Wearable biosensors have received great interest as patient-friendly diagnostic technologies because of their high flexibility and conformability.The growing research and utilization of novel materials in designing we...Wearable biosensors have received great interest as patient-friendly diagnostic technologies because of their high flexibility and conformability.The growing research and utilization of novel materials in designing wearable biosensors have accelerated the development of point-of-care sensing platforms and implantable biomedical devices in human health care.Among numerous potential materials,conjugated polymers(CPs)are emerging as ideal choices for constructing high-performance wearable biosensors because of their outstanding conductive and mechanical properties.Recently,CPs have been extensively incorporated into various wearable biosensors to monitor a range of target biomolecules.However,fabricating highly reliable CP-based wearable biosensors for practical applications remains a significant challenge,necessitating novel developmental strategies for enhancing the viability of such biosensors.Accordingly,this review aims to provide consolidated scientific evidence by summarizing and evaluating recent studies focused on designing and fabricating CP-based wearable biosensors,thereby facilitating future research.Emphasizing the superior properties and benefits of CPs,this review aims to clarify their potential applicability within this field.Furthermore,the fundamentals and main components of CP-based wearable biosensors and their sensing mechanisms are discussed in detail.The recent advancements in CP nanostructures and hybridizations for improved sensing performance,along with recent innovations in next-generation wearable biosensors are highlighted.CPbased wearable biosensors have been—and will continue to be—an ideal platform for developing effective and user-friendly diagnostic technologies for human health monitoring.展开更多
With the growth of deep drilling and the complexity of the well profile,the requirements for a more complete and efficient exploitation of productive formations increase,which increases the risk of various complicatio...With the growth of deep drilling and the complexity of the well profile,the requirements for a more complete and efficient exploitation of productive formations increase,which increases the risk of various complications.Currently,reagents based on modified natural polymers(which are naturally occurring compounds)and synthetic polymers(SPs)which are polymeric compounds created industrially,are widely used to prevent emerging complications in the drilling process.However,compared to modified natural polymers,SPs form a family of high-molecular-weight compounds that are fully synthesized by undergoing chemical polymerization reactions.SPs provide substantial flexibility in their design.Moreover,their size and chemical composition can be adjusted to provide properties for nearly all the functional objectives of drilling fluids.They can be classified based on chemical ingredients,type of reaction,and their responses to heating.However,some of SPs,due to their structural characteristics,have a high cost,a poor temperature and salt resistance in drilling fluids,and degradation begins when the temperature reaches 130℃.These drawbacks prevent SP use in some medium and deep wells.Thus,this review addresses the historical development,the characteristics,manufacturing methods,classification,and the applications of SPs in drilling fluids.The contributions of SPs as additives to drilling fluids to enhance rheology,filtrate generation,carrying of cuttings,fluid lubricity,and clay/shale stability are explained in detail.The mechanisms,impacts,and advances achieved when SPs are added to drilling fluids are also described.The typical challenges encountered by SPs when deployed in drilling fluids and their advantages and drawbacks are also discussed.Economic issues also impact the applications of SPs in drilling fluids.Consequently,the cost of the most relevant SPs,and the monomers used in their synthesis,are assessed.Environmental impacts of SPs when deployed in drilling fluids,and their manufacturing processes are identified,together with advances in SP-treatment methods aimed at reducing those impacts.Recommendations for required future research addressing SP property and performance gaps are provided.展开更多
How to achieve synergistic improvement of permittivity(ε_(r))and breakdown strength(E_(b))is a huge challenge for polymer dielectrics.Here,for the first time,theπ-conjugated comonomer(MHT)can simultaneously promote ...How to achieve synergistic improvement of permittivity(ε_(r))and breakdown strength(E_(b))is a huge challenge for polymer dielectrics.Here,for the first time,theπ-conjugated comonomer(MHT)can simultaneously promote theε_(r)and E_(b)of linear poly(methyl methacrylate)(PMMA)copolymers.The PMMA-based random copolymer films(P(MMA-co-MHT)),block copolymer films(PMMA-b-PMHT),and PMMA-based blend films were prepared to investigate the effects of sequential structure,phase separation structure,and modification method on dielectric and energy storage properties of PMMA-based dielectric films.As a result,the random copolymer P(MMA-coMHT)can achieve a maximumε_(r)of 5.8 at 1 kHz owing to the enhanced orientation polarization and electron polarization.Because electron injection and charge transfer are limited by the strong electrostatic attraction ofπ-conjugated benzophenanthrene group analyzed by the density functional theory(DFT),the discharge energy density value of P(MMA-co-PMHT)containing 1 mol%MHT units with the efficiency of 80%reaches15.00 J cm^(-3)at 872 MV m^(-1),which is 165%higher than that of pure PMMA.This study provides a simple and effective way to fabricate the high performance of polymer dielectrics via copolymerization with the monomer of P-type semi-conductive polymer.展开更多
Polymers from renewable resources have been used for a long time in biomedical applications and found an irreplaceable role in some of them.Their uses have been increasing because of their attractive properties,contri...Polymers from renewable resources have been used for a long time in biomedical applications and found an irreplaceable role in some of them.Their uses have been increasing because of their attractive properties,contributing to the improvement of life quality,mainly in drug release systems and in regenerative medicine.Formulations using natural polymer,nano and microscale particles preparation,composites,blends and chemical modification strategies have been used to improve their properties for clinical application.Although many studies have been carried out with these natural polymers,the way to reach the market is long and only very few of them become commercially available.Vegetable cellulose,bacterial cellulose,chitosan,poly(lactic acid)and starch can be found among the most studied polymers for biological applications,some with several derivatives already established in the market,and others with potential for such.In this scenario this work aims to describe the properties and potential of these renewable polymers for biomedical applications,the routes from the bench to the market,and the perspectives for future developments.展开更多
Three zincand cobaltcoordination polymers,namely{[Zn_(2)(μ_(6)-adip)(phen)_(2)]·4H_(2)O}_(n)(1),{[Co_(2)(μ_(6)-adip)(bipy)_(2)]·4H_(2)O}_(n)(2),and[Co_(2)(μ4-adip)(μ-bpa)_(2)]_(n)(3)have been constructed...Three zincand cobaltcoordination polymers,namely{[Zn_(2)(μ_(6)-adip)(phen)_(2)]·4H_(2)O}_(n)(1),{[Co_(2)(μ_(6)-adip)(bipy)_(2)]·4H_(2)O}_(n)(2),and[Co_(2)(μ4-adip)(μ-bpa)_(2)]_(n)(3)have been constructed hydrothermally using H4adip(H4adip=5,5′-azanediyldiisophthalic acid),phen(phen=1,10-phenanthroline),bipy(bipy=2,2′-bipyridine),bpa(bpa=bis(4-pyridyl)amine),and zinc and cobalt chlorides at 160℃.The products were isolated as stable crystalline solids and were characterized by IR spectra,elemental analyses,thermogravimetric analyses,and single-crystal X-ray diffrac-tion analyses.Single-crystal X-ray diffraction analyses revealed that three compounds crystallize in the orthorhom-bic system Pnna(1 and 2)or P21212(3)space groups.All compounds exhibit 3D frameworks.The catalytic perfor-mances in the Henry reaction of these compounds were investigated.Compound 3 exhibited an effective catalytic activity in the Henry reaction at 70℃.CCDC:2339391,1;2339392,2;2339393,3.展开更多
Enhancing catalytic activity of multi-enzyme in vitro through substrate channeling effect is promis-ing yet challenging.Herein,conjugated microporous polymers(CMPs)-scaffolded integrated en-zyme cascade systems(I-ECSs...Enhancing catalytic activity of multi-enzyme in vitro through substrate channeling effect is promis-ing yet challenging.Herein,conjugated microporous polymers(CMPs)-scaffolded integrated en-zyme cascade systems(I-ECSs)are constructed through co-entrapping glucose oxidase(GOx)and horseradish peroxidase(HRP),in which hydrogen peroxide(H_(2)O_(2))is the intermediate product.The interplay of low-resistance mass transfer pathway and appropriate pore wall-H_(2)O_(2)interactions facilitates the directed transfer of H_(2)O_(2),resulting in 2.4-fold and 5.0-fold elevation in catalytic activ-ity compared to free ECSs and separated ECSs,respectively.The substrate channeling effect could be regulated by altering the mass ratio of GOx to HRP.Besides,I-ECSs demonstrate excellent stabili-ties in harsh environments and multiple recycling.展开更多
Renewable resources based polymers provides a sustainable alternative to petroleum derived polymeric materials.As a part of our series on synthesis of vanillin based renewable polymers,we report the synthesis of poly(...Renewable resources based polymers provides a sustainable alternative to petroleum derived polymeric materials.As a part of our series on synthesis of vanillin based renewable polymers,we report the synthesis of poly(hydrovanilloin-furfural)[poly(HVL-Fur)]and poly(hydrovanilloin–5-hydromethylfurfural)[poly(HVL-5-HMF)].Vanillin was dimerized to a mixtures of meso/DL-hydrovanilloins with 94%meso product by electrochemical reductive coupling in aqueous sodium hydroxide using lead electrodes in quantitative yield.Then sodium hydroxide catalyzed condensation of hydrovanilloin with furfural in water at 80℃for 72 h was used to synthesize poly(HVL-Fur)with Mw=8600 g mol^(−1),PDI=1.28 in 78%yield.Similarly,condensation of hydrovanilloin with 5-hydroxymethylfurfural at 80℃for 48 h produced poly(HVL-5-HMF)with Mw=12,100 g mol−1,PDI=1.27 in 68%yield.poly(HVL-Fur)and poly(HVL-5-HMF)showed similar Tg values of 59℃and 60℃,respectively;whereas melting behaviors are dissimilar with Tm 171℃–173℃and 148℃–182℃,respectively.展开更多
Three zinc(Ⅱ),cobalt(Ⅱ),and nickel(Ⅱ)coordination polymers,namely[Zn(μ^(3-)cpna)(μ-dpea)_(0.5)]_(n)(1),[Co(μ^(3-)cpna)(μ-dpey)_(0.5)]_(n)(2),and[Ni(μ^(3-)cpna)(μ-dpey)_(0.5)(H_(2)O)]_(n)(3),have been construc...Three zinc(Ⅱ),cobalt(Ⅱ),and nickel(Ⅱ)coordination polymers,namely[Zn(μ^(3-)cpna)(μ-dpea)_(0.5)]_(n)(1),[Co(μ^(3-)cpna)(μ-dpey)_(0.5)]_(n)(2),and[Ni(μ^(3-)cpna)(μ-dpey)_(0.5)(H_(2)O)]_(n)(3),have been constructed hydrothermally using H_(2)cpna(5-(4-carboxyphenoxy)nicotinic acid),dpea(1,2-di(4-pyridyl)ethane),dpey(1,2-di(4-pyridyl)ethylene),and zinc,cobalt,and nickel chlorides at 160℃.The products were isolated as stable crystalline solids and were characterized by IR spectra,elemental analyses,thermogravimetric analyses,and single-crystal X-ray diffraction analyses.Single-crystal X-ray diffraction analyses revealed that three compounds crystallize in the triclinic system,space group P1.Compounds 1-3 show 2D layer structures.The catalytic activities in the Knoevenagel condensation reaction of these compounds were investigated.Compounds 1 and 2 exhibit effective catalytic activities in the Knoevenagel condensa-tion reaction at room temperature.For this reaction,various parameters were optimized,followed by the investiga-tion of the substrate scope.CCDC:2335676,1;2335677,2;2335678,3.展开更多
Acid loss and plasticization of phosphoric acid(PA)-doped high-temperature polymer electrolyte membranes(HT-PEMs)are critical limitations to their practical application in fuel cells.To overcome these barriers,poly(te...Acid loss and plasticization of phosphoric acid(PA)-doped high-temperature polymer electrolyte membranes(HT-PEMs)are critical limitations to their practical application in fuel cells.To overcome these barriers,poly(terphenyl piperidinium)s constructed from the m-and p-isomers of terphenyl were synthesized to regulate the microstructure of the membrane.Highly rigid p-terphenyl units prompt the formation of moderate PA aggregates,where the ion-pair interaction between piperidinium and biphosphate is reinforced,leading to a reduction in the plasticizing effect.As a result,there are trade-offs between the proton conductivity,mechanical strength,and PA retention of the membranes with varied m/p-isomer ratios.The designed PA-doped PTP-20m membrane exhibits superior ionic conductivity,good mechanical strength,and excellent PA retention over a wide range of temperature(80–160°C)as well as satisfactory resistance to harsh accelerated aging tests.As a result,the membrane presents a desirable combination of performance(1.462 W cm^(-2) under the H_(2)/O_(2)condition,which is 1.5 times higher than that of PBI-based membrane)and durability(300 h at 160°C and 0.2 A cm^(-2))in the fuel cell.The results of this study provide new insights that will guide molecular design from the perspective of microstructure to improve the performance and robustness of HT-PEMs.展开更多
The arc ignition system based on charring polymers has advantages of simple structure,low ignition power consumption and multiple ignitions,which bringing it broadly application prospect in hybrid propulsion system of...The arc ignition system based on charring polymers has advantages of simple structure,low ignition power consumption and multiple ignitions,which bringing it broadly application prospect in hybrid propulsion system of micro/nano satellite.However,charring polymers alone need a relatively high input voltage to achieve pyrolysis and ignition,which increases the burden and cost of the power system of micro/nano satellite in practical application.Adding conductive substance into charring polymers can effectively decrease the conducting voltage which can realize low voltage and low power consumption repeated ignition of arc ignition system.In this paper,a charring conductive polymer ignition grain with a cavity geometry in precombustion chamber,which is composed of PLA and multiwall carbon nanotubes(MWCNT)was proposed.The detailed ignition processes were analyzed and two different ignition mechanisms in the cavity of charring conductive polymers were revealed.The ignition characteristics of charring conductive polymers were also investigated at different input voltages,ignition grain structures,ignition locations and injection schemes in a visual ignition combustor.The results demonstrated that the ignition delay and external energy required for ignition were inversely correlated with the voltages applied to ignition grain.Moreover,the incremental depth of cavity shortened the ignition delay and external energy required for ignition while accelerated the propagation of flame.As the depth of cavity increased from 2 to 6 mm(at 50 V),the time of flame propagating out of ignition grain changed from 235.6 to 108 ms,and values of mean ignition delay time and mean external energy required for ignition decreased from 462.8 to 320 ms and 16.2 to 10.75 J,respectively.The rear side of the cavity was the ideal ignition position which had a shorter ignition delay and a faster flame propagation speed in comparison to other ignition positions.Compared to direct injection scheme,swirling injection provided a more favorable flow field environment in the cavity,which was beneficial to ignition and initial flame propagation,but the ignition position needed to be away from the outlet of swirling injector.At last,the repeated ignition characteristic of charring conductive polymers was also investigated.The ignition delay time and external energy required for ignition decreased with repeated ignition times but the variation was decreasing gradually.展开更多
Different drillingfluid systems are designed according to mineral composition,lithology and wellbore stability of different strata.In the present study,the conversion of a non-dispersed polymer drillingfluid into a low ...Different drillingfluid systems are designed according to mineral composition,lithology and wellbore stability of different strata.In the present study,the conversion of a non-dispersed polymer drillingfluid into a low potas-sium anti-collapsing drillingfluid is investigated.Since the two drillingfluids belong to completely different types,the key to this conversion is represented by new inhibitors,dispersants and water-loss agents by which a non-dispersed drillingfluid can be turned into a dispersed drillingfluid while ensuring wellbore stability and reason-able rheology(carrying sand—inhibiting cuttings dispersion).In particular,the(QYZ-1)inhibitors and(FSJSS-2)dispersants are used.The former can inhibit the hydration expansion capacity of clay,reduce the dynamic shear force and weaken the viscosity;the latter can improve the sealing effect and reduce thefiltrate loss.The results have shown that after adding a reasonable proportion of these substances(QYZ-1:FSJSS-2)to the non-dispersed polymer drillingfluid,while the apparent viscosity,plastic viscosity,structural viscosity andfluidity index under-went almost negligible changes,the dynamic plastic ratio increased,and thefiltration loss decreased significantly,thereby indicating good compatibility.According to the tests(conducted in the Leijia area),the density was 1.293 g/cm3,and after standing for 24 h,the SF(static settlement factor)was 0.51.Moreover,thefiltration loss was reduced to 4.0 mL,the rolling recovery rate reached 96.92%,with excellent plugging and anti-collapse performances.展开更多
The characterization of these molecularly imprinted polymers is essential to understanding their binding dynamics and structural properties. Through the analysis of the current research, it is found that there are ove...The characterization of these molecularly imprinted polymers is essential to understanding their binding dynamics and structural properties. Through the analysis of the current research, it is found that there are overlaps in the methods used by scholars. The Langmuir equation is frequently applied to model the adsorption isotherms of MIPs, providing critical insight into the capacity and affinity of the binding sites. Infrared Spectroscopy (IR) plays a crucial role in identifying the functional groups involved in the imprinting process and confirming the successful formation of specific binding sites. UV-visible spectrophotometry is employed to monitor the absorption characteristics of the polymers, offering data on the interactions between the template molecules and the polymer matrix. Transmission Electron Microscopy (TEM) provides detailed visualization of the internal structure of MIPs at the nanoscale, revealing the morphology and size of the imprinted cavities. Thermogravimetric Analysis (TGA) assesses the thermal stability and composition of the polymers, identifying decomposition patterns that are indicative of the material’s robustness under different conditions. Finally, the Laser Particle Size Analyzer is used to measure the size distribution of the polymer particles, which is critical for determining the uniformity and efficiency of the imprinting process. The six characterization methods discussed in this paper provide a comprehensive understanding of MIP, and it is hoped that in the future, more optimized design solutions will emerge and their applications in various fields will be enhanced.展开更多
Interest in temperature-responsive polymers has steadily grown over the past several decades, and numerous studies have been dedicated to developing temperature sensitive polymers that can be constructed into new smar...Interest in temperature-responsive polymers has steadily grown over the past several decades, and numerous studies have been dedicated to developing temperature sensitive polymers that can be constructed into new smart materials for biomedical applications. Phase behavior of a temperature-responsive polymer plays a pivotal role in determining its biological performance in certain conditions. In addition to the additives (such as salts and proteins) in aqueous solutions, molecular weight, molecular weight distribution, and structural or compositional factors can also significantly affect the transition temperatures of the polymers. This review comprehensively describes well-established and newly developed synthetic strategies for preparing temperature-responsive polymers. The structural and compositional parameters that affect the transition temperatures and self-assembly behavior are discussed. Finally, the biomedical applications of the temperature-responsive polymers in drug delivery, immunotherapy, tissue engineering, and diagnosis are summarized.展开更多
Lithium-sulfur(Li-S)batteries have attracted increased interest because of the high theoretical energy density,low cost,and environmental friendliness.Conducting polymers(CPs),as one of the most promising materials us...Lithium-sulfur(Li-S)batteries have attracted increased interest because of the high theoretical energy density,low cost,and environmental friendliness.Conducting polymers(CPs),as one of the most promising materials used in Li-S batteries,can not only facilitate electron transfer and buffer the large volumetric change of sulfur benefiting from their porous structure and excellent flexibility,but also enable stronger physical/chemical adsorption capacity toward polysulfides(LiPSs)when doped with abundant heteroatoms to promote the sulfur redox kinetics and achieve the high sulfur loading.This review firstly introduces the properties of various CPs including structural CPs(polypyrrole(PPy),polyaniline(PANi),polyethylene dioxothiophene[PEDOT])and compound CPs(polyethylene oxide(PEO),polyvinyl alcohol(PVA)and poly(acrylic acid)[PAA]),and their application potential in Li-S batteries.Furthermore,the research progress of various CPs in different components(cathode,separator,and interlayer)of Li-S batteries is systematically summarized.Finally,the application perspective of the CPs in Li-S batteries as a potential guidance is comprehensively discussed.展开更多
Metal-organic frameworks and covalent organic frameworks have been widely employed in electrochemical catalysis owing to their designable skeletons,controllable porosities,and well-defined catalytic centers.However,th...Metal-organic frameworks and covalent organic frameworks have been widely employed in electrochemical catalysis owing to their designable skeletons,controllable porosities,and well-defined catalytic centers.However,the poor chemical stability and low electron conductivity limited their activity,and single-functional sites in these frameworks hindered them to show multifunctional roles in catalytic systems.Herein,we have constructed novel metal organic polymers(Co-HAT-CN and Ni-HAT-CN)with dual catalytic centers(metal-N_(4) and metal-N_(2))to catalyze oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).By using different metal centers,the catalytic activity and selectivity were well-tuned.Among them,Co-HAT-CN catalyzed the ORR in a 4e^(-)pathway,with a half-wave potential of 0.8 V versus RHE,while the Ni-HAT-CN catalyze ORR in a 2e^(-)pathway with H_(2)O_(2) selectivity over 90%.Moreover,the Co-HAT-CN delivered an overpotential of 350 mV at 10 mA cm^(-2) with a corresponding Tafel slope of 24 mV dec^(-1) for OER in a 1.0 M KOH aqueous solution.The experimental results revealed that the activities toward ORR were due to the M-N_(4) sites in the frameworks,and both M-N_(4) and M-N_(2) sites contributed to the OER.This work gives us a new platform to construct bifunctional catalysts.展开更多
The concentration difference in the near-surface region of lithium metal is the main cause of lithium dendrite growth.Resolving this issue will be key to achieving high-performance lithium metal batteries(LMBs).Herein...The concentration difference in the near-surface region of lithium metal is the main cause of lithium dendrite growth.Resolving this issue will be key to achieving high-performance lithium metal batteries(LMBs).Herein,we construct a lithium nitrate(LiNO_(3))-implanted electroactiveβphase polyvinylidene fluoride-co-hexafluoropropylene(PVDF-HFP)crystalline polymorph layer(PHL).The electronegatively charged polymer chains attain lithium ions on the surface to form lithium-ion charged channels.These channels act as reservoirs to sustainably release Li ions to recompense the ionic flux of electrolytes,decreasing the growth of lithium dendrites.The stretched molecular channels can also accelerate the transport of Li ions.The combined effects enable a high Coulombic efficiency of 97.0%for 250 cycles in lithium(Li)||copper(Cu)cell and a stable symmetric plating/stripping behavior over 2000 h at 3 mA cm^(-2)with ultrahigh Li utilization of 50%.Furthermore,the full cell coupled with PHL-Cu@Li anode and Li Fe PO_(4) cathode exhibits long-term cycle stability with high-capacity retention of 95.9%after 900 cycles.Impressively,the full cell paired with LiNi_(0.87)Co_(0.1)Mn_(0.03)O_(2)maintains a discharge capacity of 170.0 mAh g^(-1)with a capacity retention of 84.3%after 100 cycles even under harsh condition of ultralow N/P ratio of 0.83.This facile strategy will widen the potential application of LiNO_(3)in ester-based electrolyte for practical high-voltage LMBs.展开更多
Synthesis of new carbon nanostructures with tunable properties is vital for precisely regulating electrochemical performance in the wide applications.Herein,we report a novel approach for the oxidative polymerization ...Synthesis of new carbon nanostructures with tunable properties is vital for precisely regulating electrochemical performance in the wide applications.Herein,we report a novel approach for the oxidative polymerization of N-and P-bearing copolymers from the self-assembly of three different monomers(aniline,pyrrole,and phytic acid),and further prepare the respective carbon nanostructures with relatively consistent N dopant(6.2%–8.0%,atom)and varying P concentrations(0.4%–2.8%,atom)via controllable pyrolysis.The impacts of phytic acid addition on the compositional,structural,and morphological evolution of the copolymers and the resulting nanocarbons are well studied through a spectrum of characterizations including N2 sorption,Fourier transform infrared spectroscopy,gel permeation chromatograph,scanning/transmission electron microscopy,and X-ray photoelectron spectroscopy.Gradual fragmentation of the nanosphere structures is evidenced with increasing addition of phytic acid,leading to different nanostructures from hollow nanospheres to 3D aggregates.Nanocarbons decorated with N and P dopants from pyrolysis are further utilized as anode materials in lithium-ion batteries,demonstrating enhanced electrochemical performance,i.e.,a reversible capacity of 380 mAhg^(-1)at 2 Ag^(-1)for NPC-0.5 during 200 cycles.The superior performance originates from the balanced porosity,and appropriate concentrations of P and pyrrolic N,thus pointing the direction for designing high-performance anode materials.展开更多
Sulfur-rich copolymers made through inverse vulcanization exhibit a wide range of potentially valuable applications, for example as adsorbents to capture mercury pollution. Among the diverse second monomers of the cop...Sulfur-rich copolymers made through inverse vulcanization exhibit a wide range of potentially valuable applications, for example as adsorbents to capture mercury pollution. Among the diverse second monomers of the copolymers, vegetable oil is a renewable resource, and recycled cooking oils have an important role in saving natural products. However, they need relatively high temperatures(160–180 ℃) to react with sulfur. To develop a low-temperature(130 ℃) reaction process for non-conjugated vegetable oil, we incorporate a small amount of tung oil, which contains conjugated trienes that can produce highly active free radicals during reactions. A variety of analytical techniques(proton nuclear magnetic resonance and Fourier-transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, X-ray diffraction, and dynamic mechanical analysis) are used to characterize the chemical structures and physical properties of the copolymers. The addition of tung oil is found to significantly improve the thermal stability and mechanical properties of the copolymers. We also investigate the effect of different ratios of raw materials on the gel time, free sulfur content, glass transition temperature T_(g), and degradation temperature of the copolymers. We find that increasing the amount of tung oil in the raw material mixture decreases the gel time and free sulfur content, but increases T_(g) and the degradation temperature. The copolymers exhibit a high adsorption capacity for mercury ions up to 33 mg Hg^(2+) per gram of adsorbent. These results demonstrate the feasibility of using sulfur-rich copolymers as effective mercury removal adsorbents, with the potential for further improvement by foaming the copolymers into porous materials.展开更多
Exploration of advanced gel polymer electrolytes(GPEs)represents a viable strategy for mitigating dendritic lithium(Li)growth,which is crucial in ensuring the safe operation of high energy density Li metal batteries(L...Exploration of advanced gel polymer electrolytes(GPEs)represents a viable strategy for mitigating dendritic lithium(Li)growth,which is crucial in ensuring the safe operation of high energy density Li metal batteries(LMBs).Despite this,the application of GPEs is still hindered by inadequate ionic conductivity,low Li^(+)transference number,and subpar physicochemical properties.Herein,Ti O_(2-x)nanofibers(NF)with oxygen vacancy defects were synthesized by a one-step process as inorganic fillers to enhance the thermal/mechanical/ionic-transportation performances of composite GPEs.Various characterizations and theoretical calculations reveal that the oxygen vacancies on the surface of Ti O_(2-x)NF accelerate the dissociation of Li PF_6,promote the rapid transfer of free Li^(+),and influence the formation of Li F-enriched solid electrolyte interphase.Consequently,the composite GPEs demonstrate enhanced ionic conductivity(1.90m S cm^(-1)at room temperature),higher lithium-ion transference number(0.70),wider electrochemical stability window(5.50 V),superior mechanical strength,excellent thermal stability(210℃),and improved compatibility with lithium,resulting in superior cycling stability and rate performance in both Li||Li,Li||Li Fe PO_(4),and Li||Li Ni_(0.8)Co_(0.1)Mn_(0.1)O_(2)cells.Overall,the synergistic influence of nanofiber morphology and enriched oxygen vacancy structure of fillers on electrochemical properties of composite GPEs is comprehensively investigated,thus,it is anticipated to shed new light on designing high-performance GPEs LMBs.展开更多
Polymer dielectrics capable of operating efficiently at high electric fields and elevated temperatures are urgently demanded by next-generation electronics and electrical power systems.While inorganic fillers have bee...Polymer dielectrics capable of operating efficiently at high electric fields and elevated temperatures are urgently demanded by next-generation electronics and electrical power systems.While inorganic fillers have been extensively utilized to improved high-temperature capacitive performance of dielectric polymers,the presence of thermodynamically incompatible organic and inorganic components may lead to concern about the long-term stability and also complicate film processing.Herein,zero-dimensional polymer dots with high electron affinity are introduced into photoactive allyl-containing poly(aryl ether sulfone)to form the all-organic polymer composites for hightemperature capacitive energy storage.Upon ultraviolet irradiation,the crosslinked polymer composites with polymer dots are efficient in suppressing electrical conduction at high electric fields and elevated temperatures,which significantly reduces the high-field energy loss of the composites at 200℃.Accordingly,the ultraviolet-irradiated composite film exhibits a discharged energy density of 4.2 J cm^(−3)at 200℃.Along with outstanding cyclic stability of capacitive performance at 200℃,this work provides a promising class of dielectric materials for robust high-performance all-organic dielectric nanocomposites.展开更多
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korea Government(MSIT)(No.NRF-2021R1A2C2004109)the Korea Institute for Advancement of Technology(KIAT)grant funded by the Korea Government(MOTIE)(No.P0020612,2022 The Competency Development Program for Industry Specialist).
文摘Wearable biosensors have received great interest as patient-friendly diagnostic technologies because of their high flexibility and conformability.The growing research and utilization of novel materials in designing wearable biosensors have accelerated the development of point-of-care sensing platforms and implantable biomedical devices in human health care.Among numerous potential materials,conjugated polymers(CPs)are emerging as ideal choices for constructing high-performance wearable biosensors because of their outstanding conductive and mechanical properties.Recently,CPs have been extensively incorporated into various wearable biosensors to monitor a range of target biomolecules.However,fabricating highly reliable CP-based wearable biosensors for practical applications remains a significant challenge,necessitating novel developmental strategies for enhancing the viability of such biosensors.Accordingly,this review aims to provide consolidated scientific evidence by summarizing and evaluating recent studies focused on designing and fabricating CP-based wearable biosensors,thereby facilitating future research.Emphasizing the superior properties and benefits of CPs,this review aims to clarify their potential applicability within this field.Furthermore,the fundamentals and main components of CP-based wearable biosensors and their sensing mechanisms are discussed in detail.The recent advancements in CP nanostructures and hybridizations for improved sensing performance,along with recent innovations in next-generation wearable biosensors are highlighted.CPbased wearable biosensors have been—and will continue to be—an ideal platform for developing effective and user-friendly diagnostic technologies for human health monitoring.
文摘With the growth of deep drilling and the complexity of the well profile,the requirements for a more complete and efficient exploitation of productive formations increase,which increases the risk of various complications.Currently,reagents based on modified natural polymers(which are naturally occurring compounds)and synthetic polymers(SPs)which are polymeric compounds created industrially,are widely used to prevent emerging complications in the drilling process.However,compared to modified natural polymers,SPs form a family of high-molecular-weight compounds that are fully synthesized by undergoing chemical polymerization reactions.SPs provide substantial flexibility in their design.Moreover,their size and chemical composition can be adjusted to provide properties for nearly all the functional objectives of drilling fluids.They can be classified based on chemical ingredients,type of reaction,and their responses to heating.However,some of SPs,due to their structural characteristics,have a high cost,a poor temperature and salt resistance in drilling fluids,and degradation begins when the temperature reaches 130℃.These drawbacks prevent SP use in some medium and deep wells.Thus,this review addresses the historical development,the characteristics,manufacturing methods,classification,and the applications of SPs in drilling fluids.The contributions of SPs as additives to drilling fluids to enhance rheology,filtrate generation,carrying of cuttings,fluid lubricity,and clay/shale stability are explained in detail.The mechanisms,impacts,and advances achieved when SPs are added to drilling fluids are also described.The typical challenges encountered by SPs when deployed in drilling fluids and their advantages and drawbacks are also discussed.Economic issues also impact the applications of SPs in drilling fluids.Consequently,the cost of the most relevant SPs,and the monomers used in their synthesis,are assessed.Environmental impacts of SPs when deployed in drilling fluids,and their manufacturing processes are identified,together with advances in SP-treatment methods aimed at reducing those impacts.Recommendations for required future research addressing SP property and performance gaps are provided.
基金the funding of National Key R&D Program of China(No.2020YFA0711700)Hunan National Natural Science Foundation(2021JJ30652)+3 种基金National Natural Science Foundation of China(52002404)Natural Science Foundation of Guangdong Province(2020A1515011198)Characteristic Innovation Projects of Colleges and Universities in Guangdong Province(2020KT SCX081)State Key Laboratory of Powder Metallurgy,Central South University,Changsha,China
文摘How to achieve synergistic improvement of permittivity(ε_(r))and breakdown strength(E_(b))is a huge challenge for polymer dielectrics.Here,for the first time,theπ-conjugated comonomer(MHT)can simultaneously promote theε_(r)and E_(b)of linear poly(methyl methacrylate)(PMMA)copolymers.The PMMA-based random copolymer films(P(MMA-co-MHT)),block copolymer films(PMMA-b-PMHT),and PMMA-based blend films were prepared to investigate the effects of sequential structure,phase separation structure,and modification method on dielectric and energy storage properties of PMMA-based dielectric films.As a result,the random copolymer P(MMA-coMHT)can achieve a maximumε_(r)of 5.8 at 1 kHz owing to the enhanced orientation polarization and electron polarization.Because electron injection and charge transfer are limited by the strong electrostatic attraction ofπ-conjugated benzophenanthrene group analyzed by the density functional theory(DFT),the discharge energy density value of P(MMA-co-PMHT)containing 1 mol%MHT units with the efficiency of 80%reaches15.00 J cm^(-3)at 872 MV m^(-1),which is 165%higher than that of pure PMMA.This study provides a simple and effective way to fabricate the high performance of polymer dielectrics via copolymerization with the monomer of P-type semi-conductive polymer.
基金The authors acknowledge FAPESP for funding the Research Project Number 2017-18-782-6 and the Grant 2021/07458-9.
文摘Polymers from renewable resources have been used for a long time in biomedical applications and found an irreplaceable role in some of them.Their uses have been increasing because of their attractive properties,contributing to the improvement of life quality,mainly in drug release systems and in regenerative medicine.Formulations using natural polymer,nano and microscale particles preparation,composites,blends and chemical modification strategies have been used to improve their properties for clinical application.Although many studies have been carried out with these natural polymers,the way to reach the market is long and only very few of them become commercially available.Vegetable cellulose,bacterial cellulose,chitosan,poly(lactic acid)and starch can be found among the most studied polymers for biological applications,some with several derivatives already established in the market,and others with potential for such.In this scenario this work aims to describe the properties and potential of these renewable polymers for biomedical applications,the routes from the bench to the market,and the perspectives for future developments.
文摘Three zincand cobaltcoordination polymers,namely{[Zn_(2)(μ_(6)-adip)(phen)_(2)]·4H_(2)O}_(n)(1),{[Co_(2)(μ_(6)-adip)(bipy)_(2)]·4H_(2)O}_(n)(2),and[Co_(2)(μ4-adip)(μ-bpa)_(2)]_(n)(3)have been constructed hydrothermally using H4adip(H4adip=5,5′-azanediyldiisophthalic acid),phen(phen=1,10-phenanthroline),bipy(bipy=2,2′-bipyridine),bpa(bpa=bis(4-pyridyl)amine),and zinc and cobalt chlorides at 160℃.The products were isolated as stable crystalline solids and were characterized by IR spectra,elemental analyses,thermogravimetric analyses,and single-crystal X-ray diffrac-tion analyses.Single-crystal X-ray diffraction analyses revealed that three compounds crystallize in the orthorhom-bic system Pnna(1 and 2)or P21212(3)space groups.All compounds exhibit 3D frameworks.The catalytic perfor-mances in the Henry reaction of these compounds were investigated.Compound 3 exhibited an effective catalytic activity in the Henry reaction at 70℃.CCDC:2339391,1;2339392,2;2339393,3.
文摘Enhancing catalytic activity of multi-enzyme in vitro through substrate channeling effect is promis-ing yet challenging.Herein,conjugated microporous polymers(CMPs)-scaffolded integrated en-zyme cascade systems(I-ECSs)are constructed through co-entrapping glucose oxidase(GOx)and horseradish peroxidase(HRP),in which hydrogen peroxide(H_(2)O_(2))is the intermediate product.The interplay of low-resistance mass transfer pathway and appropriate pore wall-H_(2)O_(2)interactions facilitates the directed transfer of H_(2)O_(2),resulting in 2.4-fold and 5.0-fold elevation in catalytic activ-ity compared to free ECSs and separated ECSs,respectively.The substrate channeling effect could be regulated by altering the mass ratio of GOx to HRP.Besides,I-ECSs demonstrate excellent stabili-ties in harsh environments and multiple recycling.
基金funded by United States National Science Foundation(NSF)Grant HRD-1036593USDA-NIFA Grant 12684238:Award No.2020-65209-31474United States Department of Energy Grant DE-SC0023345.
文摘Renewable resources based polymers provides a sustainable alternative to petroleum derived polymeric materials.As a part of our series on synthesis of vanillin based renewable polymers,we report the synthesis of poly(hydrovanilloin-furfural)[poly(HVL-Fur)]and poly(hydrovanilloin–5-hydromethylfurfural)[poly(HVL-5-HMF)].Vanillin was dimerized to a mixtures of meso/DL-hydrovanilloins with 94%meso product by electrochemical reductive coupling in aqueous sodium hydroxide using lead electrodes in quantitative yield.Then sodium hydroxide catalyzed condensation of hydrovanilloin with furfural in water at 80℃for 72 h was used to synthesize poly(HVL-Fur)with Mw=8600 g mol^(−1),PDI=1.28 in 78%yield.Similarly,condensation of hydrovanilloin with 5-hydroxymethylfurfural at 80℃for 48 h produced poly(HVL-5-HMF)with Mw=12,100 g mol−1,PDI=1.27 in 68%yield.poly(HVL-Fur)and poly(HVL-5-HMF)showed similar Tg values of 59℃and 60℃,respectively;whereas melting behaviors are dissimilar with Tm 171℃–173℃and 148℃–182℃,respectively.
文摘Three zinc(Ⅱ),cobalt(Ⅱ),and nickel(Ⅱ)coordination polymers,namely[Zn(μ^(3-)cpna)(μ-dpea)_(0.5)]_(n)(1),[Co(μ^(3-)cpna)(μ-dpey)_(0.5)]_(n)(2),and[Ni(μ^(3-)cpna)(μ-dpey)_(0.5)(H_(2)O)]_(n)(3),have been constructed hydrothermally using H_(2)cpna(5-(4-carboxyphenoxy)nicotinic acid),dpea(1,2-di(4-pyridyl)ethane),dpey(1,2-di(4-pyridyl)ethylene),and zinc,cobalt,and nickel chlorides at 160℃.The products were isolated as stable crystalline solids and were characterized by IR spectra,elemental analyses,thermogravimetric analyses,and single-crystal X-ray diffraction analyses.Single-crystal X-ray diffraction analyses revealed that three compounds crystallize in the triclinic system,space group P1.Compounds 1-3 show 2D layer structures.The catalytic activities in the Knoevenagel condensation reaction of these compounds were investigated.Compounds 1 and 2 exhibit effective catalytic activities in the Knoevenagel condensa-tion reaction at room temperature.For this reaction,various parameters were optimized,followed by the investiga-tion of the substrate scope.CCDC:2335676,1;2335677,2;2335678,3.
基金supported by The National Key Research and Development Program of China(2021YFB4001204)National Natural Science Foundation of China(22379143)。
文摘Acid loss and plasticization of phosphoric acid(PA)-doped high-temperature polymer electrolyte membranes(HT-PEMs)are critical limitations to their practical application in fuel cells.To overcome these barriers,poly(terphenyl piperidinium)s constructed from the m-and p-isomers of terphenyl were synthesized to regulate the microstructure of the membrane.Highly rigid p-terphenyl units prompt the formation of moderate PA aggregates,where the ion-pair interaction between piperidinium and biphosphate is reinforced,leading to a reduction in the plasticizing effect.As a result,there are trade-offs between the proton conductivity,mechanical strength,and PA retention of the membranes with varied m/p-isomer ratios.The designed PA-doped PTP-20m membrane exhibits superior ionic conductivity,good mechanical strength,and excellent PA retention over a wide range of temperature(80–160°C)as well as satisfactory resistance to harsh accelerated aging tests.As a result,the membrane presents a desirable combination of performance(1.462 W cm^(-2) under the H_(2)/O_(2)condition,which is 1.5 times higher than that of PBI-based membrane)and durability(300 h at 160°C and 0.2 A cm^(-2))in the fuel cell.The results of this study provide new insights that will guide molecular design from the perspective of microstructure to improve the performance and robustness of HT-PEMs.
基金the Fundamental Research Funds for the Central Universities(Grant No.30920041102)National Natural Science Foundation of China(Grant No.11802134).
文摘The arc ignition system based on charring polymers has advantages of simple structure,low ignition power consumption and multiple ignitions,which bringing it broadly application prospect in hybrid propulsion system of micro/nano satellite.However,charring polymers alone need a relatively high input voltage to achieve pyrolysis and ignition,which increases the burden and cost of the power system of micro/nano satellite in practical application.Adding conductive substance into charring polymers can effectively decrease the conducting voltage which can realize low voltage and low power consumption repeated ignition of arc ignition system.In this paper,a charring conductive polymer ignition grain with a cavity geometry in precombustion chamber,which is composed of PLA and multiwall carbon nanotubes(MWCNT)was proposed.The detailed ignition processes were analyzed and two different ignition mechanisms in the cavity of charring conductive polymers were revealed.The ignition characteristics of charring conductive polymers were also investigated at different input voltages,ignition grain structures,ignition locations and injection schemes in a visual ignition combustor.The results demonstrated that the ignition delay and external energy required for ignition were inversely correlated with the voltages applied to ignition grain.Moreover,the incremental depth of cavity shortened the ignition delay and external energy required for ignition while accelerated the propagation of flame.As the depth of cavity increased from 2 to 6 mm(at 50 V),the time of flame propagating out of ignition grain changed from 235.6 to 108 ms,and values of mean ignition delay time and mean external energy required for ignition decreased from 462.8 to 320 ms and 16.2 to 10.75 J,respectively.The rear side of the cavity was the ideal ignition position which had a shorter ignition delay and a faster flame propagation speed in comparison to other ignition positions.Compared to direct injection scheme,swirling injection provided a more favorable flow field environment in the cavity,which was beneficial to ignition and initial flame propagation,but the ignition position needed to be away from the outlet of swirling injector.At last,the repeated ignition characteristic of charring conductive polymers was also investigated.The ignition delay time and external energy required for ignition decreased with repeated ignition times but the variation was decreasing gradually.
文摘Different drillingfluid systems are designed according to mineral composition,lithology and wellbore stability of different strata.In the present study,the conversion of a non-dispersed polymer drillingfluid into a low potas-sium anti-collapsing drillingfluid is investigated.Since the two drillingfluids belong to completely different types,the key to this conversion is represented by new inhibitors,dispersants and water-loss agents by which a non-dispersed drillingfluid can be turned into a dispersed drillingfluid while ensuring wellbore stability and reason-able rheology(carrying sand—inhibiting cuttings dispersion).In particular,the(QYZ-1)inhibitors and(FSJSS-2)dispersants are used.The former can inhibit the hydration expansion capacity of clay,reduce the dynamic shear force and weaken the viscosity;the latter can improve the sealing effect and reduce thefiltrate loss.The results have shown that after adding a reasonable proportion of these substances(QYZ-1:FSJSS-2)to the non-dispersed polymer drillingfluid,while the apparent viscosity,plastic viscosity,structural viscosity andfluidity index under-went almost negligible changes,the dynamic plastic ratio increased,and thefiltration loss decreased significantly,thereby indicating good compatibility.According to the tests(conducted in the Leijia area),the density was 1.293 g/cm3,and after standing for 24 h,the SF(static settlement factor)was 0.51.Moreover,thefiltration loss was reduced to 4.0 mL,the rolling recovery rate reached 96.92%,with excellent plugging and anti-collapse performances.
文摘The characterization of these molecularly imprinted polymers is essential to understanding their binding dynamics and structural properties. Through the analysis of the current research, it is found that there are overlaps in the methods used by scholars. The Langmuir equation is frequently applied to model the adsorption isotherms of MIPs, providing critical insight into the capacity and affinity of the binding sites. Infrared Spectroscopy (IR) plays a crucial role in identifying the functional groups involved in the imprinting process and confirming the successful formation of specific binding sites. UV-visible spectrophotometry is employed to monitor the absorption characteristics of the polymers, offering data on the interactions between the template molecules and the polymer matrix. Transmission Electron Microscopy (TEM) provides detailed visualization of the internal structure of MIPs at the nanoscale, revealing the morphology and size of the imprinted cavities. Thermogravimetric Analysis (TGA) assesses the thermal stability and composition of the polymers, identifying decomposition patterns that are indicative of the material’s robustness under different conditions. Finally, the Laser Particle Size Analyzer is used to measure the size distribution of the polymer particles, which is critical for determining the uniformity and efficiency of the imprinting process. The six characterization methods discussed in this paper provide a comprehensive understanding of MIP, and it is hoped that in the future, more optimized design solutions will emerge and their applications in various fields will be enhanced.
基金This work was supported by the National Natural Science Foundation of China (Nos. 21374026 and 51573032), the National Science Fund for Distinguished Young Scholars (No. 51725302), Science Fund for Creative Research Groups of the National Natural Science Foundation of China (No. 11621505), CAS Key Research Program for Frontier Sciences (No. QYZDJ-SSW-SLH022), Key Project of Chinese Academy of Sciences in Cooperation with Foreign Enterprises (No. GJHZ1541), and CAS Interdisciplinary Innovation Team.
文摘Interest in temperature-responsive polymers has steadily grown over the past several decades, and numerous studies have been dedicated to developing temperature sensitive polymers that can be constructed into new smart materials for biomedical applications. Phase behavior of a temperature-responsive polymer plays a pivotal role in determining its biological performance in certain conditions. In addition to the additives (such as salts and proteins) in aqueous solutions, molecular weight, molecular weight distribution, and structural or compositional factors can also significantly affect the transition temperatures of the polymers. This review comprehensively describes well-established and newly developed synthetic strategies for preparing temperature-responsive polymers. The structural and compositional parameters that affect the transition temperatures and self-assembly behavior are discussed. Finally, the biomedical applications of the temperature-responsive polymers in drug delivery, immunotherapy, tissue engineering, and diagnosis are summarized.
基金supported by the National Natural Science Foundation of China(51978569 and 52172097)Key Research and Development Program of Shaanxi Province(2022GY-301)+4 种基金Basic and Public Projects of Zhejiang Province(LGF21E020001)China Postdoctoral Science Foundation(2020 M683467)Basic Research Operating Expenses of XJTU(xzy022022041)China Scholarship Council foundation(201906285020 and 202206280212)support from Faraday Institution LiSTAR Programme(EP/S003053/1,Grant FIRG014).
文摘Lithium-sulfur(Li-S)batteries have attracted increased interest because of the high theoretical energy density,low cost,and environmental friendliness.Conducting polymers(CPs),as one of the most promising materials used in Li-S batteries,can not only facilitate electron transfer and buffer the large volumetric change of sulfur benefiting from their porous structure and excellent flexibility,but also enable stronger physical/chemical adsorption capacity toward polysulfides(LiPSs)when doped with abundant heteroatoms to promote the sulfur redox kinetics and achieve the high sulfur loading.This review firstly introduces the properties of various CPs including structural CPs(polypyrrole(PPy),polyaniline(PANi),polyethylene dioxothiophene[PEDOT])and compound CPs(polyethylene oxide(PEO),polyvinyl alcohol(PVA)and poly(acrylic acid)[PAA]),and their application potential in Li-S batteries.Furthermore,the research progress of various CPs in different components(cathode,separator,and interlayer)of Li-S batteries is systematically summarized.Finally,the application perspective of the CPs in Li-S batteries as a potential guidance is comprehensively discussed.
基金support from the Natural Science Foundation of Shanghai (20ZR1464000)G.Zeng acknowledges the support from the National Natural Science Foundation of China (21878322,22075309)the Science and Technology Commission of Shanghai Municipality (19ZR1479200,22ZR1470100)。
文摘Metal-organic frameworks and covalent organic frameworks have been widely employed in electrochemical catalysis owing to their designable skeletons,controllable porosities,and well-defined catalytic centers.However,the poor chemical stability and low electron conductivity limited their activity,and single-functional sites in these frameworks hindered them to show multifunctional roles in catalytic systems.Herein,we have constructed novel metal organic polymers(Co-HAT-CN and Ni-HAT-CN)with dual catalytic centers(metal-N_(4) and metal-N_(2))to catalyze oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).By using different metal centers,the catalytic activity and selectivity were well-tuned.Among them,Co-HAT-CN catalyzed the ORR in a 4e^(-)pathway,with a half-wave potential of 0.8 V versus RHE,while the Ni-HAT-CN catalyze ORR in a 2e^(-)pathway with H_(2)O_(2) selectivity over 90%.Moreover,the Co-HAT-CN delivered an overpotential of 350 mV at 10 mA cm^(-2) with a corresponding Tafel slope of 24 mV dec^(-1) for OER in a 1.0 M KOH aqueous solution.The experimental results revealed that the activities toward ORR were due to the M-N_(4) sites in the frameworks,and both M-N_(4) and M-N_(2) sites contributed to the OER.This work gives us a new platform to construct bifunctional catalysts.
基金the financial support from the National Natural Science Foundation of China(Nos.22205191 and 52002346)the Science and Technology Innovation Program of Hunan Province(No.2021RC3109)+1 种基金the Natural Science Foundation of Hunan Province,China(No.2022JJ40446)Guangxi Key Laboratory of Low Carbon Energy Material(No.2020GXKLLCEM01)。
文摘The concentration difference in the near-surface region of lithium metal is the main cause of lithium dendrite growth.Resolving this issue will be key to achieving high-performance lithium metal batteries(LMBs).Herein,we construct a lithium nitrate(LiNO_(3))-implanted electroactiveβphase polyvinylidene fluoride-co-hexafluoropropylene(PVDF-HFP)crystalline polymorph layer(PHL).The electronegatively charged polymer chains attain lithium ions on the surface to form lithium-ion charged channels.These channels act as reservoirs to sustainably release Li ions to recompense the ionic flux of electrolytes,decreasing the growth of lithium dendrites.The stretched molecular channels can also accelerate the transport of Li ions.The combined effects enable a high Coulombic efficiency of 97.0%for 250 cycles in lithium(Li)||copper(Cu)cell and a stable symmetric plating/stripping behavior over 2000 h at 3 mA cm^(-2)with ultrahigh Li utilization of 50%.Furthermore,the full cell coupled with PHL-Cu@Li anode and Li Fe PO_(4) cathode exhibits long-term cycle stability with high-capacity retention of 95.9%after 900 cycles.Impressively,the full cell paired with LiNi_(0.87)Co_(0.1)Mn_(0.03)O_(2)maintains a discharge capacity of 170.0 mAh g^(-1)with a capacity retention of 84.3%after 100 cycles even under harsh condition of ultralow N/P ratio of 0.83.This facile strategy will widen the potential application of LiNO_(3)in ester-based electrolyte for practical high-voltage LMBs.
基金support from Zhejiang Normal University(YS304320035,YS304320036)the National Key Research and Development Program of China(2016YFB0100100,2016YFA0200200)+5 种基金the National Natural Science Foundation of China(51872283,22075279,21805273,22005297,22005298)the Liaoning Revitalization Talents Program(XLYC1807153)the Funds for Local Science and Technology Development by the Central Government of Liaoning Province(2021JH6/10500112)Dalian Innovation Support Plan for High Level Talents(2019RT09)Dalian National Laboratory For Clean Energy(DNL),CAS,DNL Cooperation Fund,CAS(DNL201912,DNL201915)DICP(DICP ZZBS201708,DICP ZZBS201802,DICP I2020032).
文摘Synthesis of new carbon nanostructures with tunable properties is vital for precisely regulating electrochemical performance in the wide applications.Herein,we report a novel approach for the oxidative polymerization of N-and P-bearing copolymers from the self-assembly of three different monomers(aniline,pyrrole,and phytic acid),and further prepare the respective carbon nanostructures with relatively consistent N dopant(6.2%–8.0%,atom)and varying P concentrations(0.4%–2.8%,atom)via controllable pyrolysis.The impacts of phytic acid addition on the compositional,structural,and morphological evolution of the copolymers and the resulting nanocarbons are well studied through a spectrum of characterizations including N2 sorption,Fourier transform infrared spectroscopy,gel permeation chromatograph,scanning/transmission electron microscopy,and X-ray photoelectron spectroscopy.Gradual fragmentation of the nanosphere structures is evidenced with increasing addition of phytic acid,leading to different nanostructures from hollow nanospheres to 3D aggregates.Nanocarbons decorated with N and P dopants from pyrolysis are further utilized as anode materials in lithium-ion batteries,demonstrating enhanced electrochemical performance,i.e.,a reversible capacity of 380 mAhg^(-1)at 2 Ag^(-1)for NPC-0.5 during 200 cycles.The superior performance originates from the balanced porosity,and appropriate concentrations of P and pyrrolic N,thus pointing the direction for designing high-performance anode materials.
文摘Sulfur-rich copolymers made through inverse vulcanization exhibit a wide range of potentially valuable applications, for example as adsorbents to capture mercury pollution. Among the diverse second monomers of the copolymers, vegetable oil is a renewable resource, and recycled cooking oils have an important role in saving natural products. However, they need relatively high temperatures(160–180 ℃) to react with sulfur. To develop a low-temperature(130 ℃) reaction process for non-conjugated vegetable oil, we incorporate a small amount of tung oil, which contains conjugated trienes that can produce highly active free radicals during reactions. A variety of analytical techniques(proton nuclear magnetic resonance and Fourier-transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, X-ray diffraction, and dynamic mechanical analysis) are used to characterize the chemical structures and physical properties of the copolymers. The addition of tung oil is found to significantly improve the thermal stability and mechanical properties of the copolymers. We also investigate the effect of different ratios of raw materials on the gel time, free sulfur content, glass transition temperature T_(g), and degradation temperature of the copolymers. We find that increasing the amount of tung oil in the raw material mixture decreases the gel time and free sulfur content, but increases T_(g) and the degradation temperature. The copolymers exhibit a high adsorption capacity for mercury ions up to 33 mg Hg^(2+) per gram of adsorbent. These results demonstrate the feasibility of using sulfur-rich copolymers as effective mercury removal adsorbents, with the potential for further improvement by foaming the copolymers into porous materials.
基金supported by the National Natural Science Foundation of China(52122702,52277215)the Natural Science Foundation of Heilongjiang Province of China(JQ2021E005)。
文摘Exploration of advanced gel polymer electrolytes(GPEs)represents a viable strategy for mitigating dendritic lithium(Li)growth,which is crucial in ensuring the safe operation of high energy density Li metal batteries(LMBs).Despite this,the application of GPEs is still hindered by inadequate ionic conductivity,low Li^(+)transference number,and subpar physicochemical properties.Herein,Ti O_(2-x)nanofibers(NF)with oxygen vacancy defects were synthesized by a one-step process as inorganic fillers to enhance the thermal/mechanical/ionic-transportation performances of composite GPEs.Various characterizations and theoretical calculations reveal that the oxygen vacancies on the surface of Ti O_(2-x)NF accelerate the dissociation of Li PF_6,promote the rapid transfer of free Li^(+),and influence the formation of Li F-enriched solid electrolyte interphase.Consequently,the composite GPEs demonstrate enhanced ionic conductivity(1.90m S cm^(-1)at room temperature),higher lithium-ion transference number(0.70),wider electrochemical stability window(5.50 V),superior mechanical strength,excellent thermal stability(210℃),and improved compatibility with lithium,resulting in superior cycling stability and rate performance in both Li||Li,Li||Li Fe PO_(4),and Li||Li Ni_(0.8)Co_(0.1)Mn_(0.1)O_(2)cells.Overall,the synergistic influence of nanofiber morphology and enriched oxygen vacancy structure of fillers on electrochemical properties of composite GPEs is comprehensively investigated,thus,it is anticipated to shed new light on designing high-performance GPEs LMBs.
基金the National Natural Science Foundation of China(No.51973080,92066104).
文摘Polymer dielectrics capable of operating efficiently at high electric fields and elevated temperatures are urgently demanded by next-generation electronics and electrical power systems.While inorganic fillers have been extensively utilized to improved high-temperature capacitive performance of dielectric polymers,the presence of thermodynamically incompatible organic and inorganic components may lead to concern about the long-term stability and also complicate film processing.Herein,zero-dimensional polymer dots with high electron affinity are introduced into photoactive allyl-containing poly(aryl ether sulfone)to form the all-organic polymer composites for hightemperature capacitive energy storage.Upon ultraviolet irradiation,the crosslinked polymer composites with polymer dots are efficient in suppressing electrical conduction at high electric fields and elevated temperatures,which significantly reduces the high-field energy loss of the composites at 200℃.Accordingly,the ultraviolet-irradiated composite film exhibits a discharged energy density of 4.2 J cm^(−3)at 200℃.Along with outstanding cyclic stability of capacitive performance at 200℃,this work provides a promising class of dielectric materials for robust high-performance all-organic dielectric nanocomposites.