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We developed a computational framework to extract the Raman spectra of nitrogen reduction and ammonia oxidation intermediates on high-entropy alloy (HEA) surfaces, integrating density functional theory with microstructural representations to account for the inherent lattice randomness in these materials. As a case study, we computed the Raman activities of intermediates (N2*, NNH*, N*, NH*, and NH3*) and H* adsorption on CoCuFeMoNi HEA surfaces. A comprehensive map of Raman peaks was generated and assigned to specific vibrational modes. The method highlighted the effects of lattice randomness on the Raman spectra compared to those of adsorbates on single-element catalysts. For instance, our results showed that the adsorbed N2 exhibits Raman modes that are dependent on whether the adsorption is vertical or horizontal. These peak differences could serve as unique fingerprints to identify nitrogen reduction reaction pathways. Moreover, it is also possible to detect surface poisoning by hydrogen, a common issue in reductive environments, due to the high-frequency peaks of H* compared to the typical N-metal stretching and bending frequencies. These results provide valuable references for identifying intermediates in nitrogen reduction and ammonia oxidation reactions, offering insights into reaction mechanisms and potential surface poisoning. This approach is generalizable to other reactions and surfaces in catalysis, provided that the relevant intermediates can be identified. [ABSTRACT FROM AUTHOR]

We recently presented a quantitative model to explain the particle-size dependence of photoluminescence (PL) quantum yields and revealed that exciton quenching is not diffusion controlled, but limited by surface reactions. However, the exciton decay kinetics has not been analyzed yet using our theoretical model. Here, we study kinetic aspects of the model and show that it should be extended to take into account subdiffusion rather than normal diffusion to maintain consistency with the observed complex decay kinetics; we also show that the PL decay kinetics is nonexponential even when the PL quenching is limited by surface reactions under subdiffusion. Our theoretical analysis of the PL quantum yield and the PL decay kinetics provides a comprehensive picture of mobile charge carriers, immobile polarons, and self-trapped excitons. [ABSTRACT FROM AUTHOR]

Self-propelled synthetic particles have attracted scientific interest due to their potential applications as nanomotors in drug delivery and their insight into bacterial taxis. Research on their dynamics has focused on understanding phoresis and self-phoresis in catalytic Janus particles at both the nano- and microscale. This study explores the combined effects of self-diffusiophoresis and self-thermophoresis induced by exothermic chemical reactions on the surface of active particles moving in non-electrolyte media. We examine how these phoretic phenomena interact, influenced by the coupling between chemical reactions, heat generation, and the concentration and temperature fields at the particle interface. Using a theoretical framework based on the induction of surface tension gradients at the particle interface, we analyze the phoretic dynamics, quantifying parameters such as effective diffusivities, transport coefficients, and, most importantly, phoretic coefficients. Our findings provide insights into the conditions that dictate coupled or independent phoretic behaviors, with implications for drug delivery and nanomotor applications, enabling customized transport processes at the nanoscale. [ABSTRACT FROM AUTHOR]

Small molecule inhibitors (SMIs) have been gaining attention in the field of area-selective atomic layer deposition (ALD) because they can be applied in the vapor-phase. A major challenge for SMIs is that vapor-phase application leads to a disordered inhibitor layer with lower coverage as compared to self-assembled monolayers, SAMs. A lower coverage of SMIs makes achieving high selectivity for area-selective ALD more challenging. To overcome this challenge, mechanistic understanding is required for the formation of SMI layers and the resulting precursor blocking. In this study, reflection adsorption infrared spectroscopy measurements are used to investigate the performance of aniline as an SMI. Our results show that aniline undergoes catalytic surface reactions, such as hydrogenolysis, on a Ru non-growth area at substrate temperatures above 250 °C. At these temperatures, a greatly improved selectivity is observed for area-selective TaN ALD using aniline as an inhibitor. The results suggest that catalytic surface reactions of the SMI play an important role in improving precursor blocking, likely through the formation of a more carbon-rich inhibitor layer. More prominently, catalytic surface reactions can provide a new strategy for forming inhibitor layers that are otherwise very challenging or impossible to form directly through vapor-phase application. [ABSTRACT FROM AUTHOR]

We develop an adaptive scheme in the kinetic Monte Carlo simulations, where the adsorption and activation energies of all elementary steps, including the effects of other adsorbates, are evaluated "on-the-fly" by employing the neural network potentials. The configurations and energies evaluated during the simulations are stored for reuse when the same configurations are sampled in a later step. The present scheme is applied to hydrogen adsorption and diffusion on the Pd(111) and Pt(111) surfaces and the CO oxidation reaction on the Pt(111) surface. The effects of interactions between adsorbates, i.e., adsorbate–adsorbate lateral interactions, are examined in detail by comparing the simulations without considering lateral interactions. This study demonstrates the importance of lateral interactions in surface diffusion and reactions and the potential of our scheme for applications in a wide variety of heterogeneous catalytic reactions. [ABSTRACT FROM AUTHOR]

The kinetic energy dependence of the title reaction is examined using guided ion beam tandem mass spectrometry. Because this reaction is spin-forbidden, crossings between octet and sextet hypersurfaces presumably must occur. Furthermore, Sm+ must transition from a 4f66s1 configuration in the reactant to 4f55d2 in order to have the orbital occupancy required to form the triple bond in SmO+ (6Δ). Despite being strongly exothermic (∼4 eV), the reaction proceeds with low efficiency (18% ± 4%) via a barrierless process at low energies. Below ∼0.3 eV, the cross section follows a kinetic energy dependence that roughly parallels that of the collision rate for ion–dipole reactions. At higher collision energies, the reaction cross section increases until it follows the trajectory cross section closely from 3 to 5 eV, indicating that another pathway opens on the reaction hypersurface. Modeling this increase yields a threshold energy for this new pathway at 0.54 ± 0.05 eV. Theoretical potential energy surfaces that do not include spin–orbit interactions for the reaction show that there is a barrier of height 1.19 eV (MP2) or 0.49 eV [CCSD(T)] to insertion of Sm+ into the N2–O bond and that there are several places where octet and sextet surfaces can intersect and interact. By considering the distribution of spin–orbit states generated in the ion source, the internal energy of the N2O reactant, and the influence of coupling between electronic, orbital, and rotational angular momentum, the low-efficiency, exothermic behavior as well as the increase in efficiency at higher energies can plausibly be explained. [ABSTRACT FROM AUTHOR]

The kinetic energy dependence of the title reaction is examined using guided ion beam tandem mass spectrometry. Because this reaction is spin-forbidden, crossings between octet and sextet hypersurfaces presumably must occur. Furthermore, Sm+ must transition from a 4f66s1 configuration in the reactant to 4f55d2 in order to have the orbital occupancy required to form the triple bond in SmO+ (6Δ). Despite being strongly exothermic (∼4 eV), the reaction proceeds with low efficiency (18% ± 4%) via a barrierless process at low energies. Below ∼0.3 eV, the cross section follows a kinetic energy dependence that roughly parallels that of the collision rate for ion–dipole reactions. At higher collision energies, the reaction cross section increases until it follows the trajectory cross section closely from 3 to 5 eV, indicating that another pathway opens on the reaction hypersurface. Modeling this increase yields a threshold energy for this new pathway at 0.54 ± 0.05 eV. Theoretical potential energy surfaces that do not include spin–orbit interactions for the reaction show that there is a barrier of height 1.19 eV (MP2) or 0.49 eV [CCSD(T)] to insertion of Sm+ into the N2–O bond and that there are several places where octet and sextet surfaces can intersect and interact. By considering the distribution of spin–orbit states generated in the ion source, the internal energy of the N2O reactant, and the influence of coupling between electronic, orbital, and rotational angular momentum, the low-efficiency, exothermic behavior as well as the increase in efficiency at higher energies can plausibly be explained. [ABSTRACT FROM AUTHOR]

Chemical shakers are active particles with zero propulsion velocity whose activity derives from chemical reactions on portions of their surfaces. Although they do not move, except through Brownian motion, the nonequilibrium concentration and velocity fields that they generate endow them with properties that differ from their equilibrium counterparts. In particular, collections of such shakers can actively move, reorient, and self-assemble into various cluster states, which are the subject of this paper. Elongated chemical shakers constructed from linked catalytic and noncatalytic spheres are considered, and it is shown how hydrodynamic, chemotactic, and shape-dependent interactions give rise to various self-assembled shaker structures. The chemical forces responsible for cluster formation are described in terms of a model based on pair-wise additive contributions. The forms of the self-assembled structures can be varied by changing the chemostat concentrations that control the nonequilibrium state. The resulting structures and their manipulation through chemical means suggest ways to construct a class of active materials for applications. [ABSTRACT FROM AUTHOR]

High-level potential energy surfaces for three reactions of hypobromous acid with atomic hydrogen were computed at the CCSDTQ/CBS//CCSDT(Q)/complete basis set level of theory. Focal point analysis was utilized to extrapolate energies and gradients for energetics and optimizations, respectively. The H attack at Br and subsequent Br–O cleavage were found to proceed barrierlessly. The slightly submerged transition state lies −0.2 kcal mol−1 lower in energy than the reactants and produces OH and HBr. The two other studied reaction paths are the radical substitution to produce H2O and Br with a 4.0 kcal mol−1 barrier and the abstraction at hydrogen to produce BrO and H2 with an 11.2 kcal mol−1 barrier. The final product energies lie −37.2, −67.9, and −7.3 kcal mol−1 lower in energy than reactants, HOBr + H, for the sets of products OH + HBr, H2O + Br, and H2 + BrO, respectively. Additive corrections computed for the final energetics, particularly the zero-point vibrational energies and spin–orbit corrections, significantly impacted the final stationary point energies, with corrections up to 6.2 kcal mol−1. [ABSTRACT FROM AUTHOR]

Alkoxide precursors have been highlighted for depositing carbon-free films, but their use in Atomic Layer Deposition (ALD) often exhibits a non-saturated growth. This indicates no self-limiting growth due to the chain reaction of hydrolysis or ligand decomposition caused by β-hydride elimination. In the previous study, we demonstrated that self-limiting growth of ALD can be achieved using our newly developed precursor, hafnium cyclopentadienyl tris(N-ethoxy-2,2-dimethyl propanamido) [HfCp(edpa)3]. To elucidate the growth mechanism and the role of cyclopentadienyl (Cp) ligand in a heteroleptic alkoxide precursor, herein, we compare homoleptic and heteroleptic Hf precursors consisting of N-ethoxy-2,2-dimethyl propanamido (edpa) ligands with and without cyclopentadienyl ligand—hafnium tetrakis(N-ethoxy-2,2-dimethyl propanamido) [Hf(edpa)4] and HfCp(edpa)3. We also investigate the role of a Cp ligand in growth characteristics. By substituting an alkoxide ligand with a Cp ligand, we could modify the surface reaction during ALD, preventing undesired reactions. The last remaining edpa after Hf(edpa)4 adsorption can undergo a hydride elimination reaction, resulting in surface O–H generation. In contrast, Cp remains after the HfCp(edpa)3 adsorption. Accordingly, we observe proper ALD growth with self-limiting properties. Thus, a comparative study of different ligands of the precursors can provide critical clues to the design of alkoxide precursors for obtaining typical ALD growth with a saturation behavior. [ABSTRACT FROM AUTHOR]

Quantum dots (QDs) have attracted much attention and exhibit many attractive properties, including high absorption coefficient, adjustable bandgap, high brightness, long-term stability, and size-dependent emission. It is known that to obtain high-quality luminescent properties (i.e. emission color, color purity, quantum yield, and stability), the synthesis parameters must be precisely controlled. In this work, we have constructed a database with CdTe aqueous synthesis parameters and spectroscopic results and applied machine learning algorithms to better understand the influence of the main synthesis parameters of CdTe QDs on their final emission properties. A strong dependence of the final emission wavelength with the reaction time and surface ligands and precursors concentrations was demonstrated. These parameters adjusted synchronously were shown to be very useful for provide ideal synthesis conditions for the preparation of CdTe QDs with desirable emission wavelengths. Moreover, applying the algorithms correctly allows for obtaining information and insights into the growth kinetics of QDs under different synthetic conditions. [ABSTRACT FROM AUTHOR]

The surface charges of catalysts have intricate influences on the thermodynamics and kinetics of electrochemical reactions. Herein, we develop a grand-canonical iteration method based on density functional theory calculations to explore the effect of surface charges on reaction kinetics beyond the traditional Butler–Volmer picture. Using the hydrogen evolution reaction on S vacancies of MoS2 as an example, we show how to track the change of surface charge in a reaction and to analyze its influence on the kinetics. Protons adsorb on S vacancies in a tough and charge-insensitive water splitting manner, which explains the observed large Tafel slope. Grand-canonical calculations report an unanticipated surface charge-induced change of the desorption pathway from the Heyrovsky route to a Volmer–Tafel route. During an electrochemical reaction, a net electron inflow into the catalyst may bring two effects, i.e., stabilization of the canonical energy and destabilization of the charge-dependent grand-canonical part. On the contrary, a net outflow of electrons from the catalyst can reverse the two effects. This surface charge effect has substantial impacts on the overpotential and the Tafel slope. We suggest that the surface charge effect is universal for all electrochemical reactions and significant for those involving interfacial proton transfers. [ABSTRACT FROM AUTHOR]

Perovskite fluorides are attractive anode materials for lithium-ion batteries (LIBs) because of their three-dimensional diffusion channels and robust structures, which are advantageous for the rapid transmission of lithium ions. Unfortunately, the wide band gap results in poor electronic conductivity, which limits their further development and application. Herein, the cubic perovskite iron fluoride (KFeF3, KFF) nanocrystals (∼100 nm) are synthesized by a one-step solvothermal strategy. Thanks to the good electrical conductivity of carbon nanotubes (CNTs), the overall electrochemical performance of composite anode material (KFF-CNTs) has been significantly improved. In particular, the KFF-CNTs deliver a high specific capacity (363.8 mAh g−1), good rate performance (131.6 mAh g−1 at 3.2 A g−1), and superior cycle stability (500 cycles). Note that the surface conversion reactions play a dominant role in the electrochemical process of KFF-CNTs, together with the stable octahedral perovskite structure and nanoscale particle sizes achieving high ion diffusion coefficients. Furthermore, the specific lithium storage mechanism of KFF has been explored by the distribution of relaxation times technology. This work opens up a new way for developing cubic perovskite fluorides as high-capacity and robust anode materials for LIBs. [ABSTRACT FROM AUTHOR]

Cesium‐based inorganic perovskites have emerged as promising light‐harvesting materials for perovskite solar cells (PSCs) due to their promising thermal‐ and photo‐stability. However, obstacles to commercialization remain regarding their phase instability. In this work, we report a facile and effective strategy to regulate the surface compressive strain via in situ surface reaction to stabilize CsPbI3 perovskite. The use of a chelating ligand with a molecular configuration closely matching the integer multiples of the unit cell lattice parameters of CsPbI3 induces compressive strain at the surface of CsPbI3. The chemical bonding and strain modulation synergistically not only passivate film defects, but also inhibit perovskite phase degradation, thus significantly improving the intrinsic stability of inorganic perovskite. Consequently, enhanced power conversion efficiency (PCE) of 21.0 % and 18.6 % were respectively achieved in 0.16‐cm2 lab‐scale devices and 25.3‐cm2 solar modules. Further, surface reaction enables PSCs with enhanced thermal and operational stability; these devices retain over 95 % of their initial PCE after damp‐heat tests (i.e., in 85 °C and 85 % R. H. air) for 2000 h, and remain 99 % of their initial PCE after operating for 2000 h, representing one of the most stable inorganic PSCs reported so far. [ABSTRACT FROM AUTHOR]

Converting CO2 to carbon‐based fuels using solar energy via photocatalysis is a promising approach to boost carbon neutrality. However, the solar‐to‐chemical conversion efficiency is hampered by interconnected multiple factors including insufficient light absorption, low separation efficiency of photogenerated carriers as well as complex and sluggish surface reaction kinetics. Herein, we incorporate MnO2 nanowires and Co3O4 hollow polyhedrons with abundant oxygen vacancies (VO) into MnO2/Co3O4 sugar‐gourd nanohybrids for boosting CO2 photoreduction. The MnO2/Co3O4 nanohybrids not only display strong absorption in the visible–near infrared region, but also facilitate the separation of photogenerated carriers in terms of S‐scheme transfer pathway, supplying abundant electrons for CO2 reduction reaction. Furthermore, the presence of VO enhances the separation efficiency of photogenerated carriers and promotes the chemical adsorption to CO2 molecules. In addition, the interfacial electronic interaction between MnO2 and Co3O4 also contributes to the chemical adsorption and activation to CO2. Owing to the synergy of S‐scheme transfer pathway and VO, the MnO2/Co3O4 hybrids exhibit greatly enhanced photocatalytic activity towards CO2 reduction under the irradiation of visible light in comparison with bare MnO2 and Co3O4, delivering a CO evolution rate of 15.9 umol g−1 h−1 with a 100 % selectivity. [ABSTRACT FROM AUTHOR]

CO 2 methanation has emerged as a promising strategy for the greenhouse gas CO 2 utilization and storage of hydrogen. However, achieving low temperature activity and high temperature stability remains challenging due to the sintering of Ni-based catalysts. To address these limitations, this study introduces a Ni–CaZrO 3 catalyst featuring a perovskite phase supported on ZrO 2 , prepared via citrate complexation and impregnation methods. In this approach, a perovskite-type oxide (PTO) of CaZrO 3 forms through a solid reaction on the surface of ZrO 2 with impregnated CaO. The formation of CaZrO 3 on Ni/ZrO 2 restrains the ZrO 2 support aggregation and reduces the particle size of Ni nanoparticles (NPs), thereby enhancing the activity for CO 2 methanation. The interaction between Ni–CaZrO 3 , and ZrO 2 effectively confines the Ni NPs and CaZrO 3 , enhancing the sintering resistance of Ni–CaZrO 3. This leads to excellent stability of the resulting catalyst for CO 2 methanation. The Ni–CaZrO 3 /ZrO 2 catalyst achieves 85% CO 2 conversion and maintains 100% methane selectivity at 300 °C, demonstrating the prolonged stability over 100 h at 550 °C. Notably, the loading of CaZrO 3 in a perovskite phase on ZrO 2 via solid surface reaction represents an interesting and valuable route, which could be extended to loading other PTOs for industrial applications. [Display omitted] • Ni and CaZrO 3 with perovskite phase loaded on ZrO 2 via solid surface reaction. • Perovskite-type CaZrO 3 reduced Ni particle size and enhanced surface area. • Improved interaction between Ni–CaZrO 3 and ZrO 2 compared to Ni and ZrO 2. • High Ni dispersion achieved 85% CO 2 conversion at 300 °C with 100% CH 4 selectivity. • Ni–CaZrO 3 confinement improved stability over 100 h at 550 °C and anti-sintering. [ABSTRACT FROM AUTHOR]

The autoignition of a stoichiometric hydrogen/air mixture laden with uniformly distributed coal char particles is simulated with the Eulerian-Lagrangian approach under isochoric conditions. A zero-dimensional model is adopted to assess the effects of gas temperature, pressure, particle diameter, and concentration on ignition dynamics. Increasing the initial temperature reduces the ignition time and maximum heat release rate of the homogeneous reactions, while the parameters for particle reactions stabilize after reaching a critical temperature. Initial pressure exhibits a non-monotonic influence on gas phase ignition, with higher pressures promoting particle autoignition. An increase in particle diameter decreases the ignition time for the homogeneous reaction, approaching that of particle-free conditions. Meanwhile, particle ignition time first decreases and then linearly increases. Increasing particle concentration reduces the interphase disparities of ignition times, while the two-phase ignition times rapidly rise after exceeding the critical concentration. Moreover, pre-ignition temperature equilibrium (PTE) significantly impacts the ignition parameters and processes. PTE results in a minimal ignition time disparity between the gas and particles, with coal char particles markedly influencing hydrogen ignition. Failure to reach PTE leads to significant two-phase ignition time differences, with negligible impact from the solid phase on gas phase ignition. The particle effect ratio, δ , is introduced to evaluate these effects. Notably, the evolution variations in ignition time and heat release rate are determined by the existence of the PTE under corresponding initial conditions. The findings of this study are crucial for developing strategies to mitigate explosion hazards and enhance the performance of detonation propulsion systems using hybrid fuels. • Autoignition of H 2 /air/coal particles mixture under elevated conditions is simulated. • The effects of initial conditions on two-phase ignition dynamics are discussed. • Pre-ignition temperature equilibrium between two phases markedly affects ignition. [ABSTRACT FROM AUTHOR]

Sluggish surface reaction is a critical factor that strongly governs the efficiency of photocatalytic solar fuel production, particularly ian CO2-to-ethanol photoconversion. Here, inspired by the principles underlying enzyme catalytic proficiency and specificity, we report a biomimetic photocatalyst that affords superior CO2-to-ethanol photoreduction efficiency (5.5 millimoles gram-1 hour-1 in average with 98.2% selectivity) distinctly surpassing the state of the art. The key is to create a class of catalytic pocket, which contains spatially organized NH2...Cu-Se(-Zn) multiple functionalities at close range, over ZnSe colloidal quantum wells. Such structure offers a platform to mimic the concerted cooperation between the active site and surrounding secondary/outer coordination spheres in enzyme catalysis. This is manifested by the chemical adsorption and activation of CO2 via a bent geometry, favorable stabilization toward a variety of important intermediates, promotion of multielectron/proton transfer processes, etc. These results highlight the potential of incorporating enzyme-like features into the design of photocatalysts to overcome the challenges in CO2 reduction. [ABSTRACT FROM AUTHOR]

The incorporation of defects and cocatalysts is known to be effective in improving photocatalytic activity, yet their coupled contribution to the photocatalytic hydrogen evolution process has not been well‐explored. In this study, We demonstrate that the incorporation of S vacancies and NiSe can contribute to the improvement of charge separation efficiency via the formation of a strong electric field within the bulk ZnIn2S4 (ZIS) and on its surface. More importantly, We also demonstrate that the synergy of S vacancies and NiSe benefits the overall hydrogen evolution activity by facilitating the H2O adsorption and dissociation process. This is particularly important for hydrogen evolution taking place under alkaline conditions where the proton concentration is low, allowing ZISv‐NiSe (containing abundant S vacancies) to outperform ZIS‐NiSe under alkaline conditions. In contrast, under acid conditions, since there are already sufficient amounts of protons available for reaction, the hydrogen evolution activity became governed by the hydrogen adsorption/desorption process rather than the H2O dissociation process. This leads to ZIS‐NiSe exhibiting higher activity than ZISv‐NiSe due to its more favorable hydrogen adsorption energy. The findings thus provide insights into how defect and cocatalyst modification strategies can be tailor‐made to improve hydrogen evolution activity under different pH conditions. [ABSTRACT FROM AUTHOR]

Advanced electrode materials with simple manufacturing processes and wide voltage windows are needed for the commercialization of high energy density supercapacitors. Herein, a facile method is presented for fabricating self‐supporting anodes and cathodes for quasi‐solid‐state asymmetric supercapacitors (QASCs) by hydrothermally reacting 2‐thiobarbituric acid (TBA) with Fe foam (IF) and Co foam (CF), yielding FeTBA4/FeOOH/IF and Co9S8/CF electrodes, respectively. Due to the perfect match between the two electrodes, the redox‐active TBA ligands in FeTBA4, the 2D ultrathin nanosheet structure of FeTBA4/FeOOH/IF, and multiple pairs of reversible redox reactions for suppressing water splitting, the configured Co9S8/CF//FeTBA4/FeOOH/IF QASC device delivers outstanding performance. The device possesses a wide operating voltage window of 1.6 V, leading to a high energy density of 82.64 Wh kg−1 at 486.38 W kg−1 and an equally impressive 35.36 Wh kg−1 at 4595.92 W kg−1. Furthermore, a 98.5% capacitance retention is realized after 10000 charging–discharging cycles. Impressively, density functional theory (DFT) calculations reveal the unique pseudocapacitive reactions on the surface of Co9S8/CF and FeTBA4/FeOOH/IF electrodes. Importantly, this work guides the development of high‐energy‐density supercapacitors via the matching of electrodes and the use of redox‐active complex electrodes. [ABSTRACT FROM AUTHOR]

S‐scheme heterostructure photocatalysts, distinguished by unique charge‐transfer pathways and exceptional catalytic redox capabilities, have found widespread applications in addressing challenging chemical processes, including the photocatalytic reduction of CO2 with a high reaction barrier. Nevertheless, the influence of intraband defect levels within S‐scheme heterojunctions on charge separation, carrier lifetime, and surface catalytic reactions has, for the most part, been overlooked. Herein, we develop a tunable defect‐level‐assisted strategy to construct an electron reservoir, effectively prolonging the lifetime of charge carriers through the rapid capture and gradual release of photoelectrons within WO3‐x/In2S3 S‐scheme heterojunctions, as authenticated by femtosecond transient absorption spectroscopy and theoretical simulations. The surface photoredox mechanism, unraveled by Gibbs free energy calculations, demonstrates that oxygen‐vacancy‐induced defect states in WO3‐x/In2S3 heterojunctions unlock the rate‐determining H2O oxidation into free oxygen molecules by forming metastable oxygen intermediates, contributing to the facilitation of H2O photooxidation. This distinct role, combined with the extended carrier lifetime, results in boosted CO2 photoreduction with nearly 100 % CO selectivity in the absence of any photosensitizer or scavenger. Our work sheds light on the role of controllable defect levels in governing charge transfer dynamics within S‐scheme heterojunctions, thereby inspiring the development of more advanced photocatalysts for artificial photosynthesis. [ABSTRACT FROM AUTHOR]

Hydrogen‐bonded organic frameworks (HOFs) demonstrate significant potential for application in photocatalysis. However, the low efficiency of electron‐hole separation and limited stability inhibit their practical utilization in photocatalytic hydrogen evolution from water splitting. Herein, the novel dual‐pyrene‐base supramolecular HOF/COF 2D/2D S‐scheme heterojunction between HOF‐H4TBAPy (Py‐HOF, H4TBAPy represents the 1,3,6,8‐tetrakis (p‐benzoic acid) pyrene) and Py‐COF was successfully established using a rapid self‐assembly solution dispersion method. Experimental and theoretical investigations confirm that the size‐matching of two crystalline porous materials enables the integrated heterostructure material with abundant surface reaction sites, strong interaction, and an enhanced S‐scheme built‐in electric field, thus significantly improving the efficiency of photogenerated charge carrier separation and stability. Notably, the optimal HOF/COF heterojunction achieves a photocatalytic hydrogen evolution rate of 390.68 mmol g−1 h−1, which is 2.28 times higher than that of pure Py‐HOF and 9.24 times higher than that of pure COF. These findings precisely acquire valuable atomic‐scale insights into the ingenious design of dual‐pyrene‐based S‐scheme heterojunction. This work presents an innovative perspective for forming supramolecular S‐scheme heterojunctions over HOF‐based semiconductors, offering a protocol for designing the powerful and strong‐coupling S‐scheme built‐in electric fields for efficient solar energy utilization. [ABSTRACT FROM AUTHOR]

This comprehensive review explores synthesis methodologies for ZnO nanostructures, emphasising green synthesis and doping techniques. Researchers, driven by environmental sustainability, have utilised various bio-reducing agents in synthesising both pristine and doped ZnO nanostructures. The study delves into the involvement of these structures in photo-assisted degradation of organic pollutants, showcasing the pivotal role of green-synthesised ZnO and its doped derivatives in photocatalysis. The review meticulously details alterations induced by dopants in the parent ZnO structure, highlighting their potential to enhance dye degradation efficiency. Mechanisms underlying the green synthesis approach are elucidated, exploring the interplay between surface reactions, photo energy, charge carriers, and energy band structures. Additionally, the synergistic effects of dopants on ZnO nanostructures when exposed to light are outlined, impacting various organic pollutants such as dyes, antibiotic effluents, organic solvents, and Polycyclic Aromatic Hydrocarbons (PAHs).Drawing from recent research papers predominantly from 2018–24, this review is a consolidated source on the current state-of-the-art. Its focus on doped ZnO nanostructures, commitment to sustainable synthesis, and exploration of efficiency augmentation through doping techniques distinguish it. Beyond summarising advancements, the review addresses future possibilities and challenges, significantly contributing to understanding photocatalytic excellence in green-synthesised ZnO nanostructures. [ABSTRACT FROM AUTHOR]

The exploitation of semiconductor self‐polarization is an effective mean of improving the efficiency of electron utilization. In this work, the synthesis of BiFeO3 (BFO) samples with varying photoelectric properties is achieved by modulating the concentration of KOH. The experimental results reveal that BFO‐4 (4 m KOH) has excellent carrier efficiency. Interestingly enough, the ethanol yield of up to 7.05 μmol cm−2 h−1 in the photoelectrocatalytic process, which is 1.4 times than that of single electrocatalysis. Based on the characterization data, the external electric field forms a multi‐electric field coupling in the BFO (external electric field can enhance the self‐polarization electric field), which enhances charge separation efficiency and facilitates surface reactions, and the CO2 reduction performance is improved. Finally, the free energy in the key step of CC coupling on the surface of BiFeO3 is calculated by DFT. This study offers a valuable reference for the application of ferroelectric materials in the photoelectrocatalytic reduction of CO2 and the design of catalysts for C2+ products. [ABSTRACT FROM AUTHOR]

CO2 capture and reduction with H2 (CCR) to synthesise CH4 over dual-functional materials (DFMs) possessing CO2 capture and hydrogenation abilities has recently attracted attention as a promising methodology for utilising low-concentration CO2 in air or exhaust gases without pressure and/or temperature swing operations. Much effort has been devoted to the development of Ni-based DFMs for the CCR of CH4 formation owing to their low cost and high catalytic potential for methanation. However, previous studies have been investigated under relatively high reaction temperatures (400–600 °C) and/or pressurised H2 conditions. In addition, experiments were conducted in the absence of O2 in the simulated CO2 gas. The development of efficient Ni-based DFMs under milder and more realistic reaction conditions is still necessary. In this study, we developed La-modified Al2O3-supported Ni nanoparticles (Ni–La(X)/Al2O3, X denotes the La loading) for the selective formation of CH4 from low-concentration CO2 (1%) in a simulated gas containing O2 (20%). The optimised Ni–La(15)/Al2O3 showed 99% selectivity for CH4 formation under isothermal (350 °C) and non-pressurised conditions. The effect of the La loading amount on the CCR performance was studied using X-ray diffraction, temperature-programmed surface reactions, and steady-state CO2 hydrogenation. Furthermore, the developed Ni–La(15)/Al2O3 was applied to direct capture of ultralow concentration CO2 in air (ambient direct air capture (DAC)) and methanation. [ABSTRACT FROM AUTHOR]

Background: The kallikrein-kinin system (KKS) is a complex biochemical pathway that plays a crucial role in regulating several physiological processes, including inflammation, coagulation, and blood pressure. Dysregulation of the KKS has been associated with several pathological conditions such as hereditary angioedema (HAE), hypertension, and stroke. Developing an accurate quantitative model of the KKS may provide a better understanding of its role in health and disease and facilitate the rapid and targeted development of effective therapies for KKS-related disorders. Objectives: Here, we present a novel, detailed mechanistic model of the plasma KKS, elucidating the processes of Factor XII (FXII) activation, the kallikrein feedback loop, cleavage of high molecular weight kininogen leading to bradykinin (BK) production, and the impact of inhibitors. Methods: The model incorporates both surface and solution-phase reactions of all proteins in the KKS, describing how binding site concentration affects the rate of surface reactions. The model was calibrated and validated using a variety of published and in-house experimental datasets, which encompass a range of dextran sulphate (DXS) concentrations to initiate contact activation and various KKS inhibitors to block bradykinin production. Results: Our mathematical model showed that a trace amount of activated FXII is required for subsequent FXII activation. The model also reveals a bell-shaped curve relationship between the activation of the KKS and the number of DXS surface binding sites. Simulations of BK generation in healthy and HAE plasma demonstrated the impact of C1 esterase inhibitor (C1inh) deficiency via increased peak BK levels and accelerated formation in HAE plasma. The efficacy of KKS inhibitors, such as CSL312, ecallantide, and C1inh, was also evaluated, with CSL312 showing the most potent inhibition of BK generation. Conclusions: The present model represents a valuable framework for studying the intricate interactions within the plasma KKS and provides a better understanding of the mechanism of action of various KKS-targeted therapies. Author summary: The plasma kallikrein-kinin system (KKS) is a biological pathway that impacts inflammation, blood clotting, and blood pressure. This system is regulated by endogenous inhibitors; however, in diseases such as hereditary angioedema, overactivation of the plasma KKS occurs due to insufficient inhibition. The KKS operates via a series of biochemical reactions within the blood and on the surfaces of blood vessels. Each step activates an enzyme essential for the subsequent step, ultimately leading to the formation of a pro-inflammatory peptide called bradykinin. The system is initiated by the activation of Factor XII (FXII) upon contact with negatively charged surfaces. FXII activation can also occur in vitro by the addition of dextran sulphate (DXS). In this study, we describe an innovative mechanistic model of the plasma KKS. This model integrates both surface and volume reactions within the KKS, illustrating how variations in DXS concentration can influence reaction rates in a bell-shaped manner. The model was validated using experimental data, covering a range of DXS concentrations and clinical KKS inhibitors. We demonstrate that, in contact activation-initiated systems, targeting FXII inhibition is a more effective treatment approach than inhibiting downstream enzymes for the prevention of bradykinin generation. [ABSTRACT FROM AUTHOR]

Despite the development of a range of photocatalysts for CO2 reduction, the practical applications are significantly limited by low conversion efficiencies and their reliance on sacrificial agents, which are rooted in thermodynamic and kinetic challenges related to CO2 conversion. Here, the engineering of Co single atoms in ultrathin single‐crystal BiOCl nanosheets for boosted photocatalytic CO2 reduction is reported. The engineering of Co atoms modulates the distribution of photogenerated charges at the catalyst surface, controlling key surface reaction dynamics and suppressing surface electron‐hole recombination. This modulation also improves light absorption and enhances CO2 adsorption and activation, leading to more efficient surface reactions. Notably, CO2 is stably adsorbed onto the (001) face of BiOCl through a Bi‐O‐C(= O)‐Co‐O coordination unit, which lowers the activation energy for CO2 reduction and reduces the formation energy of COOH− intermediates. As a result, the BiOCl photocatalysts achieve a CO formation rate of 183.9 µmol g−1 h−1, when irradiated with a 300 W Xe lamp without cocatalysts or sacrificial agents. It represents an ≈13‐fold increase compared to that of pristine BiOCl, and surpasses most reported Bi‐based photocatalysts to date. Current work provides valuable insights into engineering of single atoms for developing advanced CO2‐reduction photocatalysts. [ABSTRACT FROM AUTHOR]

The high‐rate electrochemical dissolution of copper in nitrate electrolytes is investigated primarily via polarization curves, while varying parameters such as the electrolyte flow velocity, the electrolyte resistance, the anode geometry, and the temperature. This study focuses on the re‐rise in current at high voltages after the limiting current plateau. As a result of the studies, a change in the complexation mechanism from hydration to "solvo‐nitration" is proposed, which requires an additional potential drop within the electrochemical double layer. [ABSTRACT FROM AUTHOR]

Covalent organic frameworks (COFs), at the forefront of porous materials, hold tremendous potential in membrane separation; however, achieving high continuity in COF membranes remains crucial for efficient gas separation. Here, we present a unique approach termed assembly‐dissociation‐reconstruction for fabricating COF membranes tailored for CO2/N2 separation. A parent COF is designed from two‐node aldehyde and three‐node amine monomers and dissociated to high‐aspect‐ratio nanosheets. Subsequently, COF nanosheets are orderly reconstructed into a crack‐free membrane by surface reaction under water evaporation. The membrane exhibits high crystallinity, open pores and a strong affinity for CO2 adsorption over N2, resulting in CO2 permeance exceeding 1060 GPU and CO2/N2 selectivity surpassing 30.6. The efficacy of this strategy offers valuable guidance for the precise fabrication of gas‐separation membranes. [ABSTRACT FROM AUTHOR]

The rational design of MgO nanomaterials with rich oxygen vacancies has garnered significant attention. However, the influence of oxygen vacancies and alkalinity on the generation and stability of active oxygen, particularly regarding the antibacterial activity of MgO nanomaterials, remains uncertain. In this work, the defective MgO nanoplates with adjustable oxygen vacancy and alkalinity were successfully designed by thermal treatment in different atmospheres (air, vacuum, and N 2). MgO nanoplates calcined in N 2 atmosphere exhibited superior antibacterial activity against Escherichia coli (ATCC 25922), reducing colony counts from 571.5 to 53.5 CFU/mL at 750 μg/mL compared with MgO nanoplates calcined in air. At a low concentration (100 μg/mL), MgO nanoplates calcined in N 2 atmosphere exhibited remarkable antibacterial performance, achieving a colony survival ratio of only 6.8 %. This enhanced performance was correlated with a higher oxygen vacancy (O A) content (51.3 %) in MgO nanoplates calcined in N 2 compared to those calcined in air (26.5 %). Advanced characterization techniques and alkalinity measurements revealed that calcination in a N 2 atmosphere promoted oxygen vacancy formation on the MgO surface, accelerated MgO surface hydrolysis owing to oxygen vacancies, and increased OH− production. Consequently, this process enhances the participation of adsorbed oxygen in surface reaction, leading to the increased generation and stability of active oxygen in an alkaline environment. These findings provide valuable insights into the design of oxygen vacancies and offer a potential approach for constructing highly antibacterial nanomaterials. Such materials could find applications in personal protection and public health. [ABSTRACT FROM AUTHOR]

In this study, we conducted a comparative analysis of the catalytic behavior of Ni-CaO-Al2O3 dual functional material (DFM) and a physical mixture of Ni-Al2O3 and CaO-Al2O3 in the integrated carbon capture methanation (ICCM) process for promoted methane production. H2-temperature-programmed surface reaction (H2-TPSR) analysis revealed that in Ni-CaO-Al2O3 DFM, CO2 adsorbed on the CaO surface can spillover to metallic Ni surface, enabling direct hydrogenation without desorption of CO2. Ni-CaO-Al2O3 DFM exhibited a rapid initial methanation rate due to CO2 spillover. The Ni-CaO-Al2O3 DFM, with Ni and CO2 adsorption sites in close distance, allows efficient utilization of the heat generated by methanation to desorb strongly adsorbed CO2, leading to enhanced methane production. Consequently, Ni-CaO-Al2O3 DFM produced 1.3 mmol/gNi of methane at 300 °C, converting 35% of the adsorbed CO2 to methane. [ABSTRACT FROM AUTHOR]

The front opening unified pod (FOUP) is a carrier that transports multiple wafers as it moves between numerous processing facilities. It is inevitably exposed to air humidity coming from the equipment front end module (EFEM), which leads to the formation of harmful residual particles on the wafer surfaces due to the reaction of moisture with airborne molecular contamination (AMC). This can cause serious defects, and thus there is a need to understand the complex flow structure inside the EFEM and FOUP. Magnetic resonance velocimetry (MRV) is hereby employed to qualitatively and quantitatively measure the 3D flow when conventional load port purge (LPP) is utilized to protect the wafers. The front LPP forms a barrier between the FOUP and EFEM, blocking the EFEM flow from entering the FOUP. Additionally, at the rear of the FOUP, flow from the rear and front LPP collide and then travels between the wafers toward the FOUP entrance, thereby protecting the wafers. Using computational fluid dynamic (CFD) simulations, various combinations of flow rates from different purge ports were simulated, leading to an optimal flow condition. These findings suggest that independent control of the flow rates can be a practical way to protect the wafers from defects. [ABSTRACT FROM AUTHOR]

Asymmetric chemical reactions on the surfaces of colloidal particles are known to propel them into directional motion. The dynamics of such chemical micromotors are sensitive to their local chemical environments, which also continually evolve with the reactions on motor surfaces. This two‐way coupling between the motor dynamics and the local environment may result in complex nonlinear behaviors. As an example, we report that Janus Ag microspheres, which self‐propel in hydrogen peroxide (H2O2), spontaneously reverse their direction of motion two or more times. We hypothesize that two distinct chemical reactions between Ag and H2O2 drive the micromotor in opposite directions, and which reaction dominates depends on the local pH. Interestingly, the local pH near a Ag micromotor oscillates spontaneously in H2O2, likely due to a complex interplay between the kinetics of the reaction between Ag and H2O2 and the diffusion of chemical species. Consequently, the pH‐sensitive Ag micromotor reverses its direction of motion in response to these pH oscillations. This study introduces a new mechanism for regulating the speed and directionality of micromotors, highlights the potential of Ag micromotors in chemical sensing, and sheds new light on the interplay between chemical kinetics and micromotor dynamics. [ABSTRACT FROM AUTHOR]

How many times can a diffusing molecule permeate across a membrane or be adsorbed on a substrate? We employ an encounter-based approach to find the statistics of adsorption or permeation events for molecular diffusion in a general confining medium. Various features of these statistics are illustrated for two practically relevant cases: a flat boundary and a spherical confinement. Some applications of these fundamental results are discussed. [ABSTRACT FROM AUTHOR]

The formation of polymeric self-organizing organosilicon surface nanolayers on copper occuring as a result of modification of the metal surface with organosilane-based formulations has been studied. The anticorrosive effect of such surface layers in corrosive chloride-containing electrolytes as well as in artificial and natural atmospheres has been studied in detail. It has been found that the maximum protective effect is observed at a thickness of 3.8 molecular layers, where the densest cross-linked polymer layers are formed that hinder the adsorption of chloride ions and other corrosive agents on the metal surface, thus significantly reducing the rate of their reactions with the surface copper atoms, and, as a result, inhibiting the corrosion and local anodic dissolution of the metal. [ABSTRACT FROM AUTHOR]

Dielectric barrier discharge (DBD) plasma is a potential tool in the field of in situ CO2 conversion with the low‐pressure environment of Mars. CO is an important intermediate product in the conversion process of CO2. Understanding the pathways and dynamics that govern the generation of CO in CO2 plasmas establishes the foundation for effective regulation. In this work, parallel‐plate DBD structure was employed in our experiment and one‐dimensional fluid simulation model. The findings indicate that CO primarily originates at the boundary of the cathode potential fall region, and it subsequently migrates toward the surface of instantaneous cathode where it accumulates. The thickness of CO‐enriched region is approximately 0.8 mm. During this process, CO migration speed reaches about 2000 m/s. It is worth noting that surface reactions at the instantaneous cathode and anode surfaces contribute only 0.24% to CO generation, in contrast to the predominant influence of impact dissociation reaction between CO2 and electrons (e + CO2 → 2e + CO + O+) at 53.21%, and two‐body decomposition reaction between O+ and CO2 (O+ + CO2 → O +2 + CO) at 35.88%. Finally, the primary factors influencing the migration of CO from production sites to enrichment regions are determined to be particle collisions and momentum exchange between ions and CO, followed by electro‐hydro dynamics force, while dielectrophoresis forces have minimal effect. [ABSTRACT FROM AUTHOR]

The permeability of ore is a key factor affecting the leaching effect of uranium ore, and the addition of surfactants can significantly improve the permeability of ore, thereby strengthening uranium ore leaching. This article simulates two infiltration leaching processes, atmospheric heap leaching and pressurized in-situ leaching, and explores the effect of surfactant cetyltrimethylammonium bromide on uranium leaching rate and ore permeability coefficient in both processes. The results showed that in the atmospheric heap leaching test, adding surfactants increased the ore leaching rate by 30.31% during the same 13 day test cycle, and the leaching process was mainly controlled by surface chemical reactions. In the pressurized in-situ leaching test, based on the results of a leaching cycle of 13 days, the average permeability coefficient increased by 72.89% and 64.07% after adding surfactants to the drained and water containing uranium deposits, respectively. In addition, the peak uranium concentration in the leaching solution appeared 2 days earlier, indicating that the addition of surfactants has a significant promoting effect on in-situ leaching of uranium, improving the leaching efficiency of uranium, and can improve the leaching rate of uranium within the same leaching cycle. [ABSTRACT FROM AUTHOR]

The hydrogenation of m-cresol was studied across a wide temperature range, revealing complex variations in product distribution and reaction mechanisms. It has been found that the hydrogenation process predominantly yields 3-methylcyclohexanone and 3-methylcyclohexanol as primary products through ring hydrogenation (HYD) within the 140–250 ℃ temperature range. Conversely, the hydrodeoxygenation (HDO) products, toluene and methylcyclohexane, remain insignificant. More interestingly, the HYD yield is observed to diminish at elevated temperatures, with HDO becoming more dominant beyond 270 ℃. Further exploration of potential factors influencing the observed reduction in HYD yield at elevated temperatures—namely site deactivation, equilibrium limitations, and variations in surface coverage—revealed that changes in the surface adsorption of m-cresol play a critical role in the observed decrease in HYD activity, rather than site deactivation or equilibrium constraints. The order of 3-methylcyclohexanone formation with respect to m-cresol increases from 0 to 1 across the examined temperature range, suggesting m-cresol adsorption follows a simple Langmuir–Hinshelwood adsorption model where r ∼ k K C P C / (1 + K C P C) . This analysis not only advances our understanding of the temperature-dependent behavior in m-cresol hydrogenation but also lays the groundwork for future kinetic modeling, offering deeper insight into the complex dynamics of m-cresol hydrogenation. [ABSTRACT FROM AUTHOR]

Improving the gas‐sensing properties of sensors is important for the detection of ultralow‐concentration gases. As sensor signals are generated from the reactions on the surface of the sensor material, improving the surface structure of the sensor material can enhance the sensing properties. In this study, nanosheet‐type tin oxide with a metastable (101) crystal facet surface was used as the gas sensor material. To enhance the sensing properties, crystal facet‐controlled cerium oxide with superior oxygen storage capacity at moderate temperatures was decorated on the surface of the nanosheet‐type tin oxide material. An investigation of the sensor properties revealed that the decorated sensor exhibited improved gas selectivity and enhanced sensitivity to all tested gases. Prior to decoration, selectivity was observed for acetone and ethanol, whereas the decorated sensor exhibited high selectivity for acetaldehyde. The limits of detection of the decorated sensors were 245, 459, and 934 ppt for acetone, ethanol, and acetaldehyde, respectively. Thus, the proposed material can effectively enhance the sensing of extremely low‐concentration gases. [ABSTRACT FROM AUTHOR]

Calcium nitrate (CN: Ca(NO3)2) has been shown to mitigate alkali–silica reaction (ASR) in concrete. Such ASR mitigation has been suggested to be on account of precipitate (i.e., barrier or passivation layer) formation‐induced dissolution inhibition of reactive/dissolving aggregate surfaces. Herein, we examine the ability of CN to mitigate ASR across two cements (Type I/II and Portland Limestone Cement), for aggregates of varying reactivity, and across different types and dosages of SCMs (supplementary cementitious materials, i.e., amorphous steel slag and Class C and Class F fly ashes). Based on expansion measurements carried out as per ASTM C1260/C1567, it is observed that CN, as a function of dosage, substantively mitigates ASR in mortar formulations across aggregate types. Careful microstructural examinations, dissolution studies, and thermodynamic calculations indicate that CN induces the formation of C–S–H, portlandite (Ca(OH)2), and calcite (CaCO3) precipitate mixtures, which form on aggregate surfaces at the expense of typical ASR gels. Such precipitates create a dissolution barrier and inhibit ASR in both SCM‐free and SCM‐containing formulations. The outcomes indicate that CN is an efficient and cost‐effective ASR mitigation additive (∼$250–$600 per tonne), particularly in a time of dwindling fly ash supplies and unaffordable lithium prices (>∼$12 000 per tonne). [ABSTRACT FROM AUTHOR]

Asymmetric chemical reactions on the surfaces of colloidal particles are known to propel them into directional motion. The dynamics of such chemical micromotors are sensitive to their local chemical environments, which also continually evolve with the reactions on motor surfaces. This two‐way coupling between the motor dynamics and the local environment may result in complex nonlinear behaviors. As an example, we report that Janus Ag microspheres, which self‐propel in hydrogen peroxide (H2O2), spontaneously reverse their direction of motion two or more times. We hypothesize that two distinct chemical reactions between Ag and H2O2 drive the micromotor in opposite directions, and which reaction dominates depends on the local pH. Interestingly, the local pH near a Ag micromotor oscillates spontaneously in H2O2, likely due to a complex interplay between the kinetics of the reaction between Ag and H2O2 and the diffusion of chemical species. Consequently, the pH‐sensitive Ag micromotor reverses its direction of motion in response to these pH oscillations. This study introduces a new mechanism for regulating the speed and directionality of micromotors, highlights the potential of Ag micromotors in chemical sensing, and sheds new light on the interplay between chemical kinetics and micromotor dynamics. [ABSTRACT FROM AUTHOR]

This study explores the application of a dopamine-assisted co-deposition strategy to modify the surface of daily disposable silicone hydrogel contact lenses. Aiming to enhance the hydrophilicity of these typically hydrophobic lenses, we developed an industry-friendly process using simple dip coating in aqueous solutions. By co-depositing tannic acid, dopamine and chitosan derivative and employing periodate oxidation, we achieved a rapid and efficient coating process. High-molecular-weight branched polyethylene imine was introduced to promote surface reactions. The resulting lenses exhibited extreme hydrophilicity and lipid repellency without compromising their intrinsic properties or causing cytotoxicity. While the coating demonstrated partial antimicrobial activity against Gram-positive Staphylococcus aureus, it offers a foundation for the further development of broad-spectrum antimicrobial coatings. This versatile and efficient process, capable of transforming hydrophobic contact lenses into hydrophilic ones in just 15 min, shows significant potential for improving comfort and performance in daily disposable contact lenses. [ABSTRACT FROM AUTHOR]

The tripartite combination of a high density and stability of surface reaction sites, complemented by the longevity and efficient transfer of interface carriers, along with the effective adsorption and activation of target gas molecules, jointly determines the efficiency of chemiresistors. In this work, the strong metal–support interaction (SMSI) of Pt─Ce3+ is formed by the NaBH4 reduction method and thus prepares metal‐dynamically stable PtNR─CeO2 with Pt─Ce3+ and Pt─Pt reaction sites. The formation of SMSI induces the recombination of the chemical structure of the CeO2 surface causing the localization of electron‐rich Ce3+, which greatly increases the charge concentration at the interface. The experimental findings of the strong interaction of Pt─Ce3+ bonding and the catalytic effect of Pt optimized the adsorption mode of PtNR─CeO2 on target gas, which maintains stable catalytic activity at 20–500 °C and achieving a notable detection response value of 1.43 for 20 ppb NO2. This work offers fresh insights into designing stable oxide chemiresistors with efficiency and stability by customizing reaction sites at the atomic level. [ABSTRACT FROM AUTHOR]

Photocatalytic carbon‐carbon (C─C) coupling of benzyl alcohol is a promising means to coproduce the value‐added chemicals with H2 but is generally subject to low efficiency in terms of photon utilization. Here, efficient benzyl alcohol C─C coupling is achieved over Zn2In2S5 containing a tunable content of Zn vacancies (VZn). The VZn tends to form shallow defect states below the conduction band that can expedite photocarrier separation by collecting the photo‐generated electrons. The VZn‐collected electrons are essential for a high selectivity of the C─C coupling reactions because they enable a fast elimination of the byproduct benzaldehyde by catalyzing its reduction back to the ketyl radicals. Under simulated sunlight, the VZn‐containing Zn2In2S5 accomplishes ≈100% conversion of benzyl alcohol for merely 1 h and attains ≈100% selectivity for the C─C coupling compounds for 2 h, delivering an apparent quantum yield as high as 7.7% at 420 ± 20 nm. The benefits of VZn have also been verified by the theoretical calculations that indicate reduced energy barriers for various surface reactions in the presence of VZn. This work brings fresh mechanistic insights into the role of VZn and can serve as a useful guideline in the design of efficient photocatalysts. [ABSTRACT FROM AUTHOR]

Clay‐based materials are an emerging family of earth‐abundant and low‐cost inorganic functional materials with an modifiable layered‐structure mode similar to hydroxides. They are considered as competitive electrocatalysts for water splitting due to their variable intra‐layer ions, exchangeable interlayer molecules/ions, and large reaction surfaces, which demonstrate fascinating engineering opportunities at the microscale, mesoscale, and macroscale levels. We systematically summarized the research progress of clay‐based materials by classifying clay‐like compounds, clay‐based composites, and clay‐based derivatives, from the viewpoint of structural geometries towards optimizing functionalities. The design strategies for regulating and optimizing clay‐based materials to meet the requirements of electrocatalysts with excellent activity and stability were outlined through representative examples. In addition, the hydrogen production applications of these clay‐based materials were discussed reasonably including recent advances. Finally, the future perspectives of clay‐based materials for electrocatalytic water splitting were demonstrated. [ABSTRACT FROM AUTHOR]

Nitrogen-containing compounds such as imides and amides have been reported as efficient materials that promote ammonia decomposition over nonnoble metal catalysts. However, these compounds decompose in an air atmosphere and become inactive, which leads to difficulty in handling. Here, we focused on perovskite oxynitrides as air-stable and efficient supports for ammonia decomposition catalysts. Ni-loaded oxynitrides exhibited 2.5–18 times greater catalytic activity than did the corresponding oxide-supported Ni catalysts, even without noticeable differences in the Ni particle size and surface area of the supports. The catalytic performance of the Ni-loaded oxynitrides is well correlated with the nitrogen desorption temperature during N2 temperature-programmed desorption, which suggests that the lattice nitrogen in the oxynitride support rather than the Ni surface is the active site for ammonia decomposition. Furthermore, NH3 temperature-programmed surface reactions and density functional theory (DFT) calculations revealed that NH3 molecules are preferentially adsorbed on the nitrogen vacancy sites on the support surface rather than on the Ni surface. Thus, the ammonia decomposition reaction is facilitated by a vacancy-mediated reaction mechanism. Oxynitride-supported Ni catalysts exhibit much higher activity than oxide-supported Ni catalysts for ammonia decomposition reaction. Ammonia is activated at nitrogen vacancy sites on the surface of oxynitride in close vicinity to the supported Ni nanoparticles rather than on the Ni surface, and therefore the catalytic performance is dominated by ease of nitrogen vacancy formation on the catalyst surface. [ABSTRACT FROM AUTHOR]

We investigated the dehydrogenation reaction and the thermal robustness of the liquid organic hydrogen carrier (LOHC) couple benzaldehyde/cyclohexylmethanol on a Pt(111) model catalyst in situ in synchrotron radiation photoelectron spectroscopy‐ and complementary temperature‐programmed desorption experiments. The system stores hydrogen in a cyclohexyl group and a primary alcohol functionality and achieves an attractive hydrogen storage capacity of 7.0 mass %. We observed a stepwise dehydrogenation mechanism, characterized by a low temperature dehydrogenation of the alcohol group at 235 K. However, stability limitations challenge the system's application as reversible hydrogen storage solution, as the resultant aldehyde was found to decompose during the dehydrogenation of its cyclohexyl group (between 250 and 350 K). A comparison of cyclohexylmethanol with the structurally related secondary alcohol (1‐cyclohexylethanol; 6.3 mass % hydrogen) revealed a parallel stepwise dehydrogenation pattern for both compounds, but a technically relevant superior thermal robustness of the latter, demonstrating the influence of the alcohol‐group's substitution degree on the dehydrogenation characteristics of alcohol‐functionalized LOHCs. Density functional theory calculations are in agreement with the experimentally observed stability trend. [ABSTRACT FROM AUTHOR]

Due to its abundance, high theoretical capacity, and environmental benefits, tin dioxide (SnO2) shows great potential as an anode material in sodium-ion batteries (SIBs). However, the inadequate electrical conductivity and significant volume fluctuations during the Na+ insertion/extraction process are major limitations to its practical application. Herein, few-layered MoS2@SnO2@C (FMSC) composites with hierarchical nanostructures were prepared through a two-step hydrothermal method. As expected, the electrochemical tests show that the FMSC exhibits superior electrochemical properties, such as an outstanding rate capability of 288.9 mA h g−1 at a current density of 2 A g−1, a high reversible capacity of 415.9 mA h g−1 after 50 cycles at a current density of 0.1 A g−1, and remarkable cycling stability of 158.4 mA h g−1 after 4400 cycles at a current density of 5 A g−1, as an anode material for SIBs. The exceptional performance can be attributed to the presence of a thin layer of MoS2, which enhances surface electrochemical reactions and provides a flexible structure. [ABSTRACT FROM AUTHOR]

Although the high‐energy Ni‐rich layered cathodes suffer from undesirable surface reactions with the electrolyte, the polyvinylidene fluoride (PVDF) binder has a limitation on surface stabilization because of its weak affinity and low adhesion/cohesion. Here, it is demonstrated that the novel fluorine‐free and hydroxyl‐rich siloxane nanohybrid (SNH) binder can enhance the electrochemical performances of LiNi0.8Mn0.1Co0.1O2 cathode (NCM811) via successful surface stabilization. The high silanol content in the SNH binder enhances the affinity to both NCM811 and conductive agent, facilitating uniform electron/ion pathways with high mass loading, improved shear thinning, and superior mechanical properties. Moreover, the fluorine‐free organic‐inorganic hybrid structure prevents the dissolution of transition metals, active material structural changes, and electrolyte interaction, leading to greatly enhanced cyclability of the SNH‐based NCM811 electrode (≈81.9% in half‐cell; ≈87.82% in full‐cell after 200 cycles) compared to PVDF‐based NCM811 electrode (≈58.8% in half‐cell; ≈61.24% in full‐cell after 200 cycles). Various analyses also indicate that the application of the fluorine‐free SNH binder successfully stabilizes both the surface and bulk structure of the NCM811 cathode during charge/discharge. The binder design represents a straightforward yet highly effective approach to achieving remarkably prolonged cyclability in lithium‐ion batteries, surpassing the performance of other fluorine‐based or polymer‐based binders. [ABSTRACT FROM AUTHOR]

[Display omitted] Coating and single crystal are two common strategies for cobalt-free nickel-rich layered oxides to solve its poor rate performance and cycle stability. However, the action mechanism of different modification protocols to suppress the attenuation are unclear yet. Herein, the Li 2 MoO 4 layer-coated polycrystalline LiNi 0.9 Mn 0.1 O 2 (1.0 %-Mo + NM91) and single crystal LiNi 0.9 Mn 0.1 O 2 (SC-NM91) are prepared to investigate this difference, respectively. By focusing on the interior of particles, the relationship between structure evolution and electrochemical behavior is systematically studied, and the intrinsic mechanism of coating/single-crystallization modifications on suppressing the attenuation is clarified. The results show that microcracks in LiNi 0.9 Mn 0.1 O 2 (NM91) are the main culprit leading to the rate capability decay, and the coating can effectively prevent the radial diffusion of microcracks from the center to surface, inhibiting the generation of surface side reactions. Therefore, the coating has a more advantage in improving the rate performance at 5.0C, the discharge capacity of 1.0 %-Mo + NM91 (130.6 mAh/g) is 7.9 % higher than that of SC-NM91 (121.0 mAh/g). In contrast, the single-crystallization can effectively prevent the formation of intergranular cracks arising from the anisotropic stress in NM91, which causes the severe cycle degradation. Correspondingly, the grain boundary-free SC-NM91 shows superior cyclability. The capacity retention rate of SC-NM91 (80.8 %) at 0.2C after 100cycles is 6.3 % higher than that of 1.0 %-Mo + NM91 (74.5 %). This work concludes the effect difference of different modification methods on enhancing the electrochemical performance, which provides theoretical and technical guidance for the optimized and targeted modification design in the cobalt-free high nickel cathode materials. [ABSTRACT FROM AUTHOR]