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.

Chelation-mediated in-situ formation of ultrathin cobalt(oxy)hydroxides on hematite photoanode towards enhanced photoelectrochemical water oxidation

In this work,a facile chelation-mediated route was developed to fabricate ultrathin cobalt(oxy)hydroxides(CoOOH)nanosheets on hematite photoanode(Fe_(2)O_(3)).The route contains two steps of the adsorption of[Co-EDTA]^(2-)species on Fe_(2)O_(3) nanorod array followed by the hydrolysis in alkaline solution.The resulting CoOOH/Fe_(2)O_(3) exhibits a remarkably improved photocurrent density of 2.10 mA cm^(-2) at 1.23 V vs.RHE,which is ca.2.8 times that of bare Fe_(2)O_(3).In addition,a negative shift of onset potential ca.200 mV is achieved.The structural characterizations reveal the chelate EDTA plays important roles that enhance the adsorption of Co species and the formation of contact between CoOOH and Fe_(2)O_(3).(Photo)electrochemical analysis suggests,besides providing active sites for water oxidation,CoOOH at large extent promotes the charge separation and the charge transfer via passivating surface states and suppressing charge recombination.It also found CoOOH possesses some oxygen vacancies,which could act as trapping centers for photogenerated holes and facilitate the charge separation.Intensity modulated photocurrent spectroscopy(IMPS)shows that,under low applied potential the water oxidation mainly occurs on CoOOH,while under high applied potential the water oxidation could occur on both CoOOH and Fe_(2)O_(3).The findings not only provide an efficient strategy for designing ultrathin(oxy)hydroxides on semiconductors for PEC applications but also put forward a new insight on the role of CoOOH during water oxidation.

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°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.

Synthesis, Characterization, and Effects of Morphology on the Magnetic Application Base Properties of Pure Nickel Oxide (NiO) and Cobalt-Doped Nickel Oxide/Nickel Hydroxide (CoxNi1-xO/Ni(OH)2) Nanocomposites

Nano particle (NP) morphology is one of the material properties at the origin of potential application base properties exploited in several engineering and technology domains, such as fuel cell, electrodes, catalysis, sensing, electric, thermal, magnetic, and photovoltaic applications. The general properties and particle morphology of nickel oxide/Nickel hydroxide NPs can be modified by the introduction of impurity atoms or ions. Nano sized nickel oxide/nickel hydroxide nanocomposites were obtained from the thermal decomposition of single molecular precursors synthesized by a modified oxalate route using Carambola fruit juice as a precipitating agent. The compositional and morphological variations were studied by introducing cobalt as an impurity ion at different w/w% fractions (0%, 0.1%, 0.3%, 0.5%, 1%, 3%, 5.0%, 40.0% and 50.0%) into the microstructure of the nickel oxide/hydroxide. The precursors were characterized by FT-IR, while TGA/DTG analysis was carried out to decompose the precursors. The precursors decomposed at 400°C and were characterized by PXRD and SEM/TEM. The results revealed that Pure Nickel Oxide (NiO) and, Cobalt-doped Nickel Oxide/nickel hydroxide (CoxNi1-xO/Ni(OH)2) Nano composites have been synthesized and the synthesized samples have exhibited three distinct morphologies (porous face-centered cubic nano rods, rough and discontinuous CoxNi1-xO/Ni(OH)2) composite and, smooth and continuous mix spherical/cuboidal mixed morphological phase of (NiO/CoO). The morphology of the NPs varied with the introduction of the dopant atoms and with increase in the concentration of dopant atoms in the composite. Magnetic studies using vibrating sample magnetometry revealed superparamagnetic properties which correlated strongly with particle size, shape and morphology. Observed values of retention (4.50 × 10-3 emu/g) and coercivity (65.321 Oe) were found for 0.5 w/w% corresponding to impregnated porous nanorods of Co-doped NiO, and retention (9.03 × 10-3 emu/g) and coercivity (64.341 Oe), for X = 50.0%, corresponding to an aggregate network of a Nano spherical/cubic CoO/NiO mixed phase. Magnetic properties within this range are known to improve the magnetic memory and hardness of the magnetic materials. Therefore, the synthesized Cobalt-doped Nickel Oxide/nickel hydroxide (CoxNi1-xO/Ni(OH)2) Nano composites have potential applications in Magnetic memories and hardness of magnetic materials.

Synthesis, Characterization, and Effects of Morphology on the Magnetic Application Base Properties of Pure Nickel Oxide (NiO) and Cobalt-Doped Nickel Oxide/Nickel Hydroxide (CoxNi1-xO/Ni(OH)2) Nanocomposites

Nano particle (NP) morphology is one of the material properties at the origin of potential application base properties exploited in several engineering and technology domains, such as fuel cell, electrodes, catalysis, sensing, electric, thermal, magnetic, and photovoltaic applications. The general properties and particle morphology of nickel oxide/Nickel hydroxide NPs can be modified by the introduction of impurity atoms or ions. Nano sized nickel oxide/nickel hydroxide nanocomposites were obtained from the thermal decomposition of single molecular precursors synthesized by a modified oxalate route using Carambola fruit juice as a precipitating agent. The compositional and morphological variations were studied by introducing cobalt as an impurity ion at different w/w% fractions (0%, 0.1%, 0.3%, 0.5%, 1%, 3%, 5.0%, 40.0% and 50.0%) into the microstructure of the nickel oxide/hydroxide. The precursors were characterized by FT-IR, while TGA/DTG analysis was carried out to decompose the precursors. The precursors decomposed at 400°C and were characterized by PXRD and SEM/TEM. The results revealed that Pure Nickel Oxide (NiO) and, Cobalt-doped Nickel Oxide/nickel hydroxide (CoxNi1-xO/Ni(OH)2) Nano composites have been synthesized and the synthesized samples have exhibited three distinct morphologies (porous face-centered cubic nano rods, rough and discontinuous CoxNi1-xO/Ni(OH)2) composite and, smooth and continuous mix spherical/cuboidal mixed morphological phase of (NiO/CoO). The morphology of the NPs varied with the introduction of the dopant atoms and with increase in the concentration of dopant atoms in the composite. Magnetic studies using vibrating sample magnetometry revealed superparamagnetic properties which correlated strongly with particle size, shape and morphology. Observed values of retention (4.50 × 10-3 emu/g) and coercivity (65.321 Oe) were found for 0.5 w/w% corresponding to impregnated porous nanorods of Co-doped NiO, and retention (9.03 × 10-3 emu/g) and coercivity (64.341 Oe), for X = 50.0%, corresponding to an aggregate network of a Nano spherical/cubic CoO/NiO mixed phase. Magnetic properties within this range are known to improve the magnetic memory and hardness of the magnetic materials. Therefore, the synthesized Cobalt-doped Nickel Oxide/nickel hydroxide (CoxNi1-xO/Ni(OH)2) Nano composites have potential applications in Magnetic memories and hardness of magnetic materials.

Kinetics Modeling of Calcium Formate Synthesis by Calcium Hydroxide Carbonylation

The synthesis of calcium formate by Ca(OH)_2 carbonylation was studied in a semi-batch stirred tank.The reaction mechanism was analyzed theoretically and the rate of each step was compared.The influence ofreaction conditions on the formation of calcium formate was investigated.The results indicate that the rate-controlling step is the reaction between dissolved CO and dissolved Ca(OH)_2,and the gaseous diffusion resistance can be eliminated when the stirring speed reached 1000 r/min.Furthermore,the reaction kinetics was studied at a stirring speed of 1000 r/min,temperature of 423–453 K,pressure of 2.0–3.5 MPa and different initial concentrations of Ca(OH)_2.An effective method was proposed to measure the reaction rate of CO.A mathematical model was developed using the dual-film theory,and the parameters were obtained using regression of experimental data.The reaction rates calculated using the kinetics model were compared with experimental data.The results show that the deviations are within ±10%,proving that the established model is valid and can provide a basis for industrial amplification.

Metal oxides heterojunction derived Bi-In hybrid electrocatalyst for robust electroreduction of CO_(2) to formate

Electrochemical reduction of Bi-based metal oxides is regarded as an effective strategy to rationally design advanced electrocatalysts for electrochemical CO_(2)reduction reaction(CO_(2)RR).Realizing high selectivity at high current density is important for formate production,but remains challenging.Herein,the BiIn hybrid electrocatalyst,deriving from the Bi2O3/In2O3heterojunction(MOD-Biln),shows excellent catalytic performance for CO_(2)RR.The Faradaic efficiency of formate(FEHCOO-) can be realized over 90% at a wide potential window from-0.4 to-1.4 V vs.RHE,while the partial current density of formate(jHCOO-) reaches about 136.7 mA cm^(-2)at-1.4 V in flow cell without IR-compensation.In additio n,the MOD-Biln exhibits superior stability with high selectivity of formate at 100 mA cm^(-2).Systematic characterizations prove the optimized catalytic sites and interface charge transfer of MOD-Biln,while theoretical calculation confirms that the hybrid structure with dual Bi/In metal sites contribute to the optimal free energy of*H and*OCHO intermediates on MOD-Biln surface,thus accelerating the formation and desorption step of*HCOOH to final formate production.Our work provides a facile and useful strategy to develop highly-active and stable electrocatalysts for CO_(2)RR.

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.

Preparation of Rare Earth Hydroxide and Oxide Nanoparticles by Precipitation Method

A series of rare earth hydroxide and oxide nanoparticles have been prepared by precipitation method with alcohol as the dispersive and protective reagent. Transmission electron microscope （TEM） images indicate that the particles are spherical in shape and smaller than 100 nm in size. The crystallite sizes of cubic Ln2O3 have lanthanide shrinking effect, while average crystal lattice distortion rates possess lanthanide swelling effect. The diffraction peak intensity of heavy rare earth oxide nanometer powders is remarkably stronger than that of light rare earth oxide nanometer powders. The variation of diffraction intensity with atomic number presents an inverted W type, forming a double peak structure. Fourier transform infrared （FTIR） spectrums reveal that Ln2O3 nanopowders have higher surface activity than that of ordinary Ln2O3 powders. The UV-vis spectra show that Ln-O bond of these particles is slightly blue-shifted, and its absorption intensity decreases.

Synthesis of cation exchange resin-supported iron and magnesium oxides/hydroxides composite for nitrate removal in water

In this study,we reported on the concept and practical use of cation exchange resin(CER)for removing anions in water via pretreating the CER with metal salts.The cation exchange resinsupported iron and magnesium oxides/hydroxides composite(FeMg/CER)was synthesized and introduced as a new and potential adsorbent for selective removal of nitrate ion in the water environment.Characteristics of FeMg/CER were determined by techniques such as Fouriertransform infrared spectroscopy,scanning electron microscopy,and Xray diffraction.The results showed that FeMg/CER material had a high nitrate adsorption capacity of 200 mg NO_(3)^()·g^(1)with a fast equilibrium adsorption time of 30 min at pH 5.In addition,it had good durability of at least 10 times of regeneration,which could be applied to practical water and wastewater treatment.

Dynamic active sites on plasma engraved Ni hydroxide for enhanced electro-catalytic urea oxidation

The urea oxidization reaction(UOR)is an important anodic reaction in electro-catalytic energy conversion.However,the sluggish reaction kinetics and complex catalyst transformation in electrocatalysis require activity improvement and better mechanistic understanding of the state-of-the-art Ni(OH)_(2) catalyst.Herein,by utilizing low-temperature argon(Ar)plasma processing,tooth-wheel Ni(OH)_(2) nanosheets self-supported on Ni foam(Ni(OH)_(2)-Ar)are demonstrated to have improved UOR activity compared to conventional Ni(OH)_(2).The theoretical assessment confirms that the edge has a smaller cation vacancy formation energy than the basal plane,consequently explaining the structural formation.Operando and quasi-operando methods are employed to investigate the dynamic evolution of the Ni(OH)_(2) film in UOR.The crucial dehydrogenation products of Ni(OH)_(5)O^(-)intermediates are identified to be stable on the etched edge and explain the enhanced UOR in the low potential region.In addition,the dynamic active sites are monitored to elucidate the reaction mechanism in different potential ranges.

Sulfide@hydroxide core–shell nanostructure via a facile heating-electrodeposition method for enhanced electrochemical and photoelectrochemical water oxidation

Designing low-cost,easy-fabricated,highly stable and active electrocatalysts for oxygen evolution reaction(OER) is crucial for electrochemical(EC) and solar-driven photoelectrochemical(PEC) water splitting.By using a facile heating-electrodeposition method,here we fabricated a porous but crystalline Fe-doped Ni3 S2.A thin porous surface NiFe hydroxide layer(~10 nm) is then formed through OER-running.By virtue of the core Fe-doped Ni3 S2 with good conductivity and the shell NiFe hydroxide surface with good electrocatalytic activity,the core-shell nanostructure on Ni foam exhibits excellent OER activity in 1 M NaOH,needing only 195 and 230 mV to deliver 10 and 100 mA/cm^(2),respectively,much more superior to those of 216 and 259 mV for the sample deposited under normal temperature.The enhanced photo-response of the sulfide@hydroxide core-shell structure was also demonstrated,due to the efficient transfer of photo-generated carriers on the core/shell interface.More interestingly,it shows a good compatibility with Si based photoanode,which exhibits an excellent PEC performance with an onset potential of 0.86 V vs.reversible hydrogen electrode,an applied bias photon-to-current efficiency of 5.5% and a durability for over 120 h under AM 1.5 G 1 sun illumination,outperforming the state-of-the-art Si based photoanodes.

Electro-oxidation treatment of Sn/PANI electrode and electrocatalytic activity of Pt/Sn hydroxide/PANI composite electrodes

After being electro-oxidized by cyclic voltammetry(CV) method in 0.5 mol/L H2SO4 solution or in 0.2 mol/L H2O2+0.5 mol/L H2SO4 solution, the Sn/polyaniline (PANI) electrodes were modified with Pt microparticles by pulse galvanostatic method, thus Pt/Sn hydroxide/PANI electrodes were prepared. The electrocatalytic activities of the Pt/Sn/PANI electrode and Pt/Sn hydroxide/PANI electrode for formaldehyde electro-oxidation were investigated by CV method. The effects of deposition charges (Qdep) of PANI, Sn and Pt, scan rate and formaldehyde concentration on the electrocatalytic activity of Pt/Sn hydroxide/PANI electrode were also studied. The results show that the electrocatalytic activities of the Pt/Sn hydroxide/PANI electrodes are much higher than those of the Pt/Sn/PANI electrode.

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.

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.

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.

Formation and Morphology of Anodic Oxide Films of Ti

The morphology and structure of the oxide films of Ti in H3PO4 were investigated by galvanos tatic anodization, SEM and XRD. The oxide film grew from some pores in the grooves to layered microdomains as increasing anodizing voltage. The crystallinity of the oxide films decreased with the increase of the concentration of the electrolyte. The model has been proposed for the growth of the oxide films by two steps, i.e. by uniform thickening and by local deposition.

FORMATION OF PROPYLENE OXIDE BY METHYLOMONAS GYJ3 IN A GAS-SOLID BIOREACTOR

Present paper deals with propylene oxide production from propylene utilizing Methylomonas sp.GYJ3 immobilized by adsorption or gel entrapment in a continuous gas flow packed bed bioreactor.The regeneration of biocatalyst in situ is al- so discussed.