600 h, hence suggesting the potential for designing cost‐effective, chlorine‐resistant systems for practical seawater splitting.

The interaction between dissolved organic matter (DOM) and minerals governs OM stabilisation in soils. Heterogeneous composition of DOM and diverse mineral surface characteristics in soils make it challenging to determine reaction mechanisms at mineral-organic interfaces. To determine the role of DOM and mineral characteristics in the formation of mineral associated organic matter (MAOM), we conducted adsorption experiments using four DOM extracts from pine, Eucalyptus, pasture and wheat residues and six minerals (i.e., kaolinite, montmorillonite, goethite, birnessite, ferrihydrite and allophane) with contrasting charge characteristics, structural order and specific surface area. Poorly crystalline and amorphous minerals generally adsorbed larger amounts of DOM than crystalline oxides and phyllosilicates. The adsorption sequence of functional groups differed with mineral surface chemistry, but C=C/C=O, C-O-C and C-O groups were consistently the most abundant adsorbed moieties. Adsorption involved both mineral-organic and organic-organic interactions, with the latter appearing with increased OM loading, yielding different mineral-OM assemblages depending on OM loading and mineral characteristics. Carboxylic, aromatic and aliphatic organic components predominantly adsorbed on the surfaces of ferrihydrite, allophane, goethite, and kaolinite, whereas quinone and phenolic organic components were preferentially adsorbed on birnessite and montmorillonite. Variations in the molecular composition within DOM also modulated adsorption behaviour at mineral-organic interfaces. The adsorption capacity of wheat DOM on mineral surfaces was lower than that of the other DOM due to its less abundance of reactive functional groups. Our results provide a mechanistic basis for understanding how DOM composition and mineral surface properties regulate the formation of MAOM under acidic conditions.

To advance seawater electrolysis technologies for green hydrogen production, it is crucial to develop efficient and durable electrocatalysts that function at high current densities during anodic reactions, preventing the unwanted chlorine evolution reaction (CER). Here, we optimise an electron-rich interface between electrochemically active Fe,B-Ti3C2Tx modified MXene (FBT) and nitrogen-doped nickel molybdenum oxide (NMO) nanosheets, synthesised using an electrostatic layer-by-layer self-assembly method. Density functional theory (DFT) analysis confirms the presence of an electron-rich interface, indicated by a concentrated negative charge of -28.42e at the interface. This charge accumulation results from the high density of oxygen atoms at the interface between NMO and FBT. High electron density and robust interfacial interactions at the interface enhanced the catalyst stability, accelerated charge transfer, and improved redox kinetics. The heterostructure achieved a current density of 500 mA cm-2 at an overpotential of only 396 mV, while delivering a stable current density above 1.5 A cm-2 for over 1000 h. Quantitative gas analysis confirms a faradaic efficiency of 95.2% and an oxygen production rate of 2.96 & micro;mol s-1 at 1.9 V vs. RHE, demonstrating highly selective oxygen evolution reaction over the CER. Potentiodynamic and thermodynamic analyses further demonstrate enhanced corrosion resistance via interfacial electronic stabilisation and Mo-assisted alkaline passivation. Compared with previously reported MXene- and Ni-Mo-based electrocatalysts, the engineered heterointerface exhibits improved kinetic performance and structural resilience under chloride-rich conditions. This work highlights interfacial electronic engineering as a viable strategy for enabling durable, high-current-density seawater electrolysis toward industrial hydrogen production.

Abstract Manganese dioxide (MnO 2 ) is a leading positive electrode candidate for aqueous zinc-ion batteries, combining safety, high voltage, low cost, and sustainability for grid-scale storage. However, its practical development remains restricted by poor reversibility, rooted in an unresolved mechanistic debate spanning over a decade. Here, we combine operando characterizations, multimodal spectroscopic analyses, and theory to establish a unified picture: proton-primed MnO 2 dissolution and subsequent redeposition as nanocrystalline and disordered MnO x nanosheets, coexisting with reversible proton intercalation in parent MnO 2 and predominantly in deposited MnO x , forming a dual redox mechanism. pH-driven insulating byproduct precipitation emerges as a significant kinetic barrier that limits deep dissolution and capacity utilization. Guided by these insights, we introduce surface activation and architectural design strategies toward mitigating kinetic barriers, enabling enhanced capacity and stability in both Swagelok and pouch-type cells. By reconciling mechanistic ambiguity and translating it into actionable design principles, this work demonstrates a framework for developing durable Mn-based positive electrodes for sustainable energy storage.

[2-(9H-Carbazol-9-yl)ethyl]phosphonic acid (2PACz) and its derivatives are being used extensively as hole-transport layers in organic and perovskite solar cells due to their ability to modify electrode work function, surface wettability, and in some cases, to improve active-layer adhesion, while minimizing interfacial energy losses. The orientation and coverage of surface modifiers significantly impact these functional properties; however, the detailed structure and packing in these overlayers are challenging to investigate, leading to a lack of understanding of how this structure and packing influence performance and limiting the ability to rationally design molecular modifiers. Here, we investigate monolayers of 2-(9H-carbazol-9-yl)ethyl phosphonic acid derivatives (from here on referred to as X-2PACz) on indium tin oxide (ITO) and alpha phase aluminum oxide (α-Al2O3) using a combination of X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, and X-ray reflectivity (XRR). By correlating elemental ratios, molecular orientation, and electron density profiles, we directly quantify surface coverage, layer thickness, and molecular tilt across a series of chemically related monolayers. We find that 2PACz and the X-2PACz derivatives form dense monolayers on α-Al2O3 and ITO, with similar surface coverages on either substrate that are inversely proportional to molecular steric bulk. These surface coverage results indicate that X-2PACz is sterically limited in its monolayer surface packing density, as opposed to site limited. Despite surface packing density differences between molecules, the NEXAFS data show a constant average molecular orientation of 61° to 65° between the plane of the carbazole and the substrate for all the molecules on both substrates. These results increase our general understanding of 2PACz derivatives as they become increasingly useful in high performance solar cells.

Fe & horbar;N & horbar;C catalysts with square-planar FeN4 sites show excellent activity for the oxygen reduction reaction (ORR), but poor activity for the oxygen evolution reaction (OER), hampering their use as air-electrode catalysts in rechargeable zinc-air batteries (ZABs). Herein, an acetate (Ac) ligand-regulation strategy was developed to prepare FeN4 & horbar;O/Clu@NC-xAc catalysts with square-pyramidal FeN4 & horbar;O sites and adjacent Fe clusters. By optimizing the mass of sodium acetate (x = 0.05-0.3 g) used during the catalyst syntheses, the electronic properties of FeN4 & horbar;O sites could be tuned to allow efficient bifunctional ORR/OER activity. A FeN4 & horbar;O/Clu@NC-0.1Ac catalyst delivered a half-wave potential of 0.89 V for ORR and a low overpotential of 330 mV at 10 mA cm-2 for OER in 0.1 m KOH. Furthermore, FeN4 & horbar;O/Clu@NC-0.1Ac demonstrates exceptional ORR activity in acidic (E 1/2 = 0.72 V) and neutral (E 1/2 = 0.70 V) media. An aqueous zinc-air battery assembled using FeN4 & horbar;O/Clu@NC-0.1Ac afforded a remarkable power density (284.5 mW cm-2) and ultralong cycling stability. Magnetic data combined with DFT calculations reveal that the axial O ligand at FeN4 sites altered the spin state of Fe2+ from low-spin to medium-spin, which along with electron transfer from adjacent Fe clusters, fine-tunes the adsorption energy of oxygen intermediates to allow efficient ORR/OER activity.

This research develops a stable, high-performance electrocatalyst with an electron-rich interface between modified MXene and nitrogen-doped nickel molybdenum oxide, enabling efficient high-current operation while suppressing chlorine evolution.

Ionically bonded interfaces are crucial for achieving selective and stable direct seawater electrolysis, yet their vulnerability under corrosive and high-current conditions limits long-term performance. Here, we report a two-dimensional Fe-MOF@PW8O26.B2O3 heterostructured electrocatalyst, synthesized via a solid-liquid interfacial growth strategy, that integrates robust Fe-O-W and tunable Fe-P-W ionic bonds to strengthen interfacial electronic coupling, redox flexibility, and structural integrity. Subsurface B2O3 enhances surface hydroxylation via Lewis acid-base interactions, facilitating catalyst assembly and OH- affinity, while phosphate polyanions at the interface act as electrostatic shields that repel Cl- ions and modulate the redox environment of Fe active sites. This interfacial configuration enables chlorine-suppressive oxygen evolution with a Faradaic efficiency of 97.93%, achieving a current density of 1.75 A cm-2 at 2.0 V and stable operation above 1.5 A cm-2 for over 500 h in alkaline seawater, with an exceptionally low corrosion rate of 0.016 μm per year. NEXAFS and XPS analyses confirm the presence of dual ionic linkages, while DFT calculations reveal their cooperative role in stabilizing the electronic structure and interfacial charge distribution. Beyond hydrogen production, the spent electrolyte is repurposed for CO2 mineralization, achieving 88.76% conversion to stable carbonates, with cytotoxicity assays confirming reduced environmental toxicity. Together, this study establishes a multifunctional ionically engineered platform for durable, chlorine-free seawater electrolysis and integrated carbon capture, advancing the prospects of circular hydrogen systems.

Direct electrocatalytic seawater splitting is a potential sustainable solution for large-scale green hydrogen production. However, anode deactivation due to impurities and unwanted reactions in seawater hinders its long-term performance. Here, we present a stable ionically bonded metal-organic framework/iron oxide (MOF/Fe2O3) heterostructured catalyst constructed via solid-liquid interfacial chemistry at room temperature. The unique M-O-M (M = metal) ionic bonds at the two-dimensional interface enhance the individual material properties, introducing additional active sites and creating facile charge flow. Theoretical calculations reveal that this system favours hydroxyl ion adsorption and inhibits the chlorine reaction, preventing corrosion and making the catalyst functional for over 900 h in complex seawater. It achieves a current density of 1 A cm-2 at an overpotential of 410 mV, which is similar to 200% higher than that of commercially used IrO2. The heterostructured catalyst demonstrated durable performance at a higher current density of similar to 1.5 A cm-2 for more than 350 h due to selective anodic reaction and anti-corrosive behaviour against chlorine corrosion. This study provides a scalable strategy to modify the chemical states at heterointerfaces to develop robust catalysts for large-scale direct seawater splitting.

Fluorescent nanodiamonds (FNDs) containing nitrogen-vacancy (NV) defects are useful probes for biological imaging and nanoscale sensing applications. Here, we explore the effect of chemical surface modifications and core-shell structures on the T1 relaxation times of 100 nm FNDs hosting nitrogen-vacancy ensembles. The results show that surface oxidation and silica coating of FNDs using the Stöber method can dramatically increase the spin relaxation time from T1 = 320 ± 9 μs to T1 = 1.00 ± 0.06 ms. Using FT-IR and NEXAFS measurements conducted on air oxidized particles, we find that changes to surface functional groups and sp2 carbon density may be responsible for the observed enhancements to the spin relaxation rate. Finally, we use a Monte Carlo model to numerically investigate the relationship between chemical sensitivity and shell thickness and find that a shell thickness on the order of 1 nm should provide the highest sensitivity. Our findings demonstrate that the surface of FNDs can be engineered to exhibit bulk-like T1 relaxation times, in the absence of complex quantum control sequences, which is crucial to advancing biosensing and imaging applications where surface spin noise currently limits measurement precision.

Sulfur radicals are highly reactive intermediates that can greatly accelerate reaction kinetics in lithium-sulfur batteries. However, the intrinsic instability restricts their applications. Herein, we reveal and validate the formation of ultrastable triplet sulfur radical pairs ([Sx·- - Sx·-], x = 2, 3, 4) by combining electron paramagnetic resonance and synchrotron radiations. These radical pairs are produced during the spontaneous decomposition of polysulfide molecules on ferrimagnetic surface, where the sulfur radicals adopt parallel spin alignment and pair into stable triplet states through Hund's Rule. These radicals enable exceptionally rapid sulfur conversion, delivering a 100-fold kinetic enhancement compared to the traditional polysulfide molecules. Using these triplet radical pairs, the lithium-sulfur battery achieves a remarkable discharge capacity of 728 mAh g-1, even at an ultrahigh current rate of 8.0 C, with high sulfur loading and lean electrolyte. Significantly, this is the highest capacity under ultrafast charge-discharge rates reported to date.

Highly conductive electrolytes and stable electrolyte|electrode interfaces are desired for next-generation batteries. Constructing solid-electrolyte interphases on electrodes is a prevailing strategy for enhancing interfacial stability but fails to prevent inevitable breakdown and reformation of interphases during prolonged cycling. Herein, a decoupled electrolyte is designed by introducing a co-solvent (tetraethylene glycol dimethyl ether) with high stability and high positive electrostatic potential values into highly conductive dimethylformamide-based electrolytes, which suffer from electrolyte|positive electrode instability. The preferential adsorption of cations solvated with co-solvents on the positive electrode during discharge induces the formation of a co-solvent-rich localized environment, inhibiting side reactions and contributing to long cyclability. Meanwhile, dimethylformamide in the bulk electrolyte helps to maintain high ionic conductivity, thus improving kinetics. Notably, lithium-carbon dioxide cells with this decoupled electrolyte demonstrate a significantly improved cycle life of ~ 2600 hours and a low overpotential of ~ 1 V, even with a metal-free commercial reduced graphene oxide catalyst. Our work provides an alternative strategy to solid-electrolyte interphase construction for stabilizing electrolyte|electrode interface and unlocks the potential of previously underexplored solvents in batteries.