Recent advances and future prospects on Ni_(3)S_(2)-Based electrocatalysts for efficient alkaline water electrolysis

Green hydrogen(H_(2))produced by renewable energy powered alkaline water electrolysis is a promising alternative to fossil fuels due to its high energy density with zero-carbon emissions.However,efficient and economic H_(2) production by alkaline water electrolysis is hindered by the sluggish hydrogen evolution reaction(HER)and oxygen evolution reaction(OER).Therefore,it is imperative to design and fabricate high-active and low-cost non-precious metal catalysts to improve the HER and OER performance,which affects the energy efficiency of alkaline water electrolysis.Ni_(3)S_(2) with the heazlewoodite structure is a potential electrocatalyst with near-metal conductivity due to the Ni–Ni metal network.Here,the review comprehensively presents the recent progress of Ni_(3)S_(2)-based electrocatalysts for alkaline water electrocatalysis.Herein,the HER and OER mechanisms,performance evaluation criteria,preparation methods,and strategies for performance improvement of Ni_(3)S_(2)-based electrocatalysts are discussed.The challenges and perspectives are also analyzed.

A novel multi-channel porous structure facilitating mass transport towards highly efficient alkaline water electrolysis

An advantageous porous architecture of electrodes is pivotal in significantly enhancing alkaline water electrolysis(AWE)efficiency by optimizing the mass transport mechanisms.This effect becomes even more pronounced when aiming to achieve elevated current densities.Herein,we employed a rapid and scalable laser texturing process to craft novel multi-channel porous electrodes.Particularly,the obtained electrodes exhibit the lowest Tafel slope of 79 mV dec^(-1)(HER)and 49 mV dec^(-1)(OER).As anticipated,the alkaline electrolyzer(AEL)cell incorporating multi-channel porous electrodes(NP-LT30)exhibited a remarkable improvement in cell efficiency,with voltage drops(from 2.28 to 1.97 V)exceeding 300 mV under 1 A cm^(-1),compared to conventional perforated Ni plate electrodes.This enhancement mainly stemmed from the employed multi-channel porous structure,facilitating mass transport and bubble dynamics through an innovative convection mode,surpassing the traditional convection mode.Furthermore,the NP-LT30-based AEL cell demonstrated exceptional durability for 300 h under 1.0 A cm^(-2).This study underscores the capability of the novel multi-channel porous electrodes to expedite mass transport in practical AWE applications.

Epitaxially Grown Ru Clusters-Nickel Nitride Heterostructure Advances Water Electrolysis Kinetics in Alkaline and Seawater Media

The epitaxial heterostructure can be rationally designed based on the in situ growth of two compatible phases with lattice similarity,in which the modulated electronic states and tuned adsorption behaviors are conducive to the enhancement of electrocatalytic activity.Herein,theoretical simulations first disclose the charge transfer trend and reinforced inherent electron conduction around the epitaxial heterointerface between Ru clusters and Ni_(3)N substrate(cRu-Ni_(3)N),thus leading to the optimized adsorption behaviors and reduced activation energy barriers.Subsequently,the defectrich nanosheets with the epitaxially grown cRu-Ni_(3)N heterointerface are successfully constructed.Impressively,by virtue of the superiority of intrinsic activity and reaction kinetics,such unique epitaxial heterostructure exhibits remarkable bifunctional catalytic activity toward electrocatalytic OER(226 mV@20 mA cm^(−2))and HER(32 mV@10 mA cm^(−2))in alkaline media.Furthermore,it also shows great application prospect in alkaline freshwater and seawater splitting,as well as solar-to-hydrogen integrated system.This work could provide beneficial enlightenment for the establishment of advanced electrocatalysts with epitaxial heterointerfaces.

Ternary layered double hydroxide oxygen evolution reaction electrocatalyst for anion exchange membrane alkaline seawater electrolysis

Anion exchange membrane(AEM)water electrolyzers are promising energy devices for the production of clean hydrogen from seawater.However,the lack of active and robust electrocatalysts for the oxygen evolution reaction(OER)severely impedes the development of this technology.In this study,a ternary layered double hydroxide(LDH)OER electrocatalyst(NiFeCo-LDH)is developed for high-performance AEM alkaline seawater electrolyzers.The AEM alkaline seawater electrolyzer catalyzed by the NiFeCo LDH shows high seawater electrolysis performance(0.84 A/cm^(2)at 1.7 Vcell)and high hydrogen production efficiency(77.6%at 0.5 A/cm^(2)),thus outperforming an electrolyzer catalyzed by a benchmark IrO_(2)electrocatalyst.The NiFeCo-LDH electrocatalyst greatly improves the kinetics of the AEM alkaline seawater electrolyzer,consequently reducing its activation loss and leading to high performance.Based on the results,this NiFeCo-LDH-catalyzed AEM alkaline seawater electrolyzer can likely surpass the energy conversion targets of the US Department of Energy.

Handily etching nickel foams into catalyst-substrate fusion self‐stabilized electrodes toward industrial‐level water electrolysis

The key challenge of industrial water electrolysis is to design catalytic electrodes that can stabilize high current density with low power consumption(i.e.,overpotential),while industrial harsh conditions make the balance between electrode activity and stability more difficult.Here,we develop an efficient and durable electrode for water oxidation reaction(WOR),which yields a high current density of 1000 mA cm−2 at an overpotential of only 284 mV in 1M KOH at 25°C and shows robust stability even in 6M KOH strong alkali with an elevated temperature up to 80°C.This electrode is fabricated from a cheap nickel foam(NF)substrate through a simple one-step solution etching method,resulting in the growth of ultrafine phosphorus doped nickel-iron(oxy)hydroxide[P-(Ni,Fe)O_(x)H_(y)]nanoparticles embedded into abundant micropores on the surface,featured as a self-stabilized catalyst–substrate fusion electrode.Such self-stabilizing effect fastens highly active P-(Ni,Fe)O_(x)H_(y)species on conductive NF substrates with significant contribution to catalyst fixation and charge transfer,realizing a win–win tactics for WOR activity and durability at high current densities in harsh environments.This work affords a cost-effective WOR electrode that can well work at large current densities,suggestive of the rational design of catalyst electrodes toward industrial-scale water electrolysis.

Exciting lattice oxygen of nickel–iron bi-metal alkoxide for efficient electrochemical oxygen evolution reaction

High efficiency,cost-effective and durable electrocatalysts are of pivotal importance in energy conversion and storage systems.The electro-oxidation of water to oxygen plays a crucial role in such energy conversion technologies.Herein,we report a robust method for the synthesis of a bimetallic alkoxide for efficient oxygen evolution reaction(OER)for alkaline electrolysis,which yields current density of 10 mA cm^(-2)at an overpotential of 215 mV in 0.1 M KOH electrolyte.The catalyst demonstrates an excellent durability for more than 540 h operation with negligible degradation in activity.Raman spectra revealed that the catalyst underwent structure reconstruction during OER,evolving into oxyhydroxide,which was the active site proceeding OER in alkaline electrolyte.In-situ synchrotron X-ray absorption experiment combined with density functional theory calculation suggests a lattice oxygen involved electrocatalytic reaction mechanism for the in-situ generated nickel–iron bimetal-oxyhydroxide catalyst.This mechanism together with the synergy between nickel and iron are responsible for the enhanced catalytic activity and durability.These findings provide promising strategies for the rational design of nonnoble metal OER catalysts.

Tailoring synergetic catalytic interface of VPO/Ni_(2)P to boost hydrogen evolution under alkaline conditions

Design of the catalyst for efficient water dissociation and hydrogen recombination is paramount in enhancement of the alkaline water electrolysis kinetics.Herein,we reported a delicate hierarchical(VO)_(2) P_(2)O_(7)-Ni_(2) P@NF(VPO-Ni_(2) P@NF)hybrid catalyst that operated efficiently in alkaline media.The VPO and Ni_(2) P respectively act as the water dissociation promoter and the hydrogen recombination center,which synergistically propel water adsorption/dissociation and H intermediates recombination.The resulting synergistic interfaces between VPO and Ni_(2) P are verified to afford the catalyst an outstanding performance for hydrogen evolution reaction in alkaline media with an overpotential of 154 mV at 10 mA cm^(-2),Tafel slope of 65 mV dec^(-1),and remarkable durability.Furthermore,the catalyst presents the potential for overall water splitting.This work may shed fresh light on the high-performance electrocatalyst design and the application of VPO on water electrolysis.

Electrochemical deposited amorphous FeNi hydroxide electrode for oxygen evolution reaction

The electrodeposition approach is significant in electrode fabrication for practical application.Herein,the electrodeposited amorphous NiFe hydroxide species for oxygen evolution reaction (OER) in water splitting reaction is demonstrated by revealing the synergistic effect influenced by the support electrode of Fe and Ni foil and the contents of Fe and Ni in the electrolyte.All the electrodeposited samples have an amorphous structure and similar profiles of binding energy and chemical states for Fe and Ni as characterized by the spectroscopic techniques.While the support effect and Fe/Ni synergistic effect are indeed observed for the varied catalytic performances observed for the different electrodes;the Ni foil supported catalyst exhibits much higher performance than that of the Fe foil supported catalyst,and the different redox potentials of Ni species in the different Fe/Ni electrode resulting from the Fe–Ni synergism are observed in the cyclic voltammetry curve analysis.The surface roughness and the electrochemical surface area are also influenced by the support effect and the Fe/Ni ratio in the plating electrolyte.The optimal electrode shows a very low overpotential of~200 mV to reach 10 mA cm^(-2),and very high catalytic stability by the consecutive cyclic voltammetry measurements and 20 h stability test.Though it has the largest electrochemical surface area,the highest catalytic efficiency for these active sites is also indicated by the specific activity and turnover frequency polarization curves.The current work shows the effective experience for the electrodeposited Fe/Ni based catalysts in large-scale fabrication,which can be more practical for hydrogen generation in the alkaline water electrolysis.

Insight into the boosted activity of TiO2–CoP composites for hydrogen evolution reaction:Accelerated mass transfer,optimized interfacial water,and promoted intrinsic activity

The use of abundant elements in the earth as electrocatalytic hydrogen production catalysts is of great significance for hydrogen energy cycling.Herein,we report amorphous TiO_(2)-decorated CoP/NF(TiO_(2)–CoP/NF)as an excellent electrocatalyst for alkaline hydrogen evolution reaction(HER).The welldispersed amorphous TiO_(2)on nanoneedle-like CoP arrays preserves the crystal structure of CoP and changes its electronic structure by interfacial charge transfer.Compared to CoP/NF catalyst,the Ti O_(2)–CoP/NF composite catalyst exhibits high HER activity with an overpotential of 61 mV at 10 mA cm^(-2)and high stability.Importantly,it almost maintains the Volmer step as a rate-determining step(RDS)and the Tafel slope at a wide cathodic potential range showing the fast kinetics under large polarization regions.Theoretical simulations reveal that the combination of TiO_(2)and CoP selectively accelerates the hydrated K+diffusion,regulates the interfacial water orientation to adapt to the subsequent smooth water dissociation,and optimizes*H adsorption/H_(2)desorption.The strengthened coupling of HER multi-scale-processes on transition metal compound composites catalysts is the underlying mechanism for improving HER activity.

Prognostics and health management of alkaline water electrolyzer: Techno-economic analysis considering replacement moment

Recently,considerable attention has been paid to the installation of renewable energy capacity to mitigate global CO_(2) emissions.H_(2) produced using water electrolysis and renewable energy is regarded as a clean energy carrier,generating electricity without CO_(2) emissions,called‘Green H 2’.In this paper,a prognostics and health man-agement model for an alkaline water electrolyzer was proposed to predict the load voltage on the electrolyzer to obtain the state of health information.The prognostics and health management model was developed by training historical operating data via machine learning models,support vector machine and gaussian process regression,showing the root mean square error of 1.28×10^(−3) and 8.03×10^(−6).In addition,a techno-economic analysis was performed for a green H_(2) production system,composed of 1 MW of photovoltaic plant and 1 MW of alkaline water electrolyzer,to provide economic insights and feasibility of the system.A levelized cost of H_(2) of$6.89 kgH_(2)−1 was calculated and the potential to reach the levelized cost of H_(2) from steam methane reforming with carbon capture and storage was shown by considering the learning rate of the photovoltaic module and elec-trolyzer.Finally,the replacement of the alkaline water electrolyzer at around 10 years was preferred to increase the net present value from the green H_(2) production system when capital expenditure and replacement cost are low enough.

Introducing sulfur to nickel-iron selenide for high-efficiency alkaline seawater electrolysis

Seawater electrolysis is an effective way to obtain hydrogen(H_(2))in a sustainable manner.However,the lack of electrocatalysts with high activity,stability,and selectivity for oxygen evolution reaction(OER)severely hinders the development of seawater electrolysis technology.Herein,sulfur-doped nickel-iron selenide nanosheets(S-NiFeSe_(2))were prepared by an ion-exchange strategy and served as highly active OER electrocatalyst for alkaline seawater electrolysis.The overpotential is 367 m V,and it can run stably for over 50 h at 100 m A cm^(-2).Excitingly,the S-NiFeSe_(2)||Pt/C pair exhibits cell voltage of 1.54 V at 10 m A cm^(-2)under alkaline seawater conditions,which can run smoothly for 100 h without decay,and the efficiency of electricity-tohydrogen(ETH)energy conversion reaches more than 80%.Such electrode,with abundant accessible reactive sites and good corrosion resistance,is a good candidate for seawater electrolysis.Moreover,density functional theory calculations reveal that the surface sulfur atoms can activate the adjacent Ni sites and decrease the free energy changes of the associated intermediates at the adjacent Ni sites for OER,and the step of~*OH→~*O is the potential rate-limiting step.In this work,the true reactive site in nickel-iron selenides is the Ni sites,but not the Fe sites as commonly believed.

Electrodeposition of self-supported NiMo amorphous coating as an efficient and stable catalyst for hydrogen evolution reaction

NiMo-based materials have been identified as potential candidates of Pt/C electrocatalysts for hydrogen evolution reaction(HER)due to appropriate binding energy to hydrogen,and good resistance to corrosive environments.However,little work has been carried out to enhance the catalytic performance in large-scale water-alkali electrolysis.The NoMo amorphous coating,as a highefficient and cost-effective catalyst toward HER,was synthesized by a facile electrodeposition strategy in this study.The effects of the pH value of electrolyte on the structure and HER activity of NiMo coating were investigated.The as-prepared NiMo_((pH10))exhibited the highest HER activity with overpotentials of 63.9 and 157.1 mV(vs.RHE,with 80%potential drop due to electrical resistance(iR)compensation)at the current density of-10 mA·cm^(-2)and-100 mA·cm^(-2).This NiMo_((pH10))coating also had excellent long-term durability of up to100 h stable operation under the constant current density of-100 mA·cm^(-2).The rapid HER kinetics and outstanding endurance can be ascribed to the NiMo compact coating with amorphous structures as well as good contact between NiMo coating and Ni foam substrate,endowing it grand feasibility in practical industrial applications.

The influence of manufacturing parameters and adding support layer on the properties of Zirfon separators

The composite separator comprising of polysulfone and zirconia was prepared by phase inversion precipitation technique. The influence of manufacturing parameters on its properties was investigated, and the results show that the manufacturing parameters affect the ionic resistance and maximum pore size significantly. A modified composite separator with a support layer was prepared to enhance the tensile strength of separator. By adding support layer, the tensile strength of the separator increases from 1.85MPa to 13.66MPa. In order to evaluate the practical applicability of the composite separator, a small-scale industrial electrolytic experiment was conducted to investigate the changes of cell voltage, gas purity and separator stability. The results show that the modified composite separator has a smaller cell voltage and a higher H2 purity than the asbestos separator, and are promising material for industrial hydrogen production.