Promoting Cross-Link Reaction of Polymers by the Matrix-Filler Interface Effect: Role of Coupling Agents and Intermediate Linkers.

The matrix-filler interface effect plays an important role in determining the structural stability and mechanical properties of polymer composite materials, which remain ambiguous and need to be studied. The network-forming dynamics of poly(3,3-bis (azidomethyl) oxetane-tetrahydrofuran) (PBT) at the ammonium perchlorate (AP) surface was studied by using atomistic molecular dynamics simulation, considering the additives of curing agent toluene diisocyanate (TDI), cross-linker trimethylolpropane (TMP), and coupling agent triethanolamine (TEA). The presence of the AP surface promotes chain cross-link reaction, which is attributed to the increased production of intermediate linkers formed by TDI, TMP, and TEA. The intermediate linker has three reactive sites that can react with PBT main chains to form a cross-linked structure. Owing to the strong interaction with the AP surface, the coupling agent TEA plays a dominant role in forming the intermediate linker. At the early stage of network forming (reaction ratio r < 30%), the AP surface adsorbs TEA, which leads to a maximum contact density to PBT. As r increases to 60%, the density of intermediate linkers near the AP surface reaches a maximum value. Consequently, the chain cross-link reactions between the intermediate linker and PBT main chains are enhanced as r > 60%. This work explains the micromechanism of the promotion of chain cross-link reaction by the interface effect and provides important insights on designing polymer materials with high mechanical properties.

Boosting Salinity Energy Extraction Efficiency in Capacitive Mixing by Polyelectrolyte Surface Coating.

The extraction of salinity gradient energy in the capacitive mixing (CapMix) technique can be enhanced by using polyelectrolyte-coated electrodes. The micromechanism of polyelectrolyte (PE) coating enhancing the salinity energy extraction is studied by using a statistical thermodynamic theory. When PE takes same charge sign as the coated electrodes, the extraction efficiency can be boosted owing to the enhanced response of electrical double layer (EDL) to external cell voltage (V0). For the optimal case studied, the extraction efficiency was boosted from 0.25 to 1.25% by PE coatings. Owing to counterion adsorption and the enhanced response of EDL, the extraction energy density presented a local maximum at V0 = 0, which is higher than another local maximum value when V0 ≠ 0. This provides important guidance on the two approaches of CapMix in terms of capacitive Donnan potential (CDP, V0 = 0) and capacitive double-layer expansion (CDLE, V0 ≠ 0). Under the effects of PE coating, the extraction efficiency by CDLE can be improved to about 11% by CDP for the optimal studied case. The synergistic effect of grafting conditions can significantly elevate the energy density and extraction efficiency of the CDP process.

Molecular Dynamics Study on the Stress Concentration in Polymer Networks with Dangling Chains.

Owing to structural defects, stress concentration frequently occurs in polymer network materials (PEMs), significantly altering their overall mechanical properties. Here, we investigate the impact of dangling chain defects on the stress concentration in PEMs using coarse-grained molecular dynamics simulation. Stress distributions on the network structure are calculated by using graph theory, with considering the effects of defect ratio (ϕ) and the distance from defects. It is found that the existence of dangling chains can alleviate stress by dissipating more internal energy. When considering the effects of all defects statistically, the stress concentration consistently occurs near the joint segments between dangling chains and the bare network (i.e., removing all of the dangling chains from the network). The stress concentration effect is significant when defects are in the region near the network edges. Stress tends to concentrate more on the dangling chains at low ϕ, while it tends to concentrate more on the bare network at high ϕ because of the enhanced chain motions in bare network. This implies that the stress concentration effect near the joint segment is predominant at low ϕ, and it is slightly weak as ϕ increased.

Liquid-free ionic conductive elastomers with high mechanical properties and ionic conductivity for multifunctional sensors and triboelectric nanogenerators.

Liquid-free ionic conductive elastomers (ICEs) are ideal materials for constructing flexible electronic devices by avoiding the limitations of liquid components. However, developing all-solid-state ionic conductors with high mechanical strength, high ionic conductivity, excellent healing, and recyclability remains a great challenge. Herein, a series of liquid-free polyurethane-based ICEs with a double dynamic crosslinked structure are reported. As a result of interactions between multiple dynamic bonds (multi-level hydrogen bonds, disulfide bonds, and dynamic D-A bonds) and lithium-oxygen bonds, the optimal ICE exhibited a high mechanical strength (1.18 MPa), excellent ionic conductivity (0.14 mS cm-1), desirable healing capacity (healing efficiency >95%), and recyclability. A multi-functional wearable sensor based on the novel ICE enabled real-time and rapid detection of various human activities and enabled recognizing writing signals and encrypted information transmission. A triboelectric nanogenerator based on the novel ICE exhibited an excellent open-circuit voltage of 464 V, a short-circuit current of 16 µA, a transferred charge of 50 nC, and a power density of 720 mW m-2, enabling powering of small-scale electronic products. This study provides a feasible strategy for designing flexible sensor products and healing, self-powered devices, with promising prospects for application in soft ionic electronics.

Enhanced Biphasic Reactions in Amphiphilic Silica Mesopores.

In this study, we investigated the effect of the pore volume and mesopore size of surface-active catalytic organosilicas on the genesis of particle-stabilized (Pickering) emulsions for the dodecanal/ethylene glycol system and their reactivity for the acid-catalyzed biphasic acetalization reaction. To this aim, we functionalized a series of fumed silica superparticles (size 100-300 nm) displaying an average mesopore size in the range of 11-14 nm and variable mesopore volume, with a similar surface density of octyl and propylsulfonic acid groups. The modified silica superparticles were characterized in detail using different techniques, including acid-base titration, thermogravimetric analysis, TEM, and dynamic light scattering. The pore volume of the particles impacts their self-assembly and coverage at the dodecanal/ethylene glycol (DA/EG) interface. This affects the stability and the average droplet size of emulsions and conditions of the available interfacial surface area for reaction. The maximum DA-EG productivity is observed for A200 super-SiNPs with a pore volume of 0.39 cm3·g-1 with an interfacial coverage by particles lower than 1 (i.e., submonolayer). Using dissipative particle dynamics and all-atom grand canonical Monte Carlo simulations, we unveil a stabilizing role of the pore volume of porous silica superparticles for generating emulsions and local micromixing of immiscible dodecanal and ethylene glycol, allowing fast and efficient solvent-free acetalization in the presence of Pickering emulsions. The micromixing level is interrelated to the adsorption energy of self-assembled particles at the DA/EG interface.

Unraveling Flow Effect on Capacitive Energy Extraction from Salinity Gradients.

The harvesting of salinity gradient energy through a capacitive double-layer expansion (CDLE) technique is directly associated with ion adsorption and desorption in electrodes. Herein, we show that energy extraction can be modulated by regulating ion adsorption/desorption through water flow. The flow effects on the output energy, capacitance, and energy density under practical conditions are systematically investigated from a theoretical perspective, upon which the optimal operating condition is identified for energy extraction. We demonstrate that the net charge accumulation displays a negative correlation with the water flow velocity and so does the surface charge density, and this causes a nontrivial variation in the magnitude of output energy when water flows are introduced. When high water flows are introduced in both the charging and discharging processes, the energy extraction can be significantly reduced by 47.69-49.32%. However, when a high flow is solely exerted in the discharging process, the energy extraction can be enhanced by 12.94-14.49% even at low operation voltages. This study not only offers a comprehensive understanding of the microscopic mechanisms of surface-engineered energy extraction with water flows but also provides a novel direction for energy extraction enhancement.

Efficient Fabrication of Self-Assembled Polylactic Acid Colloidosomes for Pesticide Encapsulation.

Colloidosomes are microcapsules whose shells are composed of cumulated or fused colloidal particles. When colloidosomes are used for in situ encapsulation, it is still a challenge to achieve a high encapsulation efficiency and controllable release by an effective fabrication method. Herein, we present a highly efficient route for the large-scale preparation of colloidosomes. The biodegradable polylactic acid (PLA) nanoparticles (NPs) as shell materials can be synthesized using an antisolvent precipitation method, and the possible formation mechanism was given through the molecular dynamics (MD) simulation. The theoretical values are basically consistent with the experimental results. Through the use of the modified and unmodified PLA NPs, the colloidosomes with controllable shell porosities can be easily constructed using spray drying technology. We also investigate the mechanism of colloidosomes successfully self-assembled by PLA NPs with various factors of inlet temperature, feed rate, and flow rates of compressed air. Furthermore, avermectin (AVM) was used as a model for in situ encapsulation and a controllable release. The spherical modified colloidosomes encapsulating AVM not only achieve a small mean diameter of 1.57 µm but also realize a high encapsulation efficiency of 89.7% and impermeability, which can be further verified by the MD simulation. AVM molecules gather around and clog the shell pores during the evaporation of water molecules. More importantly, the PLA colloidosomes also reveal excellent UV-shielding properties, which can protect AVM from photodegradation.

BaSO4-Epoxy Resin Composite Film for Efficient Daytime Radiative Cooling.

Conventional cooling methods are based on active cooling technology by air conditioning, which consumes a large amount of energy and emits greenhouse gases. Radiative cooling is a novel promising passive cooling technology that uses external space as the cooling source and requires no additional energy consumption. Herein, we propose an approach to prepare highly dispersed BaSO4 nanoparticles (NPs) using a direct precipitation method combined with the in situ surface modification technology. The as-prepared PVP-modified BaSO4 NPs with an average size of 20 nm can be stably dispersed in ethanol for more than 6 months and then were used as building blocks to prepare spherical BaSO4 clusters with an average size of 0.9 µm using a scalable spray drying technique. The BaSO4 NPs/clusters (mass ratio 1:1) were used for preparing radiative cooling epoxy resin film, showing a high solar reflectance of 71% and a high sky window emissivity of 0.94. More importantly, this composite film displays superior radiative cooling performance, which can reduce the ambient temperature by 13.5 °C for the indoor test and 7 °C for the outdoor test. Compared with the commercial BaSO4 filled film, our BaSO4-epoxy resin composite film offers advantages not only in radiative cooling but also in mechanical properties with a 16.6% increase of tensile strength and 40.1% increase of elongation at break, demonstrating its great application potential in the field of building air conditioning.

Origin of Solvent Dependency of the Potential of Zero Charge.

Fundamental properties of the Au(111)-KPF6 interface, particularly the potential of zero charge (PZC), exhibit pronounced variations among solvents, yet the origin remains largely elusive. In this study, we aim to link the solvent dependency to the microscopic phenomenon of electron spillover occurring at the metal-solution interface in heterogeneous dielectric media. Addressing the challenge of describing the solvent-modulated electron spillover under constant potential conditions, we adopt a semiclassical functional approach and parametrize it with first-principles calculations and experimental data. We unveil that the key variable governing this phenomenon is the local permittivity within the region approximately 2.5 Å above the metal edge. A higher local permittivity facilitates the electron spillover that tends to increase the PZC on the one hand and enhances the screening of the electronic charge that tends to decrease the PZC on the other. These dual effect lead to a nonmonotonic relationship between the PZC and the local permittivity. Moreover, our findings reveal that the electron spillover induces a capacitance peak at electrode potentials that are more negative than the PZC in concentrated solutions. This observation contrasts classical models predicting the peak to occur precisely at the PZC. To elucidate the contribution of electron spillover to the total capacitance, we decompose the total capacitance into a quantum capacitance of the metal Cq, a classical capacitance of electrolyte solution Cc, and a capacitance Cqc accounting for electron-ion correlations. Our calculations reveal that Cqc is negative due to the promoted electron spillover at more negative potentials. Our work not only reveals the importance of local permittivity in tuning the electron spillover but also presents a viable theoretical approach to study solvent effects on electrochemical interfaces under operating conditions.

Facile Preparation of a Low-Cost Liquid Interlayer Material with Intelligent UV-NIR-Shielding Function for Smart Windows.

High-performance interlayer materials have garnered considerable interest owing to their low manufacturing costs and applicability in smart windows. In this study, a novel smart-window interlayer material capable of selective shielding against both near-infrared (NIR) and ultraviolet (UV) radiation is developed based on the light transmittance control mechanism. An excellent thermoresponsive liquid, denoted as CDs@TRL (viz., carbon quantum dots at thermal-responsive liquid), is synthesized by compositing biomass-based fluorescent carbon quantum dots (CDs) and poly(N-isopropylacrylamide) (pNIPAM) at natural ambient temperature and in an aqueous phase. Due to the characteristics of CDs and synergistic effect of hydrogen bonds, CDs@TRL exhibits a high specific heat capacity (4.41 kJ kg-1 K-1), large thermal storage capacity (264.6 kJ kg-1), and better UV-NIR-blocking properties, compared to pure pNIPAM, as well as improves the sensitivity of thermal response. When injected into a window as a liquid interlayer, CDs@TRL can intelligently adjust the light transmittance according to ambient light intensity to achieve an intelligent response. The shielding rate of a 10 mm-thick CDs@TRL composite liquid against UV radiation (200-400 nm) was more than 95% in an overcast environment with insufficient light and close to 100% in a well-lighted environment. In addition, CDs@TRL is a cost-effective material that can be prepared from a wide range of raw material sources using a simple preparation process and exhibits excellent mobility and recyclability. Because of these features, it is considered to be a promising candidate for developing energy-saving and climate-adapted smart windows.

Synergistic Effect of Salt and Anionic Surfactants on Interfacial Tension Reduction: Insights from Molecular Dynamics Simulations.

Surfactants are commonly utilized in chemical flooding processes alongside salt to effectively decrease interfacial tension (IFT). However, the underlying microscopic mechanism for the synergistic effect of salt and surfactants on oil displacement remains ambiguous. Herein, the structure and properties of the interface between water and n-dodecane are studied by means of molecular dynamics simulations, considering three types of anionic surfactants and two types of salts. As the salt concentration (ρsalt) increases, the IFT first decreases to a minimum value, followed by a subsequent increase to higher values. The salt ions reduce the IFT only at low ρsalt due to the salt screening effect and ion bridging effect, both of which contribute to a decrease in the nearest head-to-head distance of surfactants. By incorporating salt doping, the IFTs can be reduced by at most 5%. Notably, the IFTs of different surfactants are mainly determined by the hydrogen bond interactions between oxygen atoms in the headgroup and water molecules. The presence of a greater number of oxygen atoms corresponds to lower IFT values. Specifically, for alkyl ethoxylate sulfate, the ethoxy groups play a crucial role in reducing the IFTs. This study provides valuable insights into formulating anionic surfactants that are applicable to oil recovery processes in petroleum reservoirs using saline water.

Pd-Sn Alloy Catalysts for Direct Synthesis of Hydrogen Peroxide from H2 and O2 in a Microchannel Reactor.

Direct synthesis of hydrogen peroxide (DSHP) from H2 and O2 offers a promising alternative to the present commercial anthraquinone method, but it still faces the challenges of low H2O2 productivity, low stability of catalysts, and high risk of explosion. Herein, by loading in a microchannel reactor, the as-synthesized Pd-Sn alloy materials exhibit high catalytic activity for H2O2 production, presenting a H2O2 productivity of 3124 g kgPd-1 h-1. The doped Sn atoms on the surface of Pd not only facilitate the release of H2O2 but also effectively slow down the deactivation of catalysts. Theoretical calculations demonstrate that the Pd-Sn alloy surface has the property of antihydrogen poisoning, showing higher activity and stability than pure Pd catalysts. The deactivation mechanism of the catalyst was elucidated, and the online reactivation method was developed. In addition, we show that the long-life Pd-Sn alloy catalyst can be achieved by supplying an intermittent flow of hydrogen gas. This work provides guidance on how to prepare high performance and stable Pd-Sn alloy catalysts for the continuous and direct synthesis of H2O2.

Efficient electrosynthesis of formamide from carbon monoxide and nitrite on a Ru-dispersed Cu nanocluster catalyst.

Conversion into high-value-added organic nitrogen compounds through electrochemical C-N coupling reactions under ambient conditions is regarded as a sustainable development strategy to achieve carbon neutrality and high-value utilization of harmful substances. Herein, we report an electrochemical process for selective synthesis of high-valued formamide from carbon monoxide and nitrite with a Ru1Cu single-atom alloy under ambient conditions, which achieves a high formamide selectivity with Faradaic efficiency of 45.65 ± 0.76% at -0.5 V vs. RHE. In situ X-ray absorption spectroscopy, coupled with in situ Raman spectroscopy and density functional theory calculations results reveal that the adjacent Ru-Cu dual active sites can spontaneously couple *CO and *NH2 intermediates to realize a critical C-N coupling reaction, enabling high-performance electrosynthesis of formamide. This work offers insight into the high-value formamide electrocatalysis through coupling CO and NO2- under ambient conditions, paving the way for the synthesis of more-sustainable and high-value chemical products.

Sb2S3-templated synthesis of sulfur-doped Sb-N-C with hierarchical architecture and high metal loading for H2O2 electrosynthesis.

Selective two-electron (2e-) oxygen reduction reaction (ORR) offers great opportunities for hydrogen peroxide (H2O2) electrosynthesis and its widespread employment depends on identifying cost-effective catalysts with high activity and selectivity. Main-group metal and nitrogen coordinated carbons (M-N-Cs) are promising but remain largely underexplored due to the low metal-atom density and the lack of understanding in the structure-property correlation. Here, we report using a nanoarchitectured Sb2S3 template to synthesize high-density (10.32 wt%) antimony (Sb) single atoms on nitrogen- and sulfur-codoped carbon nanofibers (Sb-NSCF), which exhibits both high selectivity (97.2%) and mass activity (114.9 A g-1 at 0.65 V) toward the 2e- ORR in alkaline electrolyte. Further, when evaluated with a practical flow cell, Sb-NSCF shows a high production rate of 7.46 mol gcatalyst-1 h-1 with negligible loss in activity and selectivity in a 75-h continuous electrolysis. Density functional theory calculations demonstrate that the coordination configuration and the S dopants synergistically contribute to the enhanced 2e- ORR activity and selectivity of the Sb-N4 moieties.

Reactivities of silane coupling agents in the silica/rubber composites: Theoretical insights into the relationships between energy barriers and electronic characteristics.

Si69 and Si75, typical commodities of silane coupling agents, are often employed in tire recipes to work as the bridges connecting silica and polymers, with which rolling resistance and wet traction are enhanced without loss in abrasion resistance. In this article, the reactivities of Si69 and Si75 with silica and various rubbers were theoretically investigated by using density functional theory (DFT). When the agents were coupled with silica, not only the acid+water condition but also the pure acid condition was confirmed to readily trigger the condensation reactions. The corresponding Gibbs free energy barriers were related to the charge distributions of reaction regions. As the agents suffered from the homolysis of central SS bonds, the generated single-S-tailer radicals (RS·) showed significantly higher reactivities of both the radical addition and the α-H transfer reactions with rubbers, due to the stronger radical philicities of the terminal sulfur radicals with larger condensed local softnesses [s0 (S)]. When the agents underwent the heterolysis of central SS bonds, the terminal sulfur anions with smaller s- (S) indices, however, facilitated the nucleophilic addition reactions with rubbers. Several derivative indices based on the condensed local softnesses were also proposed here to shed light on the reactivities from the viewpoint of the relationship between energy barriers and electronic characteristics. The above findings pave the way for the design of new kinds of silane coupling agents using computer-aided techniques, and meanwhile, provide references for the practical application of Si69 and Si75 to the silica/rubbers systems.

An intelligent cooling material modified with carbon dots for evaporative cooling and UV absorption.

The emergence of cooling technology has brought about huge social benefits to society, but it is also accompanied by the serious problem of energy consumption. In countries close to the equator, intense solar radiation is accompanied by unbearable high temperatures and strong ultraviolet radiation. Therefore, we prepared a simple hydrogel with good evaporative cooling, which can work continuously and has good UV absorption, to solve the indoor cooling and UV radiation problems. Polyacrylamide (PAM) in the hydrogel provides a mechanically strong backbone, and polyethylene glycol (PEG) slows water loss and provides the hydrogel with the ability to reflect infrared light. Lithium bromide (LiBr) is a highly efficient water vapor absorbent, which can provide the hydrogel with water regeneration capability. Carbon dots (CDs) can provide excellent UV absorption for hydrogels, and CDs (4.28 kJ kg-1 K-1) have a higher specific heat capacity than water (4.20 kJ kg-1 K-1), which can store more heat for a better indoor cooling effect. The composite hydrogel has a good prospect of application in the windows of residential and high-rise buildings.

Effect of molecular structure and ionization state on aggregation of carboxymethyl chitosan: A molecular dynamics study.

The aggregation behavior of carboxymethyl chitosan (CMCS) plays an important role in its extensive applications. Here, we perform molecular dynamics simulations to investigate aggregation behaviors of CMCS in water and the effects of degrees of deacetylation (DD) and substitution (DS) and ionization states (equivalently different pH conditions). CMCS prefers to aggregate in neutral condition, self-assembling into multimeric forms with interlaced stacking of molecular chains, while forming dimer or trimer through twisted stacking and parallel stacking in acidic and alkaline conditions, respectively. With the increase of DD and DS, the aggregation becomes weaker when in neutral and alkaline conditions, while gets stronger in acidic environment. The presence of intramolecular hydrogen bonds and exo-anomeric effect causes twisted, coplanar and extended conformations of individual chain in acidic, alkaline and neutral conditions, respectively, contributing to their distinct inter-chain stacking structures. Subsequently, the specific intermolecular hydrogen bonding, hydrophobic and electrostatic interactions stabilize the aggregation structures.

Scalable-doped Nanoporous 1T″ ReSe2 via a General Surface Co-Alloy Strategy.

Reliable and controllable doping of 2D transition metal dichalcogenides is an efficient approach to tailor their physicochemical properties and expand their functional applications. However, precise control over dopant distribution and scalability of the process remains a challenge. Here, we report a general method to achieve scalable in situ doping of centimeter-sized bicontinuous nanoporous ReSe2 films with transition metal atoms via surface coalloy growth. The distinct strains induced by the bending curvature of nanoporous structures and uniform dopants result in a local 1T' to 1T″ structure phase transition over nanoporous ReSe2 films. The as-prepared nanoporous Ru-ReSe2 with high 1T″ phase exhibits preferable electrochemical activity in hydrogen evolution reaction. The work demonstrates a unique and general approach to synthesize uniformly-doped transition metal dichalcogenides with 3D bicontinuous nanoporous structure, which can be scaled up to batch production for various applications.

Generation of liquid metal double emulsion droplets using gravity-induced microfluidics.

Several microfluidic applications are available for liquid metal droplet generation, but the surface oxidation of liquid metal has placed limitations on its application. Multiphase microfluidics makes it possible to protect the inner droplets by producing the structure of double emulsion droplets. Thus, the generation of liquid metal double emulsion droplets has been developed to prevent the surface oxidation of Galinstan. However, the generation using common methods faces considerable challenges due to the gravity effect introduced from the high density of liquid metal, making it difficult for the shell phase to wrap the inner phase. To overcome this obstacle, we introduce an innovative method - a gravity-induced microfluidic device - to creatively generate controllable liquid metal double emulsion droplets, achieved by altering the measurable inclination angle of the plane. It is found that when the inclination angle ranges from 30° to 45°, the device manages to generate liquid metal double emulsion droplets with perfect double sphere-type configuration. Additionally, the core-shell liquid metal hydrogel capsules present potential applications as multifunctional materials for controlled release systems in drug delivery and biomedical applications. By regulating pH or imposing mechanical force, the hydrogel shell can be dissolved to recover the electrical conductivity of Galinstan for applications in flexible electronics, self-healing conductors, elastomer electronic skin, and tumor therapy.

Engineering the Morphology and Microenvironment of a Graphene-Supported Co-N-C Single-Atom Electrocatalyst for Enhanced Hydrogen Evolution.

Graphene-supported single-atom catalysts (SACs) are promising alternatives to precious metals for catalyzing the technologically important hydrogen evolution reaction (HER), but their performances are limited by the low intrinsic activity and insufficient mass transport. Herein, a highly HER-active graphene-supported Co-N-C SAC is reported with unique design features in the morphology of the substrate and the microenvironment of the single metal sites: i) the crumpled and scrolled morphology of the graphene substrate circumvents the issues encountered by stacked nanoplatelets, resulting in improved exposure of the electrode/electrolyte interfaces (≈10 times enhancement); ii) the in-plane holes in graphene preferentially orientate the Co atoms at the edge sites with low-coordinated Co-N3 configuration that exhibits enhanced intrinsic activity (≈2.6 times enhancement compared to the conventional Co-N4 moiety), as evidenced by detailed experiments and density functional theory calculations. As a result, this catalyst exhibits significantly improved HER activity with an overpotential (η) of merely 82 mV at 10 mA cm-2 , a small Tafel slope of 59.0 mV dec-1 and a turnover frequency of 0.81 s-1 at η = 100 mV, ranking it among the best Co-N-C SACs.