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.

Electrokinetic-mechanism of water and furfural oxidation on pulsed laser-interlaced Cu_(2)O and CoO on nickel foam

The electrocatalytic oxidation of biomass-derived furfural(FF)feedstocks into 2-furoic acid(FA)holds immense industrial potential in optics,cosmetics,polymers,and food.Herein,we fabricated Co O/Ni O/nickel foam(NF)and Cu_(2)O/Ni O/NF electrodes via in situ pulsed laser irradiation in liquids(PLIL)for the bifunctional electrocatalysis of oxygen evolution reaction(OER)and furfural oxidation reaction(FOR),respectively.Simultaneous oxidation of NF surface to NiO and deposition of CoO and/or Cu_(2)O on NF during PLIL offer distinct advantages for enhancing both the OER and FOR.CoO/NiO/NF electrocatalyst provides a consistently low overpotential of~359 m V(OER)at 10 m A/cm^(2),achieving the maximum FA yield(~16.37 m M)with 61.5%selectivity,79.5%carbon balance,and a remarkable Faradaic efficiency of~90.1%during 2 h of FOR at 1.43 V(vs.reversible hydrogen electrode).Mechanistic pathway via in situ electrochemical-Raman spectroscopy on CoO/NiO/NF reveals the involvement of phase transition intermediates(NiOOH and CoOOH)as surface-active centers during electrochemical oxidation.The carbonyl carbon in FF is attacked by hydroxyl groups to form unstable hydrates that subsequently undergo further oxidation to yield FA products.This method holds promise for large-scale applications,enabling simultaneous production of renewable building materials and fuel.

Achieving High Strength and Tensile Ductility in Pure Nickel by Cryorolling with Subsequent Low-Temperature Short-Time Annealing

Ultra fine-grained pure metals and their alloys have high strength and low ductility.In this study,cryorolling under different strains followed by low-temperature short-time annealing was used to fabricate pure nickel sheets combining high strength with good ductility.The results show that,for different cryorolling strains,the uniform elongation was greatly increased without sacrificing the strength after annealing.A yield strength of 607 MPa and a uniform elongation of 11.7%were obtained after annealing at a small cryorolling strain(ε=0.22),while annealing at a large cryorolling strain(ε=1.6)resulted in a yield strength of 990 MPa and a uniform elongation of 6.4%.X-ray diffraction(XRD),transmission electron microscopy(TEM),scanning electron microscopy(SEM),and electron backscattered diffraction(EBSD)were used to characterize the microstructure of the specimens and showed that the high strength could be attributed to strain hardening during cryorolling,with an additional contribution from grain refinement and the formation of dislocation walls.The high ductility could be attributed to annealing twins and micro-shear bands during stretching,which improved the strain hardening capacity.The results show that the synergistic effect of strength and ductility can be regulated through low-temperature short-time annealing with different cryorolling strains,which provides a new reference for the design of future thermo-mechanical processes.

Microscopic Magnetism of Nickel-Based Infinite-Layer Superconducting Parent Compounds RNiO_(2)(R=La,Nd):AμSR Study

By using muon spin relaxation(μSR)measurements,we perform a comparative study of the microscopic magnetism in the parent compounds of infinite-layer nickelate superconductors RNiO_(2)(R=La,Nd).In either compound,the zero-fieldμSR spectra down to the lowest measured temperature reveal no long-range magnetic order.In LaNiO_(2),short-range spin correlations appear below T=150 K,and spins fully freeze below T∼10 K.NdNiO_(2)exhibits a more complex spin dynamics driven by the Nd 4𝑓and Ni3d electron spin fluctuations.Further,it shows features suggesting the proximity to a spin-glass state occurring below T=5 K.In both compounds,the spin behavior with temperature is further confirmed by longitudinal-fieldμSR measurements.These results provide new insight into the magnetism of the parent compounds of the superconducting nickelates,crucial to understanding the microscopic origin of their superconductivity.

Nickel catalysts with asymmetric steric hindrance for ethylene polymerization

α-Diimide catalysts have attracted widespread attention due to their unique chain walking characteristics.A series ofα-diimide nickel/palladium catalysts with different electronic effects and steric hindrances were designed and synthesized for olefin polymerization.In this work,we synthesized a series of asymmetricα-diimide nickel complexes with different steric hindrances and used them for ethylene polymerization.These nickel catalysts have high ethylene polymerization activity,up to 6.51×10^(6)g·mol^(−1)·h^(−1),and the prepared polyethylene has a moderate melting point and high molecular weight(up to 38.2×10^(4)g·mol^(−1)),with a branching density distribution between 7 and 94 branches per 1000 carbons.More importantly,the polyethylene prepared by these catalysts exhibits excellent tensile properties,with strain and stress reaching 800%and 30 MPa,respectively.

Probing nickelate superconductors at atomic scale:A STEM review

The discovery of nickelate superconductors,including doped infinite-layer(IL)nickelates RNiO2(R=La,Pr,Nd),layered square-planar nickelate Nd6Ni5O12,and the Ruddlesden–Popper(RP)phase La3Ni2O7,has spurred immense interest in fundamental research and potential applications.Scanning transmission electron microscopy(STEM)has proven crucial for understanding structure–property correlations in these diverse nickelate superconducting systems.In this review,we summarize the key findings from various modes of STEM,elucidating the mechanism of different nickelate superconductors.We also discuss future perspectives on emerging STEM techniques for unraveling the pairing mechanism in the“nickel age”of superconductivity.

Enhancing hydrogen evolution and oxidation kinetics through oxygen insertion into nickel lattice

Nickel-based materials,including metallic Ni and Ni oxide,have been widely studied in the exploration of non-precious-metal hydrogen electrocatalysts,but neither pure Ni nor NiO is ideal for the hydrogen evolution reaction(HER)and hydrogen oxidation reaction(HOR).In this paper,an oxygen insertion strategy was applied on nickel to regulate its hydrogen electrocatalytic performance,and the oxygen-inserted nickel catalyst was successfully obtained with the assistance of tungsten dioxide support(denoted as O-Ni/WO_(2)).The partial insertion of oxygen in Ni maintains the face-centered cubic arrangement of Ni atoms,simultaneously expanding the lattice and increasing the lattice spacing.Consequently,the adsorption strength of^(*)H and^(*)OH on Ni is optimized,thus resulting in superior electrocatalytic performance of0-Ni/WO_(2)in alkaline HER/HOR.The Tafel slope of O-Ni/WO_(2)@NF for HER is 56 mV dec^(-1),and the kinetic current density of O-Ni/WO_(2)for HOR reaches 4.85 mA cm^(-2),which is ahead of most currently reported catalysts.Our proposed strategy of inserting an appropriate amount of anions into the metal lattice could provide more possibilities for the design of high-performance catalysts.

Accurate estimation of Li/Ni mixing degree of lithium nickel oxide cathode materials

Li/Ni mixing negatively influences the discharge capacity of lithium nickel oxide and high-nickel ternary cathode materials.However,accurately measuring the Li/Ni mixing degree is difficult due to the preferred orientation of labbased XRD measurements using Bragg–Brentano geometry.Here,we find that employing spherical harmonics in Rietveld refinement to eliminate the preferred orientation can significantly decrease the measurement error of the Li/Ni mixing ratio.The Li/Ni mixing ratio obtained from Rietveld refinement with spherical harmonics shows a strong correlation with discharge capacity,which means the electrochemical capacity of lithium nickel oxide and high-nickel ternary cathode can be estimated by the Li/Ni mixing degree.Our findings provide a simple and accurate method to estimate the Li/Ni mixing degree,which is valuable to the structural analysis and screening of the synthesis conditions of lithium nickel oxide and high-nickel ternary cathode materials.

Engineering of Self-Supported Electrocatalysts on a Three-Dimensional Nickel Foam Platform for Efficient Water Electrolysis

Economical water electrolysis requires highly active non-noble electrocatalysts to overcome the sluggish kinetics of the two half-cell reactions,oxygen evolution reaction,and hydrogen evolution reaction.Although intensive efforts have been committed to achieve a hydrogen economy,the expensive noble metal-based catalysts remain under consideration.Therefore,the engineering of self-supported electrocatalysts prepared using a direct growth strategy on three-dimensional(3D)nickel foam(NF)as a conductive substrate has garnered significant interest.This is due to the large active surface area and 3D porous network offered by these electrocatalysts,which can enhance the synergistic eff ect between the catalyst and the substrate,as well as improve electrocatalytic performance.Hydrothermal-assisted growth,microwave heating,electrodeposition,and other physical methods(i.e.,chemical vapor deposition and plasma treatment)have been applied to NF to fabricate competitive electrocatalysts with low overpotential and high stability.In this review,recent advancements in the development of self-supported electrocatalysts on 3D NF are described.Finally,we provide future perspectives of self-supported electrode platforms in electrochemical water splitting.

Solubility of iron(Ⅲ) and nickel(Ⅱ) acetylacetonates in supercritical carbon dioxide

As a common precursor for supercritical CO_(2)(scCO_(2))deposition techniques,solubility data of organometallic complexes in scCO_(2)is crucial for the preparation of nanocomposites.Recently,metal acetylacetonates have shown great potential for the preparation of single-atom catalytic materials.In this study,the solubilities of iron(Ⅲ)acetylacetonate(Fe(acac)3)and nickel(Ⅱ)acetylacetonate(Ni(acac)2)were measured at the temperature from 313.15 to 333.15 K and in the pressure range of 9.5–25.2 MPa to accumulate new solubility data.Solubility was measured using a static weight loss method.The semi-empirical models proposed by Chrastil and Sung et al.were used to correlate the solubility data of Fe(acac)3 and Ni(acac)2.The equations obtained can be used to predict the solubility of the same system in the experimental range.

A universal multifunctional dual cation doping strategy towards stabilized ultra-high nickel cobalt-free lithium layered oxide cathode

Ultra-high nickel cobalt-free lithium layered oxides are promising cathode material for lithium-ion batteries(LIBs)because of their relatively high capacity and low cost.Nevertheless,the high nickel content would induce bulk structure degradation and interfacial environment deterioration,and the absence of Co element reduces the lithium diffusion kinetics,severely limiting the performance liberation of this kind of cathodes.Herein,a multifunctional Ti/Zr dual cation co-doping strategy has been employed to improve the lithium storage performance of LiNi_(0.9)Mn_(0.1)O_(2)(NM91)cathode.On the one hand,the Ti/Zr co-doping weakens the Li^(+)/Ni^(2+)mixing through magnetic interactions due to the inexistence of unpaired electrons for Ti^(4+)and Zr^(4+),increasing the lithium diffusion rate and suppressing the harmful coexistence of H1 and H2 phases.On the other hand,they enhance the lattice oxygen stability because of the strong Ti-O and Zr-O bonds,inhibiting the undesired H3 phase transition and lattice oxygen loss,improving the bulk structure and cathode-electrolyte interface stability.As a result,the Ti/Zr co-doped NM91(NMTZ)exhibits a 91.2%capacity retention rate after 100 cycles,while that of NM91 is only82.9%.Also,the NMTZ displays better rate performance than NM91 with output capacities of 115 and93 mA h g^(-1)at a high current density of 5 C,respectively.Moreover,the designed NMTZ could enable the full battery to deliver an energy density up to 263 W h kg^(-1),making the ultra-high nickel cobaltfree lithium layered oxide cathode closer to practical applications.

Indirect Electroanalysis of 3-Methyl-4-Nitrophenol in Water Using Carbon Fiber Microelectrode Modified with Nickel Tetrasulfonated Phthalocyanine Complex

Electrochemical detection of 3-methyl-4-nitrophenol (MNP) in direct phenol oxidation occurs at high potentials and generally leads to progressive passivation of the electrochemical sensor. This study describes the use of a carbon fiber microelectrode modified with a tetrasulfonated nickel phthalocyanine complex for the detection of MNP at a lower potential than that of direct phenol oxidation. The MNP voltammogram showed the presence of an anodic peak at -0.11 V vs SCE, corresponding to the oxidation of the hydroxylamine group generated after the reduction of the nitro group. The effect of buffer pH on the peak current and SWV parameters such as frequency, scan increment, and pulse amplitude were studied and optimized to have better electrochemical response of the proposed sensor. With these optimal parameters, the calibration curve shows that the peak current varied linearly as a function of MNP concentration, leading to a limit of detection (LoD) of 1.1 μg/L. These results show an appreciable sensitivity of the sensor for detecting the MNP at relatively low potentials, making it possible to avoid passivation phenomena.

Research Progress of Nickel Iron Bimetallic Series Electrocatalytic Materials

Hydrogen energy has become one of the recognized clean energy sources worldwide due to its advantages such as low cost,renewable energy,and green environmental protec-tion.Electrolytic water is currently one of the most promising solutions for providing hydrogen fuel.Nickel iron bimetallic electrocatalysts have abundant sources,low cost,clean and pollution-free properties,and strong catalytic performance,This article mainly reviews the development and research of bimetallic nickel iron oxides and nickel iron alloys in recent years,and explores their synthesis methods,properties,and stability in depth.

Synthesis of clay-supported nanoscale zero-valent iron using green tea extract for the removal of phosphorus from aqueous solutions

This study addresses the synthesis of nanoscale zero-valent iron(n ZVI) in the presence of natural bentonite(B-n ZVI) using green tea extract. The natural bentonite and B-n ZVI were then applied for the removal of phosphorus from aqueous solutions at various concentrations, p H levels and contact time. The desorption of phosphorus(P) from adsorbents was done immediately after sorption at the maximum initial concentration using the successive dilution method. The characterization of FTIR, SEM, and XRD indicated that n ZVI was successfully loaded to the surface of natural bentonite. The sorption of phosphorus on B-n ZVI was observed to be p H-dependent, with maximum phosphorus removal occurring at the p H range of 2 to 5. The results demonstrate that the maximum sorption capacities of natural bentonite and B-n ZVI were 4.61 and 27.63 mg·g^(-1), respectively.Langmuir, Freundlich, and Redlich–Peterson models properly described the sorption isotherm data. For either adsorbent, desorption isotherms did not coincide with their corresponding sorption isotherms, suggesting the occurrence of irreversibility and hysteresis. The average percentages of retained phosphorus released from natural bentonite and B-n ZVI were 80% and 9%, respectively. The results indicated that sorption kinetics was best described by the pseudo-second-order model. The present study suggests that B-n ZVI could be used as a suitable adsorbent for the removal of phosphorus from aqueous solutions.

Treatment of simulated wastewater containing Reactive Red 195 by zero-valent iron/activated carbon combined with microwave discharge electrodeless lamp/sodium hypochlorite

A comparative study of treatment of simulated wastewater containing Reactive Red 195 using zero-valent iron/activated carbon （ZVI/AC）, microwave discharge electrodeless lamp/sodium hypochlorite （MDEL/NaCIO） and the combination of ZVI/AC- MDEL/NaCIO was conducted. The preliminary results showed the two steps method of ZVI/AC-MDEL/NaCIO had much higher degradation efficiency than both single steps. The final color removal percentage was nearly up to 100% and the chemical oxygen demand reduction percentage was up to approximately 82%. The effects of operational parameters, including initial pH value of simulated wastewater, ZVI/AC ratio and particle size of ZVI were also investigated. In addition, from the discussion of synergistic effect between ZVI/AC and MEDL/NaCIO, we found that in the ZVI/AC-MEDL/NaCIO process, ZVI/AC could break the azo bond firstly and then MEDLfNaCIO degraded the aromatic amine products effectively. Reversing the order would reduce the degradation efficiency.

Eco friendly adsorbents for removal of phenol from aqueous solution employing nanoparticle zero-valent iron synthesized from modified green tea bio-waste and supported on silty clay

The present research investigated a novel route for the synthesis of nanoparticle zero-valent iron(NZVI)utilizing an aqueous extract of green tea waste as a reductant with ferric chloride.Also,the supported nanoparticle zerovalent iron was synthesized using natural silty clay as a support material(SC-NZVI).The NZVI and SC-NZVI were characterized by infrared spectroscopy(FTIR),scanning electron microscope(SEM),X-ray diffraction(XRD),Brunauer–Emmett–Teller(BET),and zeta potential(ζ).The interpretation of the results demonstrated that the polyphenol and other antioxidants in green tea waste can be used as reduction and capping agents in NZVI synthesis,with silty clay an adequate support.Additionally,the experiments were carried out to explore phenol adsorption by NZVI and SC-NZVI.To determine the optimum conditions,the impact of diverse experimental factors(i.e.,initial pH,adsorbent dose,temperature,and concentration of phenol)was studied.Langmuir,Freundlich,and Tempkin isotherms were used as representatives of adsorption equilibrium.The obtained results indicated that the adsorption processes for both NZVI and SC-NZVI well fitted by the Freundlich isotherm model.The appropriateness of pseudofirstorder and pseudosecondorder kinetics was investigated.The experimental kinetics data were good explained by the second-order model.The thermodynamic parameters(ΔH0,ΔS0,andΔG0)for NZVI and SC-NZVI were determined.The maximum removal rates of phenol at optimum conditions,when adsorbed onto NZVI and SC-NZVI,were found to be 94.8%and 90.1%,respectively.

Surfactant-assisted removal of 2,4-dichlorophenol from soil by zero-valent Fe/Cu activated persulfate

The organic compounds contaminated soil substantially threatens the growth of plants and food safety.In this study,we synthesis zero-valent bimetallic Fe/Cu catalysts for the degradation of 2,4-dichlorophenol(DCP)in soils with persulfate(PS)in combination of organic surfactants and exploring the main environmental impact factors.The kinetic experiments show that the 5%(mass)dosage of Fe/Cu exhibits a higher degradation efficiency(86%)of DCP in soils,and the degradation efficiency of DCP increases with the increase of the initial PS concentration.Acidic conditions are favorable for the DCP degradation in soils.More importantly,the addition of Tween-80,and Triton-100 can obviously desorb DCP from the soil surface,which enhances the degradation efficiency of DCP in soils by Fe/Cu and PS reaction system.Furthermore,the Quenching experiments demonstrate that SO_(4)^(-1)·and·OH are the predominant radicals for the degradation of DCP during the Fe/Cu and PS reaction system as well as non-radical also exist.The findings of this work provide an effective method for remediating DCP from soils.

Biochar Supported Nanoscale Zero-valent Iron Composites for the Removal of Petroleum from Wastewater

Considering the need for efficiently and rapidly treating oily wastewater while preventing secondary pollution,the nanoscale zero-valent iron(nZVI)was supported on biochar prepared by using a spent mushroom substrate(SMS),to produce an iron-carbon composite(SMS-nZVI).The ability of the SMS-nZVI to treat wastewater containing high concentration of oil was then comprehensively evaluated.The morphology,structure,and other properties of the composite were characterized by using scanning electron microscopy,transmission electron microscopy,the Brunauer-Emmett-Teller nitrogen sorption analysis,and the Fourier transform infrared spectroscopy.The results show that the biochar prepared by using the SMS can effectively prevent the agglomeration of nZVI and increase the overall specific surface area,thereby enhancing the absorption of petroleum by the composite.Experiments reveal that compared with the SMS and nZVI,the SMS-nZVI composite removes petroleum faster and more efficiently from wastewater.Under optimized conditions involving an nZVI to biochar mass ratio of 1:5 and a pH value of 4,the efficiency for removal of petroleum from wastewater with an initial petroleum concentration of 1000 mg/L could reach 95%within 5 h.Based on a natural aging treatment involving exposure to air for 30 d,the SMS-nZVI composite retained an oil removal rate of higher than 62%,and this result could highlight its stability for practical applications.

Study of diclofenac removal by the application of combined zero-valent iron and calcium peroxide nanoparticles in groundwater

Diclofenac(DCF)is one of the most frequently detected pharmaceuticals in groundwater,posing a great threat to the environment and human health due to its toxicity.To mitigate the DCF contamination,experiments on DCF degradation by the combined process of zero-valent iron nanoparticles(nZVI)and nano calcium peroxide(nCaO_(2))were performed.A batch experiment was conducted to examine the influence of the adding dosages of both nZVI and nCaO_(2)nanoparticles and pH value on the DCF removal.In the meantime,the continuous-flow experiment was done to explore the sustainability of the DCF degradation by jointly adding nZVI/nCaO_(2)nanoparticles in the reaction system.The results show that the nZVI/nCaO_(2)can effectively remove the DCF in the batch test with only 0.05 g/L nZVI and 0.2 g/L nCaO_(2)added,resulting in a removal rate of greater than 90%in a 2-hour reaction with an initial pH of 5.The degradation rate of DCF was positively correlated with the dosage of nCaO_(2),and negatively correlated with both nZVI dosage and the initial pH value.The order of significance of the three factors is identified as pH value>nZVI dosage>nCaO_(2)dosage.In the continuous-flow reaction system,the DCF removal rates remained above 75%within 150 minutes at the pH of 5,with the applied dosages of 0.5 g/L for nZVI and 1.0 g/L for nCaO_(2).These results provide a theoretical basis for the nZVI/nCaO_(2)application to remove DCF in groundwater.

Enhanced degradation of carbon tetrachloride by surfactant-modified zero-valent iron

Sorption of carbon tetrachloride （CT） by zero-valent iron （ZVI） is the rate-limiting step in the degradation of CT, so the sorption capacity of ZVl is of great importance. This experiment was aimed at enhancing the sorption of CT by ZVI and the degradation rate of CT by modification of surfactants. This study showed that ZVI modified by cationic surfactants has favorable synergistic effect on the degradation of CT. The CT degradation rate of ZVI modified by cetyl pyridinium bromide （CPB） was higher than that of the unmodified ZVI by 130%, and the CT degradation rate of ZVI modified by cetyl trimethyl ammonium bromide （CTAB） was higher than that of the unmodified ZVI by 81%. This study also showed that the best degradation effect is obtained at the near critical micelle concentrations （CMC） and that high loaded cationic surfactant does not have good synergistic effect on the degradation due to its hydrophilicity and the block in surface reduction sites. Furthermore degradation of CT by ZVI modified by nonionic surfactant has not positive effect on the degradation as the ionic surfactant and the ZVI modified by anionic surfactant has hardly any obvious effects on the degradation.