Quasi-Solid-State Ion-Conducting Arrays Composite Electrolytes with Fast Ion Transport Vertical-Aligned Interfaces for All-Weather Practical Lithium-Metal Batteries

The rapid improvement in the gel polymer electrolytes(GPEs)with high ionic conductivity brought it closer to practical applications in solid-state Li-metal batteries.The combination of solvent and polymer enables quasi-liquid fast ion transport in the GPEs.However,different ion transport capacity between solvent and polymer will cause local nonuniform Li+distribution,leading to severe dendrite growth.In addition,the poor thermal stability of the solvent also limits the operating-temperature window of the electrolytes.Optimizing the ion transport environment and enhancing the thermal stability are two major challenges that hinder the application of GPEs.Here,a strategy by introducing ion-conducting arrays(ICA)is created by vertical-aligned montmorillonite into GPE.Rapid ion transport on the ICA was demonstrated by 6Li solid-state nuclear magnetic resonance and synchrotron X-ray diffraction,combined with computer simulations to visualize the transport process.Compared with conventional randomly dispersed fillers,ICA provides continuous interfaces to regulate the ion transport environment and enhances the tolerance of GPEs to extreme temperatures.Therefore,GPE/ICA exhibits high room-temperature ionic conductivity(1.08 mS cm^(−1))and long-term stable Li deposition/stripping cycles(>1000 h).As a final proof,Li||GPE/ICA||LiFePO_(4) cells exhibit excellent cycle performance at wide temperature range(from 0 to 60°C),which shows a promising path toward all-weather practical solid-state batteries.

Machine Learning Assisted Design of Natural Rubber Composites with Multi⁃Performance Optimization

Multi⁃performance optimization of tread rubber composites is a key issue of great concern in automotive industry.Traditional experimental design approach via“trial and error”or intuition is ineffective due to mutual inhibition among multiple properties.A“Uniform design⁃Machine learning”strategy for performance prediction and multi⁃performance optimization of tread rubber composites was proposed.The wear resistance,rolling resistance,tensile strength and wet skid resistance were simultaneously optimized.A series of feasible optimization designs were screened via statistical analysis and machine learning analysis,and were experimentally prepared.The verification experiments demonstrate that the optimization design via machine learning analysis meets the optimization requirements of all target performance,especially for Akron abrasion and 60℃tanδ(about 21%and 9%lower than the design targets,respectively)due to the inhibition of mechanical degradation and good dispersion of fillers.

Regulating the oxidation state of Pd to enhance the selective hydrogenation for 5-hydroxymethylfurfural

The highly selective hydrogenation of 5-hydroxymethylfurfural to 2,5-dihydroxymethylfuran is an important reaction in the field of biomass hydrogenation,because it is a bridge between biomass resources and chemical industry.Here,we precisely constructed carbon nitride supported Pd-based catalysts by a simple impregnation-reduction method.By changing the reduction temperature,catalysts with different oxidation state could be precisely constructed.Moreover,the important correlation between the ratio of Pd^(0)/Pd^(2+)and catalytic activity is revealed during the selective hydrogenation of HMF.The Pd/g—C_(3)N_(4)—300 catalyst with a Pd^(0)/Pd^(2+)ratio of 3/2 showed the highest catalytic activity,which could get 96.9%5-hydroxymethylfurfural conversion and 90.3%2,5-dihydroxymethylfuran selectivity.Further density functional theory calculation revealed that the synergistic effect between Pd0and Pd2+in Pd/g—C_(3)N_(4)—300 system could boost the adsorption of the substrate and the dissociation of hydrogen.In this work,we highlight the important correlation between metal oxidation state and catalytic activity,which provides valuable insights for the rational design of precious metal catalysts for hydrogenation reactions.

Ultrathin and Flexible CNTs/MXene/Cellulose Nanofibrils Composite Paper for Electromagnetic Interference Shielding

As the rapid development of portable and wearable devices,different electromagnetic interference(EMI)shielding materials with high efficiency have been desired to eliminate the resulting radiation pollution.However,limited EMI shielding materials are successfully used in practical applications,due to the heavy thickness and absence of sufficient strength or flexibility.Herein,an ultrathin and flexible carbon nanotubes/MXene/cellulose nanofibrils composite paper with gradient and sandwich structure is constructed for EMI shielding application via a facile alternating vacuum-assisted filtration process.The composite paper exhibits outstanding mechanical properties with a tensile strength of 97.9±5.0 MPa and a fracture strain of 4.6±0.2%.Particularly,the paper shows a high electrical conductivity of 2506.6 S m?1 and EMI shielding effectiveness(EMI SE)of 38.4 dB due to the sandwich structure in improving EMI SE,and the gradient structure on regulating the contributions from reflection and absorption.This strategy is of great significance in fabricating ultrathin and flexible composite paper for highly efficient EMI shielding performance and in broadening the practical applications of MXene-based composite materials.

3D Lamellar-Structured Graphene Aerogels for Thermal Interface Composites with High Through-Plane Thermal Conductivity and Fracture Toughness

Although thermally conductive graphene sheets are efficient in enhancing in-plane thermal conductivities of polymers,the resulting nanocomposites usually exhibit low through-plane thermal conductivities,limiting their application as thermal interface materials.Herein,lamellarstructured polyamic acid salt/graphene oxide(PAAS/GO)hybrid aerogels are constructed by bidirectional freezing of PAAS/GO suspension followed by lyophilization.Subsequently,PAAS monomers are polymerized to polyimide(PI),while GO is converted to thermally reduced graphene oxide(RGO)during thermal annealing at 300℃.Final graphitization at 2800℃ converts PI to graphitized carbon with the inductive effect of RGO,and simultaneously,RGO is thermally reduced and healed to high-quality graphene.Consequently,lamellar-structured graphene aerogels with superior through-plane thermal conduction capacity are fabricated for the first time,and its superior through-plane thermal conduction capacity results from its vertically aligned and closely stacked high-quality graphene lamellae.After vacuum-assisted impregnation with epoxy,the resultant epoxy composite with 2.30 vol% of graphene exhibits an outstanding through-plane thermal conductivity of as high as 20.0 W m^−1 K^−1,100 times of that of epoxy,with a record-high specific thermal conductivity enhancement of 4310%.Furthermore,the lamellar-structured graphene aerogel endows epoxy with a high fracture toughness,~1.71 times of that of epoxy.

Earth-abundant coal-derived carbon nanotube/carbon composites as efficient bifunctional oxygen electrocatalysts for rechargeable zinc-air batteries

The exploration of active and robust electrocatalysts for both the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)is the bottleneck to realize the commercialization of rechargeable metal-air batteries and regenerative fuel cells.Here we report facile synthesis of three-dimensional(3 D)carbon nanotube(CNT)/carbon composites using earth-abundant coal as the carbon source,hydrogen reductant and heteroatom dopant to grow CNTs.The prepared composite featuring 3 D structural merits and multiple active sites can efficiently catalyze both ORR and OER,affording high activity,fast kinetics,and long-term stability.With the additional incorporation of manganese,the developed catalyst afforded a potential difference of 0.80 V between ORR at the half wave potential and OER at a current density of 10 mA cm^(-2).The optimized sample has presented excellent OER performance within a constructed solar-powered water splitting system with continuously generating oxygen bubbles at anode.Notably,it can be further used as a durable air-electrode catalyst in constructed Zn-air battery,delivering an initial discharge/charge voltage gap of 0.73 V,a remained voltaic efficiency of 61.2%after 160 cycles and capability to power LED light for at least 80 h.This study provides an efficient approach for converting traditional energy resource i.e.coal to value-added alternative oxygen electrocatalysts in renewable energy conversion systems.

A comparative study of 85 hyperelastic constitutive models for both unfilled rubber and highly filled rubber nanocomposite material

Nonlinear finite element analysis is widely used for structural optimization of the design and the reliability analysis of complex elastomeric components.However,high-precision numerical results cannot be achieved without reliable strain energy functions(SEFs)of the rubber or rubber nanocomposite material.Although hyperelastic constitutive models have been studied for nearly 80 years,selecting one that accurately describes rubber's mechanical response is still a challenge.This work reviews 85 isotropic SEFs based on both the phenomenological theory and the micromechanical network theory proposed from the 1940s to 2019.A fitting algorithm which can realize the automatic fitting optimization and determination of the parameters of all SEFs reviewed is developed.The ability of each SEF to reproduce the experimental data of both the unfilled and highly filled rubber nanocomposite is quantitatively assessed based on a new proposed evaluation index.The top 30 SEFs for the unfilled rubber and the top 14 SEFs for the highly filled rubber nanocomposite are presented in the ranking lists.Finally,some suggestions on how to select an appropriate hyperelastic constitutive model are given,and the perspective on the future progress of constitutive models is summarized.

High-gravity-assisted engineering of Ni_(2)P/g-C_(3)N_(4) nanocomposites with enhanced photocatalytic performance

Graphitic carbon nitride(g-C_(3)N_(4)) with transition metal phosphides has been studied extensively as potential photocatalysts for hydrogen evolution.However,in-situ approaches to realize intimate interfacial contacts have rarely been reported.In this study,Ni_(2)P nanoparticlesdecorated g-C_(3)N_(4)photocatalysts were prepared via liquid exfoliation of g-C_(3)N_(4) followed by in-situ loading of Ni_(2)P nanoparticles in a rotating packed bed(RPB) reactor.The optimized Ni_(2)P/g-C_(3)N_(4) exhibits high performance in visible-light-driven(λ > 420 nm) hydrogen evolution(~561 μmol g-1h-1),which is 103 times higher than that of pristine g-C_(3)N_(4).The superior photocatalytic performance and durability originate from the robust interfacial structure.Therefore,a Z-scheme route with enhanced transfer of photoinduced electron was proposed,and Ni_(2)P/gC_(3)N_(4) composites with smaller bandgaps than those of g-C_(3)N_(4) were realized.Due to the intensified mass transfer and mixing of RPB reactor,the adsorption and nucleation processes of Ni_(2)P on g-C_(3)N_(4) were enhanced,enabling scalable solar light-driven H_(2) production.

Synthesis of butterfly-like BiVO4/RGO nanocomposites and their photocatalytic activities

A simple and high efficient method was proposed for the synthesis of uniform three dimensional （3D） BiVO4/reduced graphene oxide （RGO） nanocomposite photocatalyst by adopting the microwave assistant and using Bi （NO3）3·5H2O, graphene oxide （GO） and NH4VO3 as precursor. The as-obtained composites were well characterized with the aid of various techniques to study the morphology, structure, composition, optimal and electrical property. In the as-obtained composites, the GO sheets were fully reduced into RGO, and monoclinic structure BiVO4 crystallized completely into butterfly-like BiVO4 lamellas and well bonded with the RGO lamellas. The length and the width of the butterfly-like BiVO4 particle were about 1.5 μm, and the thickness of the flake was about 20 nm. Photocatalytic performances of BiVO4/RGO composite and pure BiVO4 particle have been evaluated by investigating the reduction of Cr（VI） ion-contained wastewater under simulated solar light irradiation, where the BiVO4/RGO composite displayed enhanced photocatalytic activity. It is found that the pseudo-first-order rate constants （k） for the photocatalytic reduction of Cr （VI） by BiVO4/RGO composite was about 4 times as high as that of the pure BiVO4. The present work suggested that the combination of BiVO4 and RGO displayed a remarkable synergistic effect, which led to enhanced photo-catalytic activity on Cr（VI） reduction.

d-Orbital steered FeN_(4)moiety through N,S dual-site adjustation for zinc-air flow battery

The implementation of pristine covalent organic polymer(CO_(2)P)with well-defined structure as air electrode may spark fresh vitality to rechargeable zinc-air flow batteries(ZAFBs),but it still remains challenges in synergistically regulating their electronic states and structural porosity for the great device performance.Here,we conquer these issues by exploiting N and S co-doped graphene with COP rich in metal-ligand nitrogen to synergistically construct an effective catalyst for oxygen reduction reaction(ORR).Among them,the N and S co-doped sites with high electronegativity properties alter the number of electron occupations in the d orbital of the iron centre and form electron-transfer bridges,thereby boosting the selectivity of the ORR-catalysed four-electron pathway.Meanwhile,the introduction of COP materials aids the formation of pore interstices in the graphene lamellae,which both adequately expose the active sites and facilitate the transport of reactive substances.Benefiting from the synergistic effect,as-prepared catalyst exhibits excellent half-wave potentials(E_(1/2)=912 mV)and stability(merely 8.8%drop after a long-term durability test of 50000 s).Further,ZAFBs assembled with the N/SG@CO_(2)P catalyst demonstrate exceptional power density(163.8 mW cm^(-2))and continuous charge and discharge for approximately 140 h at 10 mA cm^(-2),outperforming the noble-metal benchmarks.

Simultaneously Improved Curing,Mechanical,Antioxidative Properties and Reduced ZnO Loading of Silica Filled NR Composites by Incorporation of Low-cost Crude Carbon Dots via Conventional Melt-milling Method

Rubbers or elastomers play an important role in hi-tech technology and civilian daily life because of their unique and strategical properties.Generally,the rubber additives are essential components for rubbers’practical application.Nowadays,developing novel multifunctional additives has attracted increasing research attention.In this work,low-cost crude carbon dots(CCDs)were used as multifunctional additives for natural rubber/silica system(without any additional modification)through industrial compatible melt-mixing method.The results revealed that the CCDs could disperse well in the NR/silica system,and they could not only endow the rubber compound with excellent anti-aging capability due to CCDs’radical scavenging activity because of their plenty of nitrogen-containing species,but also improve the curing rate and mechanical performance of the rubber composite.Also,the CCDs could reduce the rolling resistance of the rubber composites(tanδvalue at 7%strain of the rubber composite could be decreased by 34%),which is promising for the application of energy-saving tire industry.Lastly,the addition of CCDs could effectively reduce the ZnO dosage by at least 40%in the rubber composite without deteriorating its performance.Overall,this work provides valuable guidance to develop novel cheap yet effective additives for the elastomer.

Complete kinetic model for esterification reaction of lauric acid with glycerol to synthesize glycerol monolaurate

Glycerol monolaurate(GML)is a widely used industrial chemical with excellent emulsification and antibacterial effect.The direct esterification of glycerol with lauric acid is the main method to synthesize GML.In this work,the kinetic process of direct esterification was systematically studied using p-toluenesulfonic acid as catalyst.A complete kinetic model of consecutive esterification reaction has been established,and the kinetic equation of acid catalysis was deduced.The isomerization reactions of GML and glycerol dilaurate were investigated.It was found that the reaction was an equilibrium reaction and the reaction rate was faster than the esterification reaction.The kinetic equations of the consecutive esterification reaction were obtained by experiments as k_(1)=(276+92261Xcat)exp(-37720/RT)and k_(2)=(80+4413Xcat)exp(-32240/RT).The kinetic results are beneficial to the optimization of operating conditions and reactor design in GML production process.

Highly Conductive Ag/pCF/MVQ Composite Rubber for Efficient Electromagnetic Interference Shielding

In this study,flexible and highly conductive composite rubber at low filler content was successfully prepared through polydopamine-assisted electroless silver plating plus mechanical mixing.Firstly,carbon fibers(CF)were activated by polydopamine(PDA)to improve the surface activity by self-polymerization reaction.Next,because of the metal chelating ability of PDA,silver layer was firmly deposited on the surface of CF through a facile electroless silver plating method.Finally,flexible silver-plated carbon fibers(Ag/pCF)silicone rubber composites prepared by mechanical mixing.By using X-ray photoelectron spectroscopy(XPS)and X-ray diffraction(XRD),the chemical composition and crystal structure of Ag/pCF were examined,and scanning electron microscopy(SEM)was used to assess the surface morphology of the Ag/pCF.The results showed that a uniform and dense silver layer was formed on the surface of the CF,and the conductivity of the Ag/pCF could reach 7885 S/cm.It was noteworthy that the composite rubber filled with only 45 phr Ag/pCF had a high electromagnetic interference shielding effectiveness(100 dB)due to the low density and high aspect ratio of Ag/pCF.The composite rubber has excellent potential for application in the field of electromagnetic interference shielding.

Dynamic in situ reconstruction of NiSe_(2) promoted by interfacial Ce_(2)(CO_(3))_(2)O for enhanced water oxidation

Understanding and manipulating the structural evolution of water oxidation electrocatalysts lays the foundation to finetune their catalytic activity.Herein,we present a synthesis of NiSe_(2)-Ce_(2)(CO_(3))_(2)O heterostructure and demonstrate the efficacy of interfacial Ce_(2)(CO_(3))2O in promoting the formation of catalytically active centers to improve oxygen evolution activity.In-situ Raman spectroscopy shows that incorporation of Ce_(2)(CO_(3))2O into NiSe_(2) causes a cathodic shift of the Ni^(2+)→Ni~(3+) transition potential.Operando electrochemical impedance spectroscopy reveals that strong electronic coupling at heterogeneous interface accelerates charge transfer process.Furthermore,density functional theory calculations suggest that actual catalytic active species of NiOOH transformed from NiSe_(2),which is coupled with Ce_(2)(CO_(3))_(2)O,can optimize electronic structure and decrease the free energy barriers toward fast oxygen evolution reaction(OER) kinetics.Consequently,the resultant NiSe_(2)-Ce_(2)(CO_(3))_(2)O electrode exhibits remarkable electrocatalytic performance with low overpotentials(268/304 mV@50/100 mA cm^(-2)) and excellent stability(50 mA cm^(-2) for 120 h) in the alkaline electrolyte.This work emphasizes the significance of modulating the dynamic changes in developing efficient electrocatalyst.

Antibody-platinum(IV)prodrugs conjugates for targeted treatment of cutaneous squamous cell carcinoma

Antibody-drug conjugates(ADCs)are a new type of targeting antibodies that conjugate with highly toxic anticancer drugs via chemical linkers to exert high specificity and efficient killing of tumor cells,thereby attracting considerable attention in precise oncology therapy.Cetuximab(Cet)is a typical antibody that offers the benefits of good targeting and safety for individuals with advanced and inoperable cutaneous squamous cell carcinoma(cSCC);however,its anti-tumor activity is limited to a single use.Cisplatin(CisPt)shows good curative effects;however,its adverse effects and non-tumor-targeting ability are major drawbacks.In this study,we designed and developed a new ADC based on a new cytotoxic platinum(IV)prodrug(C8Pt(IV))and Cet.The so-called antibody-platinum(IV)prodrugs conjugates,named Cet-C8Pt(IV),showed excellent tumor targeting in cSCC.Specifically,it accurately delivered C8Pt(IV)into tumor cells to exert the combined anti-tumor effect of Cet and CisPt.Herein,metabolomic analysis showed that Cet-C8Pt(IV)promoted cellular apoptosis and increased DNA damage in cSCC cells by affecting the vitamin B6 metabolic pathway in tumor cells,thereby further enhancing the tumor-killing ability and providing a new strategy for clinical cancer treatment using antibody-platinum(IV)prodrugs conjugates.

Potential industrial applications of photo/electrocatalysis: Recent progress and future challenges

Nowadays,the rapid development of the social economy inevitably leads to global energy and environmental crisis.For this reason,more and more scholars focus on the development of photocatalysis and/or electrocatalysis technology for the advantage in the sustainable production of high-value-added products,and the high efficiency in pollutants remediation.Although there is plenty of outstanding research has been put forward continuously,most of them focuses on catalysis performance and reaction mechanisms in laboratory conditions.Realizing industrial application of photo/electrocatalytic processes is still a challenge that needs to be overcome by social demand.In this regard,this review comprehensively summarized several explorations in thefield of photo/electrocatalytic reduction towards potential industrial applications in recent years.Special attention is paid to the successful attempts and the current status of photo/electrocatalytic water splitting,carbon dioxide conversion,resource utilization from waste,etc.,by using advanced reactors.The key problems and challenges of photo/electrocatalysis in future industrial practice are also discussed,and the possible development directions are also pointed out from the industry view.

Flexible antibacterial degradable bioelastomer nanocomposites for ultrasensitive human–machine interaction sensing enabled by machine learning

Flexible wearables have attracted extensive interests for personal human motion sensing,intelligent disease diagnosis,and multifunctional electronic skins.How-ever,the reported flexible sensors,mostly exhibited narrow detection range,low sensitivity,limited degradability to aggravate environmental pollution from vast electronic wastes,and poor antibacterial performance to hardly improve skin dis-comfort and skin inflammation from bacterial growth under long-term wearing.Herein,bioinspired from human skin featuring highly sensitive tactile sensation with spinous microstructures for amplifying sensing sensitivity between epidermis and dermis,a wearable antibacterial degradable electronics is prepared from degrad-able elastomeric substrate with MXene-coated spinous microstructures templated from lotus leaf assembled with the interdigitated electrode.The degradable elas-tomer is facilely obtained with tunable modulus to match the modulus of human skin with improved hydrophilicity for rapid degradation.The as-obtained sensor displays ultra-low detection limit(0.2 Pa),higher sensitivity(up to 540.2 kPa^(-1)),outstand-ing cycling stability(>23,000 cycles),a wide detection range,robust degradability,and excellent antibacterial capability.Facilitated by machine learning,the collected sensing signals from the integrated sensors on volunteer's fingers to the related American Sign Language are effectively recognized with an accuracy up to 99%,showing excellent potential in wireless human movement sensing and smart machine learning-enabled human-machine interaction.

Multiplicity of thermodynamic states of van der Waals gas in nanobubbles

The gas-containing nanobubbles have attracted extensive attention due to their remarkable properties and extensive application potential.However,a number of fundamental aspects of nanobubbles,including thermodynamic states for the confined gas,remain still unclear.Here we theoretically demonstrate that the van der Waals(vd W)gases confined in nanobubbles exhibit a unique thermodynamic state of remarkably deviating from the bulk gas phase,and the state transition behavior due to the sizedependent Laplace pressure.In general,the vd W gas inside nanobubbles present multiple stable or transient states,where 0–2 states are for supercritical gas and 0–4 for subcritical gas.Our further analysis based on Rayleigh–Plesset equation and free energy determination indicates that the gas states in nanobubbles exhibits different levels of stability,from which the coexistence of multiple bubble states and microphase equilibrium between droplets and bubbles are predicted.This work provides insight to understand the thermodynamic states appeared for gas in nanobubbles.

Phase-change composite filled natural nanotubes in hydrogel promote wound healing under photothermally triggered drug release

It is of great importance to treat a bacterial-infected wound by a smart dressing capable of delivering antibiotics in a smart manner without causing drug resistance.The construction of smart release nanocontainers responsive to near-infrared(NIR)laser irradiation in an on-demand and stepwise way is a promising strategy for avoiding the emergence of multidrug-resistant bacteria.Here,we develop a hydrogel composite made of alginate and nanotubes with an efficient NIR-triggered release of rifampicin and outstanding antibacterial ability.This composite hydrogel is prepared through co-encapsulating antibacterial drug(rifampicin),NIR-absorbing dye(indocyanine green),and phase-change materials(a eutectic mixture of fatty acids)into halloysite nanotubes,followed by incorporation into alginate hydrogels,allowing the in-situ gelation at room temperature and maintaining the integrity of drug-loaded nanotubes.Among them,the eutectic mixture with a melting point of 39℃ serves as the biocompatible phase-change material to facilitate the NIR-triggered drug release.The resultant phase-change material gated-nanotubes exhibit a prominent photothermal efficiency with multistep drug release under laser irradiation.In an in vitro assay,composite hydrogel provides good antibacterial potency against Staphylococcus aureus,one of the most prevalent microorganisms of dangerous gas gangrene.A bacterial-infected rat full-thickness wound model demonstrates that the NIR-responsive composite hydrogel inhibits the bacteria colonization and suppresses the inflammatory response caused by bacteria,promoting angiogenesis and collagen deposition to accelerate wound regeneration.The NIR-responsive composite hydrogel has a great po-tential as an antibacterial wound dressing functionalized with controlled multistep treatment of the infected sites.

Progression in the Oxidation Stability of MXenes

MXenes are under the spotlight due to their versatile physicochemical characteristics. Since their discovery in 2011, significant advancements have been achieved in their synthesis and application sectors. However, the spontaneous oxidation of MXenes, which is critical to its processing and product lifespan, has gotten less attention due to its chemical complexity and poorly understood oxidation mechanism. This perspective focuses on the oxidation stability of MXenes and addresses the most recent advancements in understanding and the possible countermeasures to limit the spontaneous oxidation of MXenes. A section is dedicated to the presently accessible methods for monitoring oxidation, with a discussion on the debatable oxidation mechanism and coherently operating factors that contribute to the complexity of MXenes oxidation. The current potential solutions for mitigating MXenes oxidation and the existing challenges are also discussed with prospects to prolong MXene's shelf-life storage and expand their application scope.