Suppressing metal corrosion through identification of optimal crystallographic plane for Zn batteries.

Direct use of metals as battery anodes could significantly boost the energy density, but suffers from limited cycling. To make the batteries more sustainable, one strategy is mitigating the propensity for metals to form random morphology during plating through orientation regulation, e.g., hexagonal Zn platelets locked horizontally by epitaxial electrodeposition or vertically aligned through Zn/electrolyte interface modulation. Current strategies center around obtaining (002) faceted deposition due to its minimum surface energy. Here, benefiting from the capability of preparing a library of faceted monocrystalline Zn anodes and controlling the orientation of Zn platelet deposits, we challenge this conventional belief. We show that while monocrystalline (002) faceted Zn electrode with horizontal epitaxy indeed promises the highest critical current density, the (100) faceted electrode with vertically aligned deposits is the most important one in suppressing Zn metal corrosion and promising the best reversibility. Such uniqueness results from the lowest electrochemical surface area of (100) faceted electrode, which intrinsically builds upon the surface atom diffusion barrier and the orientation of the pallets. These new findings based on monocrystalline anodes advance the fundamental understanding of electrodeposition process for sustainable metal batteries and provide a paradigm to explore the processing-structure-property relationships of metal electrodes.

Solidophobic Surface for Electrochemical Extraction of High-Valued Mg(OH)2 Coupled with H2 Production from Seawater.

A significant challenge in direct seawater electrolysis is the rapid deactivation of the cathode due to the large scaling of Mg(OH)2. Herein, we synthesized a Pt-coated highly disordered NiCu alloy (Pt-NiCu alloy) electrode with superior solidophobic behavior, enabling stable hydrogen generation (100 mA cm-2, >1000 h durability) and simultaneous production of Mg(OH)2 (>99.0% purity) in electrolyte enriched with Mg2+ and Ca2+. The unconventional solidophobic property primarily stems from the high surface energy of the NiCu alloy substrate, which facilitates the adsorption of surface water and thereby compels the bulk formation of Mg(OH)2 via homogeneous nucleation. The discovery of this solidophobic electrode will revolutionarily simplify the existing techniques for seawater electrolysis and increase the economic viability for seawater electrolysis.

In Situ Visual Observation of Surface Energy-Controlled Heterogeneous Nucleation of Metal Nanocrystals.

Electrochemical growth of metal nanocrystals is pivotal for material synthesis, processing, and resource recovery. Understanding the heterogeneous interface between electrolyte and electrode is crucial for nanocrystal nucleation, but the influence of this interaction is still poorly understood. This study employs advanced in situ measurements to investigate the heterogeneous nucleation of metals on solid surfaces. By observing the copper nanocrystal electrodeposition, an interphase interaction-induced nucleation mechanism highly dependent on substrate surface energy is uncovered. It shows that a high-energy (HE) electrode tended to form a polycrystalline structure, while a low-energy (LE) electrode induced a monocrystalline structure. Raman and electrochemical characterizations confirmed that HE interface enhances the interphase interaction, reducing the nucleation barrier for the sturdy nanostructures. This leads to a 30.92-52.21% reduction in the crystal layer thickness and a 19.18-31.78% increase in the charge transfer capability, promoting the formation of a uniform and compact film. The structural compactness of the early nucleated crystals enhances the deposit stability for long-duration electrodeposition. This research not only inspires comprehension of physicochemical processes correlated with heterogeneous nucleation, but also paves a new avenue for high-quality synthesis and efficient recovery of metallic nanomaterials.

Effect of surface treatment strategies on bond strength of additively and subtractively manufactured hybrid materials for permanent crowns.

OBJECTIVES: The purpose of this study is to evaluate the bond strength of different computer-aided design / computer-aided manufacturing (CAD/CAM) hybrid ceramic materials following different pretreatments. METHODS: A total of 306 CAD/CAM hybrid material specimens were manufactured, n = 102 for each material (VarseoSmile Crownplus [VSCP] by 3D-printing; Vita Enamic [VE] and Grandio Blocs [GB] by milling). Each material was randomly divided into six groups regarding different pretreatment strategies: control, silane, sandblasting (50 µm aluminum oxide particles), sandblasting + silane, etching (9% hydrofluorics acid), etching + silane. Subsequently, surface roughness (Ra) values, surface free energy (SFE) were measured. Each specimen was bonded with a dual-cured adhesive composite. Half of the specimens were subjected to thermocycling (5000 cycles, 5-55 °C). The shear bond strength (SBS) test was performed. Data were analyzed by using a two-way analysis of variance, independent t-test, and Mann-Whitney-U-test (α = 0.05). RESULTS: Material type (p = 0.001), pretreatment strategy (p < 0.001), and the interaction (p < 0.001) all had significant effects on Ra value. However, only etching on VSCP and VE surface increased SFE value significantly. Regarding SBS value, no significant difference was found among the three materials (p = 0.937), while the pretreatment strategy significantly influenced SBS (p < 0.05). Etching on VSCP specimens showed the lowest mean value among all groups, while sandblasting and silane result in higher SBS for all test materials. CONCLUSIONS: The bond strength of CAD/CAM hybrid ceramic materials for milling and 3D-printing was comparable. Sandblasting and silane coupling were suitable for both millable and printable materials, while hydrofluoric etching should not be recommended for CAD/CAM hybrid ceramic materials. CLINICAL RELEVANCE: Since comparable evidence between 3D-printable and millable CAD/CAM dental hybrid materials is scarce, the present study gives clear guidance for pretreatment planning on different materials.

Plasmon Resonance Energy Transfer Nanoruler for Pinpointing Molecular Distance and Interaction on the Living Cell Membrane.

Developing novel strategies to measure nanoscale distance and molecular interaction on a living cell membrane is of great significance but challenging. Here we develop a model of a linker-free plasmon resonance energy transfer, termed "PRET nanoruler", which is composed of a single-sized nanogold-antibody conjugates donor (G26@antiCD71) and a fluorophore-labeled XQ-2d aptamer receptor (XQ-2d-Cy3), that produces a separation distance (r) dependent energy transfer (ηPRET). Both the theoretical finite element simulation and experiments evidence the observable PRET between single G26NPs and XQ-2d-Cy3. Regardless of the size of ηPRET, we could confirm r is less than 5 nm, the separation of two binding sites is in the range of 13.0-18.0 nm. There is a competitive binding of Tf and XQ-2d-Cy3 on CD71 receptors. PRET nanoruler realizes the estimation of the nanoscale separation distance, and determines the molecular interaction and competitive binding. It is an alternative tool for observing nanoscale single molecular events in the future.

Record Resolution of Nanometal Surface Energy Transfer Optical Nanoruler Projects 3D Spatial Configuration of Aptamers on a Living Cell Membrane.

Decrypting the in situ three-dimensional spatial configuration of an aptamer is of considerable significance; however, suitable nanoscale resolution tools are lacking. Herein, we show that a new nanometal surface energy transfer (NSET) optical nanoruler has a record resolution, down to single-nucleobase levels. We labeled fluorophores on different T bases of XQ-2d, including 5', 3', 6T, 22T, 38T, and 52T positions. The NSET nanoruler in situ decrypted the base sequence-dependent distance projection on the nanogold surface, demonstrating that 5', 3', stem, and loop structures are symmetrical in three-dimensional spatial configuration. The orientation of the 5' and 3' stem was toward the antiCD71-binding site, whereas the loop was in the opposite direction at a considerable distance. Molecular docking simulation was performed to list all of the possible conformations; however, all base distance parameters projecting on the nanogold surface determined a single conformation of XQ-2d. The specific binding sites of XQ-2d were Lys477, Ser691, and Arg698 on the CD71 receptor.

Can changes in land use in a semi-arid region of Brazil cause seasonal variation in energy partitioning and evapotranspiration?

Changes to forests due to deforestation, or their replacement by agricultural areas, alter evapotranspiration and the partitioning of available energy. This study investigated seasonal variations in the energy balance and evapotranspiration in landscapes under different levels of anthropogenic intervention in the semi-arid region of Brazil. Micrometeorological data was obtained from September 2020 to October 2022 for three areas of the semi-arid region: preserved Caatinga (CAA, native vegetation), Caatinga under regeneration (REGE) and a deforested area (DEFA). Here, we use the Bowen ratio energy balance method. Measurements were taken of global solar radiation, air temperature, relative humidity, vapour pressure deficit, rainfall, net radiation, latent heat flux, sensible heat flux, soil heat flux, evapotranspiration, volumetric soil water content and Normalised Difference Vegetation Index. Sensible heat flux was the dominant flux in both areas with 66% for preserved Caatinga vegetation, 63% for Caatinga under regeneration and 62% deforested area. The latent heat flux was equivalent to 28% of the net radiation for preserved Caatinga vegetation, Caatinga under regeneration and deforested area. The evapotranspiration in turn responded as a function of water availability, being higher during the rainy seasons, with average values of 1.82 mm day-1 for preserved Caatinga vegetation, 2.26 mm day-1 for Caatinga under regeneration and 1.25 mm day-1 for deforested area. The Bowen ratio presented values > 1 in deforested area, preserved Caatinga vegetation and Caatinga under regeneration. Thus, it can be concluded that the change in land use alters the energy balance components, promoting reductions in available energy and latent and sensible heat fluxes during the rainy-dry transition in the deforested area. In addition, the seasonality of energy fluxes depends on water availability in the environment.

Thermal Surface Properties, London Dispersive and Polar Surface Energy of Graphene and Carbon Materials Using Inverse Gas Chromatography at Infinite Dilution.

The thermal surface properties of graphenes and carbon materials are of crucial importance in the chemistry of materials, chemical engineering, and many industrial processes. BACKGROUND: The determination of these surface properties is carried out using inverse gas chromatography at infinite dilution, which leads to the retention volume of organic solvents adsorbed on solid surfaces. This experimental and fundamental parameter actually reflects the surface thermodynamic interactions between injected probes and solid substrates. METHODS: The London dispersion equation and the Hamieh thermal model are used to quantify the London dispersive and polar surface energy of graphenes and carbon fibers as well their Lewis acid-base constants by introducing the coupling amphoteric constant of materials. RESULTS: The London dispersive and polar acid-base surface energies, the free energy of adsorption, the polar enthalpy and entropy, and the Lewis acid-base constants of graphenes and carbon materials are determined. CONCLUSIONS: It is shown that graphene exhibited the highest values of London dispersive surface energy, polar surface energy, and Lewis acid-base constants. The highest characteristics of graphene justify its great potentiality and uses in many industrial applications.

New Progress on London Dispersive Energy, Polar Surface Interactions, and Lewis's Acid-Base Properties of Solid Surfaces.

The determination of the polar surface free energy, polar properties, and Lewis's acid base of solid materials is of capital importance in many industrial processes, such as adhesion, coatings, two-dimensional films, and adsorption phenomena. (1) Background: The physicochemical properties of many solid particles were characterized during the last forty years by using the retention time of injected well-known molecules into chromatographic columns containing the solid substrates to be characterized. The obtained net retention time of the solvents adsorbed on the solid, allowing the determination of the net retention volume directly correlated to the specific surface variables, dispersive, polar, and acid-base properties. (2) Methods: Many chromatographic methods were used to quantify the values of the different specific surface variables of the solids. However, one found a large deviation between the different results. In this paper, one proposed a new method based on the London dispersion equation that allowed the quantification of the polar free energy of adsorption, as well as the Lewis's acid-base constants of many solid surfaces. (3) Results: The newly applied method allowed us to obtain the polar enthalpy and entropy of adsorption of polar model organic molecules on several solid substrates, such as silica, alumina, MgO, ZnO, Zn, TiO2, and carbon fibers. (4) Conclusions: our new method based on the separation between the dispersive and polar free surface energy allowed us to better characterize the solid materials.

Unlocking Spatial Surface Energy in Porous Skeletons: A Pathway to Bridging Electronic Circuits from 2D to 3D Architectures.

Conventional approaches to creating high-resolution electric circuits face challenges such as the requirement for skilled personnel and expensive equipment. In response, we propose an innovative strategy that leverages a photochemically modified porous polymer skeleton for in-situ circuit fabrication. By developing maskless surface energy manipulation that guides PEDOT:PSS-based conductive ink deposition, electric circuits with high precision, density, stability and adaptability are effortlessly engineered within or atop the porous skeleton, enabling transitions between 2D and 3D circuit configurations. This process simplifies prototyping while significantly reducing costs and maintaining efficiency, promising advancements across various technological sectors.

Blade-Coating (100)-Oriented α-FAPbI3 Perovskite Films via Crystal Surface Energy Regulation for Efficient and Stable Inverted Perovskite Photovoltaics.

Photoactive black-phase formamidinium lead triiodide (α-FAPbI3) perovskite has dominated the prevailing high-performance perovskite solar cells (PSCs), normally for those spin-coated, conventional n-i-p structured devices. Unfortunately, α-FAPbI3 has not been made full use of its advantages in inverted p-i-n structured PSCs fabricated via blade-coating techniques owing to uncontrollable crystallization kinetics and complicated phase evolution of FAPbI3 perovskites during film formation. Herein, a customized crystal surface energy regulation strategy has been innovatively developed by incorporating 0.5 mol % of N-aminoethylpiperazine hydroiodide (NAPI) additive into α-FAPbI3 crystal-derived perovskite ink, which enabled the formation of highly-oriented α-FAPbI3 films. We deciphered the phase transformation mechanisms and crystallization kinetics of blade-coated α-FAPbI3 perovskite films via combining a series of in-situ characterizations and theoretical calculations. Interestingly, the strong chemical interactions between the NAPI and inorganic Pb-I framework help to reduce the surface energy of (100) crystal plane by 42 %, retard the crystallization rate and lower the formation energy of α-FAPbI3. Benefited from multifaceted advantages of promoted charge extraction and suppressed non-radiative recombination, the resultant blade-coated inverted PSCs based on (100)-oriented α-FAPbI3 perovskite films realized promising efficiencies up to 24.16 % (~26.5 % higher than that of the randomly-oriented counterparts), accompanied by improved operational stability. This result represented one of the best performances reported to date for FAPbI3-based inverted PSCs fabricated via scalable deposition methods.

Kinetics Controlled Perovskite Crystallization for High Performance Solar Cells.

The power conversion efficiencies (PCEs) of perovskite solar cells have recently developed rapidly compared to crystalline silicon solar cells. To have an effective way to control the crystallization of perovskite thin films is the key for achieving good device performance. However, a paradox in perovskite crystallization is from the mismatch between nucleation and Oswald ripening. Usually, the large numbers of nucleation sites tend to weak Oswald ripening. Here, we proposed a new mechanism to promote the formation of nucleation sites by reducing surface energy from 44.9 mN/m to 36.1 mN/m, to spontaneously accelerate the later Oswald ripening process by improving the grain solubility through the elastic modulus regulation. The ripening rate is increased from 2.37 Åm ⋅ s-1 to 4.61 Åm ⋅ s-1 during annealing. Finally, the solar cells derived from the optimized films showed significantly improved PCE from 23.14 % to 25.32 %. The long-term stability tests show excellent thermal stability (the optimized device without encapsulation maintaining 82 % of its initial PCE after 800 h aging at 85 °C) and an improved light stability under illumination. This work provides a new method, the elastic modulus regulation, to enhance the ripening process.

Nb2 CTx MXene Derived Polymorphic Nb2 O5.

Previously, heat treatment was the only feasible route for tuning the crystal phases of niobium pentoxide (Nb2 O5 ). With the use of Nb2 CTx MXene precursors, the first case of phase tuning of Nb2 O5 in the low-temperature hydrothermal synthesis using sulfuric acid regulating agents is presented. By varying the amount of the agent, four pure-phase Nb2 O5 crystals and mixed phases in-between are obtained. The required amount is found to be related to the H-covered surface energy calculated based on density functional theory. Overall, MXene-derived B-phase Nb2 O5 is of particular interest due to its exceptionally high capacities as lithium-ion battery anodes, which are three times higher than the routine synthesized one. Oxygen vacancies induced by crystallographic shear would be responsible for the extraordinary performance. The proposed phase tuning strategy encourages the prudent synthesis of difficult-to-obtain crystal phases.

Enhanced CO Functionality on Carbon Papers Ensures Lowering Nucleation Delay of ALD for Ru towards Unprecedented Alkaline HER Activity.

The success in lowering the nucleation delay for Atomic Layer Deposition (ALD) of Ru on carbon surfaces is mitigated by constructive pretreatments resulting enhancement of CO functionality. Treatment of the carbon papers (CP) allowed Ru species deposition for minimum number of ALD cycles (25 cycles) with good conformality. The development of electrocatalysts from single atoms to nanoparticles (NPs) on conductive supports with low metal loadings, thus improving performance, is essential in electrocatalysis. For alkaline hydrogen evolution reaction, ALD decorated CPs with Ru exhibit low onset potentials of ≈4.7 mV versus reversable hydrogen electrode (RHE) (at 10 mA cm-2 ) and a high turnover frequency of 1.92 H2 s-1 at 30 mV versus RHE. The Ru decorated CPs show comparable to higher catalytic activity than of Platinum (Pt) decorated CP also developed by ALD. The current representation of unfamiliar catalytic activities of Ru active centers developed by ALD, pave a bright and sustainable path for energy conversion reactions.

N-Type Small Molecule Electron Transport Layers with Excellent Surface Energy and Moisture Resistance Siloxane for Non-Fullerene Organic Solar Cells.

Electron transport layers (ETLs) generally contain polar groups for enhancing performance and reducing the work function. Nevertheless, the polar group with high surface energy may cause inferior interfacial compatibility, which challenges the ETLs to balance stability and performance. Here, two conjugated small molecules of ETLs with low surface energy siloxane, namely PDI-Si and PDIN-Si, are synthesized. The siloxane with low surface energy not only enhances the interfacial compatibility between ETLs and active layers but also improves the moisture-proof stability of the device. Impressively, the amine-functionalized PDIN-Si can simultaneously exhibit conspicuous n-type self-doping properties and outstanding moisture-proof stability. The optimization of interfacial contact and morphology enables the PM6:Y6-based OSC with PDIN-Si to achieve a power conversion efficiency (PCE) of 15.87%, which is slightly superior to that of classical ETL PDINO devices (15.27%), and when the PDIN-Si film thickness reaches 28 nm, the PCE remains at 13.19% (≈83%), which indicates that PDIN-Si has satisfactory thickness insensitivity to facilitate roll-to-roll processing. Excitingly, after 120 h of storage in an environment with humidity above 45%, the unencapsulated device with PDIN-Si as ETL remains at 75% of the initial PCE value, while the device with PDINO as ETL is only 50%.

Perspectives on the Wetting of Solids in Pharmaceutical Systems.

PURPOSE: The ability of water and aqueous solutions to wet relatively nonpolar pharmaceutical solids during the processing and administration of solid dosage forms is an important part of development. RESULTS: Various factors, both fundamental and technological, which are important to wettability are reviewed and analyzed. Initially, the ideal thermodynamic importance of liquid surface tension and solid surface energetics, determined by the contact angle and the polarity of the solid surface, are established. Then, emphasis is placed on various factors that change the surface energetics due to crystal defects, polymorphism, varying Miller Indices, crystal habit, amorphous structure, variable surface concentration of components in a formulation mixture, surface roughness, and complex pore structure. Case studies cover single component systems (APIs and excipients), binary mixtures (amorphous solid dispersions and physical mixtures), multicomponent systems (granules and tablets), as well as disintegration and dissolution of solid oral dosage forms. CONCLUSIONS: This perspective and analysis indicates the primary importance of understanding and modifying solid surface energetics, surface chemical and physical heterogeneities, and pore structure to promote wettability in pharmaceutical systems.

A Novel Anti-Flashover Superhydrophobic Coating with Self-Assembly Characteristic of Surface Energy Differences.

Because of the versatility of superhydrophobic materials, they have attracted a lot of attention even in power electronics, transportation, engineering, and other fields. The volume fraction of fluorinated silicon oxide nanoparticles in superhydrophobic materials is one of the most important factors. Increasing the volume fraction will decrease the stability between the coating and the hydrophobic surface. Especially, the flashover voltage of the coating gradually decreases from 10 to 35 vol.%. Meanwhile, the flashover voltage dispersion of the coating increases drastically after 30 vol.%. In order to improve the electrical properties of the superhydrophobic coating, self-assembly of surface energy differences strategy is proposed in this work. A binary filling phase of the coating is introduced by 2D boron nitride nanosheets and silicon oxide nanoparticles. Although Hexagonal boron nitride with high surface energy and low roughness, it will be spontaneously assembled and wrapped by silicon oxide nanoparticle based on surface energy differences, which forming a low surface energy filled phase. Experiment results prove that the flashover voltage of the superhydrophobic coating is optimized by the binary filling phase coating. This method offers new ideas for the selection of filling phase and application of superhydrophobic materials.

Anthropogenic heat variation during the COVID-19 pandemic control measures in four Chinese megacities.

Anthropogenic heat (AH) is an important input for the urban thermal environment. While reduction in AH during the Coronavirus disease 2019 (COVID-19) pandemic may have weakened urban heat islands (UHI), quantitative assessments on this are lacking. Here, a new AH estimation method based on a remote sensing surface energy balance (RS-SEB) without hysteresis from heat storage was proposed to clarify the effects of COVID-19 control measures on AH. To weaken the impact of shadows, a simple and novel calibration method was developed to estimate the SEB in multiple regions and periods. To overcome the hysteresis of AH caused by heat storage, RS-SEB was combined with an inventory-based model and thermal stability analysis framework. The resulting AH was consistent with the latest global AH dataset and had a much higher spatial resolution, providing objective and refined features of human activities during the pandemic. Our study of four Chinese megacities (Wuhan, Shanghai, Beijing, and Guangzhou) indicated that COVID-19 control measures severely restricted human activities and notably reduced AH. The reduction was up to 50% in Wuhan during the lockdown in February 2020 and gradually decreased after the lockdown was eased in April 2020, similar to that in Shanghai during the Level 1 pandemic response. In contrast, AH was less reduced in Guangzhou during the same period and increased in Beijing owing to extended central heating use in winter. AH decreased more in urban centers and the change in AH varied in terms of urban land use between cities and periods. Although UHI changes during the COVID-19 pandemic cannot be entirely attributed to AH changes, the considerable reduction in AH is an important feature accompanying the weakening of the UHI.

Experimental and Computational Study of the Orientation Dependence of Single-Crystal Ruthenium Nanowire Stability.

Single-crystal nanowires are of broad interest for applications in nanotechnology. However, such wires are subject to both the Rayleigh-Plateau instability and an ovulation process that are expected to lead to their break up into particle arrays. Single crystal Ru nanowires were fabricated with axes lying along different crystallographic orientations. Wires bound by equilibrium facets along their length did not break up through either a Rayleigh-Plateau or ovulation process, while wires with other orientations broke up through a combination of both. Mechanistic insight is provided using a level-set simulation that accounts for strongly anisotropic surface energies, providing a framework for design of morphologically stable nanostructures.

Classification of pores, water diffusivity and penetration characteristics of waste materials, and role of water as electron carrier in landfills: A review.

Coupling of biogeochemical processes occurs between different waste components and waste layers during decomposition of wastes materials deposited in landfills by mechanisms similar to those occurring in marine sediments (i.e., sediment batteries). In landfills, moisture serves as a medium for transfer of electrons and protons under anaerobic conditions for decomposition reactions to proceed spontaneously, although some reactions occur very slowly. However, the role of moisture in landfills in view of pore sizes and pore size distributions, time dependent changes in pore volumes, heterogeneity of waste layers, and associated impacts on moisture retention and transport characteristics in landfills are not well understood. The moisture transport models developed for granular materials (e.g., soils) are not appropriate to describe the conditions at landfills due compressible and dynamic conditions in landfills. During waste decomposition processes, absorbed water and water of hydration can be transformed to free water and/or become mobilized as liquid or vapor, creating a medium for transfer of electrons and protons between waste components and waste layers. The characteristics of different municipal waste components were compiled and analyzed for pore size, surface energy, and moisture retention and penetration for electron-proton transfer for continuance of decomposition reactions in landfills over time. Categorization of pore sizes appropriate for waste components and a representative water retention curve for conditions in landfills were developed to clarify the terminology and highlight the differences between the landfill conditions and granular materials (e.g., soils) for use of appropriate terminologies. Water saturation profile and water mobility were analyzed by considering water as a transfer medium for carrying electrons and protons for sustaining long-term decomposition reactions.