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.

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.

Engineer Nanoscale Defects into Selective Channels:MOF-Enhanced Li^(+) Separation by Porous Layered Double Hydroxide Membrane

Two-dimensional(2D)membrane-based ion separation technology has been increasingly explored to address the problem of lithium resource shortage,yet it remains a sound challenge to design 2D membranes of high selectivity and permeability for ion separation applications.Zeolitic imidazolate framework functionalized modified layered double hydroxide(ZIF-8@MLDH)composite membranes with high lithium-ion(Li^(+)) permeability and excellent operational stability were obtained in this work by in situ depositing functional ZIF-8 nanoparticles into the nanopores acting as framework defects in MLDH membranes.The defect-rich framework amplified the permeability of Li^(+),and the site-selective growth of ZIF-8 in the framework defects bettered its selectivity.Specifically speaking,the ZIF-8@MLDH membranes featured a high permeation rate of Li^(+) up to 1.73 mol m^(−2) h^(−1) and a desirable selectiv-ity of Li^(+)/Mg^(2+) up to 31.9.Simulations supported that the simultaneously enhanced selectivity and permeability of Li+are attributed to changes in the type of mass transfer channels and the difference in the dehydration capacity of hydrated metal cations when they pass through nanochannels of ZIF-8.This study will inspire the ongoing research of high-performance 2D membranes through the engineering of defects.

Assessing the effectiveness of nanoscale zero-valent iron particles produced by green tea for Cr(VI)-contaminated groundwater remediation

Nanoscale zero-valent iron particles(NZVI) produced by using green tea(GT) extract as a reductant can remove Cr(Ⅵ) from water effectively,which can be utilized in groundwater remediation.In order to define the reaction mechanism and removal effect in the aquifer,in this study,GT-NZVI particles were prepared and measured by some characterization methods to define their surface performance,and then batch and one-dimensional experiments were carried out to reveal the reaction properties of GT-NZVI and Cr(Ⅵ) in groundwater.The results showed that the prepared GT-NZVI particles were regular spherical with a diameter of 10-20 nm,which could disperse in water stably.The main component of GT-NZVI wasα-Fe with superficial polyphenols as a stabilizer.GT-NZVI suspension had good ability to reduce the Cr(Ⅵ) to Cr(Ⅲ) in water.When the concentration of GT-NZVI was 1 g/L,the removal efficiency of Cr(Ⅵ)with an initial concentration of 100 mg/L reached 92.8% in 1 h reaction.In column tests,GT-NZVI passed through the natural sand column successfully with an average outflow percentage of 71.2%.The simulated in-situ reaction zone(IRZ) with GT-NZVI was used to remediate Cr(Ⅵ) contaminated groundwater.The oufflow concentration of Cr(Ⅵ) kept in 0.14-0.32 mg/L corresponding to the outflow rate below 0.32%within 15 days,and the removal efficiency of Cr(Ⅵ) by IRZ with GT-NZVI decreased with the increase of aquifer medium particle size,groundwater flow rate and ionic strength.Most of Cr(Ⅲ) as reduzate was adsorbed or immobilized on the surface or in the lattice of GT-NZVI,which indicated effective immobilization for chromium.

Nanoscale transition metal catalysts anchored on perovskite oxide enabling enhanced kinetics of lithium polysulfide redox in lithium-sulfur batteries

To obtain high-performance lithium-sulfur(Li-S)batteries,it is necessary to rationally design electrocatalytic materials that can promote efficient sulfur electrochemical reactions.Herein,the robust heterostructured material of nanoscale transition metal anchored on perovskite oxide was designed for efficient catalytic kinetics of the oxidation and reduction reactions of lithium polysulphide(Li PSs),and verified by density functional theory(DFT)calculations and experimental characterizations.Due to the strong interaction of nanoscale transition metals with Li PSs through chemical coupling,heterostructured materials(STO@M)(M=Fe,Ni,Cu)exhibit excellent catalytic activity for redox reactions of Li PSs.The bifunctional heterostructure material STO@Fe exhibits good rate performance and cycling stability as the cathode host,realizing a high-performance Li-S battery that can maintain stable cycling under rapid charge-discharge cycling.This study presents a novel approach to designing electrocatalytic materials for redox reactions of Li PSs,which promotes the development of fast charge-discharge Li-S batteries.

Water-based synthesis of nanoscale hierarchical metal-organic frameworks:Boosting adsorption and catalytic performance

The combination of nano sizes,large pore sizes and green synthesis is recognized as one of the most crucial and challenging problems in constructing metal-organic frameworks(MOFs).Herein,a water-based strategy is proposed for the synthesis of nanoscale hierarchical MOFs(NH-MOFs)with high crystallinity and excellent stability.This approach allows the morphology and porosity of MOFs to be fine tuned,thereby enabling the nanoscale crystal generation and a well-defined hierarchical system.The aqueous solution facilitates rapid nucleation kinetics,and the introduced modulator acts as a deprotonation agent to accelerate the deprotonation of the organic ligand as well as a structure-directing agent(SDA)to guide the formation of hierarchical networks.The assynthesized NH-MOFs(NH-ZIF-67)were assessed as efficient adsorbents and heterogeneous catalysts to facilitate the diffusion of guest molecules,outperforming the parent microZIF-67.This study focuses on understanding the NH-MOF growth rules,which could allow tailor-designing NH-MOFs for various functions.

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.

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.

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.

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.

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...

Equilibrium position of misfit dislocation dipole and critical parameters of buried strained nanoscale inhomogeneity in system of viscoelastic matrix

A theoretical model was suggested which describes the generation of the misfit dislocation dipole in the system of the viscoelastic matrix containing a circular stiff nanoscale inhomogeneity.The critical condition of misfit dislocation dipole and the solution of equilibrium position were given.The influence of the ratio of shear modulus,the misfit strain and viscosity on the equilibrium of the dislocation and critical parameter of inhomogeneity was investigated.The result shows that the equilibrium position de increases with the increase of the ratio of original shear modulus and the effect decreases with the increase of viscosity of matrix.Along with the increase of viscosity of matrix,de first increases and then decreases and possesses maximum value when t=0.3τ and tends to a stable value when t≥1.0τ.Along with the increase of viscosity of matrix,Rc first decreases and then increases and possesses minimum value when t=0.3τ and tends to a stable value when t≥1.0τ.

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 ℃.

Recent advances in the synthesis of nanoscale hierarchically porous metal–organic frameworks

Nanoscale hierarchically porous metal–organic frameworks(NHP-MOFs)have received unprecedented attention in many fields owing to their integration of the strengths of nanoscale size(<1μm)and hierarchical porous structure(micro-,meso-and/or macro-pores)of MOFs.This review focuses on recent advances in the main synthetic strategies for NHP-MOFs based on different metal ions(e.g.,Cu,Fe,Co,Zn,Al,Zr,and Cr),including the template method,composite technology,post-synthetic modification,in situ growth and the grind method.In addition,the mechanisms of synthesis,regulation techniques and the advantages and disadvantages of various methods are discussed.Finally,the challenges and prospects of the commercialisation of promising NHP-MOFs are also presented.The purpose of this review is to provide a road map for future design and development of NHP-MOFs for practical application.

Nanoscale resetting of the Th/Pb system in an isotopically-closed monazite grain: A combined atom probe and transmission electron microscopy study

Understanding the mechanisms of parent-daughter isotopic mobility at the nanoscale is key to rigorous interpretation of Ue The Pb data and associated dating. Until now, all nanoscale geochronological studies on geological samples have relied on either Transmission Electron Microscope(TEM) or Atom Probe Microscopy(APM) characterizations alone, thus suffering from the respective weaknesses of each technique. Here we focus on monazite crystals from a ~1 Ga, ultrahigh temperature granulite from Rogaland(Norway). This sample has recorded concordant UeP b dates(measured by LA-ICP-MS) that range over 100 My, with the three domains yielding distinct isotopic Ue Pb ages of 1034 ± 6 Ma(D1; Srich core), 1005 ± 7 Ma(D2), and 935 ± 7 Ma(D3), respectively. Combined APM and TEM characterization of these monazite crystals reveal phase separation that led to the isolation of two different radiogenic Pb(Pb*) reservoirs at the nanoscale. The S-rich core of these monazite crystals contains Cae Srich clusters, 5 -10 nm in size, homogenously distributed within the monazite matrix with a mean interparticle distance of 40 -60 nm. The clusters acted as a sink for radiogenic Pb(Pb*) produced in the monazite matrix, which was reset at the nanoscale via Pb diffusion while the grain remained closed at the micro-scale. Compared to the concordant ages given by conventional micro-scale dating of the grain,the apparent nano-scale age of the monazite matrix in between clusters is about 100 Myr younger, which compares remarkably well to the duration of the metamorphic event. This study highlights the capabilities of combined APM-TEM nano-structural and nano-isotopic characterizations in dating and timing of geological events, allowing the detection of processes untraceable with conventional dating methods.

Application of Hydrosoluble Polymers to Preparation of Nanoscale Calcium Hydroxide

Calcium hydroxide with uniform diameters about 50—100 nm was firstly prepared under moderate condition by adding different kinds of hydrosoluble polymers. From the results of TEM and IR, the polymers were proved not only to improve the agglomeration of the nanoparticles but also to be used as a template to control the formation of the special structure and the needed size of Ca(OH) 2 by changing the concentration of the polymers. The experimental results of TG-DTA indicate that the Ca(OH) 2 can absorb most of the acid gases released during the decomposition of polymers. So this kind of nano- Ca(OH) 2 can be used as a useful additive of environmental friendly plastics.

Friction Characteristics of Nanoscale Sliding Contacts between Multi-Asperity Tips and Textured Surfaces

Nanoscale sliding contacts of smooth surfaces or between a single asperity and a smooth surface have been widely investigated by molecular dynamics simulations, while there are few studies on the sliding contacts between two rough surfaces. Actually, the friction of two rough surfaces considering interactions between more asperities should be more realistic. By using multiscale method, friction characteristics of two dimensional nanoscale sliding contacts between rigid multi-asperity tips and elastic textured surfaces are investigated. Four nanoscale textured surfaces with different texture shapes are designed, and six multi-asperity tips composed of cylindrical asperities with different radii are used to slide on the textured surfaces. Friction forces are compared for different tips, and effects of the asperity radii on the friction characteristics are investigated. Average friction forces for all the cases are listed and compared, and effects of texture shapes of the textured surfaces are discussed. The results show that textured surface II has a better structure to reduce friction forces. The multi-asperity tips composed of asperities with R=20r0 （r0=0.227 7 nm） or R=30r0 get higher friction forces compared with other cases, and more atoms of the textured surfaces are taken away by these two tips, which are harmful to reduce friction or wear. For the case of R=10ro, friction forces are also high due to large contact areas, but the sliding processes are stable and few atoms are taken away by the tip. The proposed research considers interactions between more asperities to make the model approach to the real sliding contact problems. The results will help to vary or even control friction characteristics by textured surfaces, or provide references to the design of textured surfaces.