Facile Construction of CuFe-Based Metal Phosphides for Synergistic NOx -Reduction to NH3 and Zn-Nitrite Batteries in Electrochemical Cell.

The electrocatalytic nitrite/nitrate reduction reaction (eNO2RR/eNO3RR) offer a promising route for green ammonia production. The development of low cost, highly selective and long-lasting electrocatalysts for eNO2RR/eNO3RR is challenging. Herein, a method is presented for constructing Cu3P-Fe2P heterostructures on iron foam (CuFe-P/IF) that facilitates the effective conversion of NO2 - and NO3 - to NH3. At -0.1 and -0.2 V versus RHE (reversible hydrogen electrode), CuFe-P/IF achieves a Faradaic efficiency (FE) for NH3 production of 98.36% for eNO2RR and 72% for eNO3RR, while also demonstrating considerable stability across numerous cycles. The superior performance of CuFe-P/IF catalyst is due tothe rich Cu3P-Fe2P heterstuctures. Density functional theory calculations have shed light on the distinct roles that Cu3P and Fe2P play at different stages of the eNO2RR/eNO3RR processes. Fe2P is notably active in the early stages, engaging in the capture of NO2 -/NO3 -, O─H formation, and N─OH scission. Conversely, Cu3P becomes more dominant in the subsequent steps, which involve the formation of N─H bonds, elimination of OH* species, and desorption of the final products. Finally, a primary Zn-NO2 - battery is assembled using CuFe-P/IF as the cathode catalyst, which exhibits a power density of 4.34 mW cm-2 and an impressive NH3 FE of 96.59%.

Thermal Conductivity of the Graphene/Polydimethylsiloxane Composite by Manipulating the Network Structure.

In this work, a nonequilibrium molecular dynamics simulation is utilized to explore the effect of network structure of graphene (GE) on the thermal conductivity of the GE/polydimethylsiloxane (PDMS) composite. First, the thermal conductivity of composites rises with increasing volume fraction of GE. The heat transfer ability via the GE channel is found to be nearly the same by analyzing the GE-GE interfacial thermal resistance (ITR). More heat energy is transferred via the GE channel at the high volume fraction of GE by calculating the GE heat transfer ratio, which leads to the high thermal conductivity. Then, the thermal conductivity of composites rises with increasing stacking area between GE, which is attributed to both the strong heat transfer ability via the GE channel and the high GE heat transfer ratio. Following it, the thermal conductivity of composites first rises and then drops down with increasing defect density for a single vacancy defect while it continuously increases for a single void defect. The heat transfer ability between GE is enhanced due to the formation of interlayer covalent bonds. However, the intrinsic thermal conductivity of GE is significantly reduced for a single vacancy defect while it remains relatively well for a single void defect. As a result, the GE heat transfer ratio is maximum at the intermediate defect density for a single vacancy defect while it rises monotonically for a single void defect, which can rationalize the thermal conductivity. Meanwhile, the relationship between ITR and the number of covalent bonds can be described by an empirical equation. Finally, the thermal conductivity for the stacked structure is larger than that for the noncontact structure or the intersected structure. In summary, this work provides a clear and novel understanding of how the network structure of GE influences the thermal conductivity of the GE/PDMS composite.

Investigating the Effect of Chain Extender on the Phase Separation and Mechanical Properties of Polybutadiene-Based Polyurethane.

The thermodynamic incompatibility between the soft and hard segments of thermoplastic polyurethane (TPU) results in a microphase-separated behavior and excellent mechanical properties. However, the effect of the chain extender on the degree of microphase separation (DMS) and the resultant mechanical properties of TPU have not been well studied because of the complex interactions between the soft and hard segments. Herein, hydroxyl-terminated polybutadiene-based TPUs(HTPB-TPUs) without hydrogen bonding between the soft and hard segments are synthesized using hydroxyl-terminated polybutadiene, toluene diisocyanate, and four different chain extenders, and the effect of the chain extender structure on DMS is analyzed experimentally using a combination of analytical techniques. Furthermore, the solubility parameters of the soft and hard segments, glass transition temperatures, and hydrogen-bond density of the HTPB-TPUs, are computed using all-atom molecular dynamics simulations. The results clearly reveal that the chain extender significantly affects the DMS and thus the mechanical properties of HTPB-TPUs. This study paves the way for studying the relationship between the structure and properties of TPU.

Flavonoid as a Potent Antioxidant: Quantitative Structure-Activity Relationship Analysis, Mechanism Study, and Molecular Design by Synergizing Molecular Simulation and Machine Learning.

In this work, a quantitative structure-antioxidant activity relationship of flavonoids was performed using a machine learning (ML) method. To achieve lipid-soluble, highly antioxidant flavonoids, 398 molecular structures with various substitute groups were designed based on the flavonoid skeleton. The hydrogen dissociation energies (ΔG1, ΔG2, and ΔG3) related to multiple hydrogen atom transfer processes and the solubility parameter (δ) of flavonoids were calculated using molecular simulation. The group decomposition results and the calculated antioxidant parameters constituted the ML data set. The artificial neural network and random forest models were constructed to predict and analyze the contribution of the substitute groups and positions to the antioxidant activity. The results showed the hydroxyl group at positions B4', B5', and B6' and the branched alkyl group at position C3 in the flavonoid skeleton were the optimal choice for improving antioxidant activity and compatibility with apolar organic materials. Compared to the pyrogallol group-grafted flavonoid, the designed potent flavonoid decreased ΔG1 and δ by 2.2 and 15.1%, respectively, while ΔG2 and ΔG3 kept the favorable lower values. These findings suggest that an efficient flavonoid prefers multiple ortho-phenolic hydroxyl groups and suitable sites with hydrophobic groups. The combination of molecular simulation and the ML method may offer a new research approach for the molecular design of novel antioxidants.

Screening of Organic Small Molecule Excipients on Ternary Solid Dispersions Based on Miscibility and Hydrogen Bonding Analysis: Experiments and Molecular Simulation.

The preparation of solid dispersions by mixing insoluble drugs with polymers is the main way to improve the aqueous solubility of drugs. The introduction of organic small molecule excipients into binary solid dispersions is expected to further enhance drug solubility by regulating intermolecular hydrogen bonding within the system at the microscopic level. In this study, we used carbamazepine (CBZ) as the target drug and polyvinylpyrrolidone as the solid dispersion matrix and screened the third component from 13 organic small molecules with good miscibility in the solid dispersion based on the principle of similarity of solubility parameters. The hydrogen bonding parameters and dissociation Gibbs free energy of the 13 organic small molecule-CBZ dimer were calculated by quantum mechanical simulation, and the tryptophan (Try) was identified as the optimal third component of organic small molecule. The migration of CBZ in binary and ternary systems was also analyzed by molecular dynamics simulation. On this theoretical basis, the corresponding solid dispersions were prepared, characterized, and tested for solubility analysis, which verified that the drug solubility was stronger for the system with the addition of polar fractions and the Try was indeed the best third component of organic small molecule compound, which was consistent with the simulation predictions. This screening method may provide theoretical guidance for drug modification design and clinical studies.

Manipulating the Thermal Conductivity of the Graphene/Poly(vinyl alcohol) Composite via Surface Functionalization: A Multiscale Simulation.

The reverse non-equilibrium molecular dynamics simulation is used to investigate the influence of functional groups (FGs) on the thermal conductivity of a graphene/poly(vinyl alcohol) (PVA) composite, which considers non-polar (methyl) and polar (hydroxyl, amino, and carboxyl) groups. First, the polar groups can be more effective to improve the interfacial thermal conductivity than the non-polar group. This can be explained well by characterizing the interfacial Coulombic energy, number and lifetime of hydrogen bonds, vibrational density of states, and integrated autocorrelation of the interfacial heat power. Moreover, the hydroxyl group can improve the interfacial thermal conductivity more than the other groups, which can be rationalized by analyzing the surface roughness of graphene and the radial distribution function of FGs and the PVA chains. However, the introduction of FGs destroys the graphene structure, which consequently reduces the intrinsic thermal conductivity. Furthermore, by adopting the effective medium approximation model and finite element method, there exists a critical graphene length where the overall thermal conductivities are equal for the functionalized and pristine graphene. Finally, the distribution state of graphene is emphasized to be more vital in determining the overall thermal conductivity than the generally accepted interfacial thermal conductivity.

Effect of Cross-Linking Density on Non-Linear Viscoelasticity of Vulcanized SBR: A MD Simulation and Experimental Study.

In recent years, there has been a growing interest in changes in dynamic mechanical properties of mixed rubber during dynamic shear, yet the influence of vulcanized characteristics on the dynamic shear behavior of vulcanized rubber, particularly the effect of cross-linking density, has received little attention. This study focuses on styrene-butadiene rubber (SBR) and aims to investigate the impact of different cross-linking densities (Dc) on dynamic shear behavior using molecular dynamics (MD) simulations. The results reveal a remarkable Payne effect, where the storage modulus experiences a significant drop when the strain amplitude (γ0) exceeds 0.1, which can be attributed to the fracture of the polymer bond and the decrease in the molecular chain's flexibility. The influence of various Dc values mainly resides at the level of molecular aggregation in the system, where higher Dc values impede molecular chain motion and lead to an increase in the storage modulus of SBR. The MD simulation results are verified through comparisons with existing literature.

Fabrication of Polyurethane Elastomer/Hindered Phenol Composites with Tunable Damping Property.

Vibration and noise-reduction materials are indispensable in various fields. Polyurethane (PU)-based damping materials can dissipate the external mechanical and acoustic energy through molecular chain movements to mitigate the adverse effects of vibrations and noise. In this study, PU-based damping composites were obtained by compositing PU rubber prepared using 3-methyltetrahydrofuran/tetrahydrofuran copolyether glycol, 4,4'-diphenylmethane diisocyanate, and trimethylolpropane monoallyl ether as raw materials with hindered phenol, viz., and 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)proponyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5.5]undecane (AO-80). Fourier transform infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry, dynamic mechanical analysis, and tensile tests were conducted to evaluate the properties of the resulting composites. The glass transition temperature of the composite increased from -40 to -23 °C, and the tan δMax of the PU rubber increased by 81%, from 0.86 to 1.56 when 30 phr of AO-80 was added. This study provides a new platform for the design and preparation of damping materials for industrial applications and daily life.

Polyurethanes Based on Polylactic Acid for 3D Printing and Shape-Memory Applications.

Polylactic acid (PLA) has received increased attention in the development of shape-memory polymers and biomedical materials owing to its excellent physical properties and good biocompatibility and biodegradability. However, the inherent brittleness and high shape-recovery temperature of this material limit its application in the human body. Herein, we fabricated a PLA-based thermoplastic polyurethane (PLA-TPU) prepared from modified PLA-diol, dicyclohexylmethane-4,4'-diisocyanate, and 1,4-butanediol to solve the limitations of pure PLA. The glass transition temperature (Tg) of the designed TPU can be tailored from 6 to 40.5 °C by adjusting the content of hard segments or molecular weight of soft segments. The shape of the designed TPU can be fixed at room temperature and recovered at temperatures above 37 °C. Moreover, the prepared PLA-TPUs exhibited recyclability, three-dimensional printing capability, non-cytotoxicity, blood compatibility, and biodegradability. The shape of PLA-TPU/nano-Fe3O4 composites can be recovered by exposure to near-infrared light. These results collectively indicate that PLA-TPUs and their composites may have potential applications as intelligent flexible medical scaffolds for surgical and medical implantation equipment.

Correction: Effect of the content and strength of hard segment on the viscoelasticity of the polyurethane elastomer: insights from molecular dynamics simulation.

Correction for 'Effect of the content and strength of hard segment on the viscoelasticity of the polyurethane elastomer: insights from molecular dynamics simulation' by Yimin Wang et al., Soft Matter, 2022, 18, 4090-4101, https://doi.org/10.1039/D2SM00463A.

Effect of the content and strength of hard segment on the viscoelasticity of the polyurethane elastomer: insights from molecular dynamics simulation.

Due to the wide application, it is very crucial to understand the viscoelasticity of the polyurethane elastomer (PU, denoted by soft-hard block copolymer), which contains the soft segments (SS) and hard segments (HS). Thus, in this work, the effect of the content and strength of HS on the viscoelasticity of PU is explored in detail by adopting a coarse-grained model. First, the phase morphology of PU is characterized where both the single continuous phase and the bicontinuous phase are observed by varying the content of HS. Then, the viscoelasticity of PU is calculated by analyzing the storage modulus, the loss modulus, and the loss factor, which depends on the content and strength of HS. To further elucidate the mechanism for the storage modulus, the normalized interaction energy, the order parameter, and the formation probability of the HS or SS phase are characterized with the shear strain amplitude, which reflects the deformation of the phase structure. Then, the energy dissipation is quantified, which can rationalize the loss modulus well. A parameter is introduced, which considers the relative slippage and the content of HS or SS. It can explain the change in the loss factor with the content and strength of HS. In summary, this work can help to further understand how the content and strength of hard segments affect the viscoelasticity of the soft-hard block PU and structure evolution at the molecular level.

Controllable Design and Preparation of Hydroxyl-Terminated Solution-Polymerized Styrene Butadiene for Polyurethane Elastomers with High-Damping Properties.

Vibration and noise are ubiquitous in social life, which severely damage machinery and adversely affect human health. Thus, the development of materials with high-damping performance is of great importance. Rubbers are typically used as damping materials because of their unique viscoelasticity. However, they do not satisfy the requirements of different applications with various working conditions. In this study, the advantages of the high loss factor of styrene butadiene rubber (SBR) are combined with the strong designability of polyurethane. Hydroxyl-terminated solution-polymerized styrene butadiene rubbers (HTSSBRs) with different structures are prepared using anionic polymerization. HTSSBRs are then used as the soft segment during the synthesis of temperature-tunable high-damping performance polyurethanes (HTSSBR-polyurethanes (PUs)). The prepared HTSSBR-PUs with different structures exhibit excellent loss performance, a maximum loss factor (tan δmax ) of above 1.60, and an effective damping performance over a wide temperature range compared to traditional SBR and polyurethane. Therefore, this work offers an effective method for the design of damping materials with adjustable properties.

Bio-Based, Recyclable and Self-Healing Polyurethane Composites with High Energy Dissipation and Shape Memory.

Rubber composites make an important contribution to eliminating vibration and noise owing to their unique viscoelasticity. However, it is important to find alternative bio-based products with high damping properties owing to the shortage of petrochemical resources and poor performance. The ability to self-heal is an additional characteristic that is highly desirable because it can further increase the service life and safety of such products. In this study, a bio-based polylactic acid thermoplastic polyurethane (PLA-TPU) and its composites (PLA-TPU/AO-80) are synthesized. The reversible sacrificial hydrogen bonds in the composites increase the peak value of the loss factor (tan δmax ) from 0.87 to 2.12 with a high energy dissipation efficiency of 99% at 50% strain. After being heated for 15 min, the healed sample recovers 81.98% of its comprehensive mechanical properties due to the reorganization of the hydrogen bonds. Its tensile strength remains at 93.4% after recycling five times. Moreover, its shape memory properties show a response temperature close to the human body temperature making it an ideal candidate for medical applications.

Optimizing the fracture toughness of a dual cross-linked hydrogel via molecular dynamics simulation.

In this work, a coarse-grained model is adopted to explore the fracture toughness of a dual cross-linked hydrogel which consists of a physically cross-linked network and a chemically cross-linked network. By calculating the fracture energy, the optimized fracture toughness of the hydrogel appears at the intermediate content of the chemical network. To understand it, the structure change of both the chemical network and the physical network is first characterized during the tensile process. For the chemical network, the fraction and rate of broken bonds gradually improve with increasing content of the chemical network while the strain range where the bond breakage occurs is reduced. For the physical network, the number of clusters and the interaction energy first increase and then decrease with increasing strain. This reflects the breakage and reformation of the physical network, which dissipates more energy and improves the fracture energy. Furthermore, by stress decomposition, the stress is mainly borne by the physical network at small strain and the chemical network at large strain, which proves their synergistic effect in enhancing the hydrogel. Then, the number of voids is calculated as a function of strain. It is found that the voids initiate in the weak region at small strain while in the position of the bond breakage at large strain. Moreover, the number of voids decreases with increasing content of the chemical network at small strain. Finally, the effect of the strength of the chemical network or the physical network on the fracture toughness is discussed. The optimized fracture toughness of hydrogel appears at the intermediate strength.

Degradation characteristics of crude oil by a consortium of bacteria in the existence of chlorophenol.

In order to enhance the degradation effect of microorganisms on crude oil in the existence of chlorophenol compounds, oil-degrading bacteria C4 (Alcaligenes faecails), C5 (Bacillus sp.) and 2,4-dichlorophenol (2,4-DCP) degrading bacteria L3 (Bacillus marisflavi), L4 (Bacillus aquimaris) were isolated to construct a highly efficient consortium named (C4C5 + L3L4). When the compound bacteria agent combination by VC4: VC5: VL3: VL4 = 1:2:2:1, the crude oil degradation efficiency of 7 days was stable at 50.63% ~ 55.43% under different conditions. Degradation mechanism was analyzed by FTIR, GC-MS and IC technology and the following conclusions showed that in the system of adding consortium (C4C5 + L3L4), the heavy components were converted into saturated and unsaturated components. The bacterial consortium could first degrade medium and long chain alkanes into short chain hydrocarbons and then further degrade. And the dechlorination efficiency of 2,4-DCP in the degradation system reached 73.83%. The results suggested that the potential applicability and effectiveness of the selected bacteria consortium for the remediation of oil-contaminated water or soil with the existence of chlorophenol compound.

Finite Element Solution for Dynamic Mechanical Parameter Influence on Underwater Sound Absorption of Polyurethane-Based Composite.

Underwater noise pollution, mainly emitted by shipping and ocean infrastructure development of human activities, has produced severe environmental impacts on marine species and seabed habitats. In recent years, a polyurethane-based (PU-based) composite with excellent damping performance has been increasingly utilized as underwater sound absorption material by attaching it to equipment surfaces. As one of the key parameters of damping materials, dynamic mechanical parameters are of vital importance to evaluating the viscoelastic damping property and thus influencing the sound absorption performance. Nevertheless, lots of researchers have not checked thoroughly the relationship and the mechanism of the material dynamic mechanical parameters and its sound absorption performance. In this work, a finite element model was fabricated and verified effectively using acoustic pulse tube tests to investigate the aforementioned issues. The influence of the dynamic mechanical parameters on underwater sound absorption performance was systematically studied with the frequency domain to reveal the mechanism and the relationship between damping properties and the sound absorption of the PU-based composite. The results indicate that the internal friction of the molecular segments and the structure stiffness were the two main contributors of the PU-based composite's consumption of sound energy, and the sound absorption peak and the sound absorption coefficient could be clearly changed by adjusting the dynamic mechanical parameters of the composite. This study will provide helpful guidance to develop the fabrication and engineering applications of the PU-based composite with outstanding underwater sound absorption performance.

Bio-Based Polyurethane and Its Composites towards High Damping Properties.

The operation of mechanical equipment inevitably generates vibrations and noise, which are harmful to not only the human body but also to the equipment in use. Damping materials, which can convert mechanical energy into thermal energy, possess excellent damping properties in the glass transition region and can alleviate the problems caused by vibration and noise. However, these materials mainly rely on petroleum-based resources, and their glass transition temperatures (Tg) are lower than room temperature. Therefore, bio-based materials with high damping properties at room temperature must be designed for sustainable development. Herein, we demonstrate the fabrication of bio-based millable polyurethane (BMPU)/hindered phenol composites that could overcome the challenges of sustainable development and exhibit high damping properties at room temperature. BMPUs with a high Tg were prepared from modified poly (lactic acid)-based polyols, the unsaturated chain extender trimethylolpropane diallylether, and 4,4'-diphenylmethane diisocyanate, and 3,9-Bis-{1,1-dimethyl-2[ß-(3-tert-butyl-4-hydroxy-5-methylphenyl-)propionyloxy]ethyl}-2,4,8,10-tetraoxaspiro [5,5]-undecane (AO-80) was added to prepare BMPU/AO-80 composites. Finally, the properties of the BMPUs and BMPU/AO-80 composites were systematically evaluated. After adding 30 phr of AO-80, the Tg and maximum loss factor (tan δmax) of BMPU/AO-80 composites increased from 7.8 °C to 13.5 °C and from 1.4 to 2.0, respectively. The tan δmax showed an improvement of 43%. Compared with other polyurethanes, the prepared BMPU/AO-80 composites exhibited higher damping properties at room temperature. This study proposes a new strategy to reduce society's current dependence on fossil resources and design materials featuring high damping properties from sustainable raw materials.

Influence of Surface Defects on the Thermal Conductivity of Hexagonal Boron Nitride/Poly(dimethylsiloxane) Nanocomposites: A Molecular Dynamics Simulation.

In this simulation, the reverse nonequilibrium molecular dynamics simulation is employed to explore how the surface defects in hexagonal boron nitride (h-BN) influence the thermal conductivity of poly(dimethylsiloxane) (PDMS)-based composites. First, the interfacial thermal conductivity and the intrinsic thermal conductivity of h-BN are obtained by tuning the defect density, the inhomogeneity of the defect distribution, and the number of h-BN layers. The defects enhance the interfacial thermal conductivity, especially for h-BNs with high inhomogeneity of the defect distribution and multilayer. However, the intrinsic thermal conductivity of h-BN is declined significantly by the defects. They can be explained well by the vibrational density of states of PDMS and h-BNs and their overlap. Then, by combining the effective medium approximation model with the simulation, the overall thermal conductivity of composites is obtained. It exhibits a gradual decrease with increasing defect density or reducing the inhomogeneity of the defect distribution. Meanwhile, the enhancement extent of the overall thermal conductivity by improving the concentration and size of h-BNs depends on the defect density and the defect distribution. Finally, the comparison between the simulation and experiment is discussed. In summary, our work provides some valuable insights into how the defect density, the defect distribution, and the number of layers influence the thermal conductivity of the PDMS-based composite.

Correction: Synergistic effect in improving the electrical conductivity in polymer nanocomposites by mixing spherical and rod-shaped fillers.

Correction for 'Synergistic effect in improving the electrical conductivity in polymer nanocomposites by mixing spherical and rod-shaped fillers' by Fan Qu et al., Soft Matter, 2020, 16, 10454-10462, DOI: .

A Multifunctional N-Doped Cu-MOFs (N-Cu-MOF) Nanomaterial-Driven Electrochemical Aptasensor for Sensitive Detection of Deoxynivalenol.

Deoxynivalenol (DON) is one of the most common mycotoxins in grains, causing gastrointestinal inflammation, neurotoxicity, hepatotoxicity and embryotoxicity, even at a low quantity. In this study, a facile electrochemical aptasensor was established for the rapid and sensitive determination of DON based on a multifunctional N-doped Cu-metallic organic framework (N-Cu-MOF) nanomaterial. The N-Cu-MOF, with a large specific surface area and good electrical conductivity, served not only as an optimal electrical signal probe but also as an effective supporting substrate for stabilizing aptamers through the interactions of amino (-NH2) and copper. Under the optimal conditions, the proposed sensor provided a wide linear concentration range of 0.02-20 ng mL-1 (R2 = 0.994), showing high sensitivity, with a lower detection limit of 0.008 ng mL-1, and good selectivity. The sensor's effectiveness was also verified in real spiked wheat samples with satisfactory recoveries of 95.6-105.9%. The current work provides a flexible approach for the rapid and sensitive analysis of highly toxic DON in food samples and may also be easily extended to detect other hazardous substances with alternative target-recognition aptamers.