NiFe Layered Double Hydroxide Research Articles

Synthesis of Zr2ON2 via a urea-glass route to modulate the bifunctional catalytic activity of NiFe layered double hydroxide in a rechargeable zinc-air battery

The development of a highly efficient, stable, and low-cost bifunctional catalyst is imperative for facilitating the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). However, significant challenges are involved in extending its applications to rechargeable zinc-air batteries. This study presents a bifunctional catalyst, Zr2ON2@NiFe layered double hydroxide (LDH), that was developed by utilizing a urea-glass route for synthesizing the Zr2ON2 precursor, followed by riveting NiFe LDH nanosheets using a hydrothermal method. Specifically, the vertical distribution of NiFe LDH on the Zr2ON2 surface ensures the maximization of the number of accessible active sites and interfacial catalysis of NiFe LDH. Notably, Zr2ON2@NiFe LDH demonstrates ORR and OER bifunctional electrocatalytic behavior and high stability owing to its heterostructure and composition. Furthermore, a rechargeable zinc-air battery using a Zr2ON2@NiFe LDH electrocatalyst as the air cathode demonstrated a high peak power density (172 mW cm−2) and galvanostatic charge-discharge cycle stability (5 mA cm−2 over 443 h). Thus, this study presents an efficient and cost-effective strategy for the design of bifunctional electrocatalysts.

Electrodeposited NiFe‐LDH on the Surface of Ni‐BDC for Electrocatalytic Water Oxidation

AbstractSubstrate surface modification with a functional material can effectively enhance the electrocatalytic performance of an electrode on oxygen evolution reaction (OER). In this work, a functional Ni‐BDC MOF nanosheet layer was in‐situ grown on the surface of nickel foam (NF). Consequently, the NiFe layered double hydroxides (NiFe‐LDH) electrodeposited on the modified layer exhibited an excellent activity and an amazing long‐term stability on electrocatalytic OER. In alkaline electrolyte, the well‐designed NiFe‐LDH/Ni‐BDC/NF drives a current density of 100 mA cm−2 at a small overpotential of 223 mV, with a low Tafel slope of 33.1 mV dec−1 and an outstanding catalytic stability of more than 10 days under continuous electrocatalysis. Such distinguished performances are attributed to the particular hydrophily and electrical conductivity of the Ni‐BDC layer. This work is an important attempt to bring a simple and effective guideline on fabricating a highly efficient catalytic electrode for OER.

Combustion Growth of NiFe Layered Double Hydroxide for Efficient and Durable Oxygen Evolution Reaction.

NiFe layered double hydroxide (LDH) with abundant heterostructures represents a state-of-the-art electrocatalyst for the alkaline oxygen evolution reaction (OER). Herein, NiFe LDH/Fe2O3 nanosheet arrays have been fabricated by facile combustion of corrosion-engineered NiFe foam (NFF). The in situ grown, self-supported electrocatalyst exhibited a low overpotential of 248 mV for the OER at 50 mA cm-2, a small Tafel slope of 31 mV dec-1, and excellent durability over 100 h under the industrial benchmarking 500 mA cm-2 current density. A balanced Ni and Fe composition under optimal corrosion and combustion contributed to the desirable electrochemical properties. Comprehensive ex-situ analyses and operando characterizations including Fourier-transformed alternating current voltammetry (FTACV) and in situ Raman demonstrate the beneficial role of modulated interfacial electron transfer, dynamic atomic structural transformation to NiOOH, and the high-valence active metal sites. This study provides a low-cost and easy-to-expand way to synthesize efficient and durable electrocatalysts.

In-situ vacancy defects triggered via organic solvent-water fusion for improved OER, HER, and supercapacitor performance

Simplifying the design of high-performance electrodes via efficient catalyst design is critical for alkaline water electrolysis and supercapacitor applications. Towards that end, we have developed the environmentally benign synthesis of ultrathin nanosheets of NiFe-layered double hydroxides (LDH) with inbuilt oxygen vacancies (VO) in this report. These NiFe-layered double hydroxide (GNiFe-LDH-VO) materials require low overpotentials for the oxygen evolution reaction (OER, η50 = 200 and η100 = 220 mV) with a small Tafel slope of 52.21 mV dec−1. The ex-situ characterizations and theoretical calculations suggest that oxygen vacancies configure to a more active state, resulting in the low binding energy of oxo intermediates, and thus much lower overpotential. Besides, it could operate stably for 100 h at current densities of 100 mA cm−2 for OER. It is significant that oxygen vacancies in GNiFe-LDH-VO aid in lowering the main obstacle of multistep OER, which will provide recommendations for the development of high-efficiency catalysts through in situ activation. In addition, GNiFe-LDH-VO exhibits a high areal capacitance of 1.6024 F cm−2 at a current density of 1 mA cm−2, with a capacitance retention ratio of 96.1% after 5000 galvanostatic charge-discharge (GCD) cycles when they are used as supercapacitor electrodes.

Interface engineering of 2D NiFe LDH/NiFeS heterostructure for highly efficient 5-hydroxymethylfurfural electrooxidation

The electrochemical oxidation of 5-hydroxymethylfurfural (HMF) to valuable chemicals is an efficient way to upgrade biomass molecules and replace traditional catalytic synthesis. It is crucial to develop efficient and low-cost earth-abundant electrocatalysts to enhance catalytic performance of HMF oxidation. Herein, a new type of two-dimensional (2D) hybrid arrays consisting of NiFe layered double hydroxides (LDH) nanosheets and bimetallic sulfide (NiFeS) is constructed via interface engineering for efficient electrocatalytic oxidation of HMF to 2,5-furandicarboxylic acid (FDCA). The preparation process of 2D NiFe LDH/NiFeS with ultrathin heterostructure involves in anchoring a Co-based metal-organic framework (Co MOF) as template onto the carbon cloth (CC) via in-situ growth, formation of NiFe LDH on the surface of Co MOF and subsequent partial sulfidation. The electrocatalyst of NiFe LDH/NiFeS exhibits outstanding performance towards HMF oxidation, about 98.5% yield for FDCA and 97.2% Faraday efficiency (FE) in the alkaline electrolyte with 10 mmol/L HMF, as well as excellent stability retaining 90.1% FE for FDCA after six cycles test. Moreover, even at an HMF concentration of 100 mmol/L, the yield and FE for FDCA remain high at 83.6% and 93.6%, respectively. These findings highlight that 2D heterostructure containing abundant interfaces between NiFe LDH nanosheets and NiFeS can enhance the intrinsic activity of LDH and thus promote the oxidation reaction kinetics. Additionally, the synergistic effect of the bimetallic NiFe compounds also improved the selectivity of HMF conversion to FDCA. Our present work demonstrates that constructing 2D ultrathin heterostructure of NiFe LDH/NiFeS is a facile strategy via interface engineering to enhance the intrinsic activity of LDH electrocatalysts, which would open new avenues toward low-cost and advanced 2D nanocatalysts for sustainable energy conversion and electrochemical valorization of biomass derivatives.

Non-precious high entropy alloys and highly alkali-resistant composite membranes based high performance anion exchange membrane water electrolyzers

Cost-effective highly efficient and stable catalysts and alkali-resistant anion exchange membranes (AEMs) are critical for practical applications of anion exchange membrane water electrolyzers (AEMWEs). Here, bifunctional non-precious FeCoNiCuMo high entropy alloys (HEAs), electrochemically deposited on nickel mesh as an anode (FeCoNiCuMo/NM) and on carbon paper as a cathode (FeCoNiCuMo/CP), together with a NiFe layered double hydroxide (LDH) loaded AEM (AEM/LDH), were developed for high performance AEMWEs. The AEMWE thus fabricated delivered an ultrahigh current density of 1777 mA cm−2 at 2 V and exhibited remarkable stability with a less than 0.1% cell voltage increase after a 100-hour operation at 100 mA cm−2 at 50 °C, largely outperforming those of the precious metal based AEMWE, composed of IrO2/NM as the anode and Pt/C/CP as the cathode, 1231 mA cm−2@2 V and 4.57% increase in cell voltages. Composition of the alkali-resistant, hydrophilic, and water electrolysis active NiFe LDH into the AEM improved not only the electrolyte uptake and operational stability, but also the efficiency of the AEMWE, with a 10% boost in current density achieved at 2 V and a reduction in cell voltage increases from 2.94% to 0.0951%. The present development demonstrates the practicality of AEMWEs toward green hydrogen production.

Integrating Sulfur Doping with a Multi-Heterointerface Fe7S8/NiS@C Composite for Wideband Microwave Absorption.

Heterointerface engineering is presently considered a valuable strategy for enhancing the microwave absorption (MA) properties of materials via compositional modification and structural design. In this study, a sulfur-doped multi-interfacial composite (Fe7S8/NiS@C) coated with NiFe-layered double hydroxides (LDHs) is successfully prepared using a hydrothermal method and post-high-temperature vulcanization. When assembled into twisted surfaces, the NiFe-LDH nanosheets exhibit porous morphologies, improving impedance matching, and microwave scattering. Sulfur doping in composites generates heterointerfaces, numerous sulfur vacancies, and lattice defects, which facilitate the polarization process to enhance MA. Owing to the controllable heterointerface design, the unique porous structure induced multiple heterointerfaces, numerous vacancies, and defects, endowing the Fe7S8/NiS@C composite with an enhanced MA capability. In particular, the minimum reflection loss (RLmin) value reached -58.1dB at 15.8GHz at a thickness of 2.1mm, and a broad effective absorption bandwidth (EAB) value of 7.3GHz is achieved at 2.5mm. Therefore, the Fe7S8/NiS@C composite exhibits remarkable potential as a high-efficiency MA material owing to the synergistic effects of the polarization processes, multiple scatterings, porous structures, and impedance matching.

Regulating the electronic state of SnO2@NiFe-LDH heterojunction: Activating lattice oxygen for efficient oxygen evolution reaction

In Oxygen Evolution Reaction (OER), catalysts with lattice oxygen, utilizing the Lattice Oxygen Mechanism (LOM), directly participate in oxygen evolution, effectively reducing activation energy. NiFe-Layered Double Hydroxides (NiFe-LDHs), rich in surface hydroxyls, are potential for LOM. However, their stability is challenged in alkaline conditions due to metal cation dissolution from the lattice, limiting catalytic efficiency. In this work, we modify NiFe-LDH by combining hydrothermal and electrodeposition techniques, coupling NiFe-LDH with the metal oxide SnO2. This process creates a heterojunction enriched with oxygen vacancies through interfacial and defect engineering. In 1 M KOH solution, this modified catalyst exhibits an OER overpotential of just 209 mV at a current density of 10 mA cm−2. Furthermore, when the current density is increased to 100 mA cm−2, the overpotential only increases by a modest 46 mV. Subsequent DFT investigations reveal that in the heterostructured system, there is an enhanced overlap between the O 2p and metal 3d orbitals, which optimizes the covalency of the metal–oxygen bond and promotes the participation of lattice oxygen in the reduction reaction. The heterojunction, in concert with oxygen vacancies, aligns the energy bands of oxygen and metal closer to the Fermi level, resulting in improved continuity of electronic orbitals near the Fermi level. This synergistic arrangement significantly reduces the energy barrier for the rate-determining step of the OER, substantiating the improved performance and activation of lattice oxygen.

Electrodeposition Fabrication of La-Doped NiFe Layered Double Hydroxide to Improve Conductivity for Efficient Overall Water Splitting

Electrodeposition Fabrication of La-Doped NiFe Layered Double Hydroxide to Improve Conductivity for Efficient Overall Water Splitting

Nickel-Iron-Layered Double Hydroxide Electrocatalyst with Nanosheets Array for High Performance of Water Splitting.

Developing high-performance and cost-competitive electrocatalysts have great significance for the massive commercial production of water-splitting hydrogen. Ni-based electrocatalysts display tremendous potential for electrocatalytic water splitting. Herein, we synthesize a novel NiFe-layered double hydroxide (LDH) electrocatalyst in nanosheets array on high-purity Ni foam. By adjusting the Ni/Fe ratio, the microstructure, and even the behavior of the electrocatalyst in the oxygen evolution reaction (OER), changes significantly. The as-obtained material shows a small overpotential of 223 mV at 10 mAcm-2 as well as a low Tafel slope of 48.9 mV·dec-1 in the 1 M KOH electrolyte. In addition, it can deliver good stability for at least 24 h of continuous working at 10 mAcm-2. This work proposes a strategy for engineering catalysts and provides a method for the development of other Ni-based catalysts with excellent performance.

Effect of Interlayer Anions on NiFe Layered Double Hydroxides for Catalytic Ozone Decomposition.

NiFe layered double hydroxides (NiFe-LDH) exhibited an outstanding performance and promising application potential for removing ozone. However, the effect of interlayer anions on ozone removal remains ambiguous. Here, a series of NiFe-LDH with different interlayer anions (F-, Cl-, Br-, NO3-, CO32-, and SO42-) were prepared to investigate the effect of the interlayer anion on ozone removal for the first time. It was found that the interlayer anions are a key factor affecting the water resistance of the NiFe-LDH catalyst under moist conditions. NiFe-LDH-CO32- exhibited the best water resistance, which was much better than that of NiFe-LDH containing other interlayer anions. The in situ DIRFTS demonstrates that the carbonates in the interlayer of NiFe-LDH-CO32- will undergo coordination changes through the interaction with water molecules under moist conditions, exposing new metal sites. As a result, the newly exposed metal sites could activate water molecules into hydroxyl groups that act as active sites for catalyzing ozone decomposition. This work provides a new insight into the interlayer anions of LDH, which is important for the design and development of LDH catalysts with excellent ozone removal properties.

Two-Dimensional SnS Mediates NiFe-LDH-Layered Electrocatalyst toward Boosting OER Activity for Water Splitting.

NiFe-layered double hydroxides (NiFe-LDHs), as promising electrocatalysts, have received significant research attention for hydrogen and oxygen generation through water splitting. However, the slow oxidation kinetics of NiFe-LDH, due to the limited number of active sites and the low conductivity, hinders the improvement of the water-splitting efficiency. Therefore, to overcome the obstacles, two-dimensional (2D) SnS was first explored to tailor the prepared NiFe-LDH via the hydrothermal method. A NiFe-LDH/SnS heterojunction is built, which is observed from the microstructural investigations. SnS incorporation could greatly improve the conductivity of the NiFe-LDH sheets, which was reflected by the reduced charge transfer resistance. Moreover, SnS layers modulated the electronic environment around the active sites, favoring the adsorption of intermediates during the oxygen evolution reaction (OER) process, which was verified by density functional theory calculations. A synergistic effect induced by the NiFe-LDH/SnS heterostructure promoted the OER activities in electrical, electronic, and energetic aspects. Consequently, the as-prepared NiFe-LDH/SnS electrocatalyst greatly improved the electrocatalytic performance, exhibiting 20% and 27% reductions in the overpotential and Tafel slope compared with those of pristine NiFe-LDH, respectively. The results provide a strategy for regulating NiFe-based electrocatalysts by using emerging 2D materials to enhance water-splitting efficiency.

Tribological Behavior of GTL Base Oil Improved by Ni-Fe Layered Double Hydroxide Nanosheets

The layered double hydroxide (LDH) has been practically applied in the field of tribology and materials science due to its unique physicochemical properties, weak bonding, flexible structural composition, and adjustable interlayer space. In this work, a series of ultrathin and flexible composition of Ni-Fe LDH samples were prepared via a cost-effective room-temperature co-precipitation process. Then, they were mechanically dispersed into GTL base oil and their lubricating performance were tested by a four-ball tribometer. It is found that the variation of Ni-Fe ratio of Ni-Fe LDH has a great influence on the improvement of lubricating performance of GTL base oil. At the same concentration (0.3 mg/mL), the Ni-Fe LDH with Ni/Fe ratio of 6 was demonstrated to exhibit the best lubricating performance and the AFC, WSD, the wear volume, surface roughness and average wear scar depth decreased 51.3%, 30.8%, 78.4%, 6.7% and 50.0%, respectively. SEM-EDS and X-ray photoelectron spectra illustrated that the tribo-chemical film consisting of iron oxides and NiO with better mechanical properties formed and slowly replaced the physical film, which resists scuffing and protect solid surface from severe collisions.

Unravelling the Photoelectrochemical Water Splitting of Nanometer-Thick Carbon Nitride Layer.

Matching the thickness of the graphitic carbon nitride (CN) nanolayer with the charge diffusion length is expected to compensate for the poor intrinsic conductivity and charge recombination in CN for photoelectrochemical cells (PEC). Herein, the compact CN nanolayer with tunable thickness is in situ coated on carbon fibers. The compact packing along with good contact with the substrate improves the electron transport and alleviates the charge recombination. The PEC investigation shows CN nanolayer of 93nm-thick yields an optimum photocurrent of 116µAcm-2 at 1.23V versus RHE, comparable to most micrometer-thick CN layers, with a low onset potential of 0.2V in 1m KOH under 1 sun illumination. This optimum performance suggests the electron diffusion length matches with the thickness of the CN nanolayer. Further deposition of NiFe-layered double hydroxide enhanced the surface water oxidation kinetics, delivering an improved photocurrent of 210µAcm-2 with IPCE of 12.8% at 400nm. The CN nanolayer also shows extended potential in PEC organic synthesis. This work experimentally reveals the PEC behavior of the nanometer-thick CN layer, providing new insights into CN in the application of energy and environment-related fields.

Highly Stable Mo-NiO@NiFe-Layered Double Hydroxide Heterojunction Anode Catalyst for Alkaline Electrolyzers with Porous Membrane.

Heterostructure catalysts are considered as promising candidates for promoting the oxygen evolution reaction (OER) process due to their strong electron coupling. However, the inevitable dissolution and detachment of the heterostructure catalysts are caused by the severe reconstruction, dramatically limiting their industrial application. Herein, the NiFe-layered double hydroxide (LDH) nanosheets attached on Mo-NiO microrods (Mo-NiO@NiFe LDH) by the preoxidation strategy of the core NiMoN layer are synthesized for ensuring the high catalytic performance and stability. Owing to the enhanced electron coupling and preoxidation process, the obtained Mo-NiO@NiFe LDH exhibits a superlow overpotential of 253 mV to achieve a practically relevant current density of 1000 mA cm-2 for OER with exceptional stability over 1200 h. Notably, the overall water splitting system based on Mo-NiO@NiFe LDH reveals remarkable stability, maintaining the catalytic activity at a current density of 1000 mA cm-2 for 140 h under industrial harsh conditions. Furthermore, the Mo-NiO@NiFe LDH demonstrates outstanding activity and long-term durability in a practical alkaline electrolyzer assembly with a porous membrane, even surpassing the performance of IrO2. This work provides a new sight for designing and synthesizing highly stable heterojunction electrocatalysts, further promoting and realizing the industrial electrocatalytic OER.

Stably Improving the Catalytic Activity of Oxygen Evolution Reactions via Two-Dimensional Graphene Oxide-Incorporated NiFe-Layered Double Hydroxides

Stably Improving the Catalytic Activity of Oxygen Evolution Reactions via Two-Dimensional Graphene Oxide-Incorporated NiFe-Layered Double Hydroxides

Dynamic Reconfiguration and Local Polarization of NiFe-Layered Double Hydroxide-Bi2MoO6- x Heterojunction for Enhancing Piezo-Photocatalytic Nitrogen Oxidation to Nitric Acid.

Constructing heterojunctions with vacancies has garnered substantial attention in the field of piezo-photocatalysis. However, the presence of interfacial vacancies can serve as charge-trapping sites, leading to the localization of electrons and hindering interfacial charge transfer. Herein, dual oxygen vacancies in the NiFe-layered double hydroxide and Bi2MoO6- x induced interfacial bonds have been designed for the piezo-photocatalytic N2 oxidation to NO3 -. Fortunately, it achieves sensational nitric acid production rates (7.23mg g-1 h-1) in the absence of cocatalysts and sacrificial agents, which is 6.03 times of pure Bi2MoO6 that under ultrasound and light illumination. Theoretical and experimental results indicate that interfacial bonds act as "charge bridge" and "strain center" to break the carrier local effect and negative effects with piezocatalysis and photocatalysis for promoting exciton dissociation and charge transfer. Moreover, the strong electronic interaction of the interfacial bond induces internal reconstruction under ultrasound for promoting the local polarization and adsorption of N2, which accelerates the fracture of the N≡N bonds and reduces the activation energy of the reaction. The research not only establishes a novel approach for optimizing the combined effects of piezo-catalysis and photocatalysis, but also achieves equilibrium between the synergistic impacts of vacancies and heterojunctions.

Guided Design of Efficient Oxygen Evolution Catalysts Using Patent Analysis.

The facile and rapid design of efficient oxygen evolution reaction (OER) catalysts holds paramount significance for energy conversion devices, such as water electrolyzers and fuel cells. Despite substantial progress in catalyst synthesis and performance exploration, the design and selection processes remain inefficient. In this context, we integrate patent analysis with catalyst design, leveraging the scholarly research functionalities within patent analyses to aid in the design and synthesis of a NiFeRu-carbon catalyst as a high-performance OER catalyst. The results demonstrate that the NiFeRu-Carbon catalyst with low Ru loading (0.3 wt %) exhibits an overpotential of only 219 mV at 10 mA cm-2 under alkaline conditions, and after continuous operation for 200 h, the overpotential only attenuates by 15 mV. The incorporation of high-valence Ru dopants elevated the intrinsic activity of individual catalytic sites within NiFe-layered double hydroxides (LDHs). During the catalytic process, the partial dissolution of Ru might lead to the generation of numerous oxygen vacancies within NiFe- LDH, thereby enhancing the catalyst's activity and stability.

Metallic nonstoichiometric WO3–x-decorated NiFe-layered double hydroxide for boosted urea electro-oxidation reaction: the facilitated dynamics and increasing active sites

Metallic nonstoichiometric WO3–x-decorated NiFe-layered double hydroxide for boosted urea electro-oxidation reaction: the facilitated dynamics and increasing active sites

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.