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.

Self-supported ultrathin NiCo layered double hydroxides nanosheets electrode for efficient electrosynthesis of formate

Electrochemical CO_(2)reduction into energy-carrying compounds,such as formate,is of great importance for carbon neutrality,which however suffers from high electrical energy input and liquid products crossover.Herein,we fabricated self-supported ultrathin NiCo layered double hydroxides(LDHs)electrodes as anode for methanol electrooxidation to achieve a high formate production rate(5.89 mmol h^(-1)cm^(-2))coupled with CO_(2)electro-reduction at the cathode.A total formate faradic efficiency of both anode for methanol oxidation and cathode for CO_(2)reduction can reach up to 188%driven by a low cell potential of only 2.06 V at 100 mA cm^(-2)in membrane-electrode assembly(MEA).Physical characterizations demonstrated that Ni^(3+)species,formed on the electrochemical oxidation of Ni-containing hydroxide,acted as catalytically active species for the oxidation of methanol to formate.Furthermore,DFT calculations revealed that ultrathin LDHs were beneficial for the formation of Ni^(3+)in hydroxides and introducing oxygen vacancy in NiCo-LDH could decrease the energy barrier of the rate-determining step for methanol oxidation.This work presents a promising approach for fabricating advanced electrodes towards electrocatalytic reactions.

Layered double hydroxides as electrode materials for flexible energy storage devices

To prevent and mitigate environmental degradation,high-performance and cost-effective electrochemical flexible energy storage systems need to be urgently developed.This demand has led to an increase in research on electrode materials for high-capacity flexible supercapacitors and secondary batteries,which have greatly aided the development of contemporary digital communications and electric vehicles.The use of layered double hydroxides(LDHs)as electrode materials has shown productive results over the last decade,owing to their easy production,versatile composition,low cost,and excellent physicochemical features.This review highlights the distinctive 2D sheet-like structures and electrochemical characteristics of LDH materials,as well as current developments in their fabrication strategies for expanding the application scope of LDHs as electrode materials for flexible supercapacitors and alkali metal(Li,Na,K)ion batteries.

Identification and comparison of the local physicochemical structures of transition metal-based layered double hydroxides for high performance electrochemical oxygen evolution reactions

Layered double hydroxides(LDHs) have attracted considerable attention as a cost effective alternative to the precious iridium-and ruthenium-based electrocatalysts for an oxygen evolution reaction(OER),a bottleneck of water electrolysis for sustainable hydrogen production.Despite their excellent OER performance,the structural and electronic properties of LDHs,particularly during the OER process,remain to be poorly understood.In this study,a series of LDH catalysts is investigated through in situ X-ray absorption fine structure analyses and density functional theory(DFT) calculations.Our experimental results reveal that the LDH catalyst with equal amounts of Ni and Fe(NF-LDH) exhibits the highest OER activity and catalytic life span when compared with its counterparts having equal amounts of Ni and Co(NC-LDH)and Ni only(Ni-LDH).The NF-LDH shows a markedly enhanced OER kinetics compared to the NC-LDH and the Ni-LDH,as proven by the lower overpotentials of 180,240,and 310 mV,respectively,and the Tafel slopes of 35.1,43.4,and 62.7 mV dec^(-1),respectively.The DFT calculations demonstrate that the lowest overpotential of the NF-LDH is associated with the active sites located at the edge planes of NF-LDH in contrast to those located at the basal planes of Ni-LDH and NC-LDH.The current study pinpoints the active sites on various LDHs and presents strategies for optimizing the OER performance of the LDH catalysts.

PREPARATION OF POLY(METHYL METHACRYLATE)/LAYERED DOUBLE HYDROXIDES NANOCOMPOSITES via in situ SOLUTION POLYMERIZATION

An exfoliated layered double hydroxides/poly（methyl methacrylate） （LDHs/PMMA） nanocomposite was prepared by in situ solution polymerization of methyl methacrylate （MMA） in the presence of 4-vinylbenzenesulfonate intercalated LDHs（MgAl-VBS LDHs）. MgAl-VBS LDHs was prepared by the ion exchange method, and the structure and composition of the MgAl-VBS LDHs were determined by X-ray diffraction （XRD）, infrared spectroscopy and elemental analysis. XRD and transmission electron microscopy （TEM） were employed to examine the structure of LDHs/PMMA nanocomposite. It was indicated that the LDHs layers were well exfoliated and dispersed in the PMMA matrix. The grafting of PMMA onto LDHs was confirmed by the extraction result and the weight fraction of grafted PMMA increased as the weight fraction of LDHs in the nanocomposites increased.

Preparation of PO_4^(3-),P_2O_7^(4-) Anion-Pillared Nanocrystalline Mg-Al and Zn-Al Layered Double Hydroxides in Microwave Fields

Using nanocrystalline [Mg-Al-CO3] and [Zn-Al-CO3] as precursors, [Mg-Al-PO4], [Zn-Al-PO4], [Mg-Al-P2O7] and [Zn-Al-P2O7] have been successfully synthesized by a direct reaction with the free PO43- or P2O74- using the microwave techniques and the anion-exchange method. And the samples thus obtained were characterized by TEM, FT-IR and XRD. The results show that the initial interlayer carbonate ions can be completely replaced by the free PO43- or P2O74-under controlled microwave conditions employed for a short time.

Design, synthesis, and nanoengineered modification of spherical graphene surface by layered double hydroxide (LDH) for removal of As (Ⅲ) from aqueous solutions

In this study, new nano spherical graphene modified with LDH(Layered Double Hydroxide) was prepared and used to remove As(Ⅲ) ion from aqueous solutions. At first, graphene oxide was synthesized from graphite using a well-known Hammer method. The obtained graphene oxide solution was sprayed in octanol solution under different temperatures and sprayed speed as influenced variables. The structure and physical characterization of synthesized spherical graphene oxide were determined by various techniques,including FT-IR, N_(2) adsorption–desorption, SEM, TEM, and EDX. In the next step, the hydrothermal method was applied to deposition LDH on the spherical graphene oxide. The synthesized spherical graphene modified by LDH was used to remove As(Ⅲ) as a toxic heavy metal ion. The effect of influenced variables including p H, contact time, amount of sorbent, and type eluent studied and the optimum values were as 8, 30, 50, and HCl(0.5 mol·L^(-1)), respectively. After optimization, the studied sorbent was shown a high adsorption capacity(149.3 mg·g^(-1)). The adsorption mechanism and kinetic models exhibited good agreement with the Langmuir isotherm and pseudo-second-order trends, respectively. Besides, the synthesized product was tested for seven times without significant loss in its sorption efficiency.

Advances in efficient electrocatalysts based on layered double hydroxides and their derivatives

The explore and development of electrocatalysts have gained significant attention due to their indispensable status in energy storage and conversion systems, such as fuel cells, metal–air batteries and solar water splitting cells. Layered double hydroxides（LDHs） and their derivatives（e.g., transition metal alloys, oxides, sulfides, nitrides and phosphides） have been adopted as catalysts for various electrochemical reactions, such as oxygen reduction, oxygen evolution, hydrogen evolution, and COreduction, which show excellent activity and remarkable durability in electrocatalytic process. In this review, the synthesis strategies, structural characters and electrochemical performances for the LDHs and their derivatives are described. In addition, we also discussed the effect of electronic and geometry structures to their electrocatalytic activity. The further development of high-performance electrocatalysts based on LDHs and their derivatives is covered by both a short summary and future outlook from the viewpoint of the material design and practical application.

Synergistic cerium doping and MXene coupling in layered double hydroxides as efficient electrocatalysts for oxygen evolution

Oxygen evolution reaction(OER) is a bottle-neck process in many sustainable energy conversion systems due to its sluggish kinetics.The development of cost-effective yet efficient electrocatalysts towards OER is highly desirable but still a great challenge at current stage.Herein,a new type of hybrid nanostructure,consisting of two-dimensional(2D) Cerium-doped NiFe-layered double hydroxide nanoflakes directly grown on the 2D Ti3C2Tx MXene surface(denoted as NiFeCe-LDH/MXene),is designed using a facile insitu coprecipitation method.The resultant NiFeCe-LDH/MXene hybrid presents a hierarchical nanoporous structure,high electrical conductivity and strong interfacial junction because of the synergistic effect of Ce doping and MXene coupling.As a result,the hybrid catalyst exhibits an excellent catalytic activity for OER,delivering a low onset overpotential of 197 mV and an overpotential of 260 mV at a current density of 10 mA·cm-2 in the alkaline medium,much lower than its pure LDH counterparts and IrO2 catalyst.Besides,the hybrid catalyst also displays a fast reaction kinetics and a remarkable stable durability.Further theoretic studies using density function theory(DFT) methods reveal that Ce doping could effectively narrow the bandgap of NiFe-LDH and reduce the overpotential in OER process.This work may shed light on the exploration of advanced electrocatalysts for renewable energy conversion and storage systems.

Layered double hydroxides:Scale production and application in soil remediation as super-stable mineralizer

Soil contamination by heavy metals has presented severe risks to human health through food chain.As one of the most promising remediation technologies,in-situ immobilization strategy has been widely adopted in practice.However,considering the large quantities of contaminated soil,it is still a huge challenge to design low-cost amendments with strong and long-term immobilization ability.Layered double hydroxides(LDHs)have drawn tremendous attention in fundamental research and practical application because of their unique properties.Moreover,owing to its super-stable mineralization effect to heavy metal ions,LDHs have exhibited great potential in the field of soil remediation.In this work,we mainly focused on the scale production strategy of LDHs with low-cost,and its application in soil remediation.Besides,several key challenges in using LDHs as amendments for immobilization of heavy metal ions are presented.We hope that this mini-review could shed light on the sustainable development of LDHs as amendment for heavy metals in future research directions.

Effect of Layered Double Hydroxides on Ultraviolet Aging Resistance of SBS Modified Bitumen Membrane

Layered double hydroxides （LDHs）/styrene-butadiene-styrene （SBS） eopolymer modified bitumen was prepared by melt blending. The effect of LDHs on the ultraviolet （UV） aging behavior of SBS modified bitumen was investigated. The changes of chemical structures of modified bitumen before and after UV aging were characterized by Fourier transform infrared spectroscopy （FTIR）. The results show that LDHs obviously reduce the variation of softening point and low temperature flexibility of SBS modified bitumen under different UV radiation intensities, which indicates that the UV aging resistance performance of SBS modified bitumen is improved effectively by LDHs. Compared with SBS modified bitumen, the changes of carbonyl, sulfoxide and butadienyl of LDHs/SBS modified bitumen decrease significantly after UV aging according to FTIR analysis, demonstrating that the oxidation and degradation reactions of SBS modified bitumen were restrained effectively by adding LDHs.

The tuning of pore structures and acidity for Zn/Al layered double hydroxides:The application on selective hydrodesulfurization for FCC gasoline

Co–Mo catalysts applied on the hydrodesulfurization（HDS） for FCC gasoline were prepared with Zn–Al layered double hydroxides（LDHs） to improve their performances,and the effects of pore structures and acidity on HDS performances were studied in detail. A series of Zn–Al/LDHs samples with different pore structures and acidities are synthesized on the bases of co-precipitation of OH-,CO2-,Al3＋,and Zn2＋. The neutralization p H is a main factor to affect the pore structures and acidity of Zn–Al/LDHs,and a series of Zn–Al/LDHs with different pore structures and acidities are obtained. Based on the representative samples with different specific surface areas（SBET） and acidities,three Co Mo/LDHs catalysts were prepared,and their HDS performances were compared with traditional Co Mo/Al2O3 catalysts. The results indicated that catalysts prepared with high SBETpossessed high HDS activity,and Br？nsted acid sites could reduce the thiol content in the product to some extent. All the three catalysts prepared with LDHs displayed little lower HDS activity but higher selectivity than Co Mo/Al2O3,and could restrain the reactions of re-combination between olefin and H2 S which could be due to the existence of Br？nsted acid sites.

Advances in Mg-Al-layered double hydroxide steam coatings on Mg alloys:A review

Layered double hydroxide(LDH)coatings on magnesium(Mg)alloys shine brightly in the field of corrosion protection because of their special ion-exchange function.State-of-the-art steam coating as a type of LDH film preparation technique has emerged in recent years because only pure water is required as the steam source and its environmentally friendly LDH coating fits the current need for green development.Moreover,this coating can effectively inhibit the corrosion of the Mg alloy substrate due to the chemical bonding between the coating and the Mg alloy substrate.This review systematically explains cutting-edge advancements in the growth mechanism and corrosion behavior of LDH steam coatings,and analyzes the advantages and limitations of the steam-coating method.The influencing factors including pressure,CO_(2)/CO_(3)^(2-),aluminum content of the substrate alloy,solution type,and acid-pickling pretreatment,as well as the post-treatment of steam-coating defects,are comprehensively elucidated,providing new insights into the development of the in situ steam-coating technique.Finally,existing issues and future prospects are discussed to further accelerate the widespread application of Mg alloys.

Ultrathin defective high-entropy layered double hydroxides for electrochemical water oxidation

One of the fundamental driving forces in the materials science community is the hunt for new materials with specific properties that meet the requirements of rapidly evolving technology.

Smart Interfacing between Co-Fe Layered Double Hydroxide and Graphitic Carbon Nitride for High-efficiency Electrocatalytic Nitrogen Reduction

Bimetallic compounds such as hydrotalcite-type layered double hydroxides(LDHs)are promising electrocatalysts owing to their unique electronic structures.However,their abilities toward nitrogen adsorption and reduction are undermined since the surface-mantled,electronegative-OH groups hinder the charge transfer between transition metal atoms and nitrogen molecules.Herein,a smart interfacing strategy is proposed to construct a coupled heterointerface between LDH and 2D g-C_(3)N_(4),which is proven by density functional theory(DFT)investigations to be favorable for nitrogen adsorption and ammonia desorption compared with neat LDH surface.The interfaced LDH and g-C_(3)N_(4) is further hybridized with a self-standing TiO_(2) nanofibrous membrane(NM)to maximize the interfacial effect owing to its high porosity and large surface area.Profited from the synergistic superiorities of the three components,the LDH@C_(3)N_(4)@TiO_(2) NM delivers superior ammonia yield(2.07×10^(−9) mol s^(−1) cm^(−2))and Faradaic efficiency(25.3%),making it a high-efficiency,noble-metal-free catalyst system toward electrocatalytic nitrogen reduction.

3D Hierarchical Co–Al Layered Double Hydroxides with Long-Term Stabilities and High Rate Performances in Supercapacitors

Three-dimensional(3D) flower-like Co–Al layered double hydroxide(Co–Al-LDH) architectures composed of atomically thin nanosheets were successfully synthesized via a hydrothermal method in a mixed solvent of water and butyl alcohol. Owing to the unique hierarchical structure and modification by butyl alcohol, the electrochemical stability and the charge/mass transport of the Co–Al-LDHs was improved. When used in supercapacitors, the obtained Co–Al-LDHs deliver a high specific capacitance of 838 Fg^(-1) at a current density of 1 Ag^(-1)and excellent rate performance(753 Fg^(-1) at 30 Ag^(-1) and 677 Fg^(-1) at 100 Ag^(-1)), as well as excellent cycling stability with 95% retention of the initial capacitance even after 20,000 cycles at a current density of 5 Ag^(-1). This work provides a promising alternative strategy to enhance the electrochemical properties of supercapacitors.

Structured NiFe catalysts derived from in-situ grown layered double hydroxides on ceramic monolith for CO_(2) methanation

Monolithic catalysts for CO_(2) methanation have become an active research area for the industrial development of Power-to-Gas technology.In this study,we developed a facile and reproducible synthesis strategy for the preparation of structured NiFe catalysts on washcoated cordierite monoliths for CO_(2) methanation.The NiFe catalysts were derived from in-situ grown layered double hydroxides(LDHs)via urea hydrolysis.The influence of different washcoat materials,i.e.,alumina and silica colloidal suspensions on the formation of LDHs layer was investigated,together with the impact of total metal concentration.NiFe LDHs were precipitated on the exterior surface of cordierite washcoated with alumina,while it was found to deposit further inside the channel wall of monolith washcoated with silica due to different intrinsic properties of the colloidal solutions.On the other hand,the thickness of in-situ grown LDHs layers and the catalyst loading could be increased by high metal concentration.The best monolithic catalyst(COR-AluCC-0.5M)was robust,having a thin and well-adhered catalytic layer on the cordierite substrate.As a result,high methane yield was obtained from CO_(2) methanation at high flow rate on this structured NiFe catalysts.The monolithic catalysts appeared as promising structured catalysts for the development of industrial methanation reactor.

Recent progress in functionalized layered double hydroxides and their application in efficient electrocatalytic water oxidation

Layered double hydroxides (LDHs), a class of anionic clays consisting of brucite-like host layers and interlayer anions, have been widely investigated in the last decade due to their promising applications in many areas such as catalysis, ion separation and adsorption. Owing to the highly tunable compositi on and uniform distribution of metal cations in the brucite-like layers, as well as the facile exchangeability of intercalated anions, LDHs can be modified and functionalized to form various nanostructures/composites through versatile processes such as anion intercalation and exfoliation, decoration of nanoparticles, selfassembly with other two-dimensional (2D) materials, and controlled growth on conductive supports (e.g., nanowire arrays, nano tubes, 3D foams). In this article, we briefly review the recent advances on both the LDH nano structures and functionalized composites toward the applications in energy conversion, especially for water oxidation.

Carbonation of Sulphoaluminate Cement with Layered Double Hydroxides

The increasing importance of the ecologically minded production of building materials makes it necessary to develop reasonable alternatives to the CO2-intense production of ordinary Portland cement （OPC）. The development of new or modified concrete is an important part of existing strategies to improve performance and minimize life-cycle costs. Therefore, we investigated carbonation resistance properties of sulphoaluminate cement （SAC） concrete incorporating layered double hydroxides （LDHs）. X-ray diffraction （XRD） and IR-spectroscopy were employed to characterize the component and structural changes of LDHs and cement paste before and after carbonation test. Carbonation resistance of concrete was experimentally evaluated. Finally, carbonation of Portland cement and SAC concrete was compared. The experimental results show that carbonation depth decreases remarkably with the addition of LDHs, especially the calcinated LDHs. Carbonation depth of SAC concrete is smaller than that of PC concrete regardless of curing time.

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.