A brief review on the recent development of phonon engineering and manipulation at nanoscales

Phonons are the quantum mechanical descriptions of vibrational modes that manifest themselves in many physical properties of condensed matter systems. As the size of electronic devices continues to decrease below mean free paths of acoustic phonons, the engineering of phonon spectra at the nanoscale becomes an important topic. Phonon manipulation allows for active control and management of heat fow, enabling functions such as regulated heat transport. At the same time, phonon transmission, as a novel signal transmission method, holds great potential to revolutionize modern industry like microelectronics technology, and boasts wide-ranging applications. Unlike fermions such as electrons, polarity regulation is difficult to act on phonons as bosons, making the development of effective phonon modulation methods a daunting task.This work reviews the development of phonon engineering and strategies of phonon manipulation at different scales, reports the latest research progress of nanophononic devices such as thermal rectifiers, thermal transistors, thermal memories, and thermoelectric devices,and analyzes the phonon transport mechanisms involved. Lastly, we survey feasible perspectives and research directions of phonon engineering. Thermoelectric analogies, external field regulation, and acousto-optic co-optimization are expected to become future research hotspots.

Nanoscale Zero-Valent Iron(nZVI)for Heavy Metal Wastewater Treatment:A Perspective

Industries such as non-ferrous metal smelting discharge billions of gallons of highly toxic heavy metal wastewater(HMW)worldwide annually,posing a severe challenge to conventional wastewater treatment plants and harming the environment.HMW is traditionally treated via chemical precipitation using lime,caustic,or sulfide,but the effluents do not meet the increasingly stringent discharge standards.This issue has spurred an increase in research and the development of innovative treatment technologies,among which those using nanoparticles receive particular interest.Among such initiatives,treatment using nanoscale zero-valent iron(nZVI)is one of the best developed.While nZVI is already well known for its site-remediation use,this perspective highlights its application in HMW treatment with metal recovery.We demonstrate several advantages of nZVI in this wastewater application,including its multifunctionality in sequestrating a wide array of metal(loid)s(>30 species);its capability to capture and enrich metal(loid)s at low concentrations(with a removal capacity reaching 500 mg·g^(-1)nZVI);and its operational convenience due to its unique hydrodynamics.All these advantages are attributable to nZVI’s diminutive nanoparticle size and/or its unique iron chemistry.We also present the first engineering practice of this application,which has treated millions of cubic meters of HMW and recovered tons of valuable metals(e.g.,Cu and Au).It is concluded that nZVI is a potent reagent for treating HMW and that nZVI technology provides an eco-solution to this toxic waste.

Preparation of high-purity fluorite and nanoscale calcium carbonate from low-grade fluorite

Flotation separation of calcite from fluorite is a challenge on low-grade fluorite flotation that limits the recovery and purity of fluorite concentrate.A new acid leaching–flotation process for fluorite is proposed in this work.This innovative process raised the fluor-ite’s grade to 97.26wt%while producing nanoscale calcium carbonate from its leachate,which contained plenty of calcium ions.On the production of nanoscale calcium carbonate,the impacts of concentration,temperature,and titration rate were examined.By modifying the process conditions and utilizing crystal conditioning agents,calcite-type and amorphous calcium carbonates with corresponding particle sizes of 1.823 and 1.511μm were produced.The influence of the impurity ions Mn^(2+),Mg^(2+),and Fe^(3+)was demonstrated to reduce the particle size of nanoscale calcium carbonate and make crystal shape easier to manage in the fluorite leach solution system compared with the calcium chloride solution.The combination of the acid leaching–flotation process and the nanoscale calcium carbonate preparation method improved the grade of fluorite while recovering calcite resources,thus presenting a novel idea for the effective and clean usage of low-quality fluorite resources with embedded microfine particles.

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.

Defect-induced synthesis of nanoscale hierarchically porous metal-organic frameworks with tunable porosity for enhanced volatile organic compound adsorption

Nanoscale hierarchically porous metal-organic frameworks(NH-MOFs)synergistically combine the advantages of nanoscale MOFs and hierarchically porous MOFs,resulting in remarkable characteristics such as increased specific surface area,greater porosity,and enhanced exposure of active sites.Herein,nanoscale hierarchically porous UIO-66(UIO-66_X)was synthesized using a defect-induced strategy that employed ethylene diamine tetraacetic acid(EDTA)as a modulator.The introduced EDTA occupies the coordination sites of organic ligands,promoting the formation and growth of UIO-66 crystal nuclei and inducing defects during synthesis.The as-synthesized UIO-66_X crystals exhibit a uniform distribution with an average size of approximately 100 nm.In addition,the total pore volume attains a remarkable value of 0.95 cm^(3)g^(-1),with mesopores constituting 36.8% of the structure.Furthermore,the porosities of UIO-66_X can be easily tuned by controlling the molar ratio of EDTA/Zr^(4+).In addition,the as-synthesized UIO-66_X exhibits excellent adsorption capacities for n-hexane(344 mg g^(-1))and pxylene(218 mg g^(-1)),which are 44.5% and 27.5% higher than those of conventional UIO-66,respectively.Finally,the adsorption behavior of n-hexane and p-xylene molecules in UIO-66_X was investigated using density functional theory simulations.

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.

Neural-Network-Based Charge Density Quantum Correction of Nanoscale MOSFETs

For the treatment of the quantum effect of charge distribution in nanoscale MOSFETs,a quantum correction model using Levenberg-Marquardt back-propagation neural networks is presented that can predict the quantum density from the classical density. The training speed and accuracy of neural networks with different hidden layers and numbers of neurons are studied. We conclude that high training speed and accuracy can be obtained using neural networks with two hidden layers,but the number of neurons in the hidden layers does not have a noticeable effect, For single and double-gate nanoscale MOSFETs, our model can easily predict the quantum charge density in the silicon layer,and it agrees closely with the Schrodinger-Poisson approach.

Self-assembly and UV-curing Property of Polymerized Lyotropic Liquid Crystal Monomer of Sodium 3,4,5-tris（ll-acryloxyundecyloxy）benzoate

A polymerized lyotropic liquid crystal monomer of sodium 3,4,5-tris（11-acryloxyundecyloxy）- benzoate was synthesized by a convenient route starting from 3,4,5-trihydroxybenzoic acid via esterification followed by etherification, acylation and finally neutralization. The chemi- cal structure was confirmed by Fourier transform infrared （FT-IR） and 1H nuclear magnetic resonance spectral analysis. The self-organization behavior of the monomer with deionized water in methanol at room temperature was also demonstrated. The assemblies were char- acterized by polarized optical microscope and X-ray diffraction. The results show that a solution containing 80：20 of the monomer to water was found to be able to self-organize into Lamellar （La） phase and 92：8 with inverted hexagonal （H]I） phase, which was in ac- cordance with the theoretical calculation of critical packing parameter. It suggests that the concentration of the monomer was the key factor to influence assembly structure. Addi- tionally, the acrylate conversion with different photoinitiators and nanostructure retention after polymerization were investigated. The research shows that the acrylate conversion of the monomer with Darocur2959 could reach up to 78% when irradiated by 30 mW/cm2 UV light of 365 nm for 30 min characterized by Real-time FT-IR as well as the sol-gel method. Meanwhile, the La and HII phase nanostructures were both retained after polymerization.

Catalytic reductive dechlorination of p-chlorophenol in water using Ni/Fe nanoscale particles

Nanoscale bimetallic Ni/Fe particles were synthesized from the reaction of sodium borohydride （NaBH4） with reduction of Ni^2＋ and Fe^2＋ in aqueous solution. The obtained Ni/Fe particles were characterized by TEM （transmission electron microscope）, XRD （X-ray diffractometer）, and N2-BET. The dechlorination activity of the Ni/Fe was investigated using p-chlorophenol （p-CP） as a probe agent. Results demonstrated that the nanoscale Ni/Fe could effectively dechlorinate p-CP at relatively low metal to solution ratio of 0.4 g/L （Ni 5 wt%）. The target with initial concentration ofp-CP 0.625 mmol/L was dechlorinted completely in 60 rain under ambient temperature and pressure. Factors affecting dechlorination efficiency, including reaction temperature, pH, Ni loading percentage over Fe, and metal to solution ratio, were investigated. The possible mechanism of dechlorination ofp-CP was proposed and discussed. The pseudo-first- order reaction took place on the surface of the Ni/Fe bimetallic particles, and the activation energy of the dechlorination reaction was determined to be 21.2 kJ/mol at the temperature rang of 287-313 K.

In Situ X-ray Absorption Spectroscopy Studies of Nanoscale Electrocatalysts

Nanoscale electrocatalysts have exhibited promising activity and stability,improving the kinetics of numerous electrochemical reactions in renewable energy systems such as electrolyzers,fuel cells,and metal-air batteries.Due to the size effect,nano particles with extreme small size have high surface areas,complicated morphology,and various surface terminations,which make them different from their bulk phases and often undergo restructuring during the reactions.These restructured materials are hard to probe by conventional ex-situ characterizations,thus leaving the true reaction centers and/or active sites difficult to determine.Nowadays,in situ techniques,particularly X-ray absorption spectroscopy(XAS),have become an important tool to obtain oxidation states,electronic structure,and local bonding environments,which are critical to investigate the electrocatalysts under real reaction conditions.In this review,we go over the basic principles of XAS and highlight recent applications of in situ XAS in studies of nanoscale electrocatalysts.

Synthesis of MnZn Ferrite Nanoscale Particles by Hydrothermal Method

Hydrothermal method was used to synthesize nanoscale particles of MnZn ferrites. The crystallites were characterized by XRD, TEM and SEM. The effects of the reaction time, temperature and additives on the product were investigated. Crystallization process would be carried out above 160 ℃ for 5 h or more, higher temperature can reduce the reaction time. Additives were used to remove impurities such as Fe 2O 3, ZnMnO 3.10～15 nm pure slightly agglomerated MnZn ferrite crystallites with a narrow grain size distribution were obtained.

Al_(80)Ni_6Y_8Co_4Cu_2 GLASS ALLOYS CONTAINING NANOSCALEPARTICLES BY ISOTHERMAL ANNEALING OR QUENCHING

Al80Ni6 Y8 Co4 Cu2 amorphous ribbons were isothermally annealed and a mixed structure consisting of α-Al particle with a size of less than 15nm and Al3Ni compound with a size of about 30nm was obtained. The crystallization kinetics of Al80Ni6 Y8 Co4 Cu2 amorphous alloy shows that the precipitation of α-Al particles is the growth process controlled by diffusion of the solute elements rejected from the growing crystals. By quenching at different cooling rates, a mixed structure consisting of nanoscale α-Al particles and the remaining glass matrix or structure consisting of nanoscale particle (Al phase or Al3Ni compound) with a size of about 100nm was formed. The addition of Co elements and Cu elements to Al-Ni-Y alloy systems increases the glass formation ability of the alloy and the thermal stability of the supercooled liquid region against crystallization, which results from significant difference of atomic size, strong bonding nature among constituent elements and the low diffisivity of the solute elements due to the concentration gradient in the growing front of crystals.

Kinetics and Mechanism of Dechlorination of o-Chlorophenol by Nanoscale Pd/Fe

Nanoscale Pd/Fe bimetallic particles were synthesized with an efficient method to dechlorinate o-chlorophenol. The nanoscale Pd/Fe particles were determined by transmission electron microscopy and BET specific surface area analysis. Most of the particles are in the size range of 20—100 nm. The BET specific surface area of synthesized nanoscale Pd/Fe particles is 12.4 m 2/g. In contrast, a commercially available fine iron powder(<100 mesh) has a specific surface area of 0.49 m 2/g. Batch studies demonstrated that the nanoscale particles can effectively dechlorinate o-chlorophenol. The dechlorination reaction takes place on the surface of synthesized nanoscale Pd/Fe bimetallic particles in a pseudo-first order reaction. The surface-area-normalized rate coefficients(k_ SA) are comparable to those reported in the literature for chlorinated ethenes. The observed reaction rate constants(k_ obs) are dominated by the mass fraction of Pd and the mass concentration of the nanoscale Pd/Fe particles.

Dechlorination of disinfection by-product monochloroacetic acid in drinking water by nanoscale palladized iron bimetallic particle

Nanoscale palladized iron(Pd/Fe)bimetallic particles were prepared by reductive deposition method.The particles were characterized by X-ray diffraction(XRD),X-ray fluorescence(XRF),scanning electron microscope(SEM),transmission electron microscope(TEM),and Brunauer-Emmett-Teller-nitrogen(BET-N_2)method.Data obtained from those methods indicated that nanoscale Pd/Fe bimetallic particles containedα-Fe^0.Detected Pd to Fe ratio by weight(Pd/Fe ratio)was close to theoretical value. Spherical granules with diame...

Synthesis of Nanoscale Shell-core Titania Coated Silica Particles in the Presence of Polyether Polyamine and the Phase Transition

The nanoscale titania coated silica was prepared via a two-step precipitating approach, where the nanoscale silica nuclei were first prepared by passing an aqueous solution of sodium silicate through an ion-exchange resin bed, then coated with the precipitation from hydrolyzed butyl titanate in an ethanol-hexane mixture at a low pH value in the presence of poly(ethylene oxide) polyamine salt(PPA) at a high temperature of 90 ℃. In the second-step precipitating process, the spontaneously precipitated titania shell on the silica nuclei was stabilized in the suspension solution with the help of the adsorption of PPA on the particles. A possible precipitating mechanism was suggested. Furthermore, the amorphous titania shell could undergo crystallization from the amorphous to the anatase structure at a high temperature of 650 ℃, and a further phase transition from the anatase to the rutile structure in the different sintering processes at a rising temperature of 750 ℃.