Due to its high efficiency,Fe(Ⅱ)-based catalytic oxidation has been one of the most popular types of technology for treating growing organic pollutants.A lot of chemical Fe sludge alongwith various refractory polluta...Due to its high efficiency,Fe(Ⅱ)-based catalytic oxidation has been one of the most popular types of technology for treating growing organic pollutants.A lot of chemical Fe sludge alongwith various refractory pollutantswas concomitantly produced,whichmay cause secondary environmental problemswithout proper disposal.We here innovatively proposed an effective method of achieving zero Fe sludge,reusing Fe resources(Fe recovery=100%)and advancing organics removal(final TOC removal>70%)simultaneously,based on the in situ formation of magnetic Ca-Fe layered double hydroxide(Fe_(3)O_(4)@CaFe-LDH)nano-material.Cations(Ca^(2+)and Fe^(3+))concentration(≥30 mmol/L)and their molar ratio(Ca:Fe≥1.75)were crucial to the success of the method.Extrinsic nano Fe_(3)O_(4)was designed to be involved in the Fe(Ⅱ)-catalytic wastewater treatment process,and was modified by oxidation intermediates/products(especially those with COO-structure),which promoted the co-precipitation of Ca^(2+)(originated from Ca(OH)_(2)added after oxidation process)and byproduced Fe^(3+)cations on its surface to in situ generate core-shell Fe_(3)O_(4)@CaFe-LDH.The oxidation products were further removed during Fe_(3)O_(4)@CaFe-LDH material formation via intercalation and adsorption.Thismethodwas applicable to many kinds of organicwastewater,such as bisphenol A,methyl orange,humics,and biogas slurry.The prepared magnetic and hierarchical CaFe-LDH nanocomposite material showed comparable application performance to the recently reported CaFe-LDHs.This work provides a new strategy for efficiently enhancing the efficiency and economy of Fe(Ⅱ)-catalyzed oxidative wastewater treatment by producing high value-added LDHs materials.展开更多
Aqueous rechargeable Ni-Fe batteries exhibit unique advantages in large-scale energy storage thanks to their affordability,safety,and reliability.However,their limited energy density and Coulombic efficiency stem from...Aqueous rechargeable Ni-Fe batteries exhibit unique advantages in large-scale energy storage thanks to their affordability,safety,and reliability.However,their limited energy density and Coulombic efficiency stem from unfavorable OH^(−)adsorption capability and low electrochemical activity of Fe sites,result in electrode kinetic delays for Fe anodes.Here,we report Mn and S co-modified FeOOH(MSFF)nanosheets as an advanced anode in Ni-Fe batteries,synthesized from a facile one-step surface-redox-etching method at room temperature.Based on the strong electronic coupling effect between Mn and S atoms,such MSFF anode presents fast electron transport capability,enhanced OH^(−)-adsorption capability,and redox reactivity.Specifically,the MSFF anode can achieve a high areal capacity of 2 mAh cm^(−2)at 10 mA cm^(−2),which retains a staggering 96%of the initial capacity after undergoing 9000 cycles at a higher current density of 30 mA cm^(−2).In addition,the assembled Ni-Fe battery can provide a capacity of 0.85 mAh cm^(−2)at 16 mA cm^(−2),significantly outperforming most recently reported aqueous rechargeable batteries.This work may offer an innovative and feasible approach for modulating the local electronic structure of high-performance Ni-Fe battery electrode materials.展开更多
Hydroxyl radical(·OH)formation from Fe(Ⅱ)-bearing clay mineral oxygenation in the shallow subsurface has been well documented under moderate environmental conditions.However,the impact of freezing processes on t...Hydroxyl radical(·OH)formation from Fe(Ⅱ)-bearing clay mineral oxygenation in the shallow subsurface has been well documented under moderate environmental conditions.However,the impact of freezing processes on the·OH production capability of Fe(Ⅱ)-bearing clay minerals for organic contaminant degradation,particularly in seasonally frozen soils,remains unclear.In this study,we investigated the influence of pre-freezing durations on the mineral proprieties,·OH production,and phenol degradation during the oxygenation of reduced Fe-rich nontronite(rNAu-2)and Fe-poor montmorillonite(rSWy-3).During the freezing process of reduced clay minerals(1 mM Fe(Ⅱ)),the content of edge surface Fe and Fe(Ⅱ)decreased by up to 46%and 58%,respectively,followed by a slight increased as clay mineral particles aggregated and subsequently partially disaggregated.As the edge surface Fe(Ⅱ)is effective in O_(2) activation but less effective in the transformation of H_(2)O_(2) to·OH,the redistribution of edge surface Fe(Ⅱ)leads to that·OH production and phenol degradation increased initially and then decreased with pre-freezing durations ranging from 0 to 20 days.Moreover,the rate constants of phenol degradation for both the rapid and slow reaction phases also first increase and then decrease with freezing time.However,pre-freezing significantly influenced the rapid phase of phenol degradation by rNAu-2 but affected the slow phase by rSWy-3 due to the much higher edge-surface Fe(Ⅱ)content in rNAu-2.Overall,these findings provide novel insights into the mechanism of·OH production and contaminant degradation during the freeze-thaw processes in clay-rich soils.展开更多
基金supported by the Chinese Agriculture Research System(No.CARS-35-06B)111 Project(No.B17030)the Sichuan Science and Technology Program(No.2021ZDZX0012).
文摘Due to its high efficiency,Fe(Ⅱ)-based catalytic oxidation has been one of the most popular types of technology for treating growing organic pollutants.A lot of chemical Fe sludge alongwith various refractory pollutantswas concomitantly produced,whichmay cause secondary environmental problemswithout proper disposal.We here innovatively proposed an effective method of achieving zero Fe sludge,reusing Fe resources(Fe recovery=100%)and advancing organics removal(final TOC removal>70%)simultaneously,based on the in situ formation of magnetic Ca-Fe layered double hydroxide(Fe_(3)O_(4)@CaFe-LDH)nano-material.Cations(Ca^(2+)and Fe^(3+))concentration(≥30 mmol/L)and their molar ratio(Ca:Fe≥1.75)were crucial to the success of the method.Extrinsic nano Fe_(3)O_(4)was designed to be involved in the Fe(Ⅱ)-catalytic wastewater treatment process,and was modified by oxidation intermediates/products(especially those with COO-structure),which promoted the co-precipitation of Ca^(2+)(originated from Ca(OH)_(2)added after oxidation process)and byproduced Fe^(3+)cations on its surface to in situ generate core-shell Fe_(3)O_(4)@CaFe-LDH.The oxidation products were further removed during Fe_(3)O_(4)@CaFe-LDH material formation via intercalation and adsorption.Thismethodwas applicable to many kinds of organicwastewater,such as bisphenol A,methyl orange,humics,and biogas slurry.The prepared magnetic and hierarchical CaFe-LDH nanocomposite material showed comparable application performance to the recently reported CaFe-LDHs.This work provides a new strategy for efficiently enhancing the efficiency and economy of Fe(Ⅱ)-catalyzed oxidative wastewater treatment by producing high value-added LDHs materials.
基金financially supported by National Natural Science Foundation of China(Nos.52407242,52162025)Specific Research Fund of the Innovation Platform for Academicians of Hainan Province(No.YSPTZX202123).
文摘Aqueous rechargeable Ni-Fe batteries exhibit unique advantages in large-scale energy storage thanks to their affordability,safety,and reliability.However,their limited energy density and Coulombic efficiency stem from unfavorable OH^(−)adsorption capability and low electrochemical activity of Fe sites,result in electrode kinetic delays for Fe anodes.Here,we report Mn and S co-modified FeOOH(MSFF)nanosheets as an advanced anode in Ni-Fe batteries,synthesized from a facile one-step surface-redox-etching method at room temperature.Based on the strong electronic coupling effect between Mn and S atoms,such MSFF anode presents fast electron transport capability,enhanced OH^(−)-adsorption capability,and redox reactivity.Specifically,the MSFF anode can achieve a high areal capacity of 2 mAh cm^(−2)at 10 mA cm^(−2),which retains a staggering 96%of the initial capacity after undergoing 9000 cycles at a higher current density of 30 mA cm^(−2).In addition,the assembled Ni-Fe battery can provide a capacity of 0.85 mAh cm^(−2)at 16 mA cm^(−2),significantly outperforming most recently reported aqueous rechargeable batteries.This work may offer an innovative and feasible approach for modulating the local electronic structure of high-performance Ni-Fe battery electrode materials.
基金supported by the National Natural Science Foundation of China(Nos.U22A20591,42077185,42107217)the Sichuan Province Science and Technology Program for Distinguished Young Scholars(No.2022JDJQ0010)+1 种基金the Sichuan Science and Technology Program(No.2024NSFSC0842)the State Key Laboratory of Geohazard Prevention and Geoenvironment Protection(No.SKLGP2020Z002)。
文摘Hydroxyl radical(·OH)formation from Fe(Ⅱ)-bearing clay mineral oxygenation in the shallow subsurface has been well documented under moderate environmental conditions.However,the impact of freezing processes on the·OH production capability of Fe(Ⅱ)-bearing clay minerals for organic contaminant degradation,particularly in seasonally frozen soils,remains unclear.In this study,we investigated the influence of pre-freezing durations on the mineral proprieties,·OH production,and phenol degradation during the oxygenation of reduced Fe-rich nontronite(rNAu-2)and Fe-poor montmorillonite(rSWy-3).During the freezing process of reduced clay minerals(1 mM Fe(Ⅱ)),the content of edge surface Fe and Fe(Ⅱ)decreased by up to 46%and 58%,respectively,followed by a slight increased as clay mineral particles aggregated and subsequently partially disaggregated.As the edge surface Fe(Ⅱ)is effective in O_(2) activation but less effective in the transformation of H_(2)O_(2) to·OH,the redistribution of edge surface Fe(Ⅱ)leads to that·OH production and phenol degradation increased initially and then decreased with pre-freezing durations ranging from 0 to 20 days.Moreover,the rate constants of phenol degradation for both the rapid and slow reaction phases also first increase and then decrease with freezing time.However,pre-freezing significantly influenced the rapid phase of phenol degradation by rNAu-2 but affected the slow phase by rSWy-3 due to the much higher edge-surface Fe(Ⅱ)content in rNAu-2.Overall,these findings provide novel insights into the mechanism of·OH production and contaminant degradation during the freeze-thaw processes in clay-rich soils.
