Structure Of Layered Double Hydroxides Research Articles

Binder free cobalt Manganese layered double hydroxide anode conjugated with bioderived rGO cathode for sustainable, high-performance asymmetric supercapacitors

Metal-organic frameworks (MOFs) possessmultifunctional characteristicssuch as tuneable pore structure and high specific surface area and are being designed with great interest to enhance the electrochemical properties of current energy storage devices. In this aspect, MOFs-derived layered double hydroxides (LDHs) are important candidates for advanced supercapacitors due to their high electrochemical activity and electric conductivity. Herein, we report synthesis of Cobalt Manganese layered double hydroxides (CoMn LDH) utilising Co MOF as a precursor via ion exchange method, while optimising the dosage of Mn to achieve the best possible structural outcome. The unique structure of CoMn LDH expressed high electrochemical parameters possessing specific capacitance of 1305F/g at 1 A/g. Afterwards, an asymmetric supercapacitor device was fabricated employing CoMn LDH as cathode and coffee grounds derived rGO (reduced graphene oxide) as anode. The as-prepared asymmetric supercapacitor device demonstrated a maximum working potential window of 1.2 V with energy and power density of 23.8 Wh/kg and 0.30 kW/Kg respectively. The device also exhibits superiorcoulombic efficiency and capacitance retention of 71.11 % and 82.7 % respectively over 3010 charge–discharge cycles that represents an effectiveapproach towards sustainable and effectiveenergy storage devices. In a nutshell, our study centred on adjusting composition, engineering structures, and assembling devices.

ZnAl LDH-based Derivative Materials as Photocatalysts: Synthesis, Characterization, and Catalytic Performance in Tetracycline Degradation

Layered Double Hydroxide (LDH)-derived materials exhibited different characteristics from LDH precursors. The conversion of ZnAl LDH into its derivative material has been carried out to find the best catalyst for TC degradation. ZnAl (LDH)-based catalysts in this study have been effectively synthesized using coprecipitation, calcination, and restacking procedures. ZnAl Layered Double Oxide (LDO) is derived from the calcination of ZnAl LDH at 500°C. ZnAl LDH was also modified by adding Garcinia mangostana pericarp extract (GME). XRD, FT-IR, UV-DRS, and SEM-EDX were used to investigate the synthesized catalyst. ZnAl LDH exhibited the typical LDH FT-IR spectra, whereas ZnAl LDO showed metal oxide-like spectra, and the ZnAl-GME composite displayed the combination spectra of precursor material. The ZnAl LDH XRD diffraction pattern exhibited the attributes of a layered material, whereas the other three catalysts did not. Calcination destroyed the layered structure of ZnAl LDH, whereas the addition of GME to LDH and LDO generated a single-layered composite. The modified ZnAl-GME composite showed a decrease in both particle size and bandgap energy. At an ideal pH of 5, the synthesized catalyst was used in a batch system photodegradation of 5 mg/L Tetracycline (TC), employing solar light irradiation. ZnAl LDO holds the most significant catalytic activity and structural stability through the fifth regeneration cycle, degraded TC up to 100% in 90 minutes.

Graphene Materials from Coke-like Wastes as Proactive Support of Nickel-Iron Electro-Catalysts for Water Splitting.

Graphene materials, used as electrocatalyst support in green hydrogen production, contribute to increasing the efficiency and robustness of various systems. However, the preparation of a hybrid catalyst containing graphene materials from industrial wastes is still a challenge due to the heterogeneity of the waste. We report the synthesis of 3D electrodes using graphene oxides (GOs) from industrial waste (IW) prepared by immersion onto Toray carbon paper as a 3D support onto GO suspensions and electrodepositing NiFe layered double hydroxides (LDHs). Standard graphite was also used as the reference. The morphology of the two hybrid electrodes was determined by SEM, HRTEM, XPS. Although very similar in both, the sample containing graphene from IW (higher Csp3 hybridization in the graphene layer) has a NiFe phase with less crystallinity and larger presence of Fe2+ ions. These electrodes exhibited similar activity and stability as electrocatalysts of the oxygen evolution reaction (OER), demonstrating the proactive effect of the graphene into the 3D electrode even when this is prepared from heterogeneous industrial waste. Moreover, the defective graphenic structure of the waste GO enhances the reaction kinetics and improves the electron transfer rate, possibly due to the small differences in the electrodeposited NiFe LDH structure.

Ni,Fe,Co-LDH Coated Porous Transport Layers for Zero-Gap Alkaline Water Electrolyzers.

Next-generation alkaline water electrolyzers will be based on zero-gap configuration to further reduce costs related to technology and to improve performance. Here, anodic porous transport layers (PTLs) for zero-gap alkaline electrolysis are prepared through a facile one-step electrodeposition of Ni,Fe,Co-based layered double hydroxides (LDH) on 304 stainless steel (SS) meshes. Electrodeposited LDH structures are characterized using Scanning Electron Microscopy (SEM) confirming the formation of high surface area catalytic layers. Finally, bi and trimetallic LDH-based PTLs are tested as electrodes for oxygen evolution reaction (OER) in 1 M KOH solution. The best electrodes are based on FeCo LDH, reaching 10 mA cm-2 with an overpotential value of 300 mV. These PTLs are also tested with a chronopotentiometric measurement carried out for 100 h at 50 mA cm-2, showing outstanding durability without signs of electrocatalytic activity degradation.

Adsorption of atrazine and paraquat on montmorillonite loaded with layered double hydroxide and active site energy distribution analysis

Abstract Clay minerals are effective adsorbents for the remediation of pesticides in wastewater due to their large superficial areas and excellent cation-exchange capabilities. However, this adsorption effect can be reduced by the accumulation of adsorbents on clay minerals, amongst other problems. Therefore, in this study, montmorillonite (Mnt) modified by layered double hydroxide (LDH) with different loading amounts was successfully prepared using an in situ method. The results from X-ray diffraction, Fourier-transform infrared spectrometry, Brunauer–Emmet–Teller (BET) and scanning electron microscopy analyses revealed that LDH structures were successfully combined with the Mnt layer and formed a porous structure. However, excess LDH still caused the aggregation and accumulation of layers. The adsorption performance of LDH@Mnt for atrazine (ATZ) and paraquat (PQ) was investigated, and the removal efficiency of the LDH@Mnt composite was higher than those of Mnt and LDH alone. The kinetic study revealed that the adsorption process fitted the pseudo-second-order model and internal diffusion model, and 3-LDH@Mnt had the greatest absorbability efficiency for both ATZ and PQ, indicating the adsorption process was controlled by the number of active sites of the adsorbent. The generalized Langmuir model accurately characterized the adsorption process of ATZ and PQ elimination in the adsorption isotherm investigation, indicating that the adsorption energies of the active sites on the adsorbents were different. 3-LDH@Mnt had better absorbability performance for ATZ/PQ, and the sorption capacities were 7.03 and 91.9 mg g–1, respectively. According to site energy distribution theory, the amount of sorption sites of the composite adsorbent was large and the average adsorption energy was high, both of which being beneficial for the adsorption of ATZ and PQ. The effects of pH, coexisting anions and reuse experiments were also tested, indicating that the LDH@Mnt composite possessed high adsorption stability. This excellent removal performance represents a promising strategy for the remediation and elimination of pesticide contaminations from the environment.

Ruthenium And Silver Synergetic Regulation NiFe LDH Boosting Long‐Duration Industrial Seawater Electrolysis

AbstractThe chloride ions in seawater result in corrosion, low catalytic efficiency, and poor stability of the electrocatalysts in direct seawater electrolysis, which limits the use of large‐scale seawater electrolysis technology. Herein, a corrosion‐resistant Ag/NiFeRu layered double hydroxide (LDH) electrocatalyst for seawater electrolysis at industrial current density, in which Ru and Ag species in the catalyst can have a corrosion‐resistance of chloride ions from the anode surface and enhance its robustness in seawater is designed. The catalyst requires the overpotentials of 256 and 287 mV to obtain a current density of 1 A cm−2 in 1 m KOH and 1 m KOH + seawater, respectively. More importantly, it works stably for over 1000 h at 1 A cm−2 in alkaline seawater. Further quasi‐industrial conditions measurement (6 m KOH + seawater, 60 °C) shows a markedly low overpotential of 174 mV at 1 A cm−2 on Ag/NiFeRu LDH, obtaining over 140 h under harsh industrial conditions. Theoretical calculations demonstrate that the Ru species can effectively regulate the local electronic structure of NiFe LDH, and enhance the intrinsic activity of NiFe LDH. The transformation of Ag2O from Ag during OER stabilizes the Fe site in NiFe LDH, which improves the overall stability of the electrocatalyst.

Insight into the flame-retardant mechanism of different organic-modified layered double hydroxide for epoxy resin

Aiming to enhance the flame-retardant efficiency of layered double hydroxide (LDH) in epoxy resin (EP), positively charged LDH was modified by incorporating various anionic modifiers, resulting in a series of organically modified LDH. These modifiers were selected based on the length of nonpolar tails with and without aromatic ring such as sodium dodecylbenzene sulfonate (SDBS), sodium dodecyl sulfate (SDS) and sodium benzene sulfonate (SBS). The chemical composition, structure and hydrophobicity of organic-modified LDH were characterized and the flame-retardant efficiency of organic-modified LDH in EP were investigated. The incorporation of organic-modified LDH into EP resulted in improved Tg and flame retardancy, which depended on the type of modifiers used as well as the structure and loading amount of LDH. Particularly, LDH@DBS exhibited higher improvement efficiency in flame retardancy and Tg than that of LDH@BS and LDH@DS due to the enlarged interlayer spacing, which facilitated the homogeneous dispersion and compatibility in the epoxy matrix. These results demonstrated that good compatibility between organic-modified LDH and polymer was advantageous to enhance the flame-retardancy efficiency and thermal mechanical properties of polymer.

Intercalated Redox-Active Anions in Layered Double Hydroxides: Toward New Electrode Designs

Layered Double Hydroxides (LDHs) are a versatile class of 2D materials, which consist of layered di- and trivalent metal cation hydroxides with intercalated anions (1). They are used in many applications including energy storage electrodes, water purification or drug delivery (2, 3).In this new study, Anthraquinone-2-sulfonate (AQS) intercalated in the LDH structure of Mg2Al(OH)6, has been investigated and a charge capacity of 100 mAh g-1 has been measured. However, the dissolution of reduced AQS into the aqueous electrolyte occurs from the first reduction leading to a drastic capacity fade upon cycling.To get around the dissolution issue, we synthesize a new intercalated LDH using ferrocene as the redox active moiety. Electrodes with this new LDH material Mg2Al(OH)6-Fc (Figure 1A) showed more stable cycling when used in combination with aqueous or organic electrolytes. However, the most significant increase in cycle life was achieved by operating this electrode in highly concentrated, highly viscous ionic liquid based electrolytes such as Pyr13TFSI. Over 97 % capacity retention was achieved after 200 cycles with a coulombic efficiency close to 100 % (Figure 1B). The higher stability of redox active anions working at positive redox potentials like ferrocene in the LDH structure is a key parameter to improve cycling ability. Moreover, the limited solubility of the intercalated redox anions into the high concentrated ionic liquid electrolyte is also a key factor for improving cycle life of this new electrode.Figure 1: A) Schematic structure of Mg2Al(OH)6-Fc, C) Improved cycling stability of Mg2Al(OH)6-Fc based electrodes in ionic liquid electrolyte Pyr13TFSI. Figure 1

Promoting AEM Water Electrolyzer Performance and Reproducibility by Tumbler Milling of Ni3fe-LDH OER Catalyst

Anion exchange membrane water electrolysis is an attractive clean energy technology for producing hydrogen for energy storage, transport 1,2 and numerous other applications. Rational choice of highly active and stable catalysts as well as the proper design of catalyst layers are crucial to achieve technical relevance of electrolyser systems. The establishment of clear understanding of optimal catalyst treatment and methods of implementation are key steps towards optimized electrolyzer performance and durability. One aspect of catalyst performance in catalyst layers is the catalyst size distribution. A multimodal size distribution of catalyst particles or agglomerates can jeopardize the layer homogeneity and thus electrode performance.In this work, the effect of high-energy ball tumbling milling on the promising Ni3Fe-LDH OER catalyst followed by catalyst dispersion control was correlated to the microstructure of the catalyst layer, the achieved catalyst activity and utilization, and the resulting single cell performance and stability. Physico-chemical characterization confirmed the stable layered double hydroxide structure of the catalyst. By milling, a 300-fold reduction of catalyst agglomerate size, and an 8.8-fold increase of the geometrical surface was achieved. The optimized solvent compositions effectively increased the catalyst ink stability. We found that a significantly decreased catalyst agglomerate size resulted in very homogeneous mixtures of catalyst and ionomer. By tailoring the electrode structure design, lower internal electronic resistances of the electrodes, decreased charge-transfer resistances (Rct) of the membrane electrode assembly, and stable single cell durability of 1000 h with a minor degradation rate of 57 µV h-1 were accomplished.This work presents a facile and scalable approach of NiFe-LDH catalyst treatment and dispersion control and provides a guideline to follow for further electrode development and increased AEM water electrolyzer performances. References (1) Hydrogen Applications. Hydrogen Europe. 2020. https://hydrogeneurope.eu/hydrogen-applications (accessed Jan 7, 2022).(2) Vincent, I.; Bessarabov, D. Low Cost Hydrogen Production by Anion Exchange Membrane Electrolysis: A Review. Renew. Sustain. Energy Rev. 2018, 81 (August 2016), 1690–1704. https://doi.org/10.1016/j.rser.2017.05.258. This work has been performed in the frame of the CHANNEL project. This project has received funding from the Fuel Cells and Hydrogen 2 Joint Undertaking (now Clean Hydrogen Partnership) under grant agreement No 875088. This Joint undertaking receives support from the European Union's Horizon 2020 Research and Innovation program, Hydrogen Europe and Hydrogen Europe Research.

"On-The-Fly" Synthesis of Self-Supported LDH Hollow Structures Through Controlled Microfluidic Reaction-Diffusion Conditions.

Layered double hydroxides (LDHs) are a class of functional materials that exhibit exceptional properties for diverse applications in areas such as heterogeneous catalysis, energy storage and conversion, and bio-medical applications, among others. Efforts have been devoted to produce millimeter-scale LDH structures for direct integration into functional devices. However, the controlled synthesis of self-supported continuous LDH materials with hierarchical structuring up to the millimeter scale through a straightforward one-pot reaction method remains unaddressed. Herein, it is shown that millimeter-scale self-supported LDH structures can be produced by means of a continuous flow microfluidic device in a rapid and reproducible one-pot process. Additionally, the microfluidic approach not only allows for an "on-the-fly" formation of unprecedented LDH composite structures, but also for the seamless integration of millimeter-scale LDH structures into functional devices. This method holds the potential to unlock the integrability of these materials, maintaining their performance and functionality, while diverging from conventional techniques like pelletization and densification that often compromise these aspects. This strategy will enable exciting advancements in LDH performance and functionality.

NiFe layered double hydroxides synthesized based on solvent properties as anode catalysts for enhanced oxygen evolution reaction

NiFe layered double hydroxides (LDH) with their high specific surface areas have been used as alternatives to noble metal catalysts for the oxygen evolution reaction (OER) in anion exchange membrane water electrolysis. However, for bulk LDH structures, relatively narrow interplanar distances can lead to the slow diffusion of OH− and the induction a local acidic atmosphere, resulting in catalyst corrosion. In this study, we synthesize solvent (water and ethanol) ratio-adjusted NiFe LDH anode catalysts to enhanced the OER. Results show that the catalyst prepared at a 5:5 ratio of water and ethanol (WE 55) delivers a low overpotential of 310 mV at 50 mA cm−2, Tafel slope of 40.5 mV dec−1, and 100 h-stability in a half-cell test, and a high current density of 744.2 mA cm−2 at 1.8 V and 70 °C in a single-cell test. WE 55 exhibits a manipulated oxygen vacancy and a substantially high specific surface area of ∼ 164.5 m2 g−1, leading to improved charge transfer and mass transport rates.

Promotion effect of Ga3+ in ZnAlGa-x mixed oxides obtained from their layered double hydroxides on the enhancement in the transient photocurrent response, the inhibition in the recombination rate of photogenerated (e−, h+) charges and the photocatalytic activity in the photodegradation of 4-chlorophenol

ZnAlGa-x (x = 0, 0.5, 0.8, 1.0, 2.0 and 3.0 mol % of Ga3+) mixed oxides (MOs) obtained by calcination of their corresponding layered double hydroxides (LDHs) were characterized and evaluated in the photodegradation of 4-chlorophenol in aqueous media (4-CP) using UV light irradiation. Structural studies by X-ray diffraction (XRD) of ZnAlGa-x MOs indicated that the incorporation of a small molar concentration of Ga3+ (0.5–0.8 mol %) within the ZnAl LDH structure changed the micro-crystalline structure to an amorphous structure. A small molar content of Ga3+ in the ZnAlGa3+ MOx promotes the formation of a high amount of structural oxygen vacancies as evidenced by Raman and EPR spectroscopy studies. Transient photocurrent response (TPC) and fluorescence spectroscopy experiments reveal that the incorporation of a small molar concentration of Ga3+ in the structure of ZnAl MO promotes the enhancement in the transient photocurrent response, the separation of photogenerated charges and the inhibition of the recombination rate of (e−, h+) pairs. Furthermore, ZnAlGa-x MOs with a small molar concentration of Ga3+ reduced their band gap energies below of 3.0 eV. ZnAl MO photodegradated 69.0 % of 4-CP after 4 h of reaction. However, the photoconversion % of 4-CP increased to 80–90 % at 3 h of reaction using ZnAlGa-x MOs with a small molar concentration of Ga3+. ZnAlGa-x with small Ga3+ concentration mineralized approximately 70–75 % of total disolved organic carbon at 3 h of reaction. The photocatalytic degradation reaction of 4-CP fitted well to a pseudo-first order kinetics of Langmuir-Hinshelwood-type. The kinetic parameters of ZnAlGa-x MOs confirmed that ZnAlGa-0.8 MO was the best photocatalyst to photodegradate 4-CP in aqueous media. The highest photocatalytic activity and efficacy of ZnAlGa-0.8 MO to mineralize 4-CP in aqueous medium may be due to its higher amount of oxygen vacancies contained in its structure promoting a better separation of charges and the inhibition of the recombination rate of photogenerated (e−, h+) charges.

Novel interface engineering of LDH-based materials on Mg alloy for efficient photocatalytic systems considering the geometrical linearity of condensed phosphates

This study presents a facile and rapid method for synthesizing novel Layered Double Hydroxide (LDH) nanoflakes, exploring their application as a photocatalyst, and investigating the influence of condensed phosphates’ geometric linearity on their photocatalytic properties. Herein, the MgO film, obtained by plasma electrolysis of AZ31 Mg alloys, was modified by growing an LDH film, which was further functionalized using cyclic sodium hexametaphosphate (CP) and linear sodium tripolyphosphate (LP). CP acted as an enhancer for flake spacing within the LDH structure, while LP changed flake dispersion and orientation. Consequently, CP@LDH demonstrated exceptional efficiency in heterogeneous photocatalysis, effectively degrading organic dyes like Methylene blue (MB), Congo red (CR), and Methyl orange (MO). The unique cyclic structure of CP likely enhances surface reactions and improves the catalyst's interaction with dye molecules. Furthermore, the condensed phosphate structure contributes to a higher surface area and reactivity in CP@LDH, leading to its superior photocatalytic performance compared to LP@LDH. Specifically, LP@LDH demonstrated notable degradation efficiencies of 93.02%, 92.89%, and 88.81% for MB, MO, and CR respectively, over a 40 min duration. The highest degradation efficiencies were observed in the case of the CP@LDH sample, reporting 99.99% for MB, 98.88% for CR, and 99.70% for MO. This underscores the potential of CP@LDH as a highly effective photocatalyst for organic dye degradation, offering promising prospects for environmental remediation and water detoxification applications.

Study on the Thermal Stabilizing Process of Layered Double Hydroxides in PVC Resin

Poly(vinyl chloride) (PVC) is widely used in various fields and requires the use of thermal stabilizers to enhance its thermal stability during processing because of its poor thermal stability. Layered double hydroxides (LDHs) are widely considered to be one kind of highly efficient and environmentally friendly PVC thermal stabilizer. To investigate the thermal stabilizing process of layered double hydroxides (LDHs) in PVC resin, PVC and MgAl-LDHs powders with different interlayer anions (CO32−, Cl−, and NO3−) were physically mixed and aged at 180 °C. The structure of LDHs at different aging times was studied using XRD, SEM, and FT-IR. The results show that the thermal stabilizing process of LDHs on PVC mainly has three stages. In the first stage, the layers of LDHs undergo a reaction with HCl, which is released during the thermal decomposition of PVC. Subsequently, the ion exchange process occurs between Cl− and interlayer CO32−, resulting in the formation of MgAl-Cl-LDHs. Finally, the layers of MgAl-Cl-LDHs react with HCl slowly. During the thermal stabilizing process of MgAl-Cl-LDHs, the peak intensity of XRD reduces slightly, and no new XRD peak emerges. It indicates that only the first step happens for MgAl-Cl-LDHs. The TG-DTA analysis of LDHs indicates that the interaction of LDHs with different interlayer anions has the following order: NO3− < CO32− < Cl−, according to the early coloring in the thermal aging test of PVC composites. The results of the thermal aging tests suggest that LDHs with a weak interaction between interlayer anions and layers can enhance the early stability of PVC significantly. Furthermore, the thermal aging test demonstrates that LDHs with high HCl absorption capacities exhibit superior long-term stabilizing effects on PVC resin. This finding provides a valuable hint for designing an LDHs/PVC resin with a novel structure and excellent thermal stability.

Converting Nanoflower-like Layered Double Hydroxides into Solvent-Free Nanofluids for CO2 Capture.

Due to the flexibility and versatility of the layered crystal structure of layered double hydroxides (LDHs), they have shown great potential in various fields. However, LDH nanosheets (LDH-NSs) are easy to agglomerate, leading to the problem of accumulation, which hinders their further application. Accordingly, once LDHs are combined with solvent-free nanofluids (SFNs), the advantages of LDHs and SFNs could be combined to achieve an extraordinary performance. However, the stacked structure of traditional LDHs is not conducive to the exposure of hydroxyl functional groups, and hydroxyl sites are key to the conversion of LDHs to SFNs. Therefore, in this work, nanoflower-like LDHs (NFLs) with abundant exposed hydroxyl groups were prepared and combined with organic oligomers to achieve a solid-to-liquid transition. The formation mechanism of NFLs and the grafting mechanism of OS-PEA on their surface were identified. The prepared NFL-F3 still has good fluidity and dispersion stability in different solvents after storage for 100 days. The high-saturated grafting density on the surface of NFLs increased the steric hindrance effect of the nanoparticles, thereby improving the dispersion stability and reducing the viscosity of NFL-F3. Notably, the CO2 sorption performance of NFL-F3 is significantly improved, which is attributed to the voids between polymers, physical sorption, and good fluidity caused by high-saturation grafting on the surface of NFL-F3. Finally, by combining the sorption behavior and model fitting, it was confirmed that the physical effect was dominant in CO2 sorption by the NFL-F, which saved energy for the sorption-desorption process of its industrial application. Moreover, NFL-F3 has a good CO2/N2 separation performance and cycle stability. We envision that this general strategy will open up new insights into the construction of innovative low-viscosity LDH-based SFNs with high CO2 capacity and facilitate CO2/N2 selectivity and offer new directions for LDH utilizations.

Highly Porous Layered Double Hydroxide and Mixed Metal Oxide by Sacrificial Bio-Template, Egg White Foam

Highly porous layered double hydroxide (LDH) and its calcined mixed metal oxide (MMO) were obtained by utilizing egg white (EW) as a biogenic porous template. The LDH was prepared through coprecipitation under the existence of a beaten EW meringue, and the corresponding MMO was obtained by calcining LDH at 500 °C. According to X-ray diffraction, the crystal structure of LDH and MMO was well-developed with or without EW. In contrast, the crystallinity analyses and microscopic investigations clearly showed differences in the particle orientation in the presence of EW; the protein arrangement in the EW foam induced the ordered orientation of LDH platelets along proteins, resulting in well-developed inter-particle pores. As a result, the distinctive particle arrangement in EW-templated samples compared with non-templated ones showed dramatically enhanced specific surface area and porosity. The nitrogen adsorption–desorption isotherm exhibited that the high specific surface area was attributed to the homogeneous nanopores in EW-templated LDH and MMO, which originated from the sacrificial role of the EW.

Hierarchically Multiscale Vertically Oriented NiFeCo Nanoflakes for Efficient Electrochemical Oxygen Evolution at High Current Densities

AbstractCrucial advancements in versatile catalyst systems capable of achieving high current densities under industrial conditions, bridging the gap between fundamental understanding and practical applications, are pivotal to propel the hydrogen economy forward. In this study, vertically oriented hierarchically multiscale nanoflakes of NiFeCo electrocatalysts are presented, developed by surface modification of a porous substrate with nano‐structured nickel. The resulting electrodes achieve remarkably low overpotentials of 139 mV at 10 mAcm−2 and 248 mV at 500 mAcm−2. Further, scaled‐up electrodes are implemented in a water‐splitting electrolyser device exhibiting a stable voltage of 1.82 V to deliver a constant current density of 500 mA cm−2 for over 17 days. Moreover, the role of the unique structures on electrochemical activity is systematically investigated by fractal analysis, involving computation of structure factors such as Minkowski connectivity, fractal dimension, and porosity using scanning electron microscope images. It is found that such structures offer higher surface area than typical layered double hydroxide structures due to morphological coherence that results in a superhydrophilic surface, while the base Ni layer boosts the charge transfer. This study demonstrates a Ni/NiFeCo(OH)x heterostructure with highly porous morphology, a key to unlocking extremely efficient oxygen evolution reaction activity with exceptional stability. Moreover, fractal analysis is presented as a valuable tool to evaluate the electrochemical performance of catalysts for their structured morphology.

Heteroatoms introduction via Temperature-Differential doping strategy achieves Long-Cycle-Life NiCoMo-P LDH cathode for rechargeable Chloride-Ion battery

As one of the most promising insertion-type cathodes for the novel chloride ion batteries (CIBs), layered double hydroxides (LDHs) materials have been extensively investigated in the recent years as the typical inorganic anion conductors. Nevertheless, poor intrinsic conductivity and sluggish reaction kinetics of LDHs challenge directly the further development in terms of chloride storage capacity and cycling life. Herein, phosphorus doped NiCoMo LDH in chloride form (NiCoMo-P LDH) is demonstrated as a high performance cathode for CIB. The unique temperature-differential doping methode allows P heteroatoms to incorporate into the metal–oxygen octahedral matrix of LDHs host layers, which have no effect on the entire crystal structure of 2D LDHs and the stable presence of interlayer Cl ions. By combining the advanced spectroscopy techniques and DFT theoretical calculations, abundant vacancies are proved to be introduced into NiCoMo-P LDH and both the conductivity and chloride-ion diffusion rate are significantly improved, providing more active adsorption sites for electrochemical reactions, thus strengthening the Cl ions storage performance with a stable discharge capacity of 150.2 after 800 charging/discharging processes at a current density of 300 mA g−1. This study presents a facile strategy for the rational doping of hetero-anions in LDHs materials for CIBs at relative low-temperature, which can also be adopted in other types of halide-ion-based rechargeable batteries.

Effect of Al-doping on structural and cyclic stability of NiCoFe layered double hydroxides as electrode material in supercapacitors

Supercapacitors are an effective energy storage device can address the issue of storing renewable energy sources. Layered double hydroxides (LDHs) have been identified as a promising electrode material for supercapacitors due to their diverse constituent elements and adjustable structure. However, LDHs tend to experience mechanical deformation during charging and discharging, which results in poor cycle performance. In this study, an Al substitution strategy for Fe was employed to adjust the interlaced structure assembled by one-dimensional nanorods and two-dimensional nanosheets in NiCoFe-LDH, which led to an enhanced stability and electrochemical performance for supercapacitors. Excessive Al doping prompted nanorods to evolve into nanosheets, resulting in loss of the interlaced structure. When the ratio of Fe and Al is 0.75:0.25, the resulted Ni2Co1Fe0.75Al0.25-LDH maintained a much more perfect interlaced structure while exhibiting the best specific capacitance reaching 2367.39 F·g−1 at 1 A·g−1 as well as a 89.79% retention rate at 20 A·g−1 in a three-electrode unit; when paired with activated carbon (AC), it exhibited a specific capacitance of 394.14 F·g−1 at 1 A·g−1 with an energy density up to 140.14 Wh·kg−1 at a high power density level of 811.46 W·kg−1 in Ni2Co1Fe0.75Al0.25-LDH//AC unit. Moreover, after undergoing rigorous testing involving 5000 cycles at 5 A·g−1, Ni2Co1Fe0.75Al0.25-LDH//AC demonstrated a 55.31% retention rate, significantly higher than that observed for Ni2Co1Fe1-LDH//AC (17.58%). The Al doping strengthened the stability of host layer structure and further improved the interlaced structure of LDH, resulted in a significant improvement in specific capacitance, energy density and cycle performance. This improved material will exhibit better application prospects in supercapacitors.

Fe Electron Center Local Regulation of CoFe‐Layered Double Hydroxides Nanosheets for Enhancing the Electrocatalytic Oxidation of Benzyl Alcohol

AbstractReplacing sluggish oxygen evolution reaction (OER) with electrocatalytic oxidation (ECO) of alcohols was a promising hotspot due to its advantages of requiring low potential, inhibiting mixing of gases, and forming value‐added products. In the ECO of alcohols process, Fe electron centers of Fe‐based layered double hydroxides (LDHs) can regulate the d band of LDHs overlap, optimize the active local structure of LDHs, and then enhance the electrocatalytic oxidation performance. In this work, CoxFey‐LDHs nanosheets with different ratios of Co/Fe were prepared for selective ECO of benzyl alcohol (BA) to benzoic acid (BAC). Comprehensive characterizations revealed that the adjustment of bandgap and OH species adsorption of CoxFey‐LDHs resulted in the appropriate thermodynamic driving force, which improved the electrical conductivity of CoxFey‐LDHs and enhanced their ECO of BA. Especially, the as‐prepared Co3Fe1‐LDH showed intriguing electrocatalytic activity and only required a potential of 1.51 V (vs. RHE) to achieve a total current density of 50 mA cm−2 in alkaline solution containing 10 mM BA with a conversion (96.79 %) of BA and selectivity (94.93 %) of BAC, which was 60 mV lower than that of OER. After six cycles, Co3Fe1‐LDH still achieved 94.74 % conversion of BA and 92.10 % selectivity of BAC without significant degradation.