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.

Overwhelming low ammonia escape and low temperature denitration efficiency via MnOx-decorated two-dimensional MgAl layered double oxides

Low temperature catalysts are attracting increasing attention in the selective catalytic reduction(SCR)of NO with NH3.Mn Ox-decorated Mg Al layered double oxide(Mn/Mg Al-LDO)was synthesized via a facile fast pour assisted co-precipitation(FP-CP)process.Compared to the Mn/Mg Al-LDO obtained via slow drop assisted coprecipitation(SD-CP)method,the Mn/Mg Al-LDO(FP-CP)has excellent activity.The Mn/Mg Al-LDO(FP-CP)catalyst was shown to possess a high NO conversion rate of 76%-100%from 25 to 150℃,which is much better than the control Mn/Mg Al-LDO(SD-CP)(29.4%-75.8%).In addition,the Mn/Mg Al-LDO(FP-CP)offered an enhanced NO conversion rate of 97%and a N2selectivity of 97.3%at 100℃;the NO conversion rate was 100%and the N2selectivity was 90%at 150℃with a GHSV of 60,000 h^-1.The Mn/Mg Al-LDO(FP-CP)catalyst exhibited a smaller fragment nano-sheet structure(sheet thickness of 7.23 nm).An apparent lattice disorder was observed in the HRTEM image confirming the presence of many defects.The H2-TPR curves show that the Mn/Mg Al-LDO(FP-CP)catalyst has abundant reducing substances.Furthermore,the enhanced surface acidity makes the NH3concentration of the Mn/Mg Al-LDO(FP-CP)catalyst lower than 100 ml·m^-3after the reaction from 25 to 400℃.This can effectively reduce the ammonia escape rate in the SCR reaction.Thus,the Mn/Mg Al-LDO(FP-CP)catalyst has potential applications in stationary industrial installations for environmentally friendly ultra-low temperature SCR.

Synthesis and highly efficient photocatalytic activity of mixed oxides derived from ZnNiAl layered double hydroxides

ZnO/NiO/ZnAl2O4 mixed-metal oxides were successfully synthesized through a hydrotalcite-like precursor route, in which appropriate amounts of metal salts solutions were mixed to obtain a new series of ZnNiAl layered double hydroxides（LDHs） as precursors, followed by calcination under different temperatures. The as-obtained samples were characterized by SEM, HRTEM, TEM, XRD, BET, TG-DTA, and UV-Vis spectra techniques. The photocatalytic activities of the samples were evaluated by degradation of methyl orange（MO） under the simulated sunlight irradiation. The effects of Zn/Ni/Al mole ratio and calcination temperature on the composition, morphology and photocatalytic activity of the samples were investigated in detail. The results indicated that compared with ZnNiAl-LDHs, the mixed-metal oxide showed superior photocatalytic performance for the degradation of MO. A maximum of 97.3% photocatalytic decoloration rate within 60 min was achieved from the LDH with the Zn/Ni/Al mole ratio of 2：1：1 and the calcination temperature of 500 ℃, which much exceeded that of Degussa P25 under the same conditions. The possible mechanism of photocatalytic degradation over ZnO/NiO/ZnAl2O4 was discussed.

Ultrafine monolayer Co-containing layered double hydroxide nanosheets for water oxidation

For many two-dimensional(2D)materials,low coordination edges and corner sites offer greatly enhanced catalytic performance compared to basal sites,motivating the search for new synthetic approaches towards ultrathin and ultrafine 2D nanomaterials with high specific surface areas.To date,the synthesis of catalysts that are both ultrathin(monolayer)and ultrafine(lateral size<10nm)has proven extremely challenging.Herein,using a facile ultrasonic exfoliation procedure,we describe the successful synthesis of ultrafine ZnCo-LDH nanosheets(denoted as ZnCo-UF)with a size^3.5 nm and thickness^0.5 nm.The single layer ZnCo-UF nanosheets possess an abundance of oxygen vacancies(Vo)and unsaturated coordination s让es,thereby affording outstanding electrocatalytic water oxidation performance.DFT calculations confirmed that Vo on the surface of ZnCo-UF enhanced H20 adsorption via increasing the electropositivity of the nanosheets.

Enhanced corrosion resistance of micro-arc oxidation coated magnesium alloy by superhydrophobic Mg-Al layered double hydroxide coating

To further enhance the corrosion resistance of the porous micro-arc oxidation(MAO) ceramic layers on AZ31 magnesium alloy, superhydrophobic Mg-Al layered double hydroxide(LDH) coating was fabricated on MAO-coated AZ31 alloy by using in-situ growth method followed by surface modification with stearic acid. The characteristics of different coatings were investigated by XRD, SEM and EDS. The effect of the hydrothermal treatment time on the formation of the LDH coatings was studied. The results demonstrated that the micro-pores and cracks of MAO coating were gradually sealed via in-situ growing LDH with prolonging hydrothermal treating time. Electrochemical measurement displayed that the lowest corrosion current density, the most positive corrosion potential and the highest impedance modulus were observed for superhydrophobic LDH/MAO coating compared with those of MAO coating and LDH/MAO coating. Immersion experiment proved that the superhydrophobic LDH/MAO coating with the active anti-corrosion capability significantly enhanced the long-term corrosion protection for MAO coated alloy.

Recent advance on VOCs oxidation over layered double hydroxides derived mixed metal oxides

Catalytic oxidation is regarded as one of the most promising strategies for volatile organic compounds(VOCs)purification.Mixed metal oxides(MMOs),after topological transformation using layered double hydroxides(LDHs)as precursors,are extensively used as catalysts for VOCs oxidation due to their uniformity advantage.This review summarizes the developments in the LDH-derived VOCs heterogeneous catalytic oxidation over the last 10 years.Particularly,it addresses the VOCs abatement performance over MMO,noble metal/MMO,core-shell structured MMO,and integral MMO film catalysts originating from LDHs.Moreover,it highlights the water vapor effect and oxidation mechanism.This review indicates that LDH-based catalysts are a category of important VOCs oxidation materials.

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.

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.

Synthesis of Ni/Mg/Al Layered Double Hydroxides and Their Use as Catalyst Precursors in the Preparation of Carbon Nanotubes

Ni/Mg/Al layered double hydroxides(LDHs) with different n(Ni)∶n(Mg)∶n(Al) ratio values were prepared via a coprecipitation reaction. Then Ni/Mg/Al mixed oxides were obtained by calcination of these LDHs precursors. Carbon nanotubes were produced in the catalytic decomposition of propane over the Ni/Mg/Al mixed oxide catalysts. The quality of as-made nanotubes was investigated by SEM and TEM. The nanotubes were multiwall with a high length-diameter ratio and appeared to be flexible. The catalytic activities of these mixed oxides increased with increasing the Ni content. The Ni/Mg/Al mixed oxide with the highest Ni content [n(Ni)/n(Mg)/n(Al)=1/1/1] showed the highest activity and the carbon nanotubes grown on its surface had the best quality.

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.

Studies of the Catalytic Activity and Deactivation of Calcined Layered Double Hydroxides in the Reaction of Ethanol with Propylene Oxide

The reaction of ethanol with propylene oxide over calcined layered double hydroxides(CLDH) was investigated. The results show that CLDH has a good activity and a good selectivity, but the activity and the selectivity of CLDH decrease when CLDH reforms LDH- the so called 'memory effect'. The influence of the 'memory effect' on the CLDH returning to LDH was studied by the hydration reaction. It is shown that the 'memory effect' is not complete, and the decreases of the Mg/Al molar ratio of LDH and the crystallite size due to the increase of the hydration reaction time result in the drop of the activity and the selectivity.

The superhydrophobic sponge decorated with Ni-Co double layered oxides with thiol modification for continuous oil/water separation

In this paper, the superhydrophobic polyurethane sponge(SS-PU) was facilely fabricated by etching with Jones reagent to bind the nanoparticles of Ni-Co double layered oxides(LDOs) on the surface, and following modification with n-dodecyl mercaptan(DDT). This method provides a new strategy to fabricate superhydrophobic PU sponge with a water contact angle of 157° for absorbing oil with low cost and in large scale. It exhibits the strong absorption capacity and highly selective characteristic for various kinds of oils which can be recycled by simple squeezing. Besides, the as-prepared sponge can deal with the floating and underwater oils, indicating its application value in handling oil spills and domestic oily wastewater. The good self-cleaning ability shows the potential to clear the pollutants due to the ultralow adhesion to water. Especially, the most important point is that the superhydrophobic sponge can continuously and effectively separate the oil/water mixture against the condition of turbulent disturbance by using our designed device system, which exhibit its good superhydrophobicity, strong stability.Furthermore, the SS-PU still maintained stable absorption performance after 150 cycle tests without losing capacity obviously, showing excellent durability in long-term operation and significant potential as an efficient absorbent in large-scale dispose of oily water.

Environmentally Friendly Room Temperature Synthesis of 1-Tetralone over Layered Double Hydroxide-Hosted Sulphonato-Salen-Nickel(II) Complex

1-Tetralone, a useful synthetic intermediate in the manufacture of pharmaceuticals, agrochemicals and dyes, can be prepared by liquid phase catalytic oxidation of tetralin. Selective oxidation of tetralin to 1-tetralone is still a big challenge with low-temperature processes using environmentally friendly routes even after decades of research. Herein, we demonstrate room-temperature oxidation of tetralin to 1-tetralone over layered double hydroxide-hosted sulphonato-salen-nickel(II) complex, LDH-[Ni-salen]. The layered double hydroxide-hosted sulphonato-salen-nickel(II) compound was characterized by powder X-ray diffraction, Fourier transform infrared spectrometer (FTIR), UV-Visible diffuse reflectance spectra, scanning electron microscopy (SEM) and elemental analysis. The theoretical calculations of free sulphonato-salen-nickel(II) complex using Density Functional Theory/CAM-B3LYP at the 6-311++ G(d,p) level of theory were also used to determine the orientation of the Ni-salen compound within the layered structure. The immobilized compound, LDH-[Ni-salen] was found to be an effective reusable catalyst for the oxidation of tetralin to 1-tetralone using a combination of trimethylacetaldehyde and molecular oxygen (14.5 psi) and at 25&deg;C. At 45.5% conversion, tetralin was converted to 1-tetralone with 77.2% selectivity at room temperature and atmospheric pressure after 24 h. The catalyst recycles test and hot filtration experiment showed that oxidation proceeded through Ni(II) sites in LDH-[Ni-salen]. The catalysts were reused several times without losing their catalytic activity and selectivity. The present results may provide a convenient strategy for the preparation of 1-tetralone using layered double hydroxide-based heterogeneous catalyst at ambient temperature for industrial application in near future.

Double-layer indium doped zinc oxide for silicon thin-film solar cell prepared by ultrasonic spray pyrolysis

Indium doped zinc oxide （ZnO：In） thin films were prepared by ultrasonic spray pyrolysis on corning eagle 2000 glass substrate. 1 and 2 at.% indium doped single-layer ZnO：In thin films with different amounts of acetic acid added in the initial solution were fabricated. The 1 at.% indium doped single-layers have triangle grains. The 2 at.% indium doped single-layer with 0.18 acetic acid adding has the resistivity of 6.82 × 10^-3 Ω. cm and particle grains. The doublelayers structure is designed to fabricate the ZnO：In thin film with low resistivity （2.58 × 10^-3 Ω. cm） and good surface morphology. It is found that the surface morphology of the double-layer ZnO：In film strongly depends on the substratelayer, and the second-layer plays a large part in the resistivity of the doublewlayer ZnO：In thin film. Both total and direct transmittances of the double-layer ZnO：In film are above 80% in the visible light region. Single junction a-Si：H solar cell based on the double-layer ZnO：In as front electrode is also investigated.

Surface-derived phosphate layer on NiFe-layered double hydroxide realizes stable seawater oxidation at the current density of 1 A·cm^(−2)

Seawater electrolysis,especially in coastlines,is widely considered as a sustainable way of making clean and high-purity H2 from renewable energy;however,the practical viability is challenged severely by the limited anode durability resulting from side reactions of chlorine species.Herein,we report an effective Cl^(−) blocking barrier of NiFe-layer double hydroxide(NiFe-LDH)to harmful chlorine chemistry during alkaline seawater oxidation(ASO),a pre-formed surface-derived NiFe-phosphate(Pi)outerlayer.Specifically,the PO_(4)^(3−)-enriched outer-layer is capable of physically and electrostatically inhibiting Cl−adsorption,which protects active Ni^(3+)sites during ASO.The NiFe-LDH with the NiFe-Pi outer-layer(NiFe-LDH@NiFe-Pi)exhibits higher current densities(j)and lower overpotentials to afford 1 A·cm^(−2)(η1000 of 370 mV versusη1000 of 420 mV)than the NiFe-LDH in 1 M KOH+seawater.Notably,the NiFe-LDH@NiFe-Pi also demonstrates longer-term electrochemical durability than NiFe-LDH,attaining 100-h duration at the j of 1 A·cm^(−2).Additionally,the importance of surface-derived PO_(4)^(3−)-enriched outer-layer in protecting the active centers,γ-NiOOH,is explained by ex situ characterizations and in situ electrochemical spectroscopic studies.

Multi-functional layered double hydroxides supported by nanoporous gold toward overall hydrazine splitting

Layered double hydroxides have demonstrated great potential for the oxygen evolution reaction,which is a crucial half-reaction of overall water splitting.However,it remains challenging to apply layered double hydroxides in other electrochemical reactions with high efficiency and stability.Herein,we report two-dimensional multifunctional layered double hydroxides derived from metalorganic framework sheet precursors supported by nanoporous gold with high porosity,which exhibit appealing performances toward oxygen/hydrogen evolution reactions,hydrazine oxidation reaction,and overall hydrazine splitting.The as-prepared catalyst only requires an overpotential of 233 mV to reach 10 mA·cm^(-2) toward oxygen evolution reaction.The overall hydrazine splitting cell only needs a cell voltage of 0.984 V to deliver 10 mA·cm^(-2),which is far more superior than that of the overall water splitting system(1.849 V).The appealing performances of the catalyst can be contributed to the synergistic effect between the metal components of the layered double hydroxides and the supporting effect of the nanoporous gold substrate,which could endow the sample with high surface area and excellent conductivity,resulting in superior activity and stability.

Removal and fluorescence detection of antibiotics from wastewater by layered double oxides/metal-organic frameworks with different topological configurations

Owing to the serious potential side-effects on the environment and human health,the rapid detection and removal of antibiotics have become an important research focus.In this work,four zinc-based metal-organic frameworks(MOFs)with different functional groups,i.e.,Zn-MOF,Zn-MOF-CH_(3),Zn-MOF-NO_(2),Zn-MOF-COOH,were utilized for the construction of LDO/MOF composite materials with a nickel-iron-cobalt-based layered double oxide,NiFeCo-LDO.The results showed that the LDO/MOF composites not only had high sensitivity in detecting sulfonamide and quinolone antibiotics,but also had an appreciable ability to adsorb them from wastewater.The maximum adsorption capacities of all the four types of LDO@Zn-MOFs to all antibiotics can at least reach 150 mg/g,and the limits of detection in relation to all four antibiotics were at least as low as 100μg/L.Our work suggested the dual-function extraction performance can be attributed to the synergistic effects between the LDO and the MOFs.Moreover,the strong ferromagnetism derived from the LDO provided great convenience for the separation and regeneration of the LDO/MOF composites.

Metal vacancy-enriched layered double hydroxide for biomass molecule electrooxidation coupled with hydrogen production

The electrochemical oxidation of biomass molecules coupling with hydrogen production is a promising strategy to obtain both green energy and value-added chemicals;however,this strategy is limited by the competing oxygen evolution reactions and high energy consumption.Herein,we report a hierarchical CoNi layered double hydroxides(LDHs)electrocatalyst with abundant Ni vacancies for the efficient anodic oxidation of 5-hydroxymethylfurfural(HMF)and cathodic hydrogen evolution.The unique hierarchical nanosheet structure and Ni vacancies provide outstanding activity and selectivity toward several biomass molecules because of the finely regulated electronic structure and highly-exposed active sites.In particular,a high faradaic efficiency(FE)at a high current density(99%at 100 mA cm^(-2))is achieved for HMF oxidation,and a two-electrode electrolyzer is assembled based on the Ni vacancies-enriched LDH,which realized a continuous synthesis of highly-pure 2,5-furandicarboxylic acid products with high yields(95%)and FE(90%).

Recent Advance in Electrocatalytic Water Splitting for Hydrogen Production by Layered Double Hydroxides

Collecting green hydrogen(H2)from water splitting driven by renewable energy is a new competition to implement the construction of H2 energy industry and promote new economic growth for global governments.The common strategy to enhance the efficiency of H2 production is to reduce the potential of electrolytic cell that is the mainstream way to prepare efficient electrocatalysts.Layered double hydroxides(LDHs)are one of the most active electrocatalysts with adjustable active sites in contemporary research.In this review,we discuss the recent advanced progress of LDHs for hydrogen evolution reaction(HER)on cathode and oxygen evolution reaction(OER)or organic oxidation on anode and emphasize the influence of LDHs structure regulation in water electrolysis process(HER/OER)as well as the current development status of organic oxidation catalyzed by active oxygen species on anode.Finally,we propose the current challenges of LDHs in electrocatalysis and prospect their developing tendency and further application.

Layered double hydroxide- and graphene-based hierarchical nanocomposites： Synthetic strategies and promising applications in energy conversion and conservation

The persistent need for a sustainable energy economy has led researchers to focus on novel energy conversion and storage technologies, inspiring the discovery of smart material designs such as hierarchical nanocomposites~ These nanocomposites have proven effective in the advancement of energy-based technologies. The synergistic properties of hierarchical nanocomposites composed of two types of two-dimensional layered materials, layered double hydroxides and graphene, have resulted in improved electrochemical as well as photocatalytic performance. Synthetic strategies and their effect on the electrochemical and photocatalytic performance of these nanocomposites as high-performance supercapacitors and water oxidation catalysts are discussed in detail in this review.