Comparative Study on Application of Bimetallic Pt-Based Alloy Electrocatalysts in Advanced Chlor-Alkali Electrolysis

Application of an oxygen-depolarized cathode will contribute to energy saving in chlor-alkali electrolysis. For this purpose, the development of high-performance cathode with the best electrocatalyst is essential. Using bimetallic Pt-based alloy electrocatalysts including PtPd and PtAg carbon-supported in oxygen-depolarized cathode chlor-alkali cell has been shown to have the high cell performance. This study presents application of PtRu carbon supported electrocatalyst oxygen-depolarized cathode and performance comparison of cells with carbon-supported PtRu, PtPd and PtAg electrocatalysts cathodes using the same DSA-Cl2 anode. Results show that there are quite similarity between the effects of various factors on the caustic current efficiency (CCE) in a zero-gap oxygen-depolarized chlor-alkali cells employing carbon-supported PtPd, PtRu and PtAg electrocatalysts. Besides, it seems that the PtPd/C electrocatalyst cathode has relatively higher performance than the other cathodes with PtAg/C and PtRu/C electrocatalysts in zero-gap chlor-alkali cells.

Development of advanced anion exchange membrane from the view of the performance of water electrolysis cell

Green hydrogen produced by water electrolysis combined with renewable energy is a promising alternative to fossil fuels due to its high energy density with zero-carbon emissions.Among water electrolysis technologies,the anion exchange membrane(AEM) water electrolysis has gained intensive attention and is considered as the next-generation emerging technology due to its potential advantages,such as the use of low-cost non-noble metal catalysts,the relatively mature stack assembly process,etc.However,the AEM water electrolyzer is still in the early development stage of the kW-level stack,which is mainly attributed to severe performance decay caused by the core component,i.e.,AEM.Here,the review comprehensively presents the recent progress of advanced AEM from the view of the performance of water electrolysis cells.Herein,fundamental principles and critical components of AEM water electrolyzers are introduced,and work conditions of AEM water electrolyzers and AEM performance improvement strategies are discussed.The challenges and perspectives are also analyzed.

Advancements,strategies,and prospects of solid oxide electrolysis cells(SOECs):Towards enhanced performance and large-scale sustainable hydrogen production

Solid oxide electrolysis cells(SOECs)represent a crucial stride toward sustainable hydrogen generation,and this review explores their current scientific challenges,significant advancements,and potential for large-scale hydrogen production.In SOEC technology,the application of innovative fabrication tech-niques,doping strategies,and advanced materials has enhanced the performance and durability of these systems,although degradation challenges persist,implicating the prime focus for future advancements.Here we provide in-depth analysis of the recent developments in SOEC technology,including Oxygen-SOECs,Proton-SOECs,and Hybrid-SOECs.Specifically,Hybrid-SOECs,with their mixed ionic conducting electrolytes,demonstrate superior efficiency and the concurrent production of hydrogen and oxygen.Coupled with the capacity to harness waste heat,these advancements in SOEC technology present signif-icant promise for pilot-scale applications in industries.The review also highlights remarkable achieve-ments and potential reductions in capital expenditure for future SOEC systems,while elaborating on the micro and macro aspects of sOECs with an emphasis on ongoing research for optimization and scal-ability.It concludes with the potential of SOEC technology to meet various industrial energy needs and its significant contribution considering the key research priorities to tackle the global energy demands,ful-fillment,and decarbonization efforts.

A robust & weak-nucleophilicity electrocatalyst with an inert response for chlorine ion oxidation in large-current seawater electrolysis

Seawater splitting into hydrogen,a promising technology,is seriously limited by the durability and tolerance of electrocatalysts for chlorine ions in seawater at large current densities due to chloride oxidation and corrosion.Here,we present a robust and weak-nucleophilicity nickel-iron hydroxide electrocatalyst with excellent selectivity for oxygen evolution and an inert response for chlorine ion oxidation which are key and highly desired for efficient seawater electrolysis.Such a weak-nucleophilicity electrocatalyst can well match with strong-nucleophilicity OH-compared with the weak-nucleophilicity Cl^(-),resultantly,the oxidation of OH-in electrolyte can be more easily achieved relative to chlorine ion oxidation,confirmed by ethylenediaminetetraacetic acid disodium probing test.Further,no strongly corrosive hypochlorite is produced when the operating voltage reaches about 2.1 V vs.RHE,a potential that is far beyond the thermodynamic potential of chlorine ion oxidatio n.This concept and approach to reasonably designing weaknucleophilicity electrocatalysts that can greatly avoid chlorine ion oxidation under alkaline seawater environments can push forward the seawater electrolysis technology and also accelerate the development of green hydrogen technique.

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.

Low carbon alcohol fuel electrolysis of hydrogen generation catalyzed by a novel and effective Pt–CoTe/C bifunctional catalyst system

Low carbon alcohol fuels electrolysis under ambient conditions is promising for green hydrogen generation instead of the traditional alcohol fuels steam reforming technique,and highly efficient bifunctional catalysts for membrane electrode fabrication are required to drive the electrolysis reactions.Herein,the efficient catalytic promotion effect of a novel catalyst promoter,CoTe,on Pt is demonstrated for low carbon alcohol fuels of methanol and ethanol electrolysis for hydrogen generation.Experimental and density functional theory calculation results indicate that the optimized electronic structure of Pt–CoTe/C resulting from the synergetic effect between Pt and CoTe further regulates the adsorption energies of CO and H*that enhances the catalytic ability for methanol and ethanol electrolysis.Moreover,the good water activation ability of CoTe and the strong electronic effect of Pt and CoTe increased the tolerance ability to the poisoning species as demonstrated by the CO-stripping technique.The high catalytic kinetics and stability,as well as the promotion effect,were also carefully discussed.Specifically,71.9%and 75.5%of the initial peak current density was maintained after 1000 CV cycles in acid electrolyte for methanol and ethanol oxidation;and a low overpotential of 30 and 35 mV was required to drive the hydrogen evolution reaction in methanol and ethanol solution at the current density of 10 mA cm^(-2).In the two-electrode system for alcohol fuels electrolysis,using the optimal Pt–CoTe/C catalyst as bi-functional catalysts,the cell potential of 0.66 V(0.67 V)was required to achieve 10 mA cm^(-2) for methanol(ethanol)electrolysis,much smaller than that of water electrolysis(1.76 V).The current study offers a novel platform for hydrogen generation via low carbon alcohol fuel electrolysis,and the result is helpful to the catalysis mechanism understanding of Pt assisted by the novel promoter.

Electrochemical reconstruction of non-noble metal-based heterostructure nanorod arrays electrodes for highly stable anion exchange membrane seawater electrolysis

Direct seawater electrolysis for hydrogen production has been regarded as a viable route to utilize surplus renewable energy and address the climate crisis.However,the harsh electrochemical environment of seawater,particularly the presence of aggressive Cl^(-),has been proven to be prone to parasitic chloride ion oxidation and corrosion reactions,thus restricting seawater electrolyzer lifetime.Herein,hierarchical structure(Ni,Fe)O(OH)@NiCoS nanorod arrays(NAs)catalysts with heterointerfaces and localized oxygen vacancies were synthesized at nickel foam substrates via the combination of hydrothermal and annealing methods to boost seawater dissociation.The hiera rchical nanostructure of NiCoS NAs enhanced electrode charge transfer rate and active surface area to accelerate oxygen evolution reaction(OER)and generated sulfate gradient layers to repulsive aggressive Cl^(-).The fabricated heterostructure and vacancies of(Ni,Fe)O(OH)tuned catalyst electronic structure into an electrophilic state to enhance the binding affinity of hydroxyl intermediates and facilitate the structural transformation into amorphousγ-NiFeOOH for promoting OER.Furthermore,through operando electrochemistry techniques,we found that theγ-NiFeOOH possessing an unsaturated coordination environment and lattice-oxygen-participated OER mechanism can minimize electrode Cl^(-)corrosion enabled by stabilizing the adsorption of OH*intermediates,making it one of the best OER catalysts in the seawater medium reported to date.Consequently,these catalysts can deliver current densities of 100 and 500 mA cm-2for boosting OER at minimal overpotentials of 245and 316 mV,respectively,and thus prevent chloride ion oxidation simultaneously.Impressively,a highly stable anion exchange membrane(AEM)seawater electrolyzer based on the non-noble metal heterostructure electrodes reached a record low degradation rate under 100μV h-1at constant industrial current densities of 400 and 600 mA cm-2over 300 h,which exhibits a promising future for the nonprecious and stable AEMWE in the direct seawater electrolysis industry.

Classification and technical target of water electrolysis for hydrogen production

Continuous efforts are underway to reduce carbon emissions worldwide in response to global climate change.Water electrolysis technology,in conjunction with renewable energy,is considered the most feasible hydrogen production technology based on the viable possibility of large-scale hydrogen production and the zero-carbon-emission nature of the process.However,for hydrogen produced via water electrolysis systems to be utilized in various fields in practice,the unit cost of hydrogen production must be reduced to$1/kg H_(2).To achieve this unit cost,technical targets for water electrolysis have been suggested regarding components in the system.In this paper,the types of water electrolysis systems and the limitations of water electrolysis system components are explained.We suggest guideline with recent trend for achieving this technical target and insights for the potential utilization of water electrolysis technology.

Covalently Bonded Ni Sites in Black Phosphorene with Electron Redistribution for Efficient Metal‑Lightweighted Water Electrolysis

The metal-lightweighted electrocatalysts for water splitting are highly desired for sustainable and economic hydrogen energy deployments,but challengeable.In this work,a low-content Ni-functionalized approach triggers the high capability of black phosphorene(BP)with hydrogen and oxygen evolution reaction(HER/OER)bifunctionality.Through a facile in situ electro-exfoliation route,the ionized Ni sites are covalently functionalized in BP nanosheets with electron redistribution and controllable metal contents.It is found that the as-fabricated Ni-BP electrocatalysts can drive the water splitting with much enhanced HER and OER activities.In 1.0 M KOH electrolyte,the optimized 1.5 wt%Nifunctionalized BP nanosheets have readily achieved low overpotentials of 136 mV for HER and 230 mV for OER at 10 mA cm^(−2).Moreover,the covalently bonding between Ni and P has also strengthened the catalytic stability of the Ni-functionalized BP electrocatalyst,stably delivering the overall water splitting for 50 h at 20 mA cm^(−2).Theoretical calculations have revealed that Ni–P covalent binding can regulate the electronic structure and optimize the reaction energy barrier to improve the catalytic activity effectively.This work confirms that Ni-functionalized BP is a suitable candidate for electrocatalytic overall water splitting,and provides effective strategies for constructing metal-lightweighted economic electrocatalysts.

Linear paired electrolysis of furfural to furoic acid at both anode and cathode in a multiple redox mediated system

Implementing a new energy-saving electrochemical synthesis system with high commercial value is a strategy of the sustainable development for upgrading the bulk chemicals preparation technology in the future.Here,we report a multiple redox-mediated linear paired electrolysis system,combining the hydrogen peroxide mediated cathode process with the I2 mediated anode process,and realize the conversion of furfural to furoic acid in both side of the dividedflow cell simultaneously.By reasonably controlling the cathode potential,the undesired water splitting reaction and furfural reduction side reactions are avoided.Under the galvanostatic electrolysis,the two-mediated electrode processes have good compatibility,which reduce the energy consumption by about 22%while improving the electronic efficiency by about 125%.This system provides a green electrochemical synthesis route with commercial prospects.

Asymmetric configuration activating lattice oxygen via weakening d-p orbital hybridization for efficient C/N separation in urea overall electrolysis

Urea oxidation reaction(UOR)is proposed as an exemplary half-reaction in renewable energy applications because of its low thermodynamical potential.However,challenges persist due to sluggish reaction kinetics and complex by-products separation.To this end,we introduce the lattice oxygen oxidation mechanism(LOM),propelling a novel UOR route using a modified CoFe layered double hydroxide(LDH)catalyst termed CFRO-7.Theoretical calculations and in-situ characterizations highlight the activated lattice oxygen(O_(L))within CFRO-7 as pivotal sites for UOR,optimizing the reaction pathway and accelerating the kinetics.For the urea overall electrolysis application,the LOM route only requires a low voltage of 1.54 V to offer a high current of 100 mA cm^(-2) for long-term utilization(>48 h).Importantly,the by-product NCO^(-)−is significantly suppressed,while the CO_(2)2/N_(2) separation is efficiently achieved.This work proposed a pioneering paradigm,invoking the LOM pathway in urea electrolysis to expedite reaction dynamics and enhance product selectivity.

Rapid prediction of flow and concentration fields in solid-liquid suspensions of slurry electrolysis tanks

Slurry electrolysis(SE),as a hydrometallurgical process,has the characteristic of a multitank series connection,which leads to various stirring conditions and a complex solid suspension state.The computational fluid dynamics(CFD),which requires high computing resources,and a combination with machine learning was proposed to construct a rapid prediction model for the liquid flow and solid concentration fields in a SE tank.Through scientific selection of calculation samples via orthogonal experiments,a comprehensive dataset covering a wide range of conditions was established while effectively reducing the number of simulations and providing reasonable weights for each factor.Then,a prediction model of the SE tank was constructed using the K-nearest neighbor algorithm.The results show that with the increase in levels of orthogonal experiments,the prediction accuracy of the model improved remarkably.The model established with four factors and nine levels can accurately predict the flow and concentration fields,and the regression coefficients of average velocity and solid concentration were 0.926 and 0.937,respectively.Compared with traditional CFD,the response time of field information prediction in this model was reduced from 75 h to 20 s,which solves the problem of serious lag in CFD applied alone to actual production and meets real-time production control requirements.

Generating highly active oxide-phosphide heterostructure through interfacial engineering to break the energy scaling relation toward urea-assisted natural seawater electrolysis

Urea-assisted natural seawater electrolysis is an emerging technology that is effective for grid-scale carbon-neutral hydrogen mass production yet challenging.Circumventing scaling relations is an effective strategy to break through the bottleneck of natural seawater splitting.Herein,by DFT calculation,we demonstrated that the interface boundaries between Ni_(2)P and MoO_(2) play an essential role in the selfrelaxation of the Ni-O interfacial bond,effectively modulating a coordination number of intermediates to control independently their adsorption-free energy,thus circumventing the adsorption-energy scaling relation.Following this conceptual model,a well-defined 3D F-doped Ni_(2)P-MoO_(2) heterostructure microrod array was rationally designed via an interfacial engineering strategy toward urea-assisted natural seawater electrolysis.As a result,the F-Ni_(2)P-MoO_(2) exhibits eminently active and durable bifunctional catalysts for both HER and OER in acid,alkaline,and alkaline sea water-based electrolytes.By in-situ analysis,we found that a thin amorphous layer of NiOOH,which is evolved from the Ni_(2)P during anodic reaction,is real catalytic active sites for the OER and UOR processes.Remarkable,such electrode-assembled urea-assisted natural seawater electrolyzer requires low voltages of 1.29 and 1.75 V to drive 10 and600 mA cm^(-2)and demonstrates superior durability by operating continuously for 100 h at 100 mA cm^(-2),beyond commercial Pt/C||RuO_(2) and most previous reports.

Manipulating d-d orbital hybridization induced by Mo-doped Co_(9)S_(8) nanorod arrays for high-efficiency water electrolysis

Precisely refining the electronic structure of electrocatalysts represents a powerful approach to further optimize the electrocatalytic performance.Herein,we demonstrate an ingenious d-d orbital hybridization concept to construct Mo-doped Co_(9)S_(8) nanorod arrays aligned on carbon cloth(CC)substrate(abbreviated as Mo-Co_(9)S_(8)@CC hereafter)as a high-efficiency bifunctional electrocatalyst toward water electrolysis.It has experimentally and theoretically validated that the 4d-3d orbital coupling between Mo dopant and Co site can effectively optimize the H_(2)O activation energy and lower H^(*)adsorption energy barrier,thereby leading to enhanced hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)activities.Thanks to the unique electronic and geometrical advantages,the optimized Mo-Co_(9)S_(8)@CC with appropriate Mo content exhibits outstanding bifunctional performance in alkaline solution,with the overpotentials of 75 and 234 mV for the delivery of a current density of 10 mA cm^(-2),small Tafel slopes of 53.8 and 39.9 mV dec~(-1)and long-term stabilities for at least 32 and 30 h for HER and OER,respectively.More impressively,a water splitting electrolylzer assembled by the self-supported Mo-Co_(9)S_(8)@CC electrode requires a low cell voltage of 1.53 V at 10 mA cm^(-2)and shows excellent stability and splendid reversibility,demonstrating a huge potential for affordable and scalable electrochemical H_(2) production.The innovational orbital hybridization strategy for electronic regulation herein provides an inspirable avenue for developing progressive electrocatalysts toward new energy systems.

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.

Practical operating flexibility of a bifunctional freestanding membrane for efficient anion exchange membrane water electrolysis across all current ranges

This study explores a symmetric configuration approach in anion exchange membrane(AEM)water electrolysis,focusing on overcoming adaptability challenges in dynamic conditions.Here,a rapid and mild synthesis technique for fabricating fibrous membrane-type catalyst electrodes is developed.Our method leverages the contrasting oxidation states between the sulfur-doped NiFe(OH)2 shell and the metallic Ni core,as revealed by electron energy loss spectroscopy.Theoretical evaluations confirm that the S–NiFe(OH)_(2) active sites optimize free energy for alkaline water electrolysis intermediates.This technique bypasses traditional energy-intensive processes,achieving superior bifunctional activity beyond current benchmarks.The symmetric AEM water electrolyzer demonstrates a current density of 2 A cm^(-2) at 1.78 V at 60℃ in 1 M KOH electrolyte and also sustains ampere-scale water electrolysis below 2.0 V for 140 h even in ambient conditions.These results highlight the system's operational flexibility and structural stability,marking a significant advance-ment in AEM water electrolysis technology.

Enhancing selectivity in acidic CO_(2) electrolysis:Cation effects and catalyst innovation

The electrochemical reduction of CO_(2)(eCO_(2)R)under ambient conditions is crucial for reducing carbon emissions and achieving carbon neutrality.Despite progress with alkaline and neutral electrolytes,their efficiency is limited by(bi)carbonates formation.Acidic media have emerged as a solution,addressing the(bi)carbonates challenge but introducing the issue of the hydrogen evolu-tion reaction(HER),which reduces CO_(2) conversion efficiency in acidic environments.This review focuses on enhancing the selectivity of acidic CO_(2) electrolysis.It commences with an overview of the latest advancements in acidic CO_(2) electrolysis,focusing on product selectivity and electrocatalytic activity enhancements.It then delves into the critical factors shaping selectivity in acidic CO_(2) electrolysis,with a special emphasis on the influence of cations and catalyst design.Finally,the research challenges and personal perspectives of acidic CO_(2) electrolysis are suggested.

Enhanced recovery of high-purity Fe powder from iron-rich electrolytic manganese residue by slurry electrolysis

Iron-rich electrolytic manganese residue(IREMR)is an industrial waste produced during the processing of electrolytic metal manganese,and it contains certain amounts of Fe and Mn resources and other heavy metals.In this study,the slurry electrolysis technique was used to recover high-purity Fe powder from IREMR.The effects of IREMR and H2SO4 mass ratio,current density,reaction temper-ature,and electrolytic time on the leaching and current efficiencies of Fe were studied.According to the results,high-purity Fe powder can be recovered from the cathode plate,and the slurry electrolyte can be recycled.The leaching efficiency,current efficiency,and purity of Fe reached 92.58%,80.65%,and 98.72wt%,respectively,at a 1:2.5 mass ratio of H2SO4 and IREMR,reaction temperature of 60℃,electric current density of 30 mA/cm^(2),and reaction time of 8 h.In addition,vibrating sample magnetometer(VSM)analysis showed that the coercivity of electrolytic iron powder was 54.5 A/m,which reached the advanced magnetic grade of electrical pure-iron powder(DT4A coercivity standard).The slurry electrolytic method provides fundamental support for the industrial application of Fe resource recovery in IRMER.

Novel Perovskite Oxide Hybrid Nanofibers Embedded with Nanocatalysts for Highly Efficient and Durable Electrodes in Direct CO_(2) Electrolysis

The unique characteristics of nanofibers in rational electrode design enable effec-tive utilization and maximizing material properties for achieving highly efficient and sustainable CO_(2) reduction reactions( CO_(2)RRs)in solid oxide elec-trolysis cells(SOECs).However,practical appli-cation of nanofiber-based electrodes faces chal-lenges in establishing sufficient interfacial contact and adhesion with the dense electrolyte.To tackle this challenge,a novel hybrid nanofiber electrode,La_(0.6)Sr_(0.4)Co_(0.15)Fe_(0.8)Pd_(0.05)O_(3-δ)(H-LSCFP),is developed by strategically incorporating low aspect ratio crushed LSCFP nanofibers into the excess porous interspace of a high aspect ratio LSCFP nanofiber framework synthesized via electrospinning technique.After consecutive treatment in 100% H_(2) and CO_(2) at 700°C,LSCFP nanofibers form a perovskite phase with in situ exsolved Co metal nanocatalysts and a high concentration of oxygen species on the surface,enhancing CO_(2) adsorption.The SOEC with the H-LSCFP electrode yielded an outstanding current density of 2.2 A cm^(-2) in CO_(2) at 800°C and 1.5 V,setting a new benchmark among reported nanofiber-based electrodes.Digital twinning of the H-LSCFP reveals improved contact adhesion and increased reaction sites for CO_(2)RR.The present work demonstrates a highly catalytically active and robust nanofiber-based fuel electrode with a hybrid structure,paving the way for further advancements and nanofiber applications in CO_(2)-SOECs.

CO_(2) electrolysis to formic acid for carbon neutralization

To avoid carbonate precipitation for CO_(2) electrolysis,developing CO_(2) conversion in an acid electrolyte is viewed as an ultimately challenging technology.In Nature,Xia et al.recently explored a proton-exchange membrane system for reducing CO_(2) to formic acid with a Pb±Pb SO_(4) composite catalyst derived from waste lead-acid batteries based on the lattice carbon activation mechanism.Up to 93%Faradaic efficiency was realized when formic acid was produced by this technology.