IONIC SELF-ASSEMBLY AND HUMIDITY SENSITIVITY OF POLYELECTROLYTE MULTILAYERS

Multilayer thin films of alternately adsorbed layers of polyelectrolytes PDDA and PS-119 were formed on both planar silica substrates and optical fibers through the ionic self-assembly technique. Intrinsic Fabry-Perot cavities were fabricated by stepwise assembling the polyelectrolytes onto the ends of optical fibers for the purposes of fiber optical device and sensor development. Ionically assembled polyelectrolyte multilayer thin films, in which. there are hydrophilic side groups with strong affinity towards water molecules, are a category of humidity-sensitive functional materials. The polyelectrolyte multilayer thin film Fabry-Perot cavity-type fiber optical humidity sensor can work over a wide range from about 0% RH to about 100% RH with a response time less than 1 s.

Self-assembly of perovskite nanocrystals:From driving forces to applications

Self-assembly of metal halide perovskite nanocrystals(NCs)into superlattices can exhibit unique collective properties,which have significant application values in the display,detector,and solar cell field.This review discusses the driving forces behind the self-assembly process of perovskite NCs,and the commonly used self-assembly methods and different self-assembly structures are detailed.Subsequently,we summarize the collective optoelectronic properties and application areas of perovskite superlattice structures.Finally,we conclude with an outlook on the potential issues and future challenges in developing perovskite NCs.

Alcohol solvent effect on the self-assembly behaviors of lignin oligomers

The interactions between lignin oligomers and solvents determine the behaviors of lignin oligomers self-assembling into uniform lignin nanoparticles(LNPs).Herein,several alcohol solvents,which readily interact with the lignin oligomers,were adopted to study their effects during solvent shifting process for LNPs’production.The lignin oligomers with widely distributed molecular weight and abundant guaiacyl units were extracted from wood waste(mainly consists of pine wood),exerting outstanding self-assembly capability.Uniform and spherical LNPs were generated in H_(2)O-n-propanol cosolvent,whereas irregular LNPs were obtained in H_(2)O-methanol cosolvent.The unsatisfactory self-assembly performance of the lignin oligomers in H_(2)O-methanol cosolvent could be attributed to two aspects.On one hand,for the initial dissolution state,the distinguishing Hansen solubility parameter and polarity between methanol solvent and lignin oligomers resulted in the poor dispersion of the lignin oligomers.On the other hand,strong hydrogen bonds between methanol solvent and lignin oligomers during solvent shifting process,hindered the interactions among the lignin oligomers for self-assembly.

Chitosan/Sodium Alginate Multilayer pH-Sensitive Films Based on Layer-by-Layer Self-Assembly for Intelligent Packaging

The abuse of plastic food packaging has brought about severe white pollution issues around the world.Developing green and sustainable biomass packaging is an effective way to solve this problem.Hence,a chitosan/sodium alginate-based multilayer film is fabricated via a layer-by-layer(LBL)self-assembly method.With the help of superior interaction between the layers,the multilayer film possesses excellent mechanical properties(with a tensile strength of 50 MPa).Besides,the film displays outstanding water retention property(blocking moisture of 97.56%)and ultraviolet blocking property.Anthocyanin is introduced into the film to detect the food quality since it is one natural plant polyphenol that is sensitive to the pH changes ranging from 1 to 13 in food when spoilage occurs.It is noted that the film is also bacteriostatic which is desired for food packaging.This study describes a simple technique for the development of advanced multifunctional and fully biodegradable food packaging film and it is a sustainable alternative to plastic packaging.

Hollow tubes constructed by carbon nanotubes self-assembly for CO_(2) capture

Carbon nanotubes(CNTs)have garnered significant attention in the fields of science,engineering,and medicine due to their numerous advantages.The initial step towards harnessing the potential of CNTs involves their macroscopic assembly.The present study employed a gentle and direct self-assembly technique,wherein controlled growth of CNT sheaths occurred on the metal wire’s surface,followed by etching of the remaining metal to obtain the hollow tubes composed of CNTs.By controlling the growth time and temperature,it is possible to alter the thickness of the CNTs sheath.After immersing in a solution containing 1 g/L of CNTs at 60℃ for 24 h,the resulting CNTs layer achieved a thickness of up to 60μm.These hollow CNTs tubes with varying inner diameters were prepared through surface reinforcement using polymers and sacrificing metal wires,thereby exhibiting exceptional attributes such as robustness,flexibility,air tightness,and high adsorption capacity that effectively capture CO_(2) from the gas mixture.

A Non-parametric Gradient-Based Shape Optimization Approach for Solving Inverse Problems in Directed Self-Assemblyof Block Copolymers

We consider the inverse problem of finding guiding pattern shapes that result in desired self-assembly morphologies of block copolymer melts.Specifically,we model polymer selfassembly using the self-consistent field theory and derive,in a non-parametric setting,the sensitivity of the dissimilarity between the desired and the actual morphologies to arbitrary perturbations in the guiding pattern shape.The sensitivity is then used for the optimization of the confining pattern shapes such that the dissimilarity between the desired and the actual morphologies is minimized.The efficiency and robustness of the proposed gradient-based algorithm are demonstrated in a number of examples related to templating vertical interconnect accesses(VIA).

Confined cobalt single-atom catalysts with strong electronic metal-support interactions based on a biomimetic self-assembly strategy

Designing high-performance and low-cost electrocatalysts for oxygen evolu-tion reaction(OER)is critical for the conversion and storage of sustainable energy technologies.Inspired by the biomineralization process,we utilized the phosphorylation sites of collagen molecules to combine with cobalt-based mononuclear precursors at the molecular level and built a three-dimensional(3D)porous hierarchical material through a bottom-up biomimetic self-assembly strategy to obtain single-atom catalysts confined on carbonized biomimetic self-assembled carriers(Co SACs/cBSC)after subsequent high-temperature annealing.In this strategy,the biomolecule improved the anchoring efficiency of the metal precursor through precise functional groups;meanwhile,the binding-then-assembling strategy also effectively suppressed the nonspecific adsorption of metal ions,ultimately preventing atomic agglomeration and achieving strong electronic metal-support interactions(EMSIs).Experimental characterizations confirm that binding forms between cobalt metal and carbonized self-assembled substrate(Co–O_(4)–P).Theoretical calculations disclose that the local environment changes significantly tailored the Co d-band center,and optimized the binding energy of oxygenated intermediates and the energy barrier of oxygen release.As a result,the obtained Co SACs/cBSC catalyst can achieve remarkable OER activity and 24 h durability in 1 M KOH(η10 at 288 mV;Tafel slope of 44 mV dec-1),better than other transition metal-based catalysts and commercial IrO_(2).Overall,we presented a self-assembly strategy to prepare transition metal SACs with strong EMSIs,providing a new avenue for the preparation of efficient catalysts with fine atomic structures.

Layer by Layer Self-assembly Fiber-based Flexible Electrochemical Transistor

Poly(3,4-ethylenedioxyethiophene)-polystyrene sulfonic acid(PEDOT:PSS)/polyallyl dimethyl ammonium chloride modified reduced graphene oxide(PDDA-rGO)was layer by layer self-assembled on the cotton fiber.The surface morphology and electric property was investigated.The results confirmed the dense membrane of PEDOT:PSS and the lamellar structure of PDDA-rGO on the fibers.It has excellent electrical conductivity and mechanical properties.The fiber based electrochemical transistor(FECTs)prepared by the composite conductive fiber has a maximum output current of 8.7 mA,a transconductance peak of 10 mS,an on time of 1.37 s,an off time of 1.6 s and excellent switching stability.Most importantly,the devices by layer by layer self-assembly technology opens a path for the true integration of organic electronics with traditional textile technologies and materials,laying the foundation for their later widespread application.

Combination therapy to overcome ferroptosis resistance by biomimetic self-assembly nano-prodrug

Ferroptosis has emerged as a potent form of no-apoptotic cell death that offers a promising alternative to avoid the chemoresistance of apoptotic pathways and serves as a vulnerability of cancer.Herein,we have constructed a biomimetic self-assembly nano-prodrug system that enables the co-delivery of gefitinib(Gefi),ferrocene(Fc)and dihydroartemisinin(DHA)for the combined therapy of both ferroptosis and apoptosis.In the tumor microenvironment,this nano-prodrug is able to disassemble and trigger drug release under high levels of GSH.Interestingly,the released DHA can downregulate GPX4 level for the enhancement of intracellular ferroptosis from Fc,further executing tumor cell death with concomitant chemotherapy by Gefi.More importantly,this nano-prodrug provides highly homologous targeting ability by coating related cell membranes and exhibits outstanding inhibition of tumor growth and metastasis,as well as no noticeable side-effects during treatments.This simple small molecular self-assembled nano-prodrug provides a new reasonably designed modality for ferroptosis-combined chemotherapy.

Efficient conversion of lignin waste and self-assembly synthesis of C@MnCo_(2)O_(4)for asymmetric supercapacitors with high energy density

Lignin waste from the papermaking and biorefineries industry is a significantly promising renewable resource to prepare advanced carbon materials for diverse applications,such as the electrodes of supercapacitors;however,the improvement of their energy density remains a challenge.Here,we design a green and universal approach to prepare the composite electrode material,which is composed of lignin-phenolformaldehyde resins derived hierarchical porous carbon(LR-HPC)as conductive skeletons and the self-assembly manganese cobaltite(MnCo_(2)O_(4))nanocrystals as active sites.The synthesized C@MnCo_(2)O_(4)composite has an abundant porous structure and superior electronic conductivity,allowing for more charge/electron mass transfer channels and active sites for the redox reactions.The composite shows excellent electrochemical performance,such as the maximum specific capacitance of~726 mF cm^(-2)at 0.5 mV s^(-1),due to the significantly enhanced interactive interface between LR-HPC and MnCo_(2)O_(4)crystals.The assembled all-solid-state asymmetric supercapacitor,with the LR-HPC and C@MnCo_(2)O_(4)as cathode and anode,respectively,exhibits the highest volumetric energy density of 0.68 mWh cm^(-3)at a power density of 8.2 mW cm^(-3).Moreover,this device shows a high capacity retention ratio of~87.6%at 5 mA cm^(-2)after 5000 cycles.

Wetting sub-nanochannels via ionic hydration effect for improving charging dynamics

The ionic transport in sub-nanochannels plays a key role in energy storage,yet suffers from a high energy barrier.Wetting sub-nanochannels is crucial to accelerate ionic transport,but the introduction of water is challenging because of the hydrophobic extreme confinement.We propose wetting the channels by the exothermic hydration process of pre-intercalated ions,the effect of which varies distinctly with different ionic hydration structures and energies.Compared to the failed pre-intercalation of SO_(4)^(2-),HSO_(4)^(-) with weak hydration energy results in a marginal effect on the HOMO(Highest Occupied Molecular Orbital)level of water to avoid water splitting during the electrochemical intercalation.Meanwhile,the ability of water introduction is reserved by the initial incomplete dissociation state of HSO_(4)^(-),so the consequent exothermic reionization and hydration processes of the intercalated HSO_(4)^(-) promote the water introduction into sub-nanochannels,finally forming the stable confined water through hydrogen bonding with functional groups.The wetted channels exhibit a significantly enhanced ionic diffusion coef-ficient by~9.4 times.

An ionic liquid-assisted strategy for enhanced anticorrosion of low-energy PEO coatings on magnesium–lithium alloy

A low-energy plasma electrolytic oxidation(LePEO)technique is developed to simultaneously improve energy efficiency and anti-corrosion.Ionic liquids(1-butyl-3-methylimidazole tetrafluoroborate(BmimBF_(4)))as sustainable corrosion inhibitors are chosen to investigate the corrosion inhibition behavior of ionic liquid(ILs)during the LePEO process for LA91 magnesium-lithium(Mg-Li)alloy.Results show that the ionic liquid BmimBF_(4)participates in the LePEO coating formation process,causing an increment in coating thickness and surface roughness.The low conductivity of the ionic liquid is responsible for the voltage and breakdown voltage increases during the LePEO with IL process(LePEO-IL).After adding BmimBF_(4),corrosion current density decreases from 1.159×10^(−4)A·cm^(−2)to 8.143×10^(−6)A·cm^(−2).The impedance modulus increases to 1.048×10^(4)Ω·cm^(−2)and neutral salt spray remains intact for 24 h.The superior corrosion resistance of the LePEO coating assisted by ionic liquid could be mainly attributed to its compact and thick barrier layer and physical absorption of ionic liquid.The ionic liquid-assisted LePEO technique provides a promising approach to reducing energy consumption and improving film performance.

Phosphotungstic acid ionic liquid for efficient photocatalytic desulfurization:Synthesis,application and mechanism

An efficient mass transfer process is a critical factor for regulating catalytic activity in a photocatalytic desulfurization system.Herein,a phosphotungstic acid(HPW)active center is successfully composited with a quaternary ammonium phosphotungstate-based hexadecyltrimethylammonium chloride ionic liquid(CTAC-HPW)by the ion exchange method for the photocatalytic oxidative desulfurization of dibenzothiophene sulfide.The keggin structure of HPW and highly mass transfer performance of organic cations synergistically enhanced the photocatalytic activity towards the effective convertion of dibenzothiophene(DBT)with the excitation of visible light.The deep desulfurization(<10 mg·kg^(-1))is attained within 30 min,and well stability is demonstrated within 25 cycles.Moreover,the CTAC-HPW photocatalyst projects well selectivity to interference from coexisting compounds such as olefins and aromatic hydrocarbons and universality of dibenzothiophenes,for example,4-methyldibenzothiophene(4-MDBT)and 4,6-dimethyldibenzothiophene(4,6-DMDBT).Ultimately,a possible photocatalytic desulfurization mechanism is proposed according to the Gaschromatography-mass spectrometry(GC-MS),proving that the final product is the corresponding sulfone.The trapping experiment and electron spin resonance(ESR)analysis confirmed that h^(+)and,COOH played critical roles in the oxidation process.The work offers a practicable strategy for efficiently converting DBT to DBTO_(2) with added value.

Ionic Liquid-Enhanced Assembly of Nanomaterials for Highly Stable Flexible Transparent Electrodes

The controlled assembly of nanomaterials has demon-strated significant potential in advancing technological devices.However,achieving highly efficient and low-loss assembly technique for nanomate-rials,enabling the creation of hierarchical structures with distinctive func-tionalities,remains a formidable challenge.Here,we present a method for nanomaterial assembly enhanced by ionic liquids,which enables the fabrication of highly stable,flexible,and transparent electrodes featuring an organized layered structure.The utilization of hydrophobic and non-volatile ionic liquids facilitates the production of stable interfaces with water,effectively preventing the sedimentation of 1D/2D nanomaterials assembled at the interface.Furthermore,the interfacially assembled nanomaterial monolayer exhibits an alternate self-climbing behavior,enabling layer-by-layer transfer and the formation of a well-ordered MXene-wrapped silver nanowire network film.The resulting composite film not only demonstrates exceptional photoelectric performance with a sheet resistance of 9.4Ωsq^(-1) and 93%transmittance,but also showcases remarkable environmental stability and mechanical flexibility.Particularly noteworthy is its application in transparent electromagnetic interference shielding materials and triboelectric nanogenerator devices.This research introduces an innovative approach to manufacture and tailor functional devices based on ordered nanomaterials.

Interfacial Modification of NiO_(x)by Self-assembled Monolayer for Efficient and Stable Inverted Perovskite Solar Cells

NiO_(x)as a hole transport material for inverted perovskite solar cells has received great attention owing to its high transparency,low fabrication temperature,and superior stability.However,the mismatched energy levels and possible redox reactions at the NiO_(x)/perovskite interface severely limit the performance of NiO_(x) based inverted perovskite solar cells.Herein,we introduce a p-type self-assembled monolayer between NiO_(x)and perovskite layers to modify the interface and block the undesirable redox reaction between perovskite and NiO_(x)The selfassembled monolayer molecules all contain phosphoric acid function groups,which can be anchored onto the NiOr surface and passivate the surface defect.Moreover,the introduction of self-assembled monolayers can regulate the energy level structure of NiO_(x),reduce the interfacial band energy offset,and hence promote the hole transport from perovskite to NiO_(x)layer.Consequently,the device performance is significantly enhanced in terms of both power conversion efficiency and stability.

Ionic liquid derived electrocatalysts for electrochemical water splitting

Hydrogen production from electrochemical water splitting is a promising strategy to generate green energy,which requires the development of efficient and stable electrocatalysts for the hydrogen evolution reaction and the oxygen evolution reaction(HER and OER).Ionic liquids(ILs)or poly(ionic liquids)(PILs),containing heteroatoms,metal-based anions,and various structures,have been frequently involved as precursors to prepare electrocatalysts for water splitting.Moreover,ILs/PILs possess high conductivity,wide electrochemical windows,and high thermal and chemical stability,which can be directly applied in the electrocatalysis process with high durability.In this review,we focus on the studies of ILs/PILs-derived electrocatalysts for HER and OER,where ILs/PILs are applied as heteroatom dopants and metal precursors to prepare catalysts or are directly utilized as the electrocatalysts.Due to those attractive properties,IL/PIL-derived electrocatalysts exhibit excellent performance for electrochemical water splitting.All these accomplishments and developments are systematically summarized and thoughtfully discussed.Then,the overall perspectives for the current challenges and future developments of ILs/PILs-derived electrocatalysts are provided.

Analysis on the formation principle and present situation of nano phase state of multi-component self-assembly of traditional Chinese compound medicine decoction

Traditional Chinese medicine decoction is a complex polydispersed phase system containing real solution,colloid solution,emulsion and suspension.The compound decoction of traditional Chinese medicine has complex components,including saponins,alkaloids,polysaccharides,flavonoids,amino acids and so on,which can be self-assembled to form gels,fibers,micelles,vesicles and so on.The self-assembled nano-phase not only neutralizes the single drug and reduces the toxicity and side effects,but also has its own pharmacological effects,which complement each other to achieve synergistic effect,so as to achieve the role of drug supplement,which is of research significance.The formation principle,solubilization and synergism principle and characterization method of multi-component self-assembly of traditional Chinese medicine compound decoction are discussed in this paper.

Honeycomb-structured solid acid catalysts fabricated via the swelling-induced self-assembly of acidic poly(ionic liquid)s for highly efficient hydrolysis reactions

The development of heterogeneous acid catalysts with higher activity than homogeneous acid catalysts is critical and still challenging.In this study,acidic poly(ionic liquid)s with swelling ability(SAPILs)were designed and synthesized via the free radical copolymerization of ionic liquid monomers,sodium p-styrenesulfonate,and crosslinkers,followed by acidification.The 31P nuclear magnetic resonance chemical shifts of adsorbed trimethylphosphine oxide indicated that the synthesized SAPILs presented moderate and single acid strength.The thermogravimetric analysis results in the temperature range of 300–345°C revealed that the synthesized SAPILs were more stable than the commercial resin Amberlite IR-120(H)(245°C).Cryogenic scanning electron microscopy testing demonstrated that SAPILs presented unique three-dimensional(3D)honeycomb structure in water,which was ascribed to the swelling-induced self-assembly of the molecules.Moreover,we used SAPILs with micron-sized honeycomb structure in water as catalysts for the hydrolysis of cyclohexyl acetate to cyclohexanol,and determined that their catalytic activity was much higher than that of homogeneous acid catalysts.The equilibrium concentrations of all reaction components inside and outside the synthesized SAPILs were quantitatively analyzed using a series of simulated reaction mixtures.Depending on the reaction mixture,the concentration of cyclohexyl acetate inside SAPIL-1 was 7.5–23.3 times higher than that outside of it,which suggested the high enrichment ability of SAPILs for cyclohexyl acetate.The excellent catalytic performance of SAPILs was attributed to their 3D honeycomb structure in water and high enrichment ability for cyclohexyl acetate,which opened up new avenues for designing highly efficient heterogeneous acid catalysts that could eventually replace conventional homogeneous acid catalysts.

Enhancing CO_(2) transport with plasma-functionalized ionic liquid membranes

The ionic liquid(IL) 1-butyl-3-methylimidazolium tetrafluoroborate treated with radiofrequency plasma is proposed for functionalization and immobilization on polyethersulfone supports to form supported ionic liquid membranes for CO_(2) separation.The effects of treatment time and transmembrane pressure difference on CO_(2) permeance were evaluated.The best gas permeation performance was obtained with a treatment time of 10 min and the transmembrane pressure difference was 0.25 MPa.Characterization of the materials by Fourier transform infrared spectroscopy,x-ray photoelectron spectroscopy and nuclear magnetic resonance spectroscopy demonstrates that the IL is grafted with carboxyl groups and deprotonated through plasma treatment.A preliminary mechanism for the plasma treatment and facilitated transport of CO_(2)has been proposed on this basis.

Electrorefining of aluminum in urea-imidazole chloride-aluminum chloride ionic liquids

The electrochemical behavior of Al(Ⅲ)in urea-1-butyl-3-methylimidazolium chloride-aluminum chloride(urea-BMIC-AlCl_(3))ionic liquids,and the effect of potential and temperature on the characterization of cathode products,current efficiency and energy consumption of aluminum electrorefining have been investigated.Cyclic voltammetry showed that the electrochemical reduction of Al(Ⅲ)was a one-step three-electron-transfer irreversible reaction,and the electrochemical reaction was controlled by diffusion.The diffusion coefficient of Al(Ⅲ)in urea-BMIC-AlCl_(3)ionic liquids at 313 K was 1.94×10^(−7)cm^(2)/s.The 7075 aluminum alloy was used as an anode for electrorefining,and the cathode products were analyzed by XRD,SEM and EDS.The results from XRD analysis indicated that the main phase of the cathode products was aluminum.The results from SEM and EDS characterization revealed that the cathode product obtained by electrorefining−1.2 V(vs.Al)was dense and uniform,and the mass fraction of aluminum decreased from 99.61%to 99.10%as the experimental temperature increased from 313 K to 333 K.In this work,the optimum experimental conditions were−1.2 V(vs.Al)and 313 K.At this time,the cathode current efficiency was 97.80%,while the energy consumption was 3.72 kW·h/kg.