Bioinspired Passive Tactile Sensors Enabled by Reversible Polarization of Conjugated Polymers

Tactile perception plays a vital role for the human body and is also highly desired for smart prosthesis and advanced robots.Compared to active sensing devices,passive piezoelectric and triboelectric tactile sensors consume less power,but lack the capability to resolve static stimuli.Here,we address this issue by utilizing the unique polarization chemistry of conjugated polymers for the first time and propose a new type of bioinspired,passive,and bio-friendly tactile sensors for resolving both static and dynamic stimuli.Specifically,to emulate the polarization process of natural sensory cells,conjugated polymers(including poly(3,4-ethylenedioxythiophen e):poly(styrenesulfonate),polyaniline,or polypyrrole)are controllably polarized into two opposite states to create artificial potential differences.The controllable and reversible polarization process of the conjugated polymers is fully in situ characterized.Then,a micro-structured ionic electrolyte is employed to imitate the natural ion channels and to encode external touch stimulations into the variation in potential difference outputs.Compared with the currently existing tactile sensing devices,the developed tactile sensors feature distinct characteristics including fully organic composition,high sensitivity(up to 773 mV N^(−1)),ultralow power consumption(nW),as well as superior bio-friendliness.As demonstrations,both single point tactile perception(surface texture perception and material property perception)and two-dimensional tactile recognitions(shape or profile perception)with high accuracy are successfully realized using self-defined machine learning algorithms.This tactile sensing concept innovation based on the polarization chemistry of conjugated polymers opens up a new path to create robotic tactile sensors and prosthetic electronic skins.

3D Printing of Periodic Porous Metamaterials for Tunable Electromagnetic Shielding Across Broad Frequencies

The new-generation electronic components require a balance between electromagnetic interference shielding efficiency and open structure factors such as ventilation and heat dissipation.In addition,realizing the tunable shielding of porous shields over a wide range of wavelengths is even more challenging.In this study,the well-prepared thermoplastic polyurethane/carbon nanotubes composites were used to fabricate the novel periodic porous flexible metamaterials using fused deposition modeling 3D printing.Particularly,the investigation focuses on optimization of pore geometry,size,dislocation configuration and material thickness,thus establishing a clear correlation between structural parameters and shielding property.Both experimental and simulation results have validated the superior shielding performance of hexagon derived honeycomb structure over other designs,and proposed the failure shielding size(D_(f)≈λ/8-λ/5)and critical inclined angle(θf≈43°-48°),which could be used as new benchmarks for tunable electromagnetic shielding.In addition,the proper regulation of the material thickness could remarkably enhance the maximum shielding capability(85-95 dB)and absorption coefficient A(over 0.83).The final innovative design of the porous shielding box also exhibits good shielding effectiveness across a broad frequency range(over 2.4 GHz),opening up novel pathways for individualized and diversified shielding solutions.

Polymer Fiber Rigid Network with High Glass Transition Temperature Reinforces Stability of Organic Photovoltaics

Organic photovoltaics(OPVs)need to overcome limitations such as insufficient thermal stability to be commercialized.The reported approaches to improve stability either rely on the development of new materials or on tailoring the donor/acceptor morphology,however,exhibiting limited applicability.Therefore,it is timely to develop an easy method to enhance thermal stability without having to develop new donor/acceptor materials or donor–acceptor compatibilizers,or by introducing another third component.Herein,a unique approach is presented,based on constructing a polymer fiber rigid network with a high glass transition temperature(T_(g))to impede the movement of acceptor and donor molecules,to immobilize the active layer morphology,and thereby to improve thermal stability.A high-T_(g) one-dimensional aramid nanofiber(ANF)is utilized for network construction.Inverted OPVs with ANF network yield superior thermal stability compared to the ANF-free counterpart.The ANF network-incorporated active layer demonstrates significantly more stable morphology than the ANF-free counterpart,thereby leaving fundamental processes such as charge separation,transport,and collection,determining the device efficiency,largely unaltered.This strategy is also successfully applied to other photovoltaic systems.The strategy of incorporating a polymer fiber rigid network with high T_(g) offers a distinct perspective addressing the challenge of thermal instability with simplicity and universality.

Thermotolerant and fireproof gel polymer electrolyte toward high-performance and safe lithium-ion battery

Poly(ethylene oxide)(PEO)and its derivatives based gel polymer electrolytes(GPEs)are severely limited in advanced and safe lithium-ion batteries(LIBs)owing to the intrinsically high flammability of liquid electrolytes and PEO.Directly adding flame retardants to the GPEs can suppress their flammability and thus improve the safety of LIBs,but results in deteriorative electrochemical performance.Herein,a novel GPE with chemically bonded flame retardant(i.e.diethyl vinylphosphonate)in cross-linked polyethylene glycol diacrylate matrix,featuring both high-safety and high-performance,is designed.This as-prepared GPE storing the commercial 1 mol L^(-1) LiPF6 electrolyte resists high temperature of 200℃and cannot be ignited as well as possesses a high ionic conductivity(0.60 m S cm^(-1))and good compatibility with lithium.Notably,the LiFePO_(4)/Li battery with this GPE delivers a satisfactory capacity of 142.2 m A h g^(-1) and a superior cycling performance with a capacity retention of 96.3%and a coulombic efficiency of close to 100%for 350 cycles at 0.2 C under ambient temperature.Furthermore,the battery can achieve steady charge–discharge for 100 cycles with a coulombic efficiency of 99.5%at 1 C under 80℃and run normally even at a high temperature of 150℃or under the exposure to butane flame.Differential scanning calorimetry manifests significantly improved battery safety compared to commercial battery systems.This work provides a new pathway for developing next-generation advanced LIBs with enhanced performance and high safety.

From trash to treasure: Chemical recycling and upcycling of commodity plastic waste to fuels, high-valued chemicals and advanced materials

Of all the existing materials, plastics are no doubt among the most versatile ones. However, the extreme increases in plastic production as well as the difficulty of the material for degradation have led to a huge number of plastic wastes. Their recycling rate after disposal is less than 10%, resulting in a series of serious environmental and ecological problems as well as a significant waste of resources. Current recycling methods generally suffer from large energy consumption, the low utilization rate of recycled products with low added value, and produce other waste during the process. Here, we summarized recentlydeveloped chemical recycling ways on commodity plastics, especially new catalytic paths in production of fuels, high-valued chemicals and advanced materials from a single virgin or a mixture of plastic waste,which have emerged as promising ways to valorize waste plastics more economically and environmentally friendly. The new catalyst design criteria as well as innovative catalytic paths and technologies for plastic upcycling are highlighted. Beyond energy recovery by incineration, these approaches demonstrate how waste plastics can be a viable feedstock for energy use with the generation of clean H_(2), high-quality liquid fuels and materials for energy storage, and help inspiring more catalytic process on plastic upcycling to overcome the economical hurdle and building a circular plastic economy.

Preparation of Copolymer of Salen-crown Ether Complexes and its Catalytic Activation for Molecular Oxygen

A new stable salen Schiff base cobalt and crown ether sodium complex （SalCo-NaB18C6） was prepared through copolymerization. This copolymer complex was applied to catalytic oxidation of hydrocarbon compound with molecular oxygen without reductant, which was shown the higher activity and selectivity for ketone, and reused effectively.

Preparation of polymer-supported phosphine from ferrocene for palladium-catalyzed Suzuki-Miyaura cross-coupling reactions

Polymer-supported phosphine ligand 3b derived from ferrocene was prepared, and applied in palladium-catalyzed Suzuki- Miyaura reactions. A range of aryl bromides can couple with phenylboronic acid to obtain corresponding biaryls in excellent yields. The recycling of the polymer-bound catalyst was tested without adding palladium.

Fabrication of segregated poly(arylene sulfide sulfone)/graphene nanoplate composites reinforced by polymer fibers for electromagnetic interference shielding

Poly(arylene sulfide sulfone)/graphene nanoplate(PASS/GNP) composites with segregated structure based on continuous polymer fiber skeletons were fabricated by coating a thin conductive layer on the PASS fibers and then performing compression molding. The formation of a unique segregated conductive network endowed the PASS/GNP composites with high electrical conductivity and excellent electromagnetic interference(EMI) shielding effectiveness(SE), reaching 17.8 S/m and 30.1 d B, respectively, when the content of the GNPs in the conductive layer was 20 wt%. The PASS/GNP composites also exhibited outstanding mechanical properties, which was attributed to the continuous PASS fiber skeletons that could withstand large loads and the strong interfacial interaction between the conductive layers and the PASS fibers that could provide good stress transfer. This approach is suitable for most soluble polymers.

Highly Active New α-Diimine Nickel Catalyst for Polymerization of Ethylene

A new α-diimine ligand 1a, bis[N,N′-（4-tert-butyl-2,6-dimethylphenyl）imino]-2,3-butanediylidene and its corresponding Ni（II） complex 2a, {bis[N,N′-（4-tert-butyl-2,6-dimethylphenyl）imino]-2,3-butanediylidene}dibromo- nickel were successfully synthesized, and characterized by 1H NMR, 13C NMR, Fourier transform infrared spectroscope（FTIR）, elemental analysis and X-ray photoelectron spectroscopy（XPS）. α-Diimine ligand 1b, bis[N,N′-（2,6- dimethylphenyl）imino]-2,3-butanediylidene and its corresponding Ni（II） complex 2b, {bis[N,N′-（2,6-dimethyl- phenyl）imino]-2,3-butanediylidene}dibromonickel were also synthesized and characterized for comparison. The pre-catalyst 2a with sterically bulky, electron-donating group tert-butyl, activated by diethylaluminum chloride （DEAC） and tested in the polymerization of ethylene, was very highly active[2.01×107 g PE/（mol Ni？h？0.1 MPa）] and led to a very highly branched polyethylene（ca. 35―103 branches/1000 C）. The state of the polyethylene obtained varied from plastic, elastomer polymers to the oil-like hyperbranched polymers.

Composition Dependence of the Thermal Behavior,Morphology and Properties of Biodegradable PBS/PTMO Segment Block Copolymer

A series of aliphatic biodegradable poly（ether-ester）s based on poly（butylene succinate）（PBS）as hard segment and poly（tetramethylene oxide）（PTMO,M_n=1 000 g/mol） as soft segment were synthesized.The composition dependence of thermal behavior,morphology and mechanical properties was investigated by differential scanning calorimetry（DSC）,atomic force microscopy（AFM）,and tensile testing.The crystallization temperature（T_c） and melting temperature（T_m） of the PBS block within poly（ether-ester）s decrease steadily at first,but decrease sharply with PTMO content above 50 wt%.Two crystallization peaks were detected for PTMO in PBSPTMO60 sample,suggesting the occurrence of fractionated crystallization.The crystallization enthalpies（△H_c） and melting enthalpies（△H_m） of PBS block decrease at first,then increase as PTMO content increases further.AFM has demonstrated that phase-separated morphology transforms from a phase of continuous hard matrix to one of continuous soft matrix containing isolated hard domain as PTMO content is increased.Finally,the results of tensile testing show that the poly（ether-ester）s present the behavior of plastics when PTMO content is below 40 wt%,and of thermoplastic elastomers with PTMO content above 50 wt%.By varying the composition of copolymer,the aliphatic poly（ether-ester）s plastics,or especially biodegradable aliphatic poly（ether-ester）s thermoplastic elastomers can be obtained.

Syntheses, Structures and Properties of Two 2D Coordination Polymers from 5-(Pyridin-2-yl-methyl)aminoisophthalate

Hydrothermal reactions of 5-（pyridin-2-yl-methyl）aminoisophthalic acid（H2paip） with Mn（OAc）2·4H2O and Cu（NO3）2·3H2O produced two 2D complexes, [Mn（paip）]n·nH2O（1） and [Cu（paip）（H2O）]n（2）. In complex 1, paip serves as a μ4-bridge, and its two carboxylate groups in μ2,η2-bridging and chelating modes connect Mn（Ⅱ） into 1D chains, which are further extended into a 2D layer through coordination of two chelating nitrogen atoms. However, paip in complex 2 acts as a μ3-bridge to link Cu（Ⅱ） into a 2D layer, in which two carboxylate groups function in a monodentate mode, and hydrogen bonds between the coordinated water and carboxylate oxygen atoms further extend the 2D layers into a 3D supramolecular network. The frameworks of complexes 1 and 2 are stable up to 470 and 250 ℃, respectively. Magnetic measurement shows that complex 2 possesses a weak antiferromagnetic interaction.

“Toolbox”for the Processing of Functional Polymer Composites

Functional polymer composites(FPCs)have attracted increasing attention in recent decades due to their great potential in delivering a wide range of functionalities.These functionalities are largely determined by functional fillers and their network morphology in polymer matrix.In recent years,a large number of studies on morphology control and interfacial modification have been reported,where numerous preparation methods and exciting performance of FPCs have been reported.Despite the fact that these FPCs have many similarities because they are all consisting of functional inorganic fillers and polymer matrices,review on the overall progress of FPCs is still missing,and especially the overall processing strategy for these composites is urgently needed.Herein,a"Toolbox"for the processing of FPCs is proposed to summarize and analyze the overall processing strategies and corresponding morphology evolution for FPCs.From this perspective,the morphological control methods already utilized for various FPCs are systematically reviewed,so that guidelines or even predictions on the processing strategies of various FPCs as well as multi-functional polymer composites could be given.This review should be able to provide interesting insights for the field of FPCs and boost future intelligent design of various FPCs.

Visualization of adaptive polymer flow and displacement in medium-permeable 3D core-on-a-chip

Polymer flooding has been witnessed an effective technology for enhancing oil recovery from medium-to low-permeability reservoirs;however, direct visualization of polymer solution flow in such reservoir condition is still lacking. In this work, a three-dimensional (3D) core-on-a-chip device with a permeability of around 200 mD was prepared and employed to visualize the pore-scale flow and displacement of a self-adaptive polymer (SAP, 8.7 × 106 g·mol−1)−whose microscopic association structure and macroscopic viscosity can reversibly change in response to shear action−versus partially hydrolyzed polyacrylamide (HPAM), by recording their flow curves, monitoring dynamic transportation process via particle imaging velocimetry, and building 3D structure of remaining oil. The results show that, in single-phase flow, all polymer solutions exhibit flow thinning and then thickening regions as flow rate increases, but the transition between two regimes occurs at a small Weissenberg number (10−3−10−1) in this medium-permeable condition. In contrast to HPAM-1 with close weight-average molecular weight (Mw), the adaptive character not only extends SAP's shear-govern region, allowing SAP to propagate piece by piece and achieve higher accessible pore volume, but it also enhances the elastic resistibility of polymer in the extension-dominated regime, increasing the microscopic displacement efficiency. These two effects result in 1.5–3 times more oil recovery factor for SAP than for HPAM-1. Regarding ultra-high-Mw HPAM-2 (25 × 106 g·mol−1), plugging and chain degradation do occur, thus producing lower oil recovery than SAP. This work provides a direct approach for in-situ assessment of polymer-based displacing system under a more authentic condition of practical reservoirs.

Crystallization Behavior of Poly(Tetramethylene Oxide) Influenced by the Crystallization Condition of Poly(Butylene Succinate) in Their Copolymers

The effect of crystallization conditions of poly(butylene succinate)(PBS) component on the crystallization of poly(tetramethylene oxide)(PTMO) component in their segment block copolymer, with a higher PTMO content(PTMO mass fraction is 67%), was investigated by DSC and temperature-dependent FTIR. It is found that the isothermal crystallization time(tIC) of PBS has an effect on the crystallization behavior of PTMO component. Perturbation correlation move-window two-dimensional(PCMW2 D) correlation analysis and generalized 2 D correlation analysis(2 DIR) were performed to explore the origin of this phenomenon. The PCMW2 D and 2 DIR results show that the correlation intensity peak observed at around 20 ℃ for PTMO is due to the PTMO chains movements forced by the PBS chains folded movements. If tIC of PBS at temperature of 20 ℃ is prolonged, more PTMO components are incorporated in the region between PBS lamellae and the peak at-7.6 ℃(belonging to less-constricted PTMO chains) changes smaller and even disappears, while the peak at-16.3 ℃ belonging to more-constricted PTMO chains gets bigger. A crystallization model was also established in this study. The results of tensile testing showed that tensile strength slightly increased and elongation at break decreased with increasing heat treatment time at 40 ℃.

In situ Hydrothermal Oxidation of Ternary FeCoNi Alloy Electrode for Overall Water Splitting

Exploring noble metal-free catalyst materials for high efficient electrochemical water splitting to produce hydrogen is strongly desired for renewable energy development.In this article,a novel bifunctional catalytic electrode of insitu-grown type for alkaline water splitting based on FeCoNi alloy substrate has been successfully prepared via a facile one-step hydrothermal oxidation route in an alkaline hydrogen peroxide medium.It shows that the matrix alloy with the atom ratio 4∶3∶3 of Fe∶Co∶Ni can obtain the best catalytic performance when hydrothermally treated at 180℃for 18 h in the solution containing 1.8 M hydrogen peroxide and 3.6 M sodium hydroxide.The as-prepared Fe_(0.4)Co_(0.3)Ni_(0.3)-1.8 electrode exhibits small overpotentials of only 184 and 175 mV at electrolysis current density of 10 mA cm^(-2)for alkaline OER and HER processes,respectively.The overall water splitting at electrolysis current density of 10 mA cm^(-2)can be stably delivered at a low cell voltage of 1.62 V.These characteristics including the large specific surface area,the high surface nickel content,the abundant catalyst species,the balanced distribution between bivalent and trivalent metal ions,and the strong binding of in-situ naturally growed catalytic layer to matrix are responsible for the prominent catalytic performance of the Fe_(0.4)Co_(0.3)Ni_(0.3)-1.8 electrode,which can act as a possible replacement for expensive noble metal-based materials.

EFFECT OF MORPHOLOGICAL STRUCTURE OF AMINOMETHYL POLYSTYRENE RESIN ON THE CATALYTIC PROPERTIES OF POLYMERSUPPORTED RUTHENIUM COMPLEXES

Polymer-supported ruthenium complexes ■-Phen-Ru-①,■-Phen-Ru-②,■-Phen-Ru-③,■-Phen-Ru-④, ■-Phen-Ru-⑤,■-Phen-Ru-⑥and ■-Phen-Ru-⑦were prepared using aminomethyl polystyrenes of different morphological structures as supports.A variety of alcohols were oxidized efficiently into the corresponding ketones, carboxylic acids or aldehydes with iodosylbenzene (PhIO) catalyzed by aminomethyl polystyrene-supported ruthenium complexes under mild reaction conditions in acetonitrile.The influences of morphological structure...

Microemulsion Polymerization of Methyl Methacrylate

The microemulsion polymerization of methyl methacrylate was studied. The effects of feeding modes on the structure and the properties of the obtained polymer microlatex were investigated by measuring the conversion, the transmittance and the refractive index of the latex, and by measuring the particle size, the molecular weight and the glass transition temperature (T_g) of the polymers. The results show that compared to the batch feeding mode, the semi-continuous feeding mode is more favorable to form a PMMA microlatex with a higher transmittance, a smaller particle size, a higher molecular weight and a higher T_g. And the obtained PMMA microlatex has a 30%—40% (mass fraction) polymer content, a 0. 03 emulsifier/water weight ratio, a 0. 05 emulsifier/monomer weight ratio and a 17 nm average particle diameter, which is very important for the industrialization of the microemulsion polymerization technique.

In situ polymerization preparation and mechanical properties of nanocomposites based on PA10T/10I-block-PEG copolymer and graphene oxide

Poly(decamethylene terephthalamide/decamethylene isophthalamide)-block-polyvinyl alcoho)(PA10 T/10 IPEG) copolymer/graphene oxide(GO) composites were prepared via in-situ melt polymerization and two different nano-filler addition approaches were compared. The relationship between the micro-structure and performance of the elastomer composites prepared by one-step and two-step methods was explored. The results show that the two-step method significantly promoted the dispersion of the GO in a polymer matrix, and facilitated the grafting of more hard molecular chains. Thus, the elastic modulus and tensile strength of the nanocomposite have been significantly improved by the presence of GO. This was because of the strong interaction between the functional groups on the surface of the GO and the hard molecular chains. This would be also be favorable to load transfer across the interface. Additionally, the elongation at the break of composites increased by 10% with the addition of a small amount of GO(0.2% wt). This is because hard domains tend to be enriched on the surface of GO in composites and act as a lubricating layer at the interface between the GO and matrix, leading to increased deformation ability. This work provides an effective strategy to prepare elastomer composites with high strength and toughness.

3D printing encouraging desired in-situ polypyrrole seed-polymerization for ultra-high energy density supercapacitors

The tireless pursuit of supercapacitors with high energy density entails the parallel advancement of wellsuited electrode materials and elaborately engineered architectures.Polypyrrole(PPy)emerges as an exceedingly conductive polymer and a prospective pseudocapacitive materials for supercapacitors,yet the inferior cyclic stability and unpredictable polymerization patterns severely impede its real-world applicability.Here,for the first time,an innovative seed-induced in-situ polymerization assisted 3D printing strategy is proposed to fabricate PPy-reduced graphene oxide/poly(vinylidene difluoride-cohexafluoropropylene)(PVDF-HFP)(PPy-rGO/PH)electrodes with controllable polymerization behavior and exceptional areal mass loading.The preferred active sites uniformly pre-planted on the 3D-printed graphene substrates serve as reliable seeds to induce efficient polypyrrole deposition,achieving an impressive mass loading of 185.6 mg cm^(-2)(particularly 79.2 mg cm^(-2)for polypyrrole)and a superior areal capacitance of 25.2 F cm^(-2)at 2 mA cm^(-2)for a 12-layer electrode.In agreement with theses appealing features,an unprecedented areal energy density of 1.47 mW h cm^(-2)for a symmetrical device is registered,a rarely achieved value for other PPy/rGO-based supercapacitors.This work highlights a promising route to preparing high energy density energy storage modules for real-world applications.