Enhancing the stability of Ni Fe-layered double hydroxide nanosheet array for alkaline seawater oxidation by Ce doping

Electrocatalytic hydrogen production from seawater holds enormous promise for clean energy generation.Nevertheless,the direct electrolysis of seawater encounters significant challenges due to poor anodic stability caused by detrimental chlorine chemistry.Herein,we present our recent discovery that the incorporation of Ce into Ni Fe layered double hydroxide nanosheet array on Ni foam(Ce-Ni Fe LDH/NF)emerges as a robust electrocatalyst for seawater oxidation.During the seawater oxidation process,CeO_(2)is generated,effectively repelling Cl^(-)and inhibiting the formation of Cl O-,resulting in a notable enhancement in the oxidation activity and stability of alkaline seawater.The prepared Ce-Ni Fe LDH/NF requires only overpotential of 390 m V to achieve the current density of 1 A cm^(-2),while maintaining long-term stability for 500 h,outperforming the performance of Ni Fe LDH/NF(430 m V,150 h)by a significant margin.This study highlights the effectiveness of a Ce-doping strategy in augmenting the activity and stability of materials based on Ni Fe LDH in seawater electrolysis for oxygen evolution.

Porous Cobalt Oxide@Layered Double Hydroxide Core-Shell Architectures on Nickel Foam as Electrode for Supercapacitor

The high performance of an electrode relies largely on a scrupulous design of nanoarchitectures and smart hybridization of electroactive materials.A porous core-shell architecture in which one-dimensional cobalt oxide(Co_3O_4)nanowire cores are grown on nickel foam prior to the growth of layered double hydroxide(LDH)shells is fabricated.Hydrothermal precipitation and thermal treatment result in homogeneous forests of 70-nm diameter Co_3O_4 nanowire,which are wrapped in LDH-nanosheet-built porous covers through a liquid phase deposition method.Due to the unique core-shell architecture and the synergetic effects of Co_3O_4and NiAl-LDH,the obtained Co_3O_4@LDH electrode exhibits a capacitance of 1 133.3F/g at a current density of 2A/g and 688.8F/g at 20A/g(5.3F/cm^(2 )at 9.4mA/cm^(2 )and 3.2F/cm^(2 )at 94mA/cm^2),which are better than those of the individual Co_3O_4nanowire.Moreover,the electrode shows excellent cycling performance with a retention rate of 90.4%after 3 000cycles at a current density of 20A/g.

Unveiling the active sites of ultrathin Co-Fe layered double hydroxides for the oxygen evolution reaction

Two-dimensional layered double hydroxides(LDHs)have been identified as promising electrocatalysts for the oxygen evolution reaction(OER);however,the simple and effective synthesis of high-quality LDHs remains extremely challenging and the active sites have not been clarified.Herein,we report a facile solution-reaction method for preparing an ultrathin(thickness<2 nm)nonprecious CoFe-based LDH.Co_(1)Fe_(0.2) LDH delivers a current density of 10 mA cm^(-2) and a high turnover frequency of 0.082 s^(-1) per total 3d metal atoms at a low overpotential of 256 mV.Its mass activity is 277.9 A g^(-1) at an overpotential of 300 mV for the OER.Kinetic studies reveal the Co site as the main active center for the OER.The doped Fe lowers the reaction barrier by accelerating the charge-transfer process.Theoretical calculations reveal that the surface Co sites adjacent to Fe atoms are the active centers for the OER and the subsurface Fe dopants excessively weaken the OH^(*)adsorption,thus increasing the energy barrier of the rate-determining step.This study can guide the rational design of high-performance CoFe-based LDHs for water splitting.

Corrosion inhibition of layered double hydroxides for metal-based systems

Layered double hydroxide(LDH),a kind of 2D layered materials,has been recognized as the promising anticorrosion materials for metal and its alloy.The microstructure,physical/chemical properties,usage in corrosion inhibition and inhibition performance of LDH have been studied separately in open literature.However,there is a lack of a complete review to summarize the status of LDH technology and the potential R&D opportunities in the field of corrosion inhibition.In addition,the challenges for LDH in corrosion inhibition of metal-based system have not been summarized systematically.Herein,we review recent advances in the rational design of LDH for corrosion inhibition of metal-based system(i.e.Mg alloy,Al alloy,steel and concrete)and high-throughput anticorrosion materials development.By evaluating the physical/chemical properties,usage in metal-based system and the corrosion inhibition mechanism of LDH,we highlight several important factors of LDH for anticorrosion performance and common features of LDH in applying different metal alloys.Finally,we provide our perspective and recommendation in this field,including high-throughput techiniques for combinatorial compositional design and rapid synthesis of anticorrosion alloys,with the goal of accelerating the development and application of LDH in corrosion inhibition of metal-based system.

Effect of nitrite intercalated Mg-Al layered double hydroxides on mortar durability under Cl−and SO_(4)^(2-) coexisting environment

The aim of this paper is to investigate the effect of nitrite intercalated Mg-Al layered double hydroxides(Mg-Al LDH-NO_(2))on mortar durability under the coexisting environment of Cl−and SO_(4)^(2-).Cl−and SO_(4)^(2-) binding properties of Mg-Al LDH-NO_(2) in simulated concrete pore solutions,Cl−and SO_(4)^(2-) diffusion properties of mortars with Mg-Al LDHNO 2 were examined.The steel corrosion and resistance of mortar against SO_(4)^(2-) attack were also evaluated.The results indicate that Mg-Al LDH-NO_(2) can effectively adsorb the Cl−and SO_(4)^(2-) in simulated concrete pore solution,and inhibit the diffusion of Cl−and SO_(4)^(2-) into cement mortars.The presence of SO_(4)^(2-) can greatly affect the uptake amount of Cl−,and there is a coupled effect of Cl−and SO_(4)^(2-) on their penetration into mortar specimens.In addition,Mg-Al LDH-NO_(2) can greatly upgrade the resistance of mortars against SO_(4)^(2-) attack and well prevent the steel from corrosion.However,Cl−will aggravate the SO_(4)^(2-) attack and SO_(4)^(2-) can initially decrease and then increase the steel corrosion.

Promoting surface reconstruction of NiFe layered double hydroxides via intercalating[Cr(C_(2)O_(4))_(3)]^(3-)for enhanced oxygen evolution

Rationally manipulating surface reconstruction of catalysts for water oxidation,inducing formation and dynamic accumulation of catalytically active centers still face numerous challenges.Herein,the introduction of[Cr(C_(2)O_(4))_(3)]^(3-)into NiFe LDHs by intercalation engineering to promote surface reconstruction achieves an advanced oxygen evolution reaction(OER)activity.In view of the weak electronegativity of Cr^(3+) in[Cr(C_(2)O_(4))_(3)]^(3-),the intercalation of[Cr(C_(2)O_(4))_(3)]^(3-)is expected to result in an electron-rich structure of Fe sites in NiFe LDHs,and higher valence state of Ni can be formed with the charge transfer between Fe and Ni.The optimized electronic structure of NiFe-[Cr(C_(2)O_(4))_(3)]^(3-)-LDHs with more active Ni^(3+) species and the expedited dynamic generation of Ni^(3+) (Fe)OOH phase during the OER process contributed to its excellent catalytic property,revealed by in situ X-ray absorption spectroscopy,Raman spectroscopy,and quasi-in situ X-ray photoelectron spectroscopy.With the modulated electronic structure of metal sites,NiFe-[Cr(C_(2)O_(4))_(3)]^(3-)-LDHs exhibited promoted OER property with a lower overpotential of 236 mV at the current density of 10 mA cm^(-2).This work illustrates the intercalation of conjugated anion to dynamically construct desired Ni^(3+) sites with the optimal electronic environment for improved OER electrocatalysis.

Desorption of Cl^(-) from Mg-Al layered double hydroxide intercalated with Cl^(-) using CO_(2) gas and water

Mg-Al layered double hydroxide intercalated with CO_(3)^(2-)(CO_(3)·Mg-Al LDH) is effective for treating HCl exhaust gas.HCl reacts with CO_(3)^(2-) in CO_(3)·Mg-Al LDH, resulting in the formation of Cl·Mg-Al LDH.We propose that CO_(2) can be used for the desorption of Cl^(-)from Cl·Mg-Al LDH to regenerate CO_(3)·Mg-Al LDH.Herein,we studied the desorption of a from CI-Mg-Al LDH by adding water to Cl·Mg-Al LDH and blowing CO_(2) into it.We also analyzed the effects of temperature and water addition speed on the desorption of CI^(-)from Cl·Mg-Al LDH.Our results show that the added water adhered to CI·Mg-Al LDH and that CO_(2) in the gaseous phase was dissolved in this adhered water,thus generating CO_(3)^(2-).Therefore,anion exchange occurred between CO_(3)^(2-) and Cl^(-)in the Cl·Mg-Al LDH,thus desorbing Cl^(-).

Corrosion Resistance of Superhydrophobic Mg-Al Layered Double Hydroxide Coatings on Aluminum Alloys

A superhydrophobic surface was successfully constructed to modify the layered double hydroxide （LDH） coatings on aluminum alloy using stearic acid. The characteristics of the coatings were investigated using SEM, XRD, FT- IR and XPS. The corrosion resistance of the prepared coatings was studied using potentiodynamic polarization and electrochemical impedance spectrum. The results revealed that the superhydrophobic surface considerably improved the corrosion-resistant performance of the LDH coatings on the aluminum alloy substrate. The formation mechanism of the superhydrophobic surface was proposed.

AlLi-LDH中Al-O八面体环吸附锂的机制

采用共沉淀法合成铝锂层状双氢氧化物(AlLi-LDH)并进行提锂试验。AlLi-LDH的空间群为P32或C2/m,微观形貌呈直径为5~10μm的规则球形。AlLi-LDH吸附Li^(+)后,空间群转化为P32。当Li^(+)浓度为95.4 mg/L时,1 h后锂吸附量为8.98 mg/g;吸附48 h后,吸附量增加到16.50 mg/g;根据二级吸附模型预测Li^(+)吸附总量为17.57 mg/g。当Mg^(2+)/Li^(+)的质量比为1067时,Mg^(2+)/Li^(+)分离系数为29536。空间群为P32时,Li-O的相互作用强度变弱,且相互作用属于静电效应。具有P32空间基团的AlLi-LDH更容易吸附和解吸Li^(+)。

Corrosion resistance of a silane/ceria modified Mg-Al-layered double hydroxide on AA5005 aluminum alloy

The present work aimed at assessing the electrochemical behavior and the corrosion inhibition performance of Mg-Al-layered double hydroxide(LDH)coatings modified with methyltrimethoxysilane(MTMS)and cerium nitrate on AA5005 aluminum alloy.The chemical compositions and surface morphologies of the coatings were investigated by XRD,FT-IR and FE-SEM,while their corrosion resistance was evaluated by electrochemical and immersion tests.An optimum corrosion resistance of the composite coatings was obtained by adding 10^−2 mol·L^−1 cerium nitrate.An excess addition of cerium nitrate resulted in a loose structure and poor corrosion resistance of the coating.The corrosion mechanism of the composite coatings was proposed and discussed.

Corrosion of in-situ grown Mg Al-LDH coating on aluminum alloy

Mg Al-layered double hydroxides（LDH） coatings were fabricated by the in-situ hydrothermal treatment method on the AA5005 aluminum alloy.The characteristics of the coatings were investigated by XRD,FT-IR,SEM and EDS.The effect of the p H value of the solution on the formation of the LDH coatings was studied.The optimum p H value of the solution was 10.0.The corrosion resistance of the LDH coatings was studied using potentiodynamic polarization tests and electrochemical impedance spectrum（EIS）.The results demonstrate that the LDH coatings,characterized by platelets vertically to the substrate surface possess excellent corrosion resistance.The influence of the hydrothermal crystallization time on the corrosion resistance was evaluated.Prolonging the crystallization time can increase the corrosion resistance of the obtained LDH coatings.The anticorrosion mechanism of the LDH coatings was discussed.

Controllable magnetic properties of cobalt ferrite particles derived from layered double hydroxide precursors

Cobalt ferrite CoxNi1-xFe2O4 （x = 0, 0.5, 1 ） particles with controllable magnetic properties have been prepared by calcination of co-substituted NiFe^2＋Fe^3＋ -layered double hydroxide （NiFe^2＋Fe^3＋-LDH） precursors prepared via a scalable method involving separate nucleation and aging steps （SNAS）. Their structural and magnetic characteristics were investigated by powder X-ray diffraction （XRD）, scanning electron microscopy （SEM） and vibrating sample magnetometry （VSM）. Measurements of magnetic properties show that the saturation magnetization （Ms） and coercivity （He） of the calcined products increased with increasing cobalt content. The LDH precursor-based product obtained by calcination of a mixture of CoFe^2＋Fe3^＋-LDH and NiFe^2＋Fe^3＋ -LDH powders with a Co/Ni molar ratio of 1：1, exhibits a moderate value of Ms and an increased value of He compared to the corresponding values for an Ni0.5Co0.5Fe2O4 material prepared by calcination of a Co0.5Ni0.5Fe^2＋Fe^3＋-LDH precursor, and a physical mixture of CoFe2O4 and NiFe2O4 with a Co/Ni molar ratio of 1 ： 1. These results may provide a way to regulate magnetic anisotropy of ferrite spinels by varying the composition of the LDH precursors.

Comments on “Efficient adsorption of Mn(Ⅱ) by layered double hydroxides intercalated with diethylenetriaminepentaacetic acid and the mechanistic study.J.Environ.Sci.85,56-65”

In the paper entitled"Efficient adsorption of Mn(Ⅱ)by layered double hydroxides intercalated with di ethylenetriaminepentaacetic acid and the mechanistic study"in Journal of Environmental Sciences,volume 85,page 56-65,there were problems with mathematical notation and dimensional errors in the calculation for Giibbs free energy.In Section 2.5:Adsorption isotherms and thermodynamics studies,authors calculated the Gibbs free energy change(△G°)

Formation of CoAl layered double hydroxide on the boehmite surface and its role in tungstate sorption

Sorption of tungstate on boehmite（γ-Al OOH）is increased by co-sorption with Co^（2＋）over the near-neutral p H range.Batch uptake experiments show up to a 3-fold increase in tungstate uptake over the range WO4^（2-）=50–1000μmol/L compared to boehmite not treated with Co^（2＋）.Desorption experiments reveal a corresponding decrease in sorption reversibility for tungstate co-sorbed with Co^（2＋）.Reaction of boehmite with Co^（2＋）results in the formation of Co Al layered double hydroxide（LDH）,as confirmed by X-ray diffraction and X-ray absorption spectroscopy.Tungsten L3-edge X-ray absorption near edge structure（XANES）reveals that W（VI）is octahedrally coordinated in all sorption samples,with polymeric tungstate species forming at higher tungstate concentrations.X-ray diffraction and X-ray absorption spectroscopy indicate that the mechanism for enhancement of tungstate uptake is the formation of surface complexes on boehmite at low tungstate concentrations,while exchange into the Co Al LDH becomes important at higher tungstate concentrations.The results provide a basis for developing strategies to enhance tungstate sorption and to limit its environmental mobility at near-neutral pH conditions.

超级电容器用NiCo-LDH电极材料研究进展

镍钴层状双金属氢氧化物(NiCo-LDH)具有理论比电容大、成本低等优势,作为超级电容器电极材料得到广泛研究,但导电性能和电化学性能较差,限制了实际应用。简要介绍NiCo-LDH电极材料的储能原理、电化学性能影响因素(如比表面积、孔径和导电性等)和制备方法,其中包括水热法(溶剂热法)、微波法、电化学沉积法、化学共沉淀法和牺牲模板法等。重点介绍NiCo-LDH电极材料的改性研究(如改变形貌、制备复合材料等),并对研究方向进行展望。

Comparative study of oxidative stress induced by sand flower and schistose nanosized layered double hydroxides in N2a cells

Magnesium-aluminum layered double hydroxide （Mg/ALLDH） nanoparticles have strong potential application as drug delivery systems because of their low toxicity and suitable biocompatibility. However, few studies have described the morphological effects of these hydroxides on nerve cells. The present study compares the oxidative stress induced by different concentrations （i.e., 0, 50, 100, 200, 400, and 800 μg/mL） of sand flower and flake nano-Mg/ AI-LDHs in mouse neuroblastoma cells （N2a） when these cells were exposed for 24 and 48 h. Cell viability was detected by MTT assay, and production of reactive oxygen species （ROS）, glutathione （GSH）, and malondialdehyde （MDA） were monitored to evaluate oxidative damage. Results suggested that sand flower nano-LDHs, at the appropriate concentrations （less than 200 μg/mL）, especially those of about 100-200 nm in size, induce no harmful effects on N2a cells.

焙烧温度对CoAl-LDH基催化剂结构和费托合成性能的影响

采用尿素水解法制备了层状双金属氢氧化物(CoAl-LDHs),经焙烧处理后得到LDH基催化剂,利用XRD、BET、SEM等分析方法对其进行表征,并在固定床上考察了焙烧温度对催化剂的层状结构及费托合成反应性能的影响。结果表明,热解LDHs会生成层状双分子氧化物(LDO),热解温度对催化剂的晶型结构、颗粒分散度和还原性能有显著影响;催化剂中钴的负载量可达50.0%以上,钴氧化物颗粒均匀分散在纳米片上,同时具有较大的比表面积。其中600℃焙烧LDHs形成催化剂的催化活性最佳,在反应温度220℃、V(H_(2))∶V(CO)=2∶1、反应压力2.5 MPa和空速为3.8 h^(-1)的条件下,CO转化率为22%,C_(5+)选择性可达91.4%。

NiAl-LDHs电极材料的水热合成及其超级电容器电化学性能

超级电容器具有大充放电速率、良好的循环稳定性及高功率密度等优点,是一种新兴的绿色环保储能器件。采用简单的水热合成法制备镍铝层状双金属氢氧化物(NiAl-LDHs)超级电容器电极材料,探究不同镍铝比对其形貌组成及电化学性能的影响。所制备的Ni1Al1-LDHs电极材料在电流密度为1A/g时表现出378F/g的高比电容。以活性炭(AC)为负极组成的Ni1Al1-LDHs//AC非对称超级电容器在能量密度为27.5 Wh/kg时,具有1.4 kW/kg的高功率密度,表现出优异的电化学性能。

CoV-LDH及其磷化物的制备和赝电容储能研究

磷化处理是一种提高电极材料活性位点的有效策略,被广泛用来增强赝电容材料的电化学储能性能。分别采用水热法和电沉积法合成了微球状和针状形貌结构的钴钒层状双金属氢氧化物(CoV-LDH),经过磷化后得到了赝电容储能性能较好的钴钒磷化物(CoV-P)电极材料。相对于水热法和电沉积法制备的CoV与CoV/NF,磷化后的CoV-P和CoV-P/NF比电容分别提高了61.5%和87.7%。在1 A·g^(-1)的电流密度下,CoV-P/NF的放电比电容达到了1871 F·g^(-1)。当电流密度增加5倍时,具有65%的容量保留率。经动力学分析表明,CoV-P/NF的比电容贡献以赝电容扩散控制过程占主导作用。以活性炭(AC)为负极组装的CoV-P//AC非对称超级电容器,当功率密度为511 W·kg^(-1)时,提供了37 W·h·kg^(-1)的能量密度,且在能量密度为12 W·h·kg^(-1)时,达到了2491 W·kg^(-1)的功率密度,表现出了良好的储能性能。

锂铝层状双金属氢氧化物的制备及其锂脱嵌过程

锂铝层状双金属氢氧化物(Li/Al-LDHs)是一种适用于高镁锂比卤水中提锂的吸附剂,但其存在吸附容量偏低、吸附机理与适用条件不够清晰等问题。本工作以铝粉、氢氧化锂为原料制备Li/Al-LDHs,考察了适用条件下溶液中阴阳离子对吸附过程的影响并进行了不同溶液组成下的提锂性能测试,结合红外光谱测试和X射线光电子能谱等表征明晰了锂脱嵌机理。结果表明,Li/Al-LDHs在卤水中的最大吸附容量为8.350mg/g,阳离子选择性顺序为Li^(+)>Na^(+)>Mg^(2+)>Ca^(2+)>K^(+)。Li/Al-LDHs对Li^(+)的吸附符合Langmuir等温吸附模型和准二级吸附动力学模型,吸附过程主要是基于尺寸筛分效应进行的,Li^(+)进入吸附剂层间的空位后需要等量的阴离子(Cl^(-)、SO_(4)^(2-)等)进行电荷平衡,其吸锂容量随溶液体系总离子浓度的增加而变大,因此更适用于从高含盐量卤水中提锂。研究结果可为后续废旧金属铝制取Li/Al-LDHs用于盐湖卤水提锂提供技术参考。