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Thermophoresis has emerged as a powerful tool for characterizing and manipulating colloids at the nano- and micro-scales due to its sensitivity to colloid–solvent interactions. The use of surfactants enables the tailoring of surface chemistry on colloidal particles and the tuning of interfacial interactions. However, the microscopic mechanisms underlying thermophoresis in surfactant solutions remain poorly understood due to the complexity of multiscale interaction coupling. To achieve a more fundamental understanding of the roles of surfactants, we investigated the thermophoretic behavior of silica beads in both ionic and nonionic surfactant solutions at various background temperatures. We provide a complete mechanistic picture of the effects of surfactants on interfacial interactions through mode-coupling analysis of both electrophoretic and thermophoretic experiments. Our results demonstrate that silica thermophoresis is predominantly governed by the dissociation of silanol functional groups at silica–water interfaces in nonionic surfactant solutions, while in ionic surfactant solutions, the primary mechanism driving silica thermophoresis is the adsorption of ionic surfactants onto the silica surface. [ABSTRACT FROM AUTHOR]

Functionalization of perovskite nanocrystal surfaces with thiocyanate anions presents a transformative approach to enhancing stability and photoluminescence quantum yield (PLQY) through surface defect passivation. This study investigates the role of thiocyanate ligands in modifying the optoelectronic properties of CsPbBr3 nanocrystals. We employed ultrafast two-dimensional infrared spectroscopy to investigate the nature of the dynamic interaction of thiocyanate ligands with nanocrystal surfaces, providing insights into the mechanisms underlying the observed increase in PLQY and stability. Our analysis reveals that the thiocyanate ligands efficiently passivate the surface defects, thereby enhancing the PLQY and the stability of the treated nanocrystals. The spectroscopic evidence supports a model where thiocyanate binds to under-coordinated lead atoms, contributing to a stable nanocrystal surface with enhanced optoelectronic performance. This ligand-induced passivation mechanism advances our understanding of surface chemistry's role in optimizing nanomaterials for solar cell and LED applications. [ABSTRACT FROM AUTHOR]

Borazine is a well-established precursor molecule for the growth of hexagonal boron nitride (h-BN) via chemical vapor deposition on metal substrates. To understand the formation of the h-BN/Rh(111) moiré from borazine on a molecular level, we investigated the low-temperature adsorption and thermally induced on-surface reaction of borazine on Rh(111) in situ using synchrotron radiation-based high-resolution x-ray photoelectron spectroscopy (XPS), temperature-programmed XPS, and near-edge x-ray absorption fine structure measurements. We find that borazine adsorbs mainly as an intact molecule and have identified a flat-lying adsorption geometry. Borazine multilayers are observed to desorb below 200 K. Starting at about 300 K, dehydrogenation of the remaining borazine and borazine fragments takes place, and disordered boron nitride starts to grow. Above 600 K, the formation of the h-BN sets in. Finally, at 1100 K, the conversion to h-BN is complete. The h-BN formed by deposition and post-annealing was compared to the h-BN grown by an established procedure, proving the successful preparation of the desired two-dimensional material. [ABSTRACT FROM AUTHOR]

Identifying the oxidation structure of two-dimensional interfaces is crucial to improve surface chemistry and electronic properties. Beyond graphene with only phenyl rings, a novel carbon-nitrogen material, C3N, presents an intrinsic heterogeneous surface morphology where each phenyl ring is encircled by six nitrogen atoms, yet its atomistic oxidation structure remains unclear. Here, combining a series of density functional theory calculations and ab initio molecular dynamics simulations, we demonstrate that thermodynamically favorable oxidation loci are confined to the phenyl ring, and kinetic transformations of oxidation structures are feasible along the phenyl ring, whereas those toward nitrogen atoms are proven to be extremely difficult. These results are attributed to the lower barrier of oxygen atom migration along the phenyl ring, while the significantly high barriers toward nitrogen atoms are due to the heterogeneous potential energy surface for oxygen–C3N interaction. This work highlights the significance of surface morphology on the characteristics of oxidation structure, offering insights into tunable electronic properties via confined interfacial oxidation. [ABSTRACT FROM AUTHOR]

This study explored the interplay between the ligand–surface chemistry of colloidal CsPbBr3 nanowires (NWs) and their optical properties. The ligand equilibrium was probed using nuclear magnetic resonance spectroscopy, and by perturbing the equilibrium via dilution, the gradual removal of ligands from the CsPbBr3 surface was observed. This removal was correlated with an increase in the surface defect density, as suggested by a broadening of the photoluminescence (PL) spectrum, a decrease in the PL quantum yield (PLQY), and quenching of the PL decay. These results highlight similar surface binding between the traditional CsPbBr3 quantum dots and our NWs, thereby expanding the scope of well-established ligand chemistry to a relatively unexplored nanocrystal morphology. By controlling the dilution factor, it was revealed that CsPbBr3 NWs achieve a PLQY of 72% ± 2% and a relatively long average PL lifetime of 400 ± 10 ns, without relying on additional surface passivation techniques, such as ligand exchange. [ABSTRACT FROM AUTHOR]

Design of next-generation membranes requires a nanoscopic understanding of the effect of biologically inspired heterogeneous surface chemistries and topologies (roughness) on local water and solute behavior. In particular, the rejection of small, neutral solutes, such as boric acid, poses a heretofore unsolved challenge. In prior work, a computational inverse design technique using an evolutionary optimization successfully uncovered new surface design strategies for optimized transport of water over solutes in smooth, model pores consisting of two surface chemistries. However, extending such an approach to more complex (and realistic) scenarios involving many surface chemistries as well as surface roughness is challenging due to the expanded design space. In this work, we develop a new approach that uses active learning to optimize in a reduced feature space of surface group interactions, finding parameters that lead to their assembly into ordered, optimal patterns. This approach rapidly identifies novel surface functionalizations that maximize the difference in water and boric acid transport through the nanopore. Moreover, we find that the roughness of the nanopore wall, independent of its chemistry, can be leveraged to enhance transport selectivity: oscillations in the pore wall diameter optimally inhibit boric acid transport by creating energetic wells from which the solute must escape to transport down the pore. This proof-of-concept demonstrates the potential for active learning strategies, in concert with molecular simulations, to rapidly navigate complex design spaces of aqueous interfaces and is promising as a tool for engineering water-mediated surface interactions for a broad range of applications. [ABSTRACT FROM AUTHOR]

The dynamics of polymer nanocomposites varies depending on the physics and chemistry at the polymer–nanoparticle interface. The physical aging of the nanocomposites is accelerated or retarded based on interfacial interactions and the state of polymer adsorption at the interfaces. In this study, we investigated the aging kinetics of silica–polystyrene nanocomposites using differential scanning calorimetry, focusing on the effect of local conformations of chains adsorbed on the nanofiller surface. The results show that the temperature dependence of the aging rate follows a Vogel–Fulcher–Tammann relationship at high temperatures, whereas it exhibits an Arrhenius-like behavior below a characteristic temperature (Tc). Notably, at T < Tc, the aging rate decreases with increasing loop height of the chains adsorbed on the filler surface, but the activation energy remains unchanged. We proposed that the suppression of the aging rate at T < Tc is likely related to an increase in the length scale over which the slow interfacial dynamics can propagate due to the increased topological interactions between the chain loops of a larger size and the free chains in the matrix. The increased packing frustration occurring at the filler surface occupied by the larger loops might also contribute to the decreased aging rate. [ABSTRACT FROM AUTHOR]

Single phase, polycrystalline perovskite oxide SrVO3, with its intrinsic low effective work function and facile synthesis process, is a promising thermionic electron emitter cathode candidate, in which previous works have shown evidence of an effective work function as low as 2.3 eV. In this work, we study the vacuum activation process of SrVO3 and find that it has promising emission stability over 15 days of continuous high temperature operation. We find that SrVO3 shows surface Sr and O segregation during its operation, which we hypothesize is needed to create a positive surface dipole, leading to a low effective work function. Emission repeatability from cyclic heating and cooling suggests the promising stability of the low effective work function surface, and additional observations of drift-free emission during 1 h of continuous emission testing at high temperature further demonstrate its excellent performance stability. This assessment of the emission stability over time and the interplay of evolving surface chemistry with emission behavior are necessary for understanding how best to prepare, process, and operate SrVO3 cathodes. [ABSTRACT FROM AUTHOR]

The activation volume, which quantifies the response of the chemical reactions to the applied stress, plays a central role in controlling the mechanochemical reactions for applications including lubricity, wear, and the topographic fabrication of the surfaces under stress. However, the physical interpretations of the activation volume remain scientifically intriguing and largely unexplored. Here, density functional theory calculations are used to investigate the general rules of charge transfer underlying activation volume in controlling the typically mechanochemical reaction process. It is found that the activation volume could be decoupled into the electronic contributions from interface chemistry and bulk physical deformation, which are commonly linear dependent on the contact pressure. Therefore, the activation volume may, indeed, be derived from the stress-driven charge transfer underlying cooperative competition between interfacial chemistry and the bulk region. This competition is related to the stiffness change from the bulk to slab. The magnitude of the stiffness change represents the degree to which the interface atoms modify the bulk properties, which is directly related to the contribution of different regions to the activation volume. This work may open up the understanding of the activation volume from dynamic electron transfer to engineer mechanochemical reactions, different from the existing insights into the geometric dimensionality of the contact configuration. [ABSTRACT FROM AUTHOR]

Understanding polymer transport in nanopores is crucial for optimizing heterogeneously catalyzed processes in polymer upcycling and fabricating high-performance nanocomposite films and membranes. Although confined polymer dynamics have been extensively studied, the behavior of polyethylene (PE)—the most widely used commodity polymer—in pores smaller than 20 nm remains largely unexplored. We investigate the effects of extreme nanoconfinement on PE transport using capillary rise infiltration in silica nanoparticle packings with average pore radii ranging from ∼1 to ∼9 nm. Using in situ ellipsometry and the Lucas–Washburn model, we discover a previously unknown inverse relationship between effective viscosity (ηeff) and average pore radius (Rpore). Additonally, we determine that PE transport under these extreme conditions is primarily governed by physical confinement, rather than pore surface chemistry. We refine an existing theory to provide a generalized formalism to describe the polymer transport dynamics over a wide range of pore radii (from 1 nm and larger). Our results offer valuable insights for optimizing catalyst supports in polymer upcycling and improving infiltration processes for nanocomposite fabrication. [ABSTRACT FROM AUTHOR]

We have investigated, using molecular dynamics, the surface chemistry of hydrogen incident on the amorphous and crystalline lithium oxide and lithium hydroxide surfaces upon being slowed down by a collision cascade and retained in the amorphous surface of either Li2O or LiOH. We looked for the bonding of H to the resident structures in the surface to understand a possible chain of chemical reactions that can lead to surface transformation upon H atom impact. Our findings, using Density-Functional Theory (DFT) trained ReaxFF force field/electronegativity equalization method potentials, stress the importance of inclusion of polarization in the dynamics of a Li–O–H system, which is also illustrated by DFT energy minimization and quantum–classical molecular dynamics using tight binding DFT. The resulting polar-covalent chemistry of the studied systems is complex and very sensitive to the instantaneous positions of all atoms as well as the ratio of concentrations of various resident atoms in the surface. [ABSTRACT FROM AUTHOR]

Hydrophobicity has proven fundamental in an inexhaustible amount of everyday applications. Material hydrophobicity is determined by chemical composition and geometrical characteristics of its macroscopic surface. Surface roughness or texturing enhances intrinsic hydrophilic or hydrophobic characteristics of a material. Here we consider crystalline surfaces presenting molecular-scale texturing typical of crystalline porous materials, e.g., metal-organic frameworks. In particular, we investigate one such material with remarkable hydrophobic qualities, ZIF-8. We show that ZIF-8 hydrophobicity is driven not only by its chemical composition but also its sub-nanoscale surface corrugations, a physical enhancement rare amongst hydrophobes. Studying ZIF-8's hydrophobic properties is challenging as experimentally it is difficult to distinguish between the materials' and the macroscopic corrugations' contributions to the hydrophobicity. The computational contact angle determination is also difficult as the standard "geometric" technique of liquid nanodroplet deposition is prone to many artifacts. Here, we characterise ZIF-8 hydrophobicity via: (i) the "geometric" approach and (ii) the "energetic" method, utilising the Young–Dupré formula and computationally determining the liquid–solid adhesion energy. Both approaches reveal nanoscale Wenzel-like bathing of the corrugated surface. Moreover, we illustrate the importance of surface linker termination in ZIF-8 hydrophobicity, which reduces when varied from sp3 N to sp2 N termination. We also consider halogenated analogues of the methyl-imidazole linker, which promote the transition from nanoWenzel-like to nanoCassie–Baxter-like states, further enhancing surface hydrophobicity. Present results reveal the complex interface physics and chemistry between water and complex porous, molecular crystalline surfaces, providing a hint to tune their hydrophobicity. [ABSTRACT FROM AUTHOR]

Polar surfaces undergo polarity compensation, which can lead to significantly different surface chemistry from their nonpolar counterparts. This process in turn can substantially alter the binding of adsorbates on the surface. Here, we find that hydrogen binds much more strongly to the polar (110) surface than the nonpolar (100) surface for a wide range of ABO3 perovskites, forming a hydroxyl layer on the O24− termination and a hydride layer on the ABO4+ termination of the (110) surface. The stronger adsorption on the polar surfaces can be explained by polarity compensation: hydrogen atoms can act as electron donors or acceptors to compensate for the polarity of perovskite surfaces. The relative stability of the surface terminations is further compared under different gas environments and several perovskites have been found to form stable surface hydride layers under oxygen-poor conditions. These results demonstrate the feasibility of creating stable surface hydrides on perovskites by polarity compensation which might lead to new hydrogenation catalysts based on ABO3 perovskites. [ABSTRACT FROM AUTHOR]

Electrodeposited amorphous hydrated iridium oxide (IrOx) is a promising material for pH sensing due to its high sensitivity and the ease of fabrication. However, durability and variability continue to restrict the sensors effectiveness. Variation in probe films can be seen in both performance and fabrication, but it has been found that performance variation can be controlled with potentiostatic conditioning (PC). To make proper use of this technique, the morphological and chemical changes affecting the conditioning process must be understood. Here, a thorough study of this material, after undergoing PC in a pH-sensing-relevant potential regime, was conducted by voltammetry, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). Fitting of XPS data was performed, guided by raw trends in survey scans, core orbitals, and valence spectra, both XPS and UPS. The findings indicate that the PC process can repeatably control and conform performance and surface bonding to desired calibrations and distributions, respectively; PC was able to reduce sensitivity and offset ranges to as low as ±0.7 mV/pH and ±0.008 V, respectively, and repeat bonding distributions over ~2 months of sample preparation. Both Ir/O atomic ratios (shifting from 4:1 to over 4.5:1) and fitted components assigned hydroxide or oxide states based on the literature (low-voltage spectra being almost entirely with suggested hydroxide components, and high-voltage spectra almost entirely with suggested oxide components) trend across the polarization range. Self-consistent valence, core orbital, and survey quantitative trends point to a likely mechanism of ligand conversion from hydroxide to oxide, suggesting that the conditioning process enforces specific state mixtures that include both theoretical Ir(III) and Ir(IV) species, and raising the conditioning potential alters the surface species from an assumed mixture of Ir species to more oxidized Ir species.

As a research hotspot in food science and nutrition, antioxidant peptides can function by scavenging free radicals, inhibiting peroxides, and chelating metal ions. Therefore, how to efficiently discover and screen antioxidant peptides has become a key issue in research and production. Traditional discovery methods are time-consuming and costly, but also challenging to resolve the quantitative structure-activity relationship of antioxidant peptides. Several novel techniques, including artificial intelligence, molecular docking, bioinformatics, quantum chemistry, phage display, switchSENSE, surface plasmon resonance, and fluorescence polarization, are emerging rapidly as solutions. These techniques possess efficient capability for the discovery of antioxidant peptides, even with the potential for high-throughput screening. In addition, the quantitative structure-activity relationship can be resolved. Notably, combining these novel techniques can overcome the drawbacks of a single one, thus improving efficiency and expanding the discovery horizon. This review has summarized eight novel and efficient techniques for discovering antioxidant peptides and the combination of techniques. This review aims to provide scientific evidence and perspectives for antioxidant peptide research. [ABSTRACT FROM AUTHOR]

[Display omitted] Förster resonance energy transfer (FRET) serves as a critical mechanism to study intermolecular interactions and the formation of macromolecular assemblies. Cascade FRET is a multi-step FRET process which can overcome limitations associated with traditional single-step FRET. Herein, a novel organic–inorganic hybrid composed of a nile red derivative attached to the edge of the layered silicate clay Laponite (Lap-NR) was used to facilitate cascade FRET between Laponite sheets. Utilizing naphthalene-diimide edge-modified Laponite (Lap-NDI) as the initial donor, Rhodamine 6G on the basal surface of Laponite as the first acceptor, and Lap-NR as the second acceptor, cascade FRET was achieved. The influence of solvent composition in a DMF/water mixture on cascade FRET was investigated, revealing that a higher water content led to an enhancement of the cascade FRET process, which is attributed to increased aggregation-induced emission of Lap-NDI and the enhanced quantum yield of R6G in water. This study provides a unique approach to achieve cascade FRET by taking advantage of the anisotropic surface chemistry of a two-dimensional nanomaterial, providing a colloidally-driven alternative with improved tunability compared to macromolecular routes. The flexibility and simplicity of this approach will advance the state of the art of organic–inorganic hybrids for applications in optoelectronics, sensors, and hybrid photovoltaics. [ABSTRACT FROM AUTHOR]

The reverse water-gas shift (RWGS) reaction offers a sustainable approach for CO2 utilization, yielding CO for vital catalytic processes. This study compares the catalytic performance of exsolved Cu- and Ni-encapsulated silicalite-1 (S-1) catalysts against those prepared by impregnation methods. Exsolved catalysts, characterized by confined metal nanoparticles and distinct surface chemistry, exhibited higher CO selectivity and lower activation energies of CO formation than their impregnated counterparts. Surface and structural analyses revealed that the exsolution process enhanced RWGS activity, driven by altered metal-support interactions and unique adsorption behaviors, offering insights for improving the efficiency of RWGS catalysis. [ABSTRACT FROM AUTHOR]

The emergence of π‐magnetism in low‐dimensional carbon‐based nanostructures, such as nanographenes (NGs), has captured significant attention due to their unique properties and potential applications in spintronics and quantum technologies. Recent advancements in on‐surface synthesis under ultra‐high vacuum conditions have enabled the atomically precise engineering of these nanostructures, effectively overcoming the challenges posed by their inherent strong chemical reactivity. This review highlights the essential concepts and synthesis methods used in studying NGs. It also outlines the remarkable progress made in understanding and controlling their magnetic properties. Advanced characterization techniques, such as scanning tunneling microscopy (STM) and non‐contact atomic force microscopy (nc‐AFM), have been instrumental in visualizing and manipulating these nanostructures, which highlighting their critical role in the field. The review underscores the versatility of carbon‐based π‐magnetic materials and their potential for integration into next‐generation electronic devices. It also outlines future research directions aimed at optimizing their synthesis and exploring applications in cutting‐edge technologies. [ABSTRACT FROM AUTHOR]

The on‐surface synthesis strategy has emerged as a promising route for fabricating well‐defined two‐dimensional (2D) BN‐substituted carbon nanomaterials with tunable electronic properties. This approach relies on specially designed precursors and requires a thorough understanding of the on‐surface reaction pathways. It promises precise structural control at the atomic scale, thus complementing chemical vapor deposition (CVD). In this study, we investigated a novel heteroatomic precursor, tetrabromoborazine, which incorporates a BN core and an OH group, on Ag(111) using low temperature scanning tunnelling microscopy/spectroscopy (LT‐STM/STS) and X‐ray photoelectron spectroscopy (XPS). Through sequential temperature‐induced reactions involving dehalogenation and dehydrogenation, distinct tetrabromoborazine derivatives were produced as reaction intermediates, leading to the formation of specific self‐assemblies. Notably, the resulting intricate supramolecular structures include a chiral kagomé lattice composed of molecular dimers exhibiting a unique electronic signature. The final product obtained was a random covalent carbon network with BN‐substitution and embedded oxygen heteroatoms. Our study offers valuable insights into the significance of the structure and functionalization of BN precursors in temperature‐induced on‐surface reactions, which can help future rational precursor design. Additionally, it introduces complex surface architectures that offer a high areal density of borazine cores. [ABSTRACT FROM AUTHOR]

γ‐Graphyne (GY), an emerging carbon allotrope, is envisioned to offer various alluring properties and broad applicability. While significant progress has been made in the synthesis of GY over recent decades, its widespread application hinges on developing efficient, scalable, and accessible synthetic methods for the production of GY and its derivatives. Here we report a facile metal‐free nucleophilic crosslinking method using wet chemistry for fast gram‐scale production of GY and its derivatives. This synthesis method involves the aromatic nucleophilic substitution reactions between fluoro‐(hetero)arenes and alkynyl silanes in the presence of a catalytic amount of tetrabutylammonium fluoride, where the fluoride plays a crucial role in removing protective groups from alkynyl silanes and generating reactive alkynylides. Our comprehensive analysis of the as‐prepared GY reveals a layered structure, characterized by the presence of the C(sp)−C(sp2) bond. The synthetic strategy shows remarkable tolerance to various functional groups and enables the preparation of diverse F‐/N‐rich GY derivatives, using electron‐deficient fluoro‐substituted (hetero)arenes as precursors. The feasibility of producing GY and derivatives from fluorinated (hetero)arenes through the metal‐free, scalable, and cost‐effective approach paves the way for broad applications of GY and may inspire the development of new carbon materials. [ABSTRACT FROM AUTHOR]

Electrochemical urea oxidation reaction (UOR) offers a promising alternative to the oxygen evolution reaction (OER) in clean energy conversion and storage systems. Nickel‐based catalysts are regarded as highly promising electrocatalysts for the UOR. However, their effectiveness is significantly hindered by the unavoidable self‐oxidation reaction of nickel species during UOR. To address this challenge, we proposed an interface chemistry modulation strategy to boost UOR kinetics by creating a high‐energy interfacial heterostructure. This heterostructure incorporates Ag at the CoOOH@NiOOH heterojunction interface, where strong interactions significantly promote the electron exchanges at the heterojunction interface between ‐OH and ‐O groups. Consequently, the improved electron delocalization leads to the formation of stronger bonds between Co sites and urea CO(NH2)2, promoting a preference for urea to occupy Co active sites over OH*. The resulting catalyst, Ag−CoOOH@NiOOH, demonstrates ultrahigh UOR activity with a low potential of 1.33 V at 100 mA cm−2. The fabricated catalyst exhibits a mass activity over 11.9 times greater than the initial cobalt oxyhydroxide. The rechargeable urea‐assisted zinc‐air batteries (ZABs) achieve a record‐breaking energy efficiency of 74.56 % at 1 mA cm−2, remarkable durability (1000 hours at a current density of 50 mA cm−2), and quick charge performances. [ABSTRACT FROM AUTHOR]

Attaching DNA oligonucleotides to gold nanoparticles (AuNPs) to prepare spherical nucleic acids (SNAs) has offered tremendous insights into surface chemistry with resulting bioconjugates serving as critical reagents in biosensors and nanotechnology. While thiolated DNA is generally required to achieve stable conjugates, we herein communicate that using a thermal drying method, a high DNA density and excellent SNA stability was achieved using nonthiolated DNA, rivaling the performance of thiolated DNA such as surviving 1 M NaCl, 2 month stability in 0.3 M NaCl and working in 50 % serum. A poly‐adenine block with as few as two consecutive terminal adenine bases is sufficient for anchoring on AuNPs. By side‐by‐side comparison with the salt‐aging method, the conjugation mechanism was attributed to competitive adenine adsorption at high temperature along with an extremely high DNA concentration upon drying. Bioanalytical applications of nonthiolated SNAs were validated in both solution and paper‐based sensor platforms, facilitating cost‐effective applications for SNAs. [ABSTRACT FROM AUTHOR]

Emerging fields of quantum technologies and biomedical applications demand pure nanodiamonds (NDs) with well-defined surface chemistry. Therefore, an inexpensive, scalable and eco-friendly ND surface purification technology is required. In this study, we report our method, salt-coated air oxidation (SCAO) thermal annealing, to achieve uniform purification of a ND surface without the loss of diamond material. A photoluminescence (PL) spectroscopy quality control method is proposed to evaluate the degree of purification. The presence of an isoemission point in the set of nitrogen vacancy (NV) center PL spectra, obtained through the photochromic effect, is examined as a surface purity indicator. The ratio of the NV centers in NDs after the SCAO treatment was determined by decomposing the PL spectra using the non-negative matrix factorization technique. [ABSTRACT FROM AUTHOR]

We report here the preparation and characterization of new well‐defined silica‐supported Ti imido complexes that present an L‐ligand variation in a structure of currently the most active oxo/imido heterometathesis catalyst (≡SiO)Ti(=NtBu)(Me2Pyr)(py)2 (1s), where py is replaced with stronger electron‐donating 4‐(N,N‐dimethylamino)pyridine (2s) or bidentate 2,2′‐bipyridine (3s). The materials were characterized with elemental and mass balance analyses and IR and solid‐state NMR that confirmed the selective formation of surface Ti species with terminal imido ligand. Evaluation of the catalytic oxo/imido heterometathesis activity of the obtained materials demonstrated that L‐ligands have a pronounced influence on the catalytic performance. In particular, the replacement of pyridine with stronger donating ligands resulted in a significant drop of activity. The catalytic results are discussed in view of the reaction mechanism and implications for further catalyst development. [ABSTRACT FROM AUTHOR]

Multifunctional robust protective coatings that combine biocompatibility, antifouling and antimicrobial properties play an essential role in reducing host reactions and infection on invasive medical devices. However, developing these protective coatings generally faces a paradox: coating materials capable of achieving robust adhesion to substrates via spontaneous deposition inevitably initiate continuous biofoulant adsorption, while those employing strong hydration capability to resist biofoulant attachment have limited substrate binding ability and durability under wear. Herein, we designed a multifunctional terpolymer of poly(dopamine methyacrylamide-co-2-methacryloyloxyethyl phoasphorylcholine-co-2-(dimethylamino)-ethyl methacrylate) (P(DMA-co-MPC-co-DMAEMA)), which integrates desired yet traditionally incompatible functions (i.e., robust adhesion, antifouling, lubrication, and antimicrobial properties). Direct normal and lateral force measurements, dynamic adsorption tests, surface ion conductance mapping were applied to comprehensively investigate the nanomechanics of coating-biofloulant interactions. Catechol groups of DMA act as basal anchors for robust substrate deposition, while the highly hydrated zwitterion of MPC provides apical protection to resist biofouling and wear. Moreover, the antimicrobial property is conferred through the protonation of tertiary amine groups on DMAEMA, inhibiting infection under physiological conditions. This work provides an effective strategy for harmonizing demanded yet incompatible properties in one coating material, with significant implications for the development of multifunctional surfaces towards the advancement of invasive biomedical devices. Multifunctional robust protective coatings have been widely utilized in invasive medical devices to mitigate host responses and infection. However, modified surface coatings often encounter a trade-off between robust adhesion to substrates and strong hydration capability for antifouling and antimicrobial properties. We propose a universal strategy for surface modification by dopamine-assisted co-deposition with a multifunctional terpolymer of P(DMA-co-MPC-co-DMAEMA) that simultaneously achieves robust adhesion, antifouling, and antimicrobial properties. Through elucidating the nanomechanics with fundamentally understanding the interactions between the coating and biomacromolecules, we highlight the role of DMA for substrate adhesion, MPC for biofouling resistance, and DMAEMA for antimicrobial activity. This approach presents a promising strategy for constructing multifunctional coatings on minimally invasive medical devices by tuning interfacial molecular asymmetricity to reconcile incompatible properties within one coating. [Display omitted] [ABSTRACT FROM AUTHOR]

Polyproline II (PPII) peptide sequences are recognized as promising biomaterials because of their attractive antifouling properties. However, the mechanisms behind their antifouling behavior have not been fully characterized. In this work we show that PPII peptide coverage, controlled by adsorption time, significantly reduces the fouling of bovine serum albumin (BSA, a model foulant). In addition, guest residues introduced into the PPII sequence are shown to significantly impact BSA adsorption as well as human mesenchymal stem cell (hMSC) spreading. This research will help guide future PPII peptide designs for incorporation into novel biomaterials. [ABSTRACT FROM AUTHOR]

Acrylamide (AA) is a deleterious compound produced in starchy foods cooked at high temperatures. It is formed primarily due to the combined reaction of amino acid asparagine and sugars during heating processes such as cooking, baking and roasting. AAs create harmful health effects, and an increased risk of cancer. AA containment is integral part to reduce dietary exposure, but balanced with maintaining the desired sensory qualities and food safety. This review surface out the chemistry of AA formation, factors affecting it, toxicity data, regulatory limits, and strategies for mitigation. It further examines various analytical techniques, including chromatography and innovative methods, emphasizing their sensitivity, specificity, and rapid detection capabilities for acrylamide. Key approaches include modifying recipes, controlling cooking conditions, and exploring new nonthermal processing technologies. Each type of food presents unique mitigation challenges and may demand combined and tailored strategies rather than a one-size-fits-all solution. [ABSTRACT FROM AUTHOR]

A self-floating amphiphilic biosorbent (SFAB) was prepared by dispersing the plasma-modified water hyacinth (WH) (Eichhornia crassipes) fibers on the beeswax support. The synthesis process takes advantage of the functionalising properties of plasma with polar groups (–OH, –CO, –COOH) and the binding effect of beeswax. The characteristics of the obtained biosorbent exhibited significant changes in surface chemistry and roughness confirmed by scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR), and energy dispersive X-ray spectroscopy (EDX). The resulting functionalised material offers appropriate anchoring sites for pollutants leading to a biomaterial with hydrophilic and lipophilic properties. The removal performance of the SFAB outperforms the natural biomass fibers taking alone, with an uptake capacity of 20.83 mg/g for merbromin (MB) (50 mg/L) and 19.90 mg/g for Green Naphthol B (GNB) (50 mg/L), based on the successfully fitted general-order kinetic model. The effects of some key adsorption parameters were optimised, and the equilibrium data (298–323 K) were best fitted by the Liu isotherm reaching 47.20 and 36.40 mg/g of uptake amounts for MB and GNB, respectively at 298 K. The removal mechanism is governed by π–π interplay, hydrophobic interaction, and hydrogen bonding effects. [ABSTRACT FROM AUTHOR]

Self-assembled non-covalent nanoparticle-polymer hybrids, that can combine a variety of desired properties in a single material with highly dynamic structure, have great potential in the field of functional nanosystems. In this study, we present a method for preparing such hybrids from silica nanoparticles and polymer structures of polystyrene-block-polyacrylic acid (PS-b-PAA). We show that the surface chemistry of the nanoparticles has a major influence on the encapsulation efficiency and the localization of the particles in the vesicles. Furthermore, an increase in vesicle size was observed with higher vesicle loading. A particular highlight of this work is that the morphology of the hybrids could be subsequently modified by adjusting the solvent composition. It was also found that the presence of the particles led to faster transitions due to the increased free energy of the system. This type of morphological change therefore offers promising potential applications, such as self-healing materials. [ABSTRACT FROM AUTHOR]

The passive film on a dual-phase Al0.3Cr0.5Fe2Mn0.25Mo0.15Ni1.5Ti0.3 FCC + Heusler (L21) compositionally concentrated alloy formed during extended exposure to an applied potential in the passive range in dilute chloride solution was characterized. Each phase, with its own distinct composition of passivating elements, formed unique passive films separated by a heterophase interface. High-resolution, surface sensitive characterization enabled chemical analysis of the passive film formed over individual phases. The film formed over the L21 phase had a higher concentration of Al, Ni, and Ti, while the film formed over FCC phase was of similar thickness but contained comparatively higher Cr, Fe, and Mo concentrations, consistent with the differences in bulk microstructure composition. The passive film was continuous across phase boundaries and the distribution of passivating elements (Al, Cr, and Ti) indicated both phases were independently passivated. Spatially resolved analysis of the surface chemistry of the dual-phase CCA revealed that the cation with the highest composition in passive film formed on the FCC phase was Cr (52.4 at. pct) and for the L21 phase was Ti (53.1 at. pct) despite the bulk concentration of each element being below 20 at. pct in their respective phases. Al, Cr, and Ti were enriched in both phases within the passive film relative to their respective bulk compositions. In parallel studies, single-phase alloys with compositions representative of the FCC and L21 phases were synthesized to evaluate the corrosion behavior of each phase in isolation. The corrosion behavior of the dual-phase alloy showed passivity evidenced by a pitting potential of 0.615 VSCE in 0.01 M NaCl. The pitting potential and other electrochemical parameters suggested a combination of behaviors of both single-phase samples, suggesting that the global corrosion behavior may be represented by a composite theory applied to phases, their area fractions, and interphase length. However, the interphase in the dual-phase CCA was a local corrosion initiation site and may limit localized corrosion protectiveness. The alloy design implications for optimization of second phase structure and morphology are discussed. [ABSTRACT FROM AUTHOR]

Heavy alkali‐metal treatments have been the most recent breakthrough in improving the efficiency of Cu(In,Ga)Se2 (CIGS) solar cells. Alkali halides are generally evaporated onto the surface of the CIGS thin film by a vacuum process. Here, we report an alternative, low‐cost solution process for the surface treatment of CIGS thin films using cesium carbonate (CsCO3) as a new route to incorporate cesium (Cs) for improving solar cell performance. CIGS thin films were fabricated using pulsed hybrid reactive magnetron sputtering and the surface treatment was performed by spin‐coating CsCO3 solution on the surface of CIGS at room temperature, followed by vacuum annealing at 400°C. The surface chemistry of the CIGS thin film changed after the treatment and the efficiency of respective solar cells improved by more than 30%, mostly driven by an enhancement in open‐circuit voltage. X‐ray photoelectron spectroscopy revealed the depletion of copper and the presence of Cs on the surface of the CIGS thin film. Ultraviolet photoelectron spectroscopy showed the lowering of the valence band maximum by around 0.25 eV after the treatment, which plays a positive role in reducing interfacial recombination. High‐resolution transmission electron microscopy indicates the presence of Cs and depletion of Cu at the grain boundaries of the CIGS thin film. These findings open a low‐cost route for improving the performance of CIGS solar cells by surface modification using a solution process. [ABSTRACT FROM AUTHOR]

Many next‐generation materials for Li‐ion batteries are limited by material instabilities. To stabilize these materials, ultrathin, protective coatings are needed that conduct both lithium ions and electrons. Here, we demonstrate a hybrid chemistry combining molecular layer deposition (MLD) of trimethylaluminum (TMA) and p‐hydroquinone (HQ) with oxidative molecular layer deposition (oMLD) of molybdenum pentachloride (MoCl5) and HQ to enable vapor‐phase molecular layer growth of poly(p‐hydroquinone) (PHQ)—a mixed electron and lithium ion conducting polymer. We employ quartz crystal microbalance (QCM) studies to understand the chemical mechanism and demonstrate controlled linear growth with a 0.5 nm/cycle growth rate. Spectroscopic characterization indicates that this hybrid MLD/oMLD chemistry polymerizes surface HQ monomers from the TMA‐HQ chemistry to produce PHQ. The polymerization to PHQ improves air stability over MLD TMA‐HQ films without crosslinking. Electrochemical measurements on hybrid MLD/oMLD films indicate electronic conductivity of ~10−9 S/cm and a Li‐ion conductivity of ~10−4 S/cm. While these coatings show promise for Li‐ion battery applications, this work focuses on establishing the coating chemistry and future studies are needed to examine the stability, structure, and cycling performance of these coatings in full Li‐ion cells. [ABSTRACT FROM AUTHOR]

A significant obstacle in the manufacturing and practical application of Ni‐rich cathode materials is decreasing the manufacturing cost without sacrificing the cycling stability. Here a high‐energy, ultrahigh‐Ni, and nearly Co‐free cathode with outstanding cycling performance is proposed. This promising cathode is enabled by artificially constructing an “outside‐in” interface structure toward LiNi0.94Co0.05Mn0.01O2 (NCM94) cathodes. Combining theoretical prediction and experimental results, it is revealed that high interfacial stability is achieved by a specific surface chemistry with an outside‐in structure composed of an inner organic layer and an outer inorganic layer. Benefiting from the protection effect of the robust outside layer and the strain relieve function of the inside layer, the intrinsic challenges of interfacial reactions, transition metal (TM) dissolution, and micro‐crack propagation have been mitigated for the Ni‐rich cathode. As a result, the “outside‐in” strategy enables superior cycling stability with a 92.7% retention after 200 cycles and an excellent rate capability of 149.1 mAh g−1 at 10 C, achieved by adding only 0.5% of the production cost. This study unlocks the possibilities of achieving outstanding performance for ultrahigh Ni cathode by spending minimum cost through the facile surface chemistry method. [ABSTRACT FROM AUTHOR]

Vibrational strong coupling can modify chemical reaction pathways in unconventional ways. Thus far, Fabry‐Perot cavities formed by pairs of facing mirrors have been mostly utilized to achieve vibrational strong coupling. In this study, we demonstrate the application of non‐local metasurfaces that can sustain surface lattice resonances, enabling chemical reactions under vibrational strong coupling. We show that the solvolysis kinetics of para‐nitrophenyl acetate can be accelerated by a factor of 2.7 by strong coupling to the carbonyl bond of the solvent and the solute with a surface lattice resonance. Our work introduces a new platform to investigate polaritonic chemical reactions. In contrast to Fabry‐Perot cavities, metasurfaces define open optical cavities with single surfaces, which removes alignment hurdles, facilitating polaritonic chemistry across large areas. [ABSTRACT FROM AUTHOR]

Designing ultrathin transition metal electrocatalysts with optimal surface chemistry state is crucial for oxygen evolution reaction (OER). However, the structure‐dependent electrochemical performance and the underlying catalytic mechanisms are still not clearly distinguished. Herein, we synthesize ultrathin Co6.8Se8 nanosheets (NSs) with subnanometer thickness by incorporating catalytically inactive selenium (Se) into ultrathin Co(OH)2, thereby switching the OER reaction pathway from adsorbate evolution mechanism (AEM) to oxide path mechanism (OPM). The prepared ultrathin Co6.8Se8 NSs exhibit an overpotential of 253 mV at 10 mA/cm2, outperforming the mostly reported Co‐based electrocatalysts. Advanced operando synchrotron spectroscopies and X‐ray absorption spectroscopy reveal the ultrathin Co6.8Se8 NSs, whose surface is reconstructed into Se‐doped Co(OH)2 during the OER process, could trigger direct O*−O* radical coupling rather than OOH* intermediates within AEM pathway thus lowering the energy input. Density functional theory calculations confirm that Co6.8Se8 NSs with shorter Co−Co bond length and stable Co−Se bond could optimize the rate‐determining step barrier via OPM pathway. Besides, rechargeable zinc‐air batteries based on Co6.8Se8 NSs exhibit excellent stability for more than 500 h of continuous charge–discharge cycles at 4 mA/cm2. The present study highlights the structural‐dependent switch of OER pathways and provides valuable insights for further development of ultrathin OER catalysts. [ABSTRACT FROM AUTHOR]

Regulating interfacial chemistry at electrode‐electrolyte interface by designing catalytic electrode material is crucial and challenging for optimizing battery performance. Herein, a novel single atom Cu regulated Bi@C with Cu−C3 site (Bi@SA Cu−C) have been designed via the simple pyrolysis of metal‐organic framework. Experimental investigations and theoretical calculations indicate the Cu−C3 sites accelerate the dissociation of P−F and C−O bonds in NaPF6‐ether‐based electrolyte and catalyze the formation of inorganic‐rich and powerful solid electrolyte interphase. In addition, the Cu−C3 sites with delocalized electron around Cu trigger an uneven charge distribution and induce an in‐plane local electric field, which facilitates the adsorption of Na+ and reduces the Na+ migration energy barrier. Consequently, the obtained Bi@SA Cu−C achieves a state‐of‐the‐art reversible capacity, ultrahigh rate capability, and long‐term cycling durability. The as‐constructed full cell delivers a high capacity of 351 mAh g−1 corresponding to an energy density of 265 Wh kg−1. This work provides a new strategy to realize high‐efficient sodium ion storage for alloy‐based anode through constructing single‐atom modulator integrated catalysis and promotion effect into one entity. [ABSTRACT FROM AUTHOR]

The development of rechargeable lithium batteries (RLBs) has made a great contribution in solving the problems in the current era, such as energy shortage and climate change. With the expanding of application field of RLBs from portable device to large‐scale electric equipment, it is an urgent demand for RLBs to operate in a wide range of temperature. More and more attention has been paid to the design of wide‐temperature RLBs. Therefore, a timely and critical overview of the latest development in the field of RLBs operating at wide temperatures is needed. In this review, an in‐depth understanding on how the temperature affects the thermodynamics of lithium‐ion transport at electrodes, electrolytes, and electrode/electrolyte interfaces is emphasized. Recent progress in probing the temperature effects on electrochemical performance fading is comprehensively discussed. Different strategies to widen the working temperature of RLBs, including regulating the electrode degradation, interface evolution, and electrolyte solvation chemistry are also reviewed. Finally, an outlook of potential future research directions is also proposed, which sheds light on the design of novel electrodes and electrolytes for next‐generation RLBs operating at wide temperatures. [ABSTRACT FROM AUTHOR]

Chemical vapor deposition (CVD) polymerization is a commonly used approach in surface chemistry, providing a substrate‐independent platform for bioactive surface functionalization strategies. This work investigates the Arbuzov reaction of halogenated polymer coatings readily available via CVD polymerization, using poly(4‐chloro‐para‐xylylene) (Parylene C) as a model substance. Postpolymerization modification of these coatings via catalyst‐free and UV‐induced Arbuzov reaction using phosphites results in phosphonate‐functionalized polymers. The combination of infrared reflection‐absorption spectroscopy (IRRAS), X‐ray photoelectron spectroscopy (XPS), and time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) provides detailed insights into the reaction progress. Time‐dependent studies suggest that the non‐polar phosphites penetrate deep into the CVD films and react with the polymer film. In addition, ToF‐SIMS, scanning electron microscopy (SEM), and atomic force microscopy (AFM) confirm spatial control of the reaction, resulting in localized chemical and topographical surface modification, recognizable by changes in interference color, fluorescence, and wettability. Preliminary 3D fluorescence spectroscopy investigations indicate tunable near‐infrared emission of these polymer films. This work is the first step toward generating multifunctional polymer coatings based on chemically modifiable, CVD polymers with potential applications in biomaterials, sensors, or optoelectronics. [ABSTRACT FROM AUTHOR]

In the spirit of pursuing collaborative research at the interface of chemistry and materials science for engineering cyclophane‐based functional systems, the journey from molecules to materials and a portion of the accomplishments exploring technologically‐relevant small‐molecule organic emitters, polymer thin films, and supra‐sensing through supramolecular host‐guest interactions (molecular self‐assembly) is shared. This report highlights diverse research trajectories and the importance of active collaboration within the chemistry community. It is also intended to serves young scientists who are committed to research in interdisciplinary domains. This inspires fostering global research networks and promoting industrial−academic symbiosis that bring innovations to the education environment and curriculum by sharing mutual experiences, knowledge, and specialized skills which may cut across several inter‐related disciplines. [ABSTRACT FROM AUTHOR]

Carbon materials are considered among the most promosing candidates for sodium ion batteries because of their competitive performance. Nevertheless, they suffer from low initial coulombic efficiencies (ICEs) and limited electrochemical performance. Herein, nitrogen-doped hollow carbon spheres (NHCSs) with a distinct porous structure are developed by a template-assisted carbonization of dopamine, followed by a template removal procedure. This advanced structural design, coupled with the surface chemistry of carbonized polydopamine, leads to an impressive ICE of 89.18% and a reversible capacity stabilized at ∼700 mA h g−1 at 50 mA g−1 after 100 cycles. Compared to commercial hard carbon anodes, NHCSs demonstrate superior rate performance, delivering a capacity of ∼200 mA g h−1 at 5 A g−1 with minimal capacity fading of ∼0.057 mA h g−1 per cycle over 1000 cycles. These findings highlight the potential of NHCSs as a high-performance anode material for sodium-ion batteries, offering both high efficiency and excellent cycling stability. [ABSTRACT FROM AUTHOR]

Nanomaterials with enzyme-like properties are known as 'nanozymes'. Nanozymes are preferred over natural enzymes due to their nanoscale characteristics and ease of tailoring of their physicochemical properties such as size, structure, composition, surface chemistry, crystal planes, oxygen vacancy, and surface valence state. Interestingly, nanozymes can be precisely controlled to improve their catalytic ability, stability, and specificity which is unattainable by natural enzymes. Therefore, tailor-made nanozymes are being favored over natural enzymes for a range of potential applications and better prospects. In this context, metal oxide nanoparticles with nanozyme-mimicking characteristics are exclusively being used in biomedical sectors and opening new avenues for future nanomedicine. Realising the importance of this emerging area, here, we discuss the mechanistic actions of metal oxide nanozymes along with their key characteristics which affect their enzymatic actions. Further, in this critical review, the recent progress towards the development of point-of-care (POC) diagnostic devices, cancer therapy, drug delivery, advanced antimicrobials/antibiofilm, dental caries, neurodegenerative diseases, and wound healing potential of metal oxide nanozymes is deliberated. The advantages of employing metal oxide nanozymes, their potential limitations in terms of nanotoxicity, and possible prospects for biomedical applications are also discussed with future recommendations. [ABSTRACT FROM AUTHOR]

This study explores the effects of atomic-level factors on the performance of CeO 2 when interacting with SiO 2 films. It specifically examines how different precursors, the ratio of Ce to OH, and reaction temperatures influence outcomes. Our findings reveal that smaller particles, around 5 nm in size, created using a Ce4+ precursor, are more effective at removing SiO 2 films compared to larger, more crystalline particles from a Ce3+ precursor. This is due to their increased interaction with the SiO 2 film during the polishing process, challenging the conventional emphasis on mechanical abrasion in chemical mechanical planarization (CMP) and highlighting the crucial role of chemical interactions. Further analysis through FT-IR and TGA-FTIR techniques showed distinct functional group profiles on the ceria surfaces. Ceria derived from Ce4+ exhibited a higher presence of OH and NO 3 groups, enhancing adsorption capabilities, as verified by CHN analysis. Importantly, first-principles calculations identified these surface groups as key to improving adhesion to SiO 2 films. Surfaces of amorphous CeO 2 , rich in -OH and -NO 3 groups, showed significantly higher adhesion levels than their crystalline counterparts, connecting crystallinity to chemical functionality. This new insight leads to the possibility of designing next-generation CeO 2 abrasives with increased chemical activity. [ABSTRACT FROM AUTHOR]

The commercial use of Si3N4 ceramics in the biomedical field dates back to the early 1980s and, initially, did not show promising results, which is why their biocompatibility was not then investigated further until about 10 years later. Over the years, a change in trend has been observed; more and more studies have shown that this material could possess high biocompatibility and antibacterial properties. However, the relevant literature struggles to find mechanisms that can incontrovertibly explain the reasons behind the biological activity of Si3N4. The proposed mechanisms are often pure hypotheses or are not substantiated by comprehensive analyses. This review begins by studying the early references to the biological activity of Si3N4 and then reviews the literature regarding the bioactivity of this ceramic over time. An examination of the early insights into surface chemistry and biocompatibility lays the foundation for a detailed examination of the chemical reactions that Si3N4 undergoes in biological environments. Next, the analysis focuses on the mechanisms of bioactivity and antipathogenicity that the material exhibits both alone and in combination with modern bioglass. However, it is highlighted that despite the general consensus on the biocompatibility and bioactivity of Si3N4 ceramics, sometimes the proposed biological mechanisms behind its behavior are discordant or unsupported by the direct evaluation of specific biochemical activities. This review highlights both the reliable information in the literature and the gaps in research that need to be filled in order to fully understand the reasons behind the biological properties of this material. [ABSTRACT FROM AUTHOR]

[Display omitted] Alloying-type anode materials are considered promising candidates for next-generation alkali-ion batteries. However, they face significant challenges owing to severe volume variations and sluggish kinetics, which hinder their practical applications. To address these issues, we propose a universal synthetic strategy, which can realize the facile synthesis of various alloying-type anode materials composed of a porous carbon matrix with uniformly embedded nanoparticles (Sb, Bi, or Sn). Besides, we construct the interactions among active materials, electrolyte compositions, and the resulting interface chemistries. This understanding assists in establishing balanced kinetics and stability. As a result, the fabricated battery cells based on the above strategy demonstrate high reversible capacity (515.6 mAh g−1), long cycle life (200 cycles), and excellent high-rate capability (at 5.0 C). Additionally, it shows improved thermal stability at 45 and 60 °C. Moreover, our alloying-type anodes exhibit significant potential for constructing a 450 Wh kg−1 battery system. This proposed strategy could boost the development of alloying-type anode materials, aligning with the future demands for low-cost, high stability, high safety, wide-temperature, and fast-charging battery systems. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Graphene nanoribbons (GNRs), which can be considered as a special type of conjugated polymers, are quasi‐one‐dimensional graphene cutouts with an opened band gap, revealing great potential as functional materials in optoelectronic, spintronic, and energy‐related applications. An effective strategy to modulate the properties of GNRs is doping heteroatoms into the π‐skeleton. Thanks to the bottom‐up synthetic approach, a number of heteroatom‐doped GNRs with precise structures have been reported, exhibiting intriguing properties. Nevertheless, a comprehensive summary of the progress of this field has remained elusive. In this review, we summarize the history and advances in bottom‐up synthesized heteroatom‐doped GNRs, including their synthetic routes, electronic properties, and promising applications. We hope to establish the reliable structure–property relationship, and provide guidance for the molecular design of heteroatom‐doped GNRs in the future. [ABSTRACT FROM AUTHOR]

The study successfully enabled the creation of ceramic surfaces with multi functionalities, including superhydrophilicity, self-cleaning, antibacterial properties, and photocatalytic activity, by applying a glaze composition rich in nano ZnO/Cu–ZnO and utilizing surface chemistry and unique texturing on porcelain tiles. The tiles, coated with unique glaze compositions, were fired in an industrial furnace and heat treated. The crystalline phases and surface morphology of glazed surfaces were systematically evaluated using XRD, SEM, FT-IR, drop shape analyzer, and surface roughness profilometer. Key-factors affecting the wettability, self-clean ability, photocatalytic activity and antibacterial efficacy were discussed. Adding nano Cu into the glaze mixture that is rich in ZnO improves the evolution of zincite crystals, increases the specific surface energy, decreases surface roughness, provide superhydrophilicity and promotes the antibacterial effectiveness and photocatalytic activity. Superhydrophilic surfaces doped with nano Cu–ZnO display antibacterial characteristics that do not require UV or visible light. The quick achievement of complete self-cleaning, up to 100 %, is due to the presence of nano Cu particles in its structure. Hydrophilicity has the ability to improve the efficiency of photocatalysis. If a surface exhibits superhydrophilic properties, it shows exceptional photocatalytic performance. A surface that is solely photohydrophilic may not maintain self-cleaning. Hydrophilicity may be more important than photocatalysis in the self-cleaning effect. [ABSTRACT FROM AUTHOR]

A novel cobalt-free, high-nickel cathode material, named 0.01B-LiNi 0.98 Mg 0.01 Zr 0.01 O 2 (NMZB), is introduced, aimed at enhancing stability. Mg, Zr, and B elements are strategically incorporated, with Mg and Zr primarily located inside particles and B predominantly on the surface, boosting both bulk and surface stability. NMZB exhibits outstanding electrochemical performance, with 90.5% capacity retention after 200 cycles at a 1C rate. This composition offers a pathway for cost-effective, high-performance lithium-ion battery technology. [Display omitted] Cobalt-free, high-nickel cathode materials are essential for the sustainable evolution of energy storage technologies, reducing the dependence on resources with significant environmental and social implications and simultaneously improving the efficiency and cost effectiveness of batteries. This paper introduces a cobalt-free, high-nickel cathode material called 0.01B-LiNi 0.98 Mg 0.01 Zr 0.01 O 2 (NMZB) developed using a novel blend of elements to enhance mechanical and surface chemical stability. Detailed evaluations confirmed the successful integration of Mg, Zr, and B into the particles, with Mg and Zr primarily located within the particle interior and B predominantly on the surface. This unique elemental configuration significantly improves the stability of the bulk phase and surface structure of the material. In addition, the refinement of primary particles within NMZB further enhances its mechanical stability. As a result, NMZB exhibits exceptional electrochemical stability, achieving 90.5 % capacity retention after 200 cycles at a 1C rate. This compositional strategy incorporates a high nickel content into layered materials while eliminating cobalt, which is crucial for advancing the development of cost effective and high-performance lithium-ion battery technology. [ABSTRACT FROM AUTHOR]

This work combines the nanoconfined material with the air-breathing gas diffusion electrode equips a wide practical range of applications for the synthesis of high-yield H 2 O 2 and upgrading of H 2 O 2 products. [Display omitted] • Yolk-shell SnS 2 @CSs Z-scheme nanoreactor is controllably synthesized. • Hydrogen peroxide production is increased through the nano-confinement effect. • Continuous hydrophobic layers allow air to spontaneously diffuse into the AGPE. • The photoelectrode has a good reusability and stability for activation of O 2 /H 2 O. • Hydrogen peroxide is produced under neutral condition media. The diffusion and adsorption properties of the O 2 /H 2 O corpuscles at active sites play a crucial role in the fast photo-electrocatalytic reaction of hydrogen peroxide (H 2 O 2) production. Herein, SnS 2 nanosheets with abundant interfacial boundaries and large specific areas are encapsulated into hollow mesoporous carbon spheres (CSs) with flexibility, producing a yolk-shell SnS 2 @CSs Z-scheme photocatalyst. The nanoconfined microenvironment of SnS 2 @CSs could enrich O 2 /H 2 O in catalyst cavities, which allows sufficient internal O 2 transfer, improving the surface chemistry of catalytic O 2 to O 2 − conversion and increasing reaction kinetics. By shaping the mixture of SnS 2 @CSs and polytetrafluoroethylene (PTFE) on carbon felt (CF) using the vacuum filtration method, the natural air-breathing gas diffusion photoelectrode (AGPE) was prepared, and it can achieve an accumulated concentration of H 2 O 2 about 12 mM after a 10 h stability test from pure water at natural pH without using electrolyte and sacrificial agents. The H 2 O 2 product is upgraded through one downstream route of conversion of H 2 O 2 to sodium perborate. The improved H 2 O 2 production performance could be ascribed to the combination of the confinement effect of SnS 2 @CSs and the rich triple phase interfaces with the continuous hydrophobic layer and hydrophilic layer to synergistically modulate the photoelectron catalytic microenvironment, which enhanced the transfer of O 2 mass and offered a stronger affinity to oxygen bubbles. The strategy of combining the confined material with the air-breathing gas diffusion electrode equips a wide practical range of applications for the synthesis of high-yield hydrogen peroxide. [ABSTRACT FROM AUTHOR]

[Display omitted] Dielectric effects and the coupled electrostatics between the nanoconfined and the internal/external aqueous media contribute to the observed deviations of chemistry within the nanoconfined environment when compared with unconfined systems. A systematic understanding has remained elusive, especially with respect to background salt concentration and boundary condition effects like the nanopore surface chemistry and the reference state used to calculate free energies. We utilize molecular dynamics simulations along with thermodynamic integration to determine the free energy difference associated with acid-base chemistry in 2 nm and 4 nm slit pores open to a bulk-like reservoir. pK a increases are predicted when confining acetic acid, formic acid, and bicarbonate in the slits at infinite dilution conditions. We find that confinement weakens the acids, and the modulation of outer pore surface dipole magnitudes can tune the pK a shift values, suggesting that purely "intrinsic" electrostatic effect on confinement may not exist. At sufficiently high salt concentrations, the dielectric/electrostatic effects on pK a values diminish due to charge screening effects. These discoveries enable future modifications of nanopore chemistries to achieve desirable properties for industrial applications. [ABSTRACT FROM AUTHOR]