Exsolved materials for CO_(2)reduction in high-temperature electrolysis cells

Electrochemical reduction of CO_(2)into valuable fuels and chemicals has become a contemporary research area,where the heterogeneous catalyst plays a critical role.Metal nanoparticles supported on oxides performing as active sites of electrochemical reactions have been the focus of intensive investigation.Here,we review the CO_(2)reduction with active materials prepared by exsolution.The fundamental of exsolution was summarized in terms of mechanism and models,materials,and driven forces.The advances in the exsolved materials used in hightemperature CO_(2)electrolysis were catalogued into tailored interfaces,synergistic effects on alloy particles,phase transition,reversibility and electrochemical switching.

Unraveling the relationship between Sr stoichiometry in Sr_(x)Fe_(1.5)Mo_(0.5)O_(6)-σ and its catalytic performance for high-temperature CO_(2) electrolysis

The solid oxide electrolytic cell(SOEC)is one of the most promising energy conversion and storage devices,which could convert CO_(2) to CO with high Faradaic efficiency and production rate.However,the lack of active and stable cathode materials impedes their practical applications.Here we focus on the promising perovskite oxide cathode material Sr_(2)Fe_(1.5)Mo_(0.5)O_(6)-σ,with the aim of understanding how A-atom stoichiometry and catalytic performance are linked.We find that increasing the strontium content in the perovskite improves the chemisorption of CO_(2) on its surface,forming a SrCO_(3) phase.This hinders the charge transfer and oxygen exchange processes.Simulta-neously,strontoium segregation to the cathode surface facilitates coking of the surface during CO_(2) electrolysis,which poisons the electrode.Consequently,a small number of Sr deficiencies are optimal for both electrochemical performance and long-term stability.Our results provide new insights for designing high-performance CO_(2) electrolysis cathode materials.

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.

Harness High-Temperature Thermal Energy via Elastic Thermoelectric Aerogels

Despite notable progress in thermoelectric(TE)materials and devices,developing TE aerogels with high-temperature resistance,superior TE performance and excellent elasticity to enable self-powered high-temperature monitoring/warning in industrial and wearable applications remains a great challenge.Herein,a highly elastic,flame-retardant and high-temperature-resistant TE aerogel,made of poly(3,4-ethylene dioxythiophene):poly(styrenesulfonate)/single-walled carbon nanotube(PEDOT:PSS/SWCNT)composites,has been fabricated,displaying attractive compression-induced power factor enhancement.The as-fabricated sensors with the aerogel can achieve accurately pressure stimuli detection and wide temperature range monitoring.Subsequently,a flexible TE generator is assembled,consisting of 25 aerogels connected in series,capable of delivering a maximum output power of 400μW when subjected to a temperature difference of 300 K.This demonstrates its outstanding high-temperature heat harvesting capability and promising application prospects for real-time temperature monitoring on industrial high-temperature pipelines.Moreover,the designed self-powered wearable sensing glove can realize precise wide-range temperature detection,high-temperature warning and accurate recognition of human hand gestures.The aerogel-based intelligent wearable sensing system developed for firefighters demonstrates the desired self-powered and highly sensitive high-temperature fire warning capability.Benefitting from these desirable properties,the elastic and high-temperature-resistant aerogels present various promising applications including self-powered high-temperature monitoring,industrial overheat warning,waste heat energy recycling and even wearable healthcare.

Enhanced High-Temperature Energy Storage Performance of All-Organic Composite Dielectric via Constructing Fiber-Re in forced Structure

Optimizing the high-temperature energy storage characteristics of energy storage dielectrics is of great significance for the development of pulsed power devices and power control systems.Selecting a polymer with a higher glass transition temperature(T_(g))as the matrix is one of the effective ways to increase the upper limit of the polymer operating temperature.However,current high-T_(g)polymers have limitations,and it is difficult to meet the demand for high-temperature energy storage dielectrics with only one polymer.For example,polyetherimide has high-energy storage efficiency,but low breakdown strength at high temperatures.Polyimide has high corona resistance,but low high-temperature energy storage efficiency.In this work,combining the advantages of two polymer,a novel high-T_(g)polymer fiber-reinforced microstructure is designed.Polyimide is designed as extremely fine fibers distributed in the composite dielectric,which will facilitate the reduction of high-temperature conductivity loss for polyimide.At the same time,due to the high-temperature resistance and corona resistance of polyimide,the high-temperature breakdown strength of the composite dielectric is enhanced.After the polyimide content with the best high-temperature energy storage characteristics is determined,molecular semiconductors(ITIC)are blended into the polyimide fibers to further improve the high-temperature efficiency.Ultimately,excellent high-temperature energy storage properties are obtained.The 0.25 vol%ITIC-polyimide/polyetherimide composite exhibits high-energy density and high discharge efficiency at 150℃(2.9 J cm^(-3),90%)and 180℃(2.16 J cm^(-3),90%).This work provides a scalable design idea for high-performance all-organic high-temperature energy storage dielectrics.

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.

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.

TiN/Fe_(2)N/C composite with stable and broadband high-temperature microwave absorption

Facing the complex variable high-temperature environment,electromagnetic wave(EMW)absorbing materials maintaining high stability and satisfying absorbing properties is essential.This study focused on the synthesis and EMW absorbing performance evaluation of TiN/Fe_(2)N/C composite materials,which were prepared using electrostatic spinning followed by a high-temperature nitridation process.The TiN/Fe_(2)N/C fibers constructed a well-developed conductive network that generates considerable conduction loss.The heterogeneous interfaces between different components generated a significant level of interfacial polarization.Thanks to the synergistic effect of stable dielectric loss and optimized impedance matching,the TiN/Fe_(2)N/C composite materials demonstrated excellent and stable absorption performance across a wide temperature range(293-453 K).Moreover,TiN/Fe_(2)N/C-15 achieved a minimum reflection loss(RL)of−48.01 dB and an effective absorption bandwidth(EAB)of 3.64 GHz at 2.1 mm and 373 K.This work provides new insights into the development of high-efficiency and stabile EMW absorbing materials under complex variable high-temperature conditions.

HZSM-5 zeolites undergoing the high-temperature process for boosting the bimolecular reaction in n-heptane catalytic cracking

High-temperature treatment is key to the preparation of zeolite catalysts.Herein,the effects of hightemperature treatment on the property and performance of HZSM-5 zeolites were studied in this work.X-Ray diffraction,N2physisorption,27Al magic angle spinning nuclear magnetic resonance(MAS NMR),and temperature-programmed desorption of ammonia results indicated that the hightemperature treatment at 650℃ hardly affected the inherent crystal and texture of HZSM-5zeolites but facilitated the conversion of framework Al to extra-framework Al,reducing the acid site and enhancing the acid strength.Moreover,the high-temperature treatment improved the performance of HZSM-5 zeolites in n-heptane catalytic cracking,promoting the conversion and light olefins yield while inhibiting coke formation.Based on the kinetic and mechanism analysis,the improvement of HZSM-5 performance caused by high-temperature treatment has been attributed to the formation of extra-framework Al,which enhanced the acid strength,facilitated the bimolecular reaction,and promoted the entropy change to overcome a higher energy barrier in n-heptane catalytic cracking.

Synergistic effect of Zr and Mo on precipitation and high-temperature properties of Al-Si-Cu-Mg alloys

This study focuses on finding a solution to the sharp decline in mechanical properties of Al-Si-Cu-Mg alloys due to rapid coarsening of traditional intermediate phases at high temperature.A new type of modified al oy,to be used in automobile engines at high temperatures,was prepared by adding Zr and Mo into Al-Si-Cu-Mg alloy.The synergistic effects of Zr and Mo on the microstructure evolution and high-temperature mechanical properties were studied.Results show that the addition of Zr and Mo generates a series of intermetallic phases dispersed in the alloy.They can improve the strength of the alloy by hindering dislocation movement and crack propagation.In addition,some nano-strengthened phases show coherent interfaces with the matrix and improve grain refinement.The addition of Mo greatly improves the heat resistance of the alloy.The extremely low diffusivity of Mo enables it to improve the thermal stability of the intermetallic phases,inhibit precipitation during aging,reduce the size of the precipitates,and improve the heat resistance of the alloy.

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.

A review of in-situ high-temperature characterizations for understanding the processes in metallurgical engineering

For the rational manipulation of the production quality of high-temperature metallurgical engineering,there are many challenges in understanding the processes involved because of the black box chemical/electrochemical reactors.To overcome this issue,various in-situ characterization methods have been recently developed to analyze the interactions between the composition,microstructure,and solid-liquid interface of high-temperature electrochemical electrodes and molten salts.In this review,recent progress of in-situ hightemperature characterization techniques is discussed to summarize the advances in understanding the processes in metallurgical engineering.In-situ high-temperature technologies and analytical methods mainly include synchrotron X-ray diffraction(s-XRD),laser scanning confocal microscopy,and X-ray computed microtomography(X-rayμ-CT),which are important platforms for analyzing the structure and morphology of the electrodes to reveal the complexity and variability of their interfaces.In addition,laser-induced breakdown spectroscopy,high-temperature Raman spectroscopy,and ultraviolet-visible absorption spectroscopy provide microscale characterizations of the composition and structure of molten salts.More importantly,the combination of X-rayμ-CT and s-XRD techniques enables the investigation of the chemical reaction mechanisms at the two-phase interface.Therefore,these in-situ methods are essential for analyzing the chemical/electrochemical kinetics of high-temperature reaction processes and establishing the theoretical principles for the efficient and stable operation of chemical/electrochemical metallurgical processes.

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.

Natural Lignin:A Sustainable and Cost-Effective Electrode Material for High-Temperature Na-Ion Battery

Rechargeable sodium-ion batteries usually suffer from accelerated electrode destruction at high temperatures and high synthesis costs of electrode materials.Therefore,it is highly desirable to explore novel organic electrodes considering their cost-effectiveness and large adaptability to volume changes.Herein,natural biomass,pristine lignin,is employed as the sodium-ion battery anodes,and their sodium storage performance is investigated at room temperature and 60℃.The lignin anodes exhibit excellent high-temperature sodium-ion battery performance.This mainly results from the generation of abundant reactive sites(C=O)due to the high temperature-induced homogeneous cleavage of the C_(β)-O bond in the lignin macromolecule.This work can inspire researchers to explore other natural organic materials for large-scale applications and high-value utilization in advanced energy storage devices.

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.