Nickel Nitride Research Articles

Vanadium-Doped Heterointerfaced Ni3N-MoOx Nanosheets with Optimized H and H2O Adsorption for Effective Alkaline Hydrogen Electrocatalysis.

Nickel (Ni)-based materials represent a compelling avenue as platinum alternatives in the realm of alkaline hydrogen electrocatalysis. However, conventional nickel nitrides (Ni3N) have long been hindered by sluggish hydrogen evolution kinetics in alkaline environments, owing to inadequate adsorption strengths of both hydrogen and water molecules. Herein, a novel approach is presented involving the design of vanadium (V)-doped Ni3N/MoOx heterogeneous nanosheets (V-Ni3N@MoOx), engineered to achieve optimized adsorption strengths for hydrogen evolution and oxidation reactions (HER/HOR). Theoretical insights underscore the superior catalytic performance of this composite, attributed to a synergistic interplay between unique V doping and the heterointerfaced structure. This synergistic effect not only fine-tunes the electronic structure, establishing an optimal d band center to mitigate proton over-bonding, but also ameliorates the energy barrier through enhanced H2O dissociation capability. Consequently, V-Ni3N@MoOx manifests remarkable catalytic activities, evincing an overpotential of 56mV at 10mAcm-2 for HER and an exchange current density of 1.91mAcm-2 for HOR in alkaline media. Notably, the stability assessment reveals the enduring performance of V-Ni3N@MoOx for HER/HOR, exhibiting no activity decay over extended operational durations. This study underscores the efficacy of heterogeneous interface modulation as a transformative strategy in designing Ni-based materials for alkaline hydrogen electrocatalysis.

Nanoarchitectonics of Nickel Nitride‐V2CTX Mxene: An Efficient Bifunctional Catalyst for Alkaline Water/Seawater Applications

AbstractSeawater, being the most plentiful natural water source worldwide, is a highly abundant and cost‐efficient medium for producing hydrogen by alkaline water electrolysis. However, the advancement of seawater electrolysis is hindered by notable impediments caused by chloride corrosion at the anode and the simultaneous chlorine evolution process. Only a limited number of non‐noble electrocatalysts demonstrate noteworthy bifunctional catalytic efficacy and long‐term durability. In this regard, Nickel Nitride tailored V2CTX Mxene nanostructures is reported as a bifunctional catalyst for overall water/seawater applications. The optimized sample Ni3N@3000‐V2CTx exhibits low overpotential values of 90 and 300 mV in acidic and alkaline + seawater solutions respectively at 10 mA cm−2 for hydrogen evolution reaction. Similarly, this catalyst shows 70 and 240 mV overpotential values in alkaline water and alkaline + seawater solutions respectively at the same current density for oxygen evolution reaction. Synergetic effects of Multiple Vanadium and Nickel valency along with compelling nitrogen bonds creates elevated density of exposed functional sites for electrocatalytic activity. Furthermore, the notable electrochemical active surface area and mass activity suggest an enhanced and significant presence of abundant active sites. Additionally, the high stability and significantly decreased charge transfer resistance expedited the overall water/seawater‐splitting reaction rate.

Review on Nickel Nitride Composite Coatings

Abstract Nickel based composite coating has been widely used in many field applications such as wear and corrosion resistance since it is possible to improve its properties by depositing a variety reinforcement and process parameters. In this work, a variety of reinforced nitride particles such as TiN, AlN and Si were used to enhance the microstructure, mechanical and oxidation properties of nickel nitride composite coating in improving the coating density and surface morphology. The electrodeposition method was used to develop the composite coating with variety process parameters including temperature and current density. The coating stress was calculated from crystal structure data to investigate its involvement in the mechanical properties of coatings. The high temperature oxidation behavior of nickel nitride composite coatings was studied by heating process. The review highlights the reinforced nitride particles and process parameters improve the hardness and wear resistance of nickel based composite coating, however, the improvement also involves the coating stress. From study result of high temperature oxidation process, it obtained that the aluminum oxide remains within the coating indicating its role play in protecting substrate from corrosion. Experimental study on surface modification and microstructure of nickel based composite coating are highly expected and meet a great challenge for different applications with superior mechanical and tribological properties.

Dual Polarization of Ni Sites at VOx-Ni3N Interface Boosts Ethanol Oxidation Reaction.

Substituting thermodynamically favorable ethanol oxidation reaction (EOR) for oxygen evolution reaction (OER) engenders high-efficiency hydrogen production and generates high value-added products as well. However, the main obstacles have been the low activity and the absence of an explicit catalytic mechanism. Herein, a heterostructure composed of amorphous vanadium oxide and crystalline nickel nitride (VOx-Ni3N) is developed. The heterostructure immensely boosts the EOR process, achieving the current density of 50mA cm-2 at the low potential of 1.38V versus reversible hydrogen electrode (RHE), far surpassing the sluggish OER (1.65V vs RHE). Electrochemical impedance spectroscopy indicates that the as-fabricated heterostructure can promote the adsorption of OH- and the generation of the reactive species (O*). Theoretical calculations further outline the dual polarization of the Ni site at the interface, specifically the asymmetric charge redistribution (interfacial polarization) and in-plane polarization. Consequently, the dual polarization modulates the d-band center, which in turn regulates the adsorption/desorption strength of key reaction intermediates, thereby facilitating the entire EOR process. Moreover, a VOx-Ni3N-based electrolyzer, coupling hydrogen evolution reaction (HER) and EOR, attains 50mA cm-2 at a low cell voltage of ≈1.5V. This work thus paves the way for creating dual polarization through interface engineering toward broad catalysis.

Complementary Multisite Turnover Catalysis toward Superefficient Bifunctional Seawater Splitting at Ampere-Level Current Density.

The utilization of seawater for hydrogen production via water splitting is increasingly recognized as a promising avenue for the future. The key dilemma for seawater electrolysis is the incompatibility of superior hydrogen- and oxygen-evolving activities at ampere-scale current densities for both cathodic and anodic catalysts, thus leading to large electric power consumption of overall seawater splitting. Here, in situ construction of Fe4N/Co3N/MoO2 heterostructure arrays anchoring on metallic nickel nitride surface with multilevel collaborative catalytic interfaces and abundant multifunctional metal sites is reported, which serves as a robust bifunctional catalyst for alkaline freshwater/seawater splitting at ampere-level current density. Operando Raman and X-ray photoelectron spectroscopic studies combined with density functional theory calculations corroborate that Mo and Co/Fe sites situated on the Fe4N/Co3N/MoO2 multilevel interfaces optimize the reaction pathway and coordination environment to enhance water adsorption/dissociation, hydrogen adsorption, and oxygen-containing intermediate adsorption, thus cooperatively expediting hydrogen/oxygen evolution reactions in base. Inspiringly, this electrocatalyst can substantially ameliorate overall freshwater/seawater splitting at 1000mA cm-2 with low cell voltages of 1.65/1.69V, along with superb long-term stability at 500-1500mA cm-2 for over 200 h, outperforming nearly all the ever-reported non-noble electrocatalysts for freshwater/seawater electrolysis. This work offers a viable approach to design high-performance bifunctional catalysts for seawater splitting.

A Guide to Electrocatalyst Stability Using Lab-Scale Alkaline Water Electrolyzers

Green hydrogen from low-temperature water electrolysis has received significant attention with a projected thousand-fold global capacity expansion by 2030.1 Electrocatalyst research is crucial for water electrolysis technologies and has garnered substantial attention. However, despite a surge in publications centered on promising electrocatalytic materials, often claiming "outstanding" performance, few studies have scaled these materials to more realistic setups. This gap primarily stems from the inadequacy of testing environments and operating conditions in academic research. The prevalent use of three-electrode cell configurations fails to mimic practical electrolyzer conditions accurately.2,3 Electrocatalytic performance in these setups does not effectively represent real electrolysis devices operating in zero-gap configurations. Therefore, implementing stability tests in realistic device configurations is essential to assess compounded instability from all components, including the catalyst.2,4 Our group has developed and optimized a lab-scale electrochemical flow cell for alkaline water electrolysis (AWE), refined over four years of dedicated research (Figure 1a).4–7 This work outlines the operation of this device in a laboratory environment, focusing on accelerating the evaluation of electrocatalytic materials and their durability in alkaline conditions. We examined the performance of this lab-scale electrolyzer under industrially relevant conditions, including varying temperatures (Figure 1b). We examined the stability of three standard electrocatalytic materials to demonstrate the electrolyzer performance under fluctuating current conditions, including a benchmark NiFe anode for the oxygen evolution reaction (Figure 1c) and nickel nitride (Ni3N) precatalyst (Figure 1d). Furthermore, we propose a standardized protocol for assessing electrocatalysts under fluctuating and reverse currents, contributing to the understanding of catalyst deactivation. This initiative marks a significant advancement in AWE electrocatalysis research. Our goal is to establish an effective and straightforward protocol for evaluating and validating electrocatalysts in AWE, fostering accurate performance comparisons.

Active Electrode for Ammonia Direct Utilization and the Reactivity of Metal Component in High-Temperature SOFCs

We have been conducting the international collaboration study on “Green ammonia synthesis and utilization by solid electrolysis cells for maritime application” between Germany and Japan (term:2022-2024) under the SICORP program of Japan Science and Technology Agency (JST). The contributors of this project are AIST, Kyoto University, and Morimura SOFC Technology from Japan side and Fraunhofer IKTS and EDL from German side.The purpose of this project is to establish a new concept for energy loop based on the ammonia synthesis and utilization with maritime application. The task of Japan side is to make a new anode material for direct utilization of ammonia (cracking and oxidation of NH3 component) and degradation mechanism at anode. Addition of BaO into Ni/YSZ anode improved the decomposition rates of NH3 and anode performance in NH3 fuels. We have succeeded the decomposition rate of NH3 over 99.9 % with an optimum addition amounts of BaO into Ni-YSZ electrode. An excellent performance of BaO-added Ni-YSZ cermet electrode was observed with a stable performance over 80 hours operation.Preliminary analysis using secondary ion mass spectrometry (SIMS) indicated possible nickel nitride (NiN) formation in the Ni/YSZ substrate of commercial cells exposed to NH3 and possible degradation mechanisms are considered taking into account the thermodynamics and electrochemical oxidation.This presentation will show the recent progress of this research.

Engineering of Soft Urea Synthesized Ni3n Nanomaterials for Oxygen Evolution Reaction

Most active electrocatalysts include platinum-group metals (PGMs) and their alloys for electrochemical water splitting, but they are strongly limited by material cost and scarcity. [1] On the other hand, transition metal nitrides overcome this bottleneck and show high electrical conductivity, making them catalytically active for water electrolysis. The high conductivity is based on the incorporation of nitrogen atoms into the unit cell of metal, leading to their d-band contraction with electron density enhancement below Fermi level. [2] For instance, metallic nickel nitride (Ni3N) has been widely reported as a promising electrocatalyst material to accelerate the oxygen evolution reaction (OER) by in-situ forming a nickel (oxy)hydroxide [Ni(OH)2 and NiOOH] layer. [3] The Ni3N materials can be prepared by single step soft-urea route to obtain pure crystal phase [4] or a composite with carbon [5], which rises the following two research questions: 1. What are the optimal synthesis parameters of the soft-urea route to control the structure of Ni3N? 2. What is the relationship between structure and OER activity for Ni3N materials?In this work, we used the soft-urea route to prepare Ni3N materials by varying the ratios of NiCl2, urea and ethanol as precursor chemicals. The precursors were made into a gel by magnetic stirring having metal:urea ratio of 1:5, and then heated up to 400 ºC in a tubular furnace with constant flow of argon. The as-prepared Ni3N were then characterized by X-ray diffraction (XRD), elemental analysis (CHN), transmission electron microscopy (TEM) equipped with an energy-dispersive X-ray spectroscopy (EDX) and X-ray absorption spectroscopy (XAS).Based on the quantitative Rietveld refinement, the formation of pristine Ni3N materials is strongly controlled by the annealing temperature. In addition to the Ni3N phase, we observed the formation of the fcc Ni phase (0 – 10 wt.%) as a minor phase. The TEM images show individual particles of below 100 nm in size. Rotating disc electrode (RDE) technique was employed to establish the electrochemical OER activity of Ni3N materials by sweeping the potential from 1.3 to 1.8 VRHE at 10 mV s-1 in Ar-saturated 0.1 M KOH. Polycrystalline Ni and Ni particles are taken as reference materials. We observed an improvement of the OER activity as the overpotential at 10 mA cm-2 (normalized by the geometric surface area) reduced from 379 mV (poly-Ni) to 358 mV (Ni3N). Furthermore, in-situ XAS studies were performed to better understand the nature of the redox reactions between Ni species and the in-situ formation of nickel (oxy)hydroxide [Ni(OH)2 and NiOOH] layers before and during the OER as a function of the applied potential. Based on the in-situ XANES data, we correlated the structure of Ni3N/fcc-Ni/carbon composite with observed OER activity under alkaline conditions.To summarize, we were able to prepare a composite of Ni3N/fcc-Ni/carbon material with improved OER activity via soft-urea route. The in-situ formation of the layered nickel (oxy)hydroxide [Ni(OH)2 and NiOOH] layers as the catalytically active OER species were probed by in-situ XANES data.

Oxygen Vacancy-Enhanced Ni3N-CeO2/NF Nanoparticle Catalysts for Efficient and Stable Electrolytic Water Splitting.

Highly efficient and cost-effective electrocatalysts are of critical significance in the domain of water electrolysis. In this study, a Ni3N-CeO2/NF heterostructure is synthesized through a facile hydrothermal technique followed by a subsequent nitridation process. This catalyst is endowed with an abundance of oxygen vacancies, thereby conferring a richer array of active sites. Therefore, the catalyst demonstrates a markedly low overpotential of 350 mV for the Oxygen Evolution Reaction (OER) at 50 mA cm-2 and a low overpotential of 42 mV for the Hydrogen Evolution Reaction (HER) at 10 mA cm-2. Serving as a dual-function electrode, this electrocatalyst is employed in overall water splitting in alkaline environments, demonstrating impressive efficiency at a cell voltage of 1.52 V of 10 mA cm-2. The in situ Raman spectroscopic analysis demonstrates that cerium dioxide (CeO2) facilitates the rapid reconfiguration of oxygen vacancy-enriched nickel oxyhydroxide (NiOOH), thereby enhancing the OER performance. This investigation elucidates the catalytic role of CeO2 in augmenting the OER efficiency of nickel nitride (Ni3N) for water electrolysis, offering valuable insights for the design of high-performance bifunctional catalysts tailored for water splitting applications.

Nickel nitride-mediated nitric oxide generation for combating implant-associated infections

NiTi alloys are widely used in the fabrication of biomedical implants, and it is essential to endow them with selective antibacterial properties to avoid implant-associated infection. In this study, nickel nitride (Ni3N), as a promising new inorganic nitric oxide (NO) donor, was in situ constructed on the surface of NiTi alloys through a straightforward two-step plasma immersion ion implantation (PIII) strategy. Nickel sites were first exposed by physical bombardment with argon or metal plasma, followed by reaction with nitrogen plasma to form Ni3N. Ni3N can disrupt the transmembrane proton electrochemical gradient by capturing protons to produce ammonia species (NHx), resulting in the accumulation of reactive oxygen species (ROS) as a result of bacterial metabolic disruption. On the other hand, the generated NHx can further react with ROS to produce NO and reactive nitrogen species (RNS). As a result, the Ni3N films exhibited more than 99 % antibacterial efficiency against both gram-negative and gram-positive bacteria. They also demonstrated effective antibacterial properties in a rat subcutaneous implant model. In addition, the modified NiTi alloys exhibit good corrosion resistance and cytocompatibility. This study provides a green, safe, and inexpensive method for constructing metal nitride films on implant surfaces and offers new ideas for the clinical design and fabrication of novel antibacterial implants.

Charge distribution modulation of hollow flower-like tungsten doped nickel nitride for alkaline hydrogen oxidation

Exploring efficient nickel (Ni)-based catalysts for alkaline hydrogen oxidation reaction (HOR) to replace platinum group metal (PGM) is highly essential for the development of anion exchange membrane fuel cells. Nevertheless, the HOR activity of Ni is far away from PGM owing to the strong hydrogen adsorption. Herein, the tungsten-doped nickel nitride (W-Ni3N) with modulated local charge distribution and hollow flower structure is presented to improve the HOR performance. Mechanism studies reveal that W doping induces the redistribution of local charge around Ni sites due to the electron transfer from Ni to W, which strengthens the hydroxyl adsorption and simultaneously weakens hydrogen adsorption. Benefitting from the optimized adsorption of HOR intermediates and hollow flower structure, W-Ni3N exhibits improved intrinsic activity and mass activity, which are 1.7 and 10 times higher than that of pure Ni3N, respectively. This work presents a promising way to design cost-effective electrocatalysts by fine-tuning the electronic structure.

Mechanical properties of nickel nitrides under high pressures

The mechanical properties of previously known nickel nitrides, Ni6N-R-3, Ni3N-P6322, Ni3N-Cmcm, and Ni7N3-Pbca, were calculated from first principles using density functional theory at various pressures. Considered nickel nitrides are mechanically stable in the entire considered pressure ranges. It was shown that all phases are ductile and have low Vickers hardness values which are below the minimal criteria of hard materials, HV > 20 GPa. In addition, the fracture toughness was estimated.

Bi-cation incorporated Ni3N nanosheets boost water dissociation kinetics for enhanced alkaline hydrogen evolution activity.

Nickel nitride (Ni3N) is a promising electrocatalyst for the hydrogen evolution reaction (HER) owing to its excellent metallic features and has been demonstrated to exhibit considerable activity for water oxidation. However, its undesirable characteristics as an HER electrocatalyst due to its poor unfavourable d-band energy level significantly limit its water dissociation kinetics. Herein, the HER electrocatalytic activity of Ni3N was prominently enhanced via the simultaneous incorporation of bi-cations (vanadium (V) and iron (Fe), denoted as V-Fe-Ni3N). The optimized V-Fe-Ni3N displays impressive performance with an overpotential of 69 mV at 10 mA cm-2 and good stability in 1.0 M KOH, which is remarkably better than pristine Ni3N, V-doped Ni3N, and Fe-doped Ni3N and considerably closer to a commercial Pt/C catalyst. Based on density functional theory (DFT) studies, V and Fe atoms not only serve as active sites for promoting water dissociation kinetics but also tune the electronic structure of Ni3N to achieve optimized hydrogen adsorption capabilities. This work presents an inclusive understanding of the rational designing of high-performance transition metal nitride-based electrocatalysts for hydrogen production. Its electrocatalytic performance can be significantly enhanced by doping transition metal cations.

C(sp2)–S cross-coupling reactions with nickel, visible light, and mesoporous graphitic carbon nitride

Operationally simple photo-nickel C(sp2)–S cross-coupling with a reusable heterogeneous photocatalyst.

Highly efficient enzyme less glucose sensor based on cross-linked nitrogen-doped graphene aerogel incorporated with ytterbium oxide and decorated with nickel nitride nanoparticles

Highly efficient enzyme less glucose sensor based on cross-linked nitrogen-doped graphene aerogel incorporated with ytterbium oxide and decorated with nickel nitride nanoparticles

Understanding Degradation Behavior of Direct-Ammonia Solid Oxide Fuel Cells Using Nanoscale Analyses

Direct-ammonia solid oxide fuel cells (SOFCs) offer a cost-effective and efficient avenue for accelerating the use of hydrogen as a major energy vector. The effect of directly feeding ammonia as a fuel into SOFCs and their associated degradation behavior, however, needs to be fully understood in order to design robust cells capable of operating with good performance and durability at the required high temperatures for extended periods of time. In this study, we performed detailed analyses using advanced techniques such as high-resolution secondary ion mass spectrometry (SIMS) imaging and microscopy methods to examine the microstructural evolution and factors affecting nickel nitriding behavior of model Ni metal surfaces as well as Ni/yttria-stabilized zirconia (YSZ) cermet anodes directly exposed to ammonia as a function of temperature. The results show preferential formation of nickel nitride and presence of OH- species on Ni metal surfaces directly exposed to ammonia, as well as grain boundaries in the bulk which were not directly exposed to ammonia, suggesting enhanced ionic diffusion along these regions. Nickel nitriding is also accompanied by volume expansion which is considered to result in additional mechanical stress. Ni/YSZ cermet anodes, on the other hand, exhibit a significantly higher amount of nickel nitride formed preferentially in pore regions at lower temperatures, suggesting the possibility of nickel nitride decomposition occurring at higher temperatures. The results further suggest a correlation between nickel nitride formation and microstructural features of Ni/YSZ cermet anodes which influence gas diffusion properties. Lastly, a model for the degradation behavior of Ni/YSZ cermet anodes on the basis these results will be proposed and discussed.

Iron and cobalt co-doped nickel nitride in situ grown on carbon cloth for oxygen evolution reaction

It’s a great challenge to design an effective electrochemical water splitting catalyst, especially oxygen evolution reaction (OER) catalyst due to its slow kinetics. Transition metal nitride can be used as an electrocatalyst to reduce the energy barrier of the reaction because of its high conductivity and catalytic activity. Here, we synthesize iron and cobalt co-doped nickel nitride in situ grown on carbon cloth through an electrodeposition method followed by annealing under NH3. The catalyst exhibits an excellent performance which reaches a current density of 10 mA cm−2 at around 1.50 V.

Endowing nickel nitride with moderate amount of Ni0 species for the enhanced urea oxidation reaction reactivity

Urea oxidation reaction (UOR) can be used to rebalance the nitrogen cycle and decrease the overpotential of some renewable energy conversion reactions. Herein, nickel nitride was successfully synthesized via the nitridation process of β-Ni(OH)2 by urea. Nitriding temperature was utilized to regulate the yield of Ni0 species on the surface of nickel nitride. The as-synthesized Ni3N-400 with moderate amount of Ni0 species on the surface exhibits superior d band center position which facilitates the adsorption and desorption of intermediates, thus demonstrating excellent UOR reactivity (70 mA·cm−2 at 1.6 V vs. RHE), high selectivity, and superior stability, which is comparable to the most excellent catalysts ever reported. This work presents a feasible pathway to tailor the electro-catalytic reactivity of transition metal nitride.

Modification of Multi-Functional Composites by Using Particles with High Thermal Conductivity to Improve Heat Management and Electromagnetic Shielding Performance

Packaging materials with thermal management and electromagnetic protection are designed to develop miniaturized high-power airborne electronic equipment and meet the overall design requirements. In this study, graphene/paraffin composite material modified by high thermal conductivity particles is used to improve thermal conductivity, thermal management efficiency, and electromagnetic performance. Four kinds of high thermal conductivity particles including nickel, silver, copper, and hexagonal boron nitride were selected. Modified phase change material composite with carbon matrix was prepared by melt blending and pressure molding. Microstructure, thermal conductivity, latent heat, and electromagnetic properties were tested. Particles with different high thermal conductivity values could be uniformly distributed in the composite material by melt blending. Adding particles can improve the thermal conductivity of the composite to varying degrees, and copper and silver can also improve the electromagnetic shielding effectiveness of the composite. The composite material added with silver particles has the best modification effect, with a 92.3% increase in thermal conductivity and a 32.8% increase in shielding efficiency.

Preparation by two simple methods and characterization of Ni3N and use in the hydrogenation of isopropanol

The catalytic dehydrogenation of isopropanol is an important area of the catalytic process to produce fine chemicals and has important applications in heat pumps, fuel cells, and acetone production. Thereby, the catalytic liquid-phase dehydrogenation of isopropanol has gained attention over the last decades and has used a large variety of homogeneous and heterogeneous catalysts. In this paper, nickel nitride (Ni3N) nanoparticles, having a cubic structure, were successfully synthesized in simple and efficient methods either from nickel oxide or from nickel complex. The morphological and structural analyses of the obtained nanoparticles were performed by using powder X-ray diffraction (XRD) and scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM/EDX). At room temperature and under atmospheric pressure, the dehydrogenation test of isopropanol, using nickel nitride as a catalyst, revealed very high activity and better Hydrogen production.