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The molecular weight of polymers can influence the material properties, but the molecular weight at the experiment level sometimes can be a huge burden for property prediction with full-atomic simulations. The traditional bottom-up coarse grain (CG) simulation can reduce the computation cost. However, the dynamic properties predicted by the CG simulation can deviate from the full-atomic simulation result. Usually, in CG simulations, the diffusion is faster and the viscosity and modulus are much lower. The fast dynamics in CG are usually solved by a posteriori scaling on time, temperature, or potential modifications, which usually have poor transferability to other non-fitted physical properties because of a lack of fundamental physics. In this work, a priori scaling factors were calculated by the loss of degrees of freedom and implemented in the iterative Boltzmann inversion. According to the simulation results on 3 different CG levels at different temperatures and loading rates, such a priori scaling factors can help in reproducing some dynamic properties of polycaprolactone in CG simulation more accurately, such as heat capacity, Young's modulus, and viscosity, while maintaining the accuracy in the structural distribution prediction. The transferability of entropy-enthalpy compensation and a dissipative particle dynamics thermostat is also presented for comparison. The proposed method reveals the huge potential for developing customized CG thermostats and offers a simple way to rebuild multiphysics CG models for polymers with good transferability.

Stable, high-efficiency, and highly active electrocatalysts are critical for the conversion of renewable energy through overall water splitting. Our first-principles calculations identify two-dimensional conjugated metal-organic frameworks (2D c-MOFs) with dual metal sites as promising candidates for this process. Among them, PcCo-O 8 -Rh stands out as the best catalyst, with Rh serving as the active site for both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER), resulting in a low η HER / η OER of -0.19/0.25 V. Our findings suggest that the HER/OER activity of PcTM-O 8 -TM' can be optimized through tensile strain, as it is related to the absorption strength of intermediates and the d-band center ( ε d ) of the TM atom. This study presents a new family of 2D c-MOFs as high-performance bifunctional electrocatalysts for overall water splitting, paving the way towards sustainable energy conversion.

Evaluating the mechanical properties of biodegradable implants can be challenging for in situ experiments and time-consuming for materials with a slow degradation rate, such as polycaprolactone (PCL). In this work, the effects of chain scission and water erosion on the mechanical properties of degraded PCL are investigated by molecular dynamics simulation. The decrease of the mechanical performance is correlated with the increase of the nonaffine displacement during the degradation. The nonaffine squared displacements (NSD) during the tensile deformation are calculated by subtracting the affine squared displacements from the mean squared displacements. After chain scission, short polymer chains increase the NSD of the system and weaken the modulus of the polymer matrix. The effect of the NSD is also observed in a water erosion model. When the bond break ratio is less than 5%, PCL still maintains a well-entangled network, which constrains the diffusion of the water molecules, resulting in a higher modulus of the erosion model than the chain scission model at a low degradation rate. The effect of NSD is also found in the PCL/graphene composites. For the degraded polymer chains, the diffusion of PCL is constrained by the graphene network, and such an effect increases during the degradation. As a result, the addition of graphene nanosheets slows down the decreasing trend of Young's modulus. Such findings can also explain the size effect of the graphene reinforcement on the mechanical properties of the polymer composites. This work provides atomistic insights into the mechanical property evolution during polymer degradation, revealing the possibility of tuning the mechanical performance by controlling the diffusion, which could be beneficial for the design and lifetime prediction of degradable implants.

Catalysts, which can accelerate chemical reactions, show promising potential to alleviate environmental pollution and the energy crisis. However, their wide application is severely limited by their low efficiency and poor selectivity due to the recombination of photogenerated electron-hole pairs, the back-reaction of interactants. Accordingly, ferroelectrics have emerged as promising catalysts to address these issues with the advantages of promoted light adsorption, boosted catalytic efficiency as a result of their intrinsic polarization, suppressed electron-hole pair recombination, and superior selectivity via the ferroelectric switch. This review summarizes the recent research progress of catalytic studies based on ferroelectric materials and highlights the controllability of catalytic activity by the ferroelectric switch. More importantly, we also comprehensively highlight the underlying working mechanism of ferroelectric-controlled catalysis to facilitate a deep understanding of this novel chemical reaction and guide future experiments. Finally, the perspectives of catalysis based on ferroelectrics and possible research opportunities are discussed. This review is expected to inspire wide research interests and push ferroelectric catalysis to practical applications.

Two-dimensional (2D) multiferroics exhibit cross-control capacity between magnetic and electric responses in a reduced spatial domain, making them well suited for next-generation nanoscale devices; however, progress has been slow in developing materials with required characteristic properties. Here we identify by first-principles calculations robust 2D multiferroic behaviors in decorated Fe2O3 monolayers, showcasing Li@Fe2O3 as a prototypical case, where ferroelectricity and ferromagnetism stem from the same origin, namely Fe d-orbital splitting induced by the Jahn-Teller distortion and associated crystal field changes. These findings establish strong material phenomena and elucidate the underlying physics mechanism in a family of truly 2D multiferroics that are highly promising for advanced device applications.

Bridging S22- moieties have been demonstrated to be highly active sites existing in metal polysulfides for the hydrogen evolution reaction (HER), thus the incorporation of high-density bridging S22- into a Ni3S2 material to improve its electrocatalytic HER performance is highly desirable and challenging. Herein, we report a novel Ni3S2 nanorod array decorated with (020)-oriented VS4 nanocrystals grown on nickel foam (Shig-NS-rod/NF) via a simple and facile solvothermal method. Results show that the in situ incorporation of VS4 not only triggers the formation of such a nanorod array structure, but also contributes to the uniform grafting of high-density and high catalytically active bridging S22- sites on the interface between Ni3S2 and VS4 for enhanced HER activity, and also promotes the absorption ability of OH- radicals and thus accelerates the HER Volmer step in alkaline media. As expected, the resultant Shig-NS-rod/NF material exhibits impressive catalytic performance toward the HER, with a much lower overpotential of 137 mV at 10 mA cm-2 and a long-term durability for at least 22 h, and is superior to Ni3S2 nanorod arrays with low-density bridging S22- (Slow-NS-rod/NF) and NS-film/NF counterparts (without VS4), even outperforming the NF-supported 20% Pt/C at a large current density of over 120 mA cm-2. Our findings put forward fresh insight into the rational design of highly efficient electrocatalysts toward the HER for green hydrogen fuel production.

Recent reports of successful synthesis of atomically thin boron films have raised great prospects of discovering novel electronic and transport properties in a new type of 2D materials. Here we show by first-principles calculations that monolayer and bilayer γ-B 28 films are intrinsically metallic while the thicker films possess intriguing electronic states that exhibit moderate to large bandgaps in all the interior layers but are nearly gapless at the surface. Remarkably, these surface electronic states are tunable by strain, allowing the outermost layer to transition between a semimetal and a narrow-gap semiconductor. Moreover, these surface states almost exclusively occupy a wide energy range around the Fermi level, thus dominating the electronic transport in γ-B 28 films. The dispersions of the surface electronic bands are direction sensitive, and with hole injection producing anisotropic and very high carrier mobility up to 104 cm 2 V -1 s -1 . Surprisingly, surface passivation can open a sizable bandgap, which offers an additional avenue for effective band engineering and explains the experimental observation of a large bandgap in the synthesized film. These results make few-layer γ-B 28 films desirable candidate materials for catalysis and electronics applications.

Supercapacitors with porous electrodes of graphene macroscopic assembly are supposed to have high energy storage capacity. However, a great number of "close pores" in porous graphene electrodes are invalid because electrolyte ions cannot infiltrate. A quick method to prepare porous graphene electrodes with reduced "close pores" is essential for higher energy storage. Here we propose a wet-spinning assembly approach based on the liquid crystal behavior of graphene oxide to continuously spin orientational graphene hydrogel films with "open pores", which are used directly as binder-free supercapacitor electrodes. The resulting supercapacitor electrodes show better electrochemical performance than those with disordered graphene sheets. Furthermore, three reduction methods including hydrothermal treatment, hydrazine and hydroiodic acid reduction are used to evaluate the specific capacitances of the graphene hydrogel film. Hydrazine-reduced graphene hydrogel film shows the highest capacitance of 203 F g(-1) at 1 A g(-1) and maintains 67.1% specific capacitance (140 F g(-1)) at 50 A g(-1). The combination of scalable wet-spinning technology and orientational structure makes graphene hydrogel films an ideal electrode material for supercapacitors.

Graphene-bismuth oxide nanotube fiber as electrode material for constituting flexible supercapacitors using a PVA/H3PO4 gel electrolyte is reported with a high specific capacitance (Ca) of 69.3 mF cm(-2) (for a single electrode) and 17.3 mF cm(-2) (for the whole device) at 0.1 mA cm(-2), respectively. Our approach opens the door to metal oxide-graphene hybrid fibers and high-performance flexible electronics.

Developing graphene-based nanoelectronics hinges on opening a band gap in the electronic structure of graphene, which is commonly achieved by breaking the inversion symmetry of the graphene lattice via an electric field (gate bias) or asymmetric doping of graphene layers. Here we introduce a new design strategy that places a bilayer graphene sheet sandwiched between two cladding layers of materials that possess strong spin-orbit coupling (e.g., Bi2Te3). Our ab initio and tight-binding calculations show that a proximity enhanced spin-orbit coupling effect opens a large (44 meV) band gap in bilayer graphene without breaking its lattice symmetry, and the band gap can be effectively tuned by an interlayer stacking pattern and significantly enhanced by interlayer compression. The feasibility of this quantum-well structure is demonstrated by recent experimental realization of high-quality heterojunctions between graphene and Bi2Te3, and this design also conforms to existing fabrication techniques in the semiconductor industry. The proposed quantum-well structure is expected to be especially robust since it does not require an external power supply to open and maintain a band gap, and the cladding layers provide protection against environmental degradation of the graphene layer in its device applications.

Nanomaterials are prone to influence by chemical adsorption because of their large surface to volume ratios. This enables sensitive detection of adsorbed chemical species which, in turn, can tune the properties of the host material. Recent studies discovered that single and multi-layer molybdenum disulfide (MoS2) films are ultra-sensitive to several important environmental molecules. Here we report new findings from ab inito calculations that reveal substantially enhanced adsorption of NO and NH3 on strained monolayer MoS2 with significant impact on the properties of the adsorbates and the MoS2 layer. The magnetic moment of adsorbed NO can be tuned between 0 and 1 μB; strain also induces an electronic phase transition between the half-metal and the metal. Adsorption of NH3 weakens the MoS2 layer considerably, which explains the large discrepancy between the experimentally measured strength and breaking strain of MoS2 films and previous theoretical predictions. On the other hand, adsorption of NO2, CO, and CO2 is insensitive to the strain conditions in the MoS2 layer. This contrasting behavior allows sensitive strain engineering of selective chemical adsorption on MoS2 with effective tuning of mechanical, electronic, and magnetic properties. These results suggest new design strategies for constructing MoS2-based ultrahigh-sensitivity nanoscale sensors and electromechanical devices.

Nacre is characterized by its excellent mechanical performance due to the well-recognized "brick and mortar" structure. Many efforts have been applied to make nacre-mimicking materials, but it is still a big challenge to realize their continuous production. Here, we prepared sandwich-like building blocks of poly(vinyl alcohol) (PVA)-coated graphene, and achieved high-nanofiller-content kilometers-long fibers by continuous wet-spinning assembly technology. The fibers have a strict "brick and mortar" layered structure, with graphene sheet as rigid brick and PVA as soft mortar. The mortar thickness can be precisely tuned from 2.01 to 3.31 nm by the weight feed ratio of PVA to graphene, as demonstrated by both atomic force microscopy and X-ray diffraction measurements. The mechanical strength of the nacre-mimicking fibers increases with increasing the content of PVA, and it rises gradually from 81 MPa for the fiber with 53.1 wt% PVA to 161 MPa for the fiber with 65.8 wt% PVA. The mechanical performance of our fibers was independent of the molecular weight (MW) of PVA in the wide range of 2-100 kDa, indicating that low MW polymers can also be used to make strong nanocomposites. The tensile stress of fibers immersed in PVA 5 wt% solution reached ca. 200 MPa, surpassing the values of nacre and most of other nacre-mimicking materials. The nacre-mimicking fibers are highly electrically conductive (∼350 S m(-1)) after immersing in hydroiodic acid, enabling them to connect a circuit to illuminate an LED lamp.

Using density functional theory calculations, we show that recently synthesized carbon nanocomposites of graphene nanoribbons encapsulated in a carbon nanotube (GNR@CNT) possess rich emergent electronic and magnetic properties that offer new functionality and tunability and display systematic trends that are sensitive to the matchup of constitutive GNRs and CNTs. The encapsulation of H-passivated GNRs in metallic armchair CNTs always leads to a metallic complex while those in semiconducting zigzag CNTs can be either metallic or semiconducting depending on the chirality of GNRs. In particular, the complex of armchair GNRs in a zigzag CNT exhibits an oscillating electronic band gap with changing GNR width and a well-separated spatial distribution of electrons and holes localized in the CNT and GNR components, respectively. When bare large zigzag GNRs are encapsulated in an armchair CNT, the resulting complex shows strong structural stability and enhanced magnetism and, most interestingly, such GNR@CNT configurations can be tuned to be metallic or semiconducting depending on relative bond position and magnetic order. These results offer key insights for understanding and predicting emergent properties of GNR@CNT, which establish a roadmap for guiding design and synthesis of specific nanocomposite configurations with tailor-made properties for nanoelectronic, photovoltaic and spintronic applications.

We report a facile strategy to synthesize silica nanoparticles-coated graphene oxide (GO-SiO2) nanohybrids in a water-alcohol mixture at room temperature. AFM observations revealed that silica nanoparticles with ca. 50 nm in size were densely and evenly covered on graphene oxide sheets. Due to the space layer of silica nanoparticles, micro-scale GO-SiO2 hybrid plates could be individually dispersed in water and polar organic solvents, promising good solution-based processibility. The growth process of GO-supported silica is traced by TGA and XRD measurements, showing that 24 hours is enough to achieve a fine cover effect for the disappearance of (002) diffraction peak of GO. Based on the high dense overlaying of silica nanoparticles, up to micro-scale silica sheets with thickness of ca. 8 nm were readily fabricated by burning GO-SiO2 at 650 °C in air. Likewise, a centimeter-scale semitransparent film of silica nanosheets was prepared by calcining a GO-SiO2 film. Interestingly, the GO-SiO2 nanohybrids exhibit excellent hydrophilic nature and can be directly applied as a general kind of building blocks to construct large-area superhydrophilic surfaces on arbitrary substrates (e.g., lotus leaf, ceramic tile and polypropylene) through the simple drop-coating method. Such a coating methodology paves the way for making large-area superhydrophilic surface without extra process treatments and damaging the intrinsic structure of substrates.