PPMG-based composite electrolytes were fabricated via the solution method using the polyvinyl alcohol and polyvinylpyrrolidone blend reinforced with various contents of sulfonated inorganic filler.Sulfuric acid was em...PPMG-based composite electrolytes were fabricated via the solution method using the polyvinyl alcohol and polyvinylpyrrolidone blend reinforced with various contents of sulfonated inorganic filler.Sulfuric acid was employed as the sulfonating agent to functionalize the external surface of the inorganic filler,i.e.,graphene oxide.The proton conductivities of the newly prepared proton exchange membranes(PEMs)were increased by increasing the temperature and content of sulfonated graphene oxide(SGO),i.e.,ranging from 0.025 S/cm to 0.060 S/cm.The induction of the optimum level of SGO is determined to be an excellent route to enhance ionic conductivity.The single-cell performance test was conducted by sandwiching the newly prepared PEMs between an anode(0.2 mg/cm^(2) Pt/Ru)and a cathode(0.2 mg/cm^(2) Pt)to prepare membrane electrode assemblies,followed by hot pressing under a pressure of approximately 100 kg/cm^(2) at 60℃for 5–10 min.The highest power densities achieved with PPMG PEMs were 14.9 and 35.60 mW/cm^(2) at 25℃and 70℃,respectively,at ambient pressure with 100%relative humidity.Results showed that the newly prepared PEMs exhibit good electrochemical performance.The results indicated that the prepared composite membrane with 6 wt%filler can be used as an alternative membrane for applications of high-performance proton exchange membrane fuel cell.展开更多
Constrained Friction Processing(CFP)is a novel solid-state processing technique suitable for lightweight materials,such Mg-and Al-alloys.The technique enables grain size refinement to fine or even ultrafine scale.In t...Constrained Friction Processing(CFP)is a novel solid-state processing technique suitable for lightweight materials,such Mg-and Al-alloys.The technique enables grain size refinement to fine or even ultrafine scale.In this study,the effect of CFP on the microstructural refinement of AM50 rods is investigated in terms of particle size and morphology of the eutectic and secondary phases originally present in the base material,in particular the eutecticβ-Mg_(17)Al_(12)and Al-Mn phases.For that purpose,as-cast and solution heat-treated base material and processed samples were analyzed.The Al_(8)Mn_(5) intermetallic phase was identified as the main secondary phase present in all samples before and after the processing.A notorious refinement of these particles was observed,starting from particles with an average equivalent length of a few micrometers to around 560 nm after the processing.The refinement of the secondary phase refinement is attributed to a mechanism analogous to the attrition comminution,where the combination of temperature increase and shearing of the material enables the continuous breaking of the brittle intermetallic particles into smaller pieces.As for the eutectic phase,the results indicate the presence of the partially divorcedβ-Mg_(17)Al_(12)particles exclusively in the as-cast base material,indicating that no further phase transformations regarding the eutectic phase,such as dynamic precipitation,occurred after the CFP.In the case of the processed as-cast material analyzed after the CFP,the thermal energy generated during the processing led to temperature values above the solvus limit of the eutectic phase,which associated with the mechanical breakage of the particles,enabled the complete dissolution of this phase.Therefore,CFP was successfully demonstrated to promote an extensive microstructure refinement in multiple aspects,in terms of grain sizes of theα-Mg phase and presence and morphology of the Al-Mn and eutecticβ-Mg_(17)Al_(12).展开更多
High-performance proton exchange membranes are of great importance for fuel cells.Here,we have synthesized polycarboxylate plasticizer modified MIL-101-Cr-NH_(2)(PCP-MCN),a kind of hybrid metal-organic framework,which ...High-performance proton exchange membranes are of great importance for fuel cells.Here,we have synthesized polycarboxylate plasticizer modified MIL-101-Cr-NH_(2)(PCP-MCN),a kind of hybrid metal-organic framework,which exhibits a superior proton conductivity.PCP-MCN nanoparticles are used as additives to fabricate PCP-MCN/Nafion composite membranes.Microstructures and characteristics of PCP-MCN and these membranes have been extensively investigated.Significant enhancement in proton conduction for PCP-MCN around 55℃ is interestingly found due to the thermal motion of the PCP molecular chains.Robust mechanical properties and higher thermal decomposition temperature of the composite membranes are directly ascribed to strong intermolecular interactions between PCP-MCN and Nafion side chains,i.e.,the formation of substantial acid–base pairs(-SO_(3)^(-)…^(+)H–NH-),which further improves compatibility between additive and Nafion matrix.At the same humidity and temperature condition,the water uptake of composite membranes significantly increases due to the incorporation of porous additives with abundant functional groups and thus less crystallinity degree in comparison to pristine Nafion.Proton conductivity(σ)over wide ranges of humidities(30-100%RH at 25℃)and temperatures(30-98℃ at 100%RH)for prepared membranes is measured.The s in PCPMCN/Nafion composite membranes is remarkably enhanced,i.e.0.245 S/cm for PCP-MCN-3wt.%/Nafion is twice that of Nafion membrane at 98℃ and 100%RH,because of the establishment of well-interconnected proton transport ionic water channels and perhaps faster protonation–deprotonation processes.The composite membranes possess weak humidity-dependence of proton transport and higher water uptake due to excellent water retention ability of PCP-MCN.In particular,when 3 wt.%PCP-MCN was added to Nafion,the power density of a single-cell fabricated with this composite membrane reaches impressively 0.480,1.098 W/cm^(2) under 40%RH,100%RH at 60℃,respectively,guaranteeing it to be a promising proton exchange membrane.展开更多
Sustainable energy conversion and storage technologies are a vital prerequisite for neutral future carbon.To this end,carbon materials with attractive features,such as tunable pore architecture,good electrical conduct...Sustainable energy conversion and storage technologies are a vital prerequisite for neutral future carbon.To this end,carbon materials with attractive features,such as tunable pore architecture,good electrical conductivity,outstanding physicochemical stability,abundant resource,and low cost,have used as promising electrode materials for energy conversion and storage.Defect engineering could modulate the structures of carbon materials,thereby affecting their electronic properties.The presence of defects on carbons may lead to asymmetric charge distribution,change in geometrical configuration,and distortion of the electronic structure that may result in unexpected electrochemical performances.In this review,recent advances in defects of carbons used for energy conversion and storage were examined in terms of types,regulation strategies,and fine characterization means of defects.The applications of such carbons in supercapacitors,rechargeable batteries,and electrocatalysis were also discussed.The perspectives toward the development of defect engineering carbons were proposed.In all,novel insights related to improvement in high-performance carbon materials for future energy conversion and storage applications were provided.展开更多
Metal corrosion causes billions of dollars of economic losses yearly.As a smart and new energy-harvesting device,triboelectric nanogenerators(TENGs)can convert almost all mechanical energy into electricity,which leads...Metal corrosion causes billions of dollars of economic losses yearly.As a smart and new energy-harvesting device,triboelectric nanogenerators(TENGs)can convert almost all mechanical energy into electricity,which leads to great prospects in metal corrosion prevention and cathodic protection.In this work,flexible TENGs were designed to use the energy harvested by flexible polydimethylsiloxane(PDMS)films with ZrB_(2)nanoparticles and effectively improve the dielectric constant by incorporating ZrB_(2).The open-circuit voltage and short-circuit current were 264 V and 22.9μA,respectively,and the power density of the TENGs reached 6 W·m^(-2).Furthermore,a selfpowered anti-corrosion system was designed by the rectifier circuit integrated with TENGs,and the open-circuit potential(OCP)and Tafel curves showed that the system had an excellent anti-corrosion effect on carbon steel.Thus,the system has broad application prospects in fields such as metal cultural relics,ocean engineering,and industry.展开更多
The emerging SiP2with large capacity and suitable plateau is proposed to be the alternative anode for Li-ion batteries.However,typical SiP2still suffers from serious volume expansion and structural destruction,resulti...The emerging SiP2with large capacity and suitable plateau is proposed to be the alternative anode for Li-ion batteries.However,typical SiP2still suffers from serious volume expansion and structural destruction,resulting in much Li-consumption and capacity fading.Herein,a novel stretchable and conductive Li-PAA@PEDOT:PSS binder is rationally designed to improve the cyclability and reversibility of SiP2.Interestingly,such Li-PAA@PEDOT:PSS hydrogel enables a better accommodation of volume expansion than PVDF binder(e.g.5.94% vs.68.73% of expansivity).More specially,the SiP2electrode with LiPAA@PEDOT:PSS binder is surprisingly found to enable unexpected structural recombination and selfhealing Li-storage processes,endowing itself with a high initial Coulombic efficiency(ICE) up to 93.8%,much higher than PVDF binder(ICE=70.7%) as well.Such unusual phenomena are investigated in detail for Li-PAA@PEDOT:PSS,and the possible mechanism shows that its Li-PAA component enables to prevent the pulverization of SiP2nanoparticles while the PEDOT:PSS greatly bridges fast electronic connection for the whole electrode.Consequently,after being further composited with carbon matrix,the SiP2/C with LiPAA@PEDOT:PSS hydrogel exhibits high reversibility(ICE> 93%),superior cyclability(>450 cycles),and rate capability(1520 mAh/g at 2000 mA/g) for LIBs.This highly stretchable and conductive binder design can be easily extended to other alloying materials toward advanced energy storage.展开更多
Urea oxidation reaction(UOR) has been selected as substitution for oxygen evolution reaction ascribing to its low thermodynamic voltage as well as utilization of nickel as electrocatalyst.Herein,we report the formatio...Urea oxidation reaction(UOR) has been selected as substitution for oxygen evolution reaction ascribing to its low thermodynamic voltage as well as utilization of nickel as electrocatalyst.Herein,we report the formation of nickel single atoms(Ni-SAs) as exceptional bifunctional electrocatalyst toward UOR and hydrogen evolution reaction(HER) in urea-assisted water splitting.In UOR catalysis,Ni-SAs perform a superior catalytic performance than Ni-NP/NC and Pt/C ascribing to the formation of HOO-Ni-N_(4) structure evidenced by in-situ Raman spectroscopy,corresponding to a boosted mass activity by 175-fold at 1.4 V vs.RHE than Ni-NP/NC.Furthermore,Ni-SAs requires only 450 mV overpotential to obtain HER current density of 500 mA cm^(-2).136 mA cm^(-2) is achieved in urea-assisted water splitting at1.7 V for Ni-SAs,boosted by 5.7 times than Pt/C-IrO_(2) driven water splitting.展开更多
With the rapid development of portable technology,lithium batteries have emerged as potential candidates for high-performance energy storage systems owing to their high energy density and cycling stability.Among the k...With the rapid development of portable technology,lithium batteries have emerged as potential candidates for high-performance energy storage systems owing to their high energy density and cycling stability.Among the key components of a lithium battery system,the separator plays a critical role as it directly influences the battery performance benchmark(cycling performance and safety).However,traditional polyolefin separators(polypropylene/polyethylene)are unable to meet the demands of highperformance and safer battery systems due to their poor electrolyte compatibility,thermal runaways,and ultimate growth of dendrites.In contrast,membranes fabricated using polybenzimidazole(PBI)exhibit excellent electrolyte wettability and outstanding thermal dimensional stability,thus holding great potential as separators for high-performance and high-safety batteries.In this paper,we present a comprehensive review of the general requirements for separators,synthesis technology for separators,and research trends focusing PBI membranes in lithium batteries to alleviate the current commercial challenges faced by conventional polyolefin separators.In addition,we discuss the future development direction for PBI battery separators by considering various factors such as production cost,ecological footprint,preparation technology,and battery component compatibility.By exploring these perspectives,we aim to promote the continued application and exploration of PBI-based materials to advance lithium battery technology.展开更多
Aqueous organic redox flow batteries(RFBs)exhibit favorable characteristics,such as tunability,multielectron transfer capability,and stability of the redox active molecules utilized as anolytes and catholytes,making t...Aqueous organic redox flow batteries(RFBs)exhibit favorable characteristics,such as tunability,multielectron transfer capability,and stability of the redox active molecules utilized as anolytes and catholytes,making them very viable contenders for large-scale grid storage applications.Considerable attention has been paid on the development of efficient redox-active molecules and their performance optimization through chemical substitutions at various places on the backbone as part of the pursuit for high-performance RFBs.Despite the fact that electrodes are vital to optimal performance,they have not garnered significant attention.Limited research has been conducted on the effects of electrode modifications to improve the performance of RFBs.The primary emphasis has been given on the impact of electrode engineering to augment the efficiency of aqueous organic RFBs.An overview of electron transfer at the electrode-electrolyte interface is provided.The implications of electrode modification on the performance of redox flow batteries,with a particular focus on the anodic and cathodic half-cells separately,are then discussed.In each section,significant discrepancies surrounding the effects of electrode engineering are thoroughly examined and discussed.Finally,we have presented a comprehensive assessment along with our perspectives on the future trajectory.展开更多
The conversion of solar energy to produce clean hydrogen fuel through water splitting is an emerging strategy for efficiently storing solar energy in the form of solar fuel.This aligns with the increasing global deman...The conversion of solar energy to produce clean hydrogen fuel through water splitting is an emerging strategy for efficiently storing solar energy in the form of solar fuel.This aligns with the increasing global demand for the development of an ideal energy alternative to fossil fuels that does not emit greenhouse gases.Electrochemical(EC) and photoelectrochemical(PEC) water splitting technologies have garnered significant attention worldwide for advanced hydrogen solar fuel production in recent decades.To achieve sustainable green H_(2) production,it is essential to create efficient catalyst materials that are low-cost and can replace expensive noble metal-based catalysts.These characteristics make them an ideal catalyst material for the process.Two-dimensional MXenes with M_(n+1)X_(n) structure have been identified as a promising option for EC and PEC water splitting due to their superior hydrophilicity,metal-like conductivity,large surface area,and adjustable surface chemistry.Here,we present a summary of recent advancements in the synthesis and performance enhancement methods for MXene hybrid materials in hydrogen production through EC and PEC water splitting.Furthermore,we examine the challenges and insights associated with the rational design of MXene-based hybrid materials to facilitate efficient water splitting for sustainable solar fuel production.展开更多
Traditional garnet solid electrolyte(Li_(7)La_(3)Zr_(2)O_(12))suffers from low room temperature ionic conductivity,poor air stability,high sintering temperature and energy consumption.Considering the development prosp...Traditional garnet solid electrolyte(Li_(7)La_(3)Zr_(2)O_(12))suffers from low room temperature ionic conductivity,poor air stability,high sintering temperature and energy consumption.Considering the development prospects of high-entropy materials with high structural disorder and strong component controllability in the field of electrochemical energy storage,herein,a novel high-entropy garnet-type oxide solid electrolyte,Li_(5.75)Ga_(0.25)La_(3)Zr_(0.5)Ti_(0.5)Sn_(0.5)Nb_(0.5)O_(12)(LGLZTSNO)was constructed by partially replacing the Li and Zr sites in Li_(7)La_(3)Zr_(2)O_(12)with Ga and Ti/Sn/Nb elements,respectively.The experimental and density functional theory(DFT)calculation results show that the high-entropy LGLZTSNO electrolyte has preferable room temperature ion conductivity,air stability,interface contact performance with lithium anode,and the ability to suppress lithium dendrites.Thanks to the improvement of electrolyte performance,the critical current density of Li/Ag@LGLZTSNO/Li symmetric cell was increased from 0.42 to 1.57 mA cm^(−2),and the interface area specific impedance(IASR)was reduced from 765.2 to 42.3Ωcm^(2).Meanwhile,the Li/Ag@LGLZTSNO/LFP full cell also exhibits excellent rate performance and cycling performance(148 mA h g^(−1)at 0.1 C and 124 mA h g^(−1)at 0.5 C,capacity retention up to 84.8%after 100 cycles at 0.1 C),showing the application prospects of high-entropy LGLZTSNO solid electrolyte in high-performance all solid state lithium batteries.展开更多
Efficient and cost-effective electrocatalysts that can operate across a wide range of pH conditions are essential for green hydrogen production.Inspired by biological systems,Fe_(7)S_(8)nanoparticles incorporated on p...Efficient and cost-effective electrocatalysts that can operate across a wide range of pH conditions are essential for green hydrogen production.Inspired by biological systems,Fe_(7)S_(8)nanoparticles incorporated on polydopamine matrix electrocatalyst were synthesized by co-precipitation and annealing process.The resulting Fe_(7)S_(8)/C electrocatalyst possesses a three-dimensional structure and exhibits enhanced electrocatalytic performance for hydrogen production across various pH conditions.Notably,the Fe_(7)S_(8)/C electrocatalyst demonstrates exceptional activity,achieving low overpotentials of 90.6,45.9,and 107.4 mV in acidic,neutral,and alkaline environments,respectively.Electrochemical impedance spectroscopy reveals that Fe_(7)S_(8)/C exhibits the lowest charge transfer resistance under neutral conditions,indicating an improved proton-coupled electron transfer process.Continuous-wave electron paramagnetic resonance results confirm a change in the valence state of Fe from 3+to 1+during the hydrogen evolution reaction(HER).These findings closely resemble the behavior of natural[FeFe]-hydrogenase,known for its superior hydrogen production in neutral conditions.The remarkable performance of our Fe_(7)S_(8)/C electrocatalyst opens up new possibilities for utilizing bioinspired materials as catalysts for the HER.展开更多
Over the last decade’s magnesium and magnesium based compounds have been intensively investigated as potential hydrogen storage as well as thermal energy storage materials due to their abundance and availability as w...Over the last decade’s magnesium and magnesium based compounds have been intensively investigated as potential hydrogen storage as well as thermal energy storage materials due to their abundance and availability as well as their extraordinary high gravimetric and volumetric storage densities.This review work provides a broad overview of the most appealing systems and of their hydrogenation/dehydrogenation properties.Special emphasis is placed on reviewing the efforts made by the scientific community in improving the material’s thermodynamic and kinetic properties while maintaining a high hydrogen storage capacity.展开更多
With the increased use of renewable energy sources,the need to store large amounts of energy will become increasingly important in the near future.A cost efficient possibility is to use the reaction of recycled Mg was...With the increased use of renewable energy sources,the need to store large amounts of energy will become increasingly important in the near future.A cost efficient possibility is to use the reaction of recycled Mg waste with hydrogen as thermo-chemical energy storage.Owing to the high reaction enthalpy,the moderate pressure and appropriate temperature conditions,the broad abundance and the recyclability,the Mg/Al alloy is perfectly suitable for this purpose.As further development of a previous work,in which the performance of recycled Mg/Al waste was presented,a kinetic model for hydro-and dehydrogenation is derived in this study.Temperature and pressure dependencies are determined,as well as the rate limiting step of the reaction.First experiments are carried out in an autoclave with a scaled-up powder mass,which is also used to validate the model by simulating the geometry with the scaled-up experiments at different conditions.展开更多
Copper(Cu)provides a cost-effective means of producing value-added fuels through the electrochemical reduction of carbon dioxide(CO_(2)RR).However,we observed the production of hydrocarbons via CO_(2)RR on commercial ...Copper(Cu)provides a cost-effective means of producing value-added fuels through the electrochemical reduction of carbon dioxide(CO_(2)RR).However,we observed the production of hydrocarbons via CO_(2)RR on commercial Cu films is less efficient because of the surface impurities,i.e.,Fe.Carbon monoxide(CO),a reaction intermediate of CO_(2)RR to hydrocarbons,binds strongly to the Fe sites and interrupts the production of hydrocarbons,resulting in an active hydrogen evolution reaction(HER).Herein,we report a method of blocking the effect of Fe impurities on the Cu surface through the preferential growth of nano-sized metal-organic frameworks(MOFs)on Fe site.When zirconium(Zr)-based MOFs(UiO-66)forms a compensating layer on Cu film via the terephthalic acid(TPA)-Fe coordination bond,the Ui O-66 coated Cu film(UiO-66@Cu)presents significantly improved hydrocarbon Faradaic efficiency(FE)of 37.59%compared to 14.68%FE on commercial Cu film(99.9%purity)by suppressing HER.According to X-ray photoelectron spectroscopy(XPS)analysis,the UiO-66 ligand binds to entire metallic Fe site on the Cu surface,while metallic Cu is retained.Thus,UiO-66@Cu provides active sites of Cu for CO_(2)RR and leads to highly efficient and selective production of hydrocarbons.展开更多
The purpose of this study is to point out the dominant factor of heat and mass distribution in single-cell PEFC (polymer electrolyte fuel cell). The numerical simulation by simple 3D model to clarify the influence o...The purpose of this study is to point out the dominant factor of heat and mass distribution in single-cell PEFC (polymer electrolyte fuel cell). The numerical simulation by simple 3D model to clarify the influence of cell components structure on heat and mass transfer phenomena as well as power generation experiment and measurement of in-plane temperature distribution by thermograph was carried out. From the simulation, the gas channel pitch of separator was the key factor to unify in-plane distribution of temperature and gas concentration on reaction surface in cell. The compression of GDL (gas diffusion layer) by cell binding caused wider distribution of mass concentration in GDL. From the experiment, the power generation performance was promoted with decreasing gas channel pitch. The temperature range in observation area was reduced with decreasing gas channel pitch. It can be concluded that the power generation performance is promoted by decreasing gas channel pitch.展开更多
1.Introduction Controlled combustion is perhaps the oldest human invention,providing food,warmth,protection,and power over millennia.In the last century,for example,it has enabled the United Kingdom to cut its agricul...1.Introduction Controlled combustion is perhaps the oldest human invention,providing food,warmth,protection,and power over millennia.In the last century,for example,it has enabled the United Kingdom to cut its agricultural labor force to near 1% of the population,replacing the horse and muscle power that dominated the 19th and earlier centuries[1].展开更多
Nucleophile oxidation reaction(NOR), represented by ethanol oxidation reaction(EOR), is a promising pathway to replace oxygen evolution reaction(OER). EOR can effectively reduce the driving voltage of hydrogen product...Nucleophile oxidation reaction(NOR), represented by ethanol oxidation reaction(EOR), is a promising pathway to replace oxygen evolution reaction(OER). EOR can effectively reduce the driving voltage of hydrogen production in direct water splitting. In this work, large current and high efficiency of EOR on a Ni, Fe layered double hydroxide(NiFe-LDH) catalyst were simultaneously achieved by a facile fluorination strategy. F in NiFe-LDH can reduce the activation energy of the dehydrogenation reaction, thus promoting the deprotonation process of NiFe-LDH to achieve a lower EOR onset potential. It also weakens the absorption of OH-and nucleophile electrooxidation products on the surface of NiFe-LDH at a higher potential, achieving a high current density and EOR selectivity, according to density functional theory calculations. Based on our experiment results, the optimized fluorinated NiFe-LDH catalyst achieves a low potential of 1.386 V to deliver a 10 mA cm^(-2)EOR. Moreover, the Faraday efficiency is greater than 95%, with a current density ranging from 10 to 250 mA cm^(-2). This work provides a promising pathway for an efficient and cost-effective NOR catalyst design for economic hydrogen production.展开更多
The engineering of the electronic configurations of active sites,together with the production of more accessible active sites through heterostructure design,has been established as a forceful methodology for boosting ...The engineering of the electronic configurations of active sites,together with the production of more accessible active sites through heterostructure design,has been established as a forceful methodology for boosting water electrolysis performance.Herein,a facile approach is developed to fabricate well-dispersed MoO_(2) and WO_(2) nanoparticles with abundant heterointerfaces entrapped in N,P-doped carbon nanofibers(referred to as MoO_(2)/WO_(2)@N,P-CNFs hereafter)as hydrogen evolution reaction(HER)electrocatalysts in alkaline and acidic electrolytes.Extensive spectroscopic analyses and theoretical findings manifest that the heterointerface formed by the work function modulation of MoO_(2)/WO_(2) triggers the spontaneous electron redistribution from MoO_(2)to WO_(2) and a built-in electric field,which is essential to promote water adsorption,optimize the H-intermediate adsorption energy,result in the enhanced charge transfer efficiency,and ultimately increase the intrinsic HER activity.Simultaneously,the intimate confinement of MoO_(2)/WO_(2) heterostructures in the porous carbon substrate can restrain the active sites from unfavorable coarsening and detachment,thus ensuring facilitated HER kinetics and outstanding structural robustness.As a result,MoO_(2)/WO_(2)@N,P-CNFs exhibit superior catalytic HER performance in acidic and basic solutions,requiring 118 and 95 mV overpotentials to achieve 10 mA·cm^(−2),respectively,surpassing a number of reported non-noble metal-based electrocatalysts.This work provides guidelines for the rational design and construction of special metallic heterocomponents with optimized interfacial electronic structure for various electrochemical technologies.展开更多
Ruthenium(Ru)is an attractive potential alternative to platinum as an electrocatalyst for the oxygen reduction reaction(ORR),in virtue of its high catalytic selectivity and relatively low price.In this work,a series o...Ruthenium(Ru)is an attractive potential alternative to platinum as an electrocatalyst for the oxygen reduction reaction(ORR),in virtue of its high catalytic selectivity and relatively low price.In this work,a series of well-dispersed nitrogen-coordinated Ru-clusters on carbon black(Ru_(x)N_(y)/C)were prepared by pyrolyzing different Ru-containing sandwich compounds as the Ru sources.The higher thermal stability of these complexed sandwich precursors(bis(1,2,3,4,5-pentamethylcyclopentadienyl)Ru(II)monomer,dichloro(p-cymene)Ru(II)dimer,and chloro(1,2,3,4,5-pentamethylcyclopentadienyl)Ru(II)tetramer)affords the control of coordinated state for the resulting Ru-clusters,in comparison of that derived from ruthenium chlorides.After the pyrolysis treatment,the Ru coordinated state in Ru_(x)N_(y)/C,with the Ru–N and Ru–Ru bonds,still showed the structural inheritance from the Ru(II)monomer,dimer,and tetramer,but using ruthenium chlorides as the Ru source resulted in the nanoscale Ru agglomerations.The ORR testing exhibited that the Ru_(x)N_(y)/C sample derived from the Ru(II)tetramer(Ru_(x)N_(y)/C-T)presents the higher catalytic activity than the other obtained samples in either alkaline or acidic electrolytes.Even in the acidic electrolyte,Ru_(x)N_(y)/C-T shows the comparable ORR activity to that of Pt/C catalysts,and it shows the superior tolerance against methanol and CO.The X-ray absorption spectroscopy and density functional theory calculations demonstrate that these tetra-nuclear Ru-clusters could be the most active site due to their broadened d-orbital bands and lower energy d-band center than those of other subnano species and nanocrystals,and their favorable Yeager-type adsorption of O_(2)-molecules is also contributed to promoting O–O bond cleavage and accelerating the ORR process.展开更多
文摘PPMG-based composite electrolytes were fabricated via the solution method using the polyvinyl alcohol and polyvinylpyrrolidone blend reinforced with various contents of sulfonated inorganic filler.Sulfuric acid was employed as the sulfonating agent to functionalize the external surface of the inorganic filler,i.e.,graphene oxide.The proton conductivities of the newly prepared proton exchange membranes(PEMs)were increased by increasing the temperature and content of sulfonated graphene oxide(SGO),i.e.,ranging from 0.025 S/cm to 0.060 S/cm.The induction of the optimum level of SGO is determined to be an excellent route to enhance ionic conductivity.The single-cell performance test was conducted by sandwiching the newly prepared PEMs between an anode(0.2 mg/cm^(2) Pt/Ru)and a cathode(0.2 mg/cm^(2) Pt)to prepare membrane electrode assemblies,followed by hot pressing under a pressure of approximately 100 kg/cm^(2) at 60℃for 5–10 min.The highest power densities achieved with PPMG PEMs were 14.9 and 35.60 mW/cm^(2) at 25℃and 70℃,respectively,at ambient pressure with 100%relative humidity.Results showed that the newly prepared PEMs exhibit good electrochemical performance.The results indicated that the prepared composite membrane with 6 wt%filler can be used as an alternative membrane for applications of high-performance proton exchange membrane fuel cell.
文摘Constrained Friction Processing(CFP)is a novel solid-state processing technique suitable for lightweight materials,such Mg-and Al-alloys.The technique enables grain size refinement to fine or even ultrafine scale.In this study,the effect of CFP on the microstructural refinement of AM50 rods is investigated in terms of particle size and morphology of the eutectic and secondary phases originally present in the base material,in particular the eutecticβ-Mg_(17)Al_(12)and Al-Mn phases.For that purpose,as-cast and solution heat-treated base material and processed samples were analyzed.The Al_(8)Mn_(5) intermetallic phase was identified as the main secondary phase present in all samples before and after the processing.A notorious refinement of these particles was observed,starting from particles with an average equivalent length of a few micrometers to around 560 nm after the processing.The refinement of the secondary phase refinement is attributed to a mechanism analogous to the attrition comminution,where the combination of temperature increase and shearing of the material enables the continuous breaking of the brittle intermetallic particles into smaller pieces.As for the eutectic phase,the results indicate the presence of the partially divorcedβ-Mg_(17)Al_(12)particles exclusively in the as-cast base material,indicating that no further phase transformations regarding the eutectic phase,such as dynamic precipitation,occurred after the CFP.In the case of the processed as-cast material analyzed after the CFP,the thermal energy generated during the processing led to temperature values above the solvus limit of the eutectic phase,which associated with the mechanical breakage of the particles,enabled the complete dissolution of this phase.Therefore,CFP was successfully demonstrated to promote an extensive microstructure refinement in multiple aspects,in terms of grain sizes of theα-Mg phase and presence and morphology of the Al-Mn and eutecticβ-Mg_(17)Al_(12).
基金supported by the National Natural Science Foundation of China(NSFC)(Nos.12075172,12375288,12205089,and 12105048)National Key R&D Program of China(Grant No.2019YFA0210003)Guangdong Basic and Applied Basic Research Foundation(No.2020A1515110817).
文摘High-performance proton exchange membranes are of great importance for fuel cells.Here,we have synthesized polycarboxylate plasticizer modified MIL-101-Cr-NH_(2)(PCP-MCN),a kind of hybrid metal-organic framework,which exhibits a superior proton conductivity.PCP-MCN nanoparticles are used as additives to fabricate PCP-MCN/Nafion composite membranes.Microstructures and characteristics of PCP-MCN and these membranes have been extensively investigated.Significant enhancement in proton conduction for PCP-MCN around 55℃ is interestingly found due to the thermal motion of the PCP molecular chains.Robust mechanical properties and higher thermal decomposition temperature of the composite membranes are directly ascribed to strong intermolecular interactions between PCP-MCN and Nafion side chains,i.e.,the formation of substantial acid–base pairs(-SO_(3)^(-)…^(+)H–NH-),which further improves compatibility between additive and Nafion matrix.At the same humidity and temperature condition,the water uptake of composite membranes significantly increases due to the incorporation of porous additives with abundant functional groups and thus less crystallinity degree in comparison to pristine Nafion.Proton conductivity(σ)over wide ranges of humidities(30-100%RH at 25℃)and temperatures(30-98℃ at 100%RH)for prepared membranes is measured.The s in PCPMCN/Nafion composite membranes is remarkably enhanced,i.e.0.245 S/cm for PCP-MCN-3wt.%/Nafion is twice that of Nafion membrane at 98℃ and 100%RH,because of the establishment of well-interconnected proton transport ionic water channels and perhaps faster protonation–deprotonation processes.The composite membranes possess weak humidity-dependence of proton transport and higher water uptake due to excellent water retention ability of PCP-MCN.In particular,when 3 wt.%PCP-MCN was added to Nafion,the power density of a single-cell fabricated with this composite membrane reaches impressively 0.480,1.098 W/cm^(2) under 40%RH,100%RH at 60℃,respectively,guaranteeing it to be a promising proton exchange membrane.
基金the National Natural Science Foundation of China(52062012)Key Science&Technology Project of Hainan Province(ZDYF2020028)+2 种基金Key-Area Research and Development Program of Guangdong Province(2019B1102109003)the Innovation Team of Universities of Guangdong Province(2020KCXTD011)Guangdong Province Key Discipline Construction Project(2021ZDJS102).
文摘Sustainable energy conversion and storage technologies are a vital prerequisite for neutral future carbon.To this end,carbon materials with attractive features,such as tunable pore architecture,good electrical conductivity,outstanding physicochemical stability,abundant resource,and low cost,have used as promising electrode materials for energy conversion and storage.Defect engineering could modulate the structures of carbon materials,thereby affecting their electronic properties.The presence of defects on carbons may lead to asymmetric charge distribution,change in geometrical configuration,and distortion of the electronic structure that may result in unexpected electrochemical performances.In this review,recent advances in defects of carbons used for energy conversion and storage were examined in terms of types,regulation strategies,and fine characterization means of defects.The applications of such carbons in supercapacitors,rechargeable batteries,and electrocatalysis were also discussed.The perspectives toward the development of defect engineering carbons were proposed.In all,novel insights related to improvement in high-performance carbon materials for future energy conversion and storage applications were provided.
基金supported by the Scientific Research Project of Guangdong Provincial Education Department (Nos.2022KTSCX123 and 2022KTSCX118)the Key Plat Form Programs and Technology Innovation Team Project of Guangdong Provincial Department of Education (Nos.2019GCZX002 and 2020KCXTD011)+1 种基金Guang dong Basic and Applied Basic Research Foundation (Nos.2019A1515110444,2020B1515120097,and 2020 A1515111107)funded by the Open Project Program of Guangdong Provincial Key Laboratory of Electronic Functional Materials and Devices,Huizhou University (No.EFMD2021005Z)。
文摘Metal corrosion causes billions of dollars of economic losses yearly.As a smart and new energy-harvesting device,triboelectric nanogenerators(TENGs)can convert almost all mechanical energy into electricity,which leads to great prospects in metal corrosion prevention and cathodic protection.In this work,flexible TENGs were designed to use the energy harvested by flexible polydimethylsiloxane(PDMS)films with ZrB_(2)nanoparticles and effectively improve the dielectric constant by incorporating ZrB_(2).The open-circuit voltage and short-circuit current were 264 V and 22.9μA,respectively,and the power density of the TENGs reached 6 W·m^(-2).Furthermore,a selfpowered anti-corrosion system was designed by the rectifier circuit integrated with TENGs,and the open-circuit potential(OCP)and Tafel curves showed that the system had an excellent anti-corrosion effect on carbon steel.Thus,the system has broad application prospects in fields such as metal cultural relics,ocean engineering,and industry.
基金financially supported by the National Natural Science Foundation of China (22269008 and 52162026)the Hainan Province Science and Technology Special Fund(ZDYF2022SHFZ297)+4 种基金the Hainan Provincial Natural Science Foundation of China (521QN207 and 521RC499)the Hainan University’s Scientific Research Foundation (KYQD(ZR)-21088)the Graduate Innovation Research Project of Hainan(Qhys2021-156)the Guangdong Province Key Discipline Construction Project (2021ZDJS102)the Innovation Team of Universities of Guangdong Province (2022KCXTD030)。
文摘The emerging SiP2with large capacity and suitable plateau is proposed to be the alternative anode for Li-ion batteries.However,typical SiP2still suffers from serious volume expansion and structural destruction,resulting in much Li-consumption and capacity fading.Herein,a novel stretchable and conductive Li-PAA@PEDOT:PSS binder is rationally designed to improve the cyclability and reversibility of SiP2.Interestingly,such Li-PAA@PEDOT:PSS hydrogel enables a better accommodation of volume expansion than PVDF binder(e.g.5.94% vs.68.73% of expansivity).More specially,the SiP2electrode with LiPAA@PEDOT:PSS binder is surprisingly found to enable unexpected structural recombination and selfhealing Li-storage processes,endowing itself with a high initial Coulombic efficiency(ICE) up to 93.8%,much higher than PVDF binder(ICE=70.7%) as well.Such unusual phenomena are investigated in detail for Li-PAA@PEDOT:PSS,and the possible mechanism shows that its Li-PAA component enables to prevent the pulverization of SiP2nanoparticles while the PEDOT:PSS greatly bridges fast electronic connection for the whole electrode.Consequently,after being further composited with carbon matrix,the SiP2/C with LiPAA@PEDOT:PSS hydrogel exhibits high reversibility(ICE> 93%),superior cyclability(>450 cycles),and rate capability(1520 mAh/g at 2000 mA/g) for LIBs.This highly stretchable and conductive binder design can be easily extended to other alloying materials toward advanced energy storage.
基金supported by the National Natural Science Foundation of China(No.22209126)。
文摘Urea oxidation reaction(UOR) has been selected as substitution for oxygen evolution reaction ascribing to its low thermodynamic voltage as well as utilization of nickel as electrocatalyst.Herein,we report the formation of nickel single atoms(Ni-SAs) as exceptional bifunctional electrocatalyst toward UOR and hydrogen evolution reaction(HER) in urea-assisted water splitting.In UOR catalysis,Ni-SAs perform a superior catalytic performance than Ni-NP/NC and Pt/C ascribing to the formation of HOO-Ni-N_(4) structure evidenced by in-situ Raman spectroscopy,corresponding to a boosted mass activity by 175-fold at 1.4 V vs.RHE than Ni-NP/NC.Furthermore,Ni-SAs requires only 450 mV overpotential to obtain HER current density of 500 mA cm^(-2).136 mA cm^(-2) is achieved in urea-assisted water splitting at1.7 V for Ni-SAs,boosted by 5.7 times than Pt/C-IrO_(2) driven water splitting.
基金supported by the Natural Science Foundation of China(22105129)the Guangdong Basic and Applied Basic Research Foundation(2022A1515011048)the Science and Technology Innovation Commission of Shenzhen(JCYJ20200109105618137)。
文摘With the rapid development of portable technology,lithium batteries have emerged as potential candidates for high-performance energy storage systems owing to their high energy density and cycling stability.Among the key components of a lithium battery system,the separator plays a critical role as it directly influences the battery performance benchmark(cycling performance and safety).However,traditional polyolefin separators(polypropylene/polyethylene)are unable to meet the demands of highperformance and safer battery systems due to their poor electrolyte compatibility,thermal runaways,and ultimate growth of dendrites.In contrast,membranes fabricated using polybenzimidazole(PBI)exhibit excellent electrolyte wettability and outstanding thermal dimensional stability,thus holding great potential as separators for high-performance and high-safety batteries.In this paper,we present a comprehensive review of the general requirements for separators,synthesis technology for separators,and research trends focusing PBI membranes in lithium batteries to alleviate the current commercial challenges faced by conventional polyolefin separators.In addition,we discuss the future development direction for PBI battery separators by considering various factors such as production cost,ecological footprint,preparation technology,and battery component compatibility.By exploring these perspectives,we aim to promote the continued application and exploration of PBI-based materials to advance lithium battery technology.
基金the financial support received from Interdisciplinary Research Center for Hydrogen Technologies and Carbon Management(IRC-HTCM)at King Fahd University of Petroleum and Minerals(KFUPM),specifically under project#INHE2213。
文摘Aqueous organic redox flow batteries(RFBs)exhibit favorable characteristics,such as tunability,multielectron transfer capability,and stability of the redox active molecules utilized as anolytes and catholytes,making them very viable contenders for large-scale grid storage applications.Considerable attention has been paid on the development of efficient redox-active molecules and their performance optimization through chemical substitutions at various places on the backbone as part of the pursuit for high-performance RFBs.Despite the fact that electrodes are vital to optimal performance,they have not garnered significant attention.Limited research has been conducted on the effects of electrode modifications to improve the performance of RFBs.The primary emphasis has been given on the impact of electrode engineering to augment the efficiency of aqueous organic RFBs.An overview of electron transfer at the electrode-electrolyte interface is provided.The implications of electrode modification on the performance of redox flow batteries,with a particular focus on the anodic and cathodic half-cells separately,are then discussed.In each section,significant discrepancies surrounding the effects of electrode engineering are thoroughly examined and discussed.Finally,we have presented a comprehensive assessment along with our perspectives on the future trajectory.
基金the result of a research project conducted with the funds of the Open R&D program of Korea Electric Power Corporation (R23XO04)supported by the Technology Innovation Program funded by the Ministry of Trade, Industry & Energy (MOTIE, Korea) (K_G012002238601)+2 种基金by “Regional Innovation Strategy (RIS)” through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (MOE) (2021RIS-002)by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MSIT) (No. 2021M3I3A1082880)by the Korea Institute of Energy Technology Evaluation and Planning (KETEP) and the Ministry of Trade, Industry & Energy (MOTIE) of the Republic of Korea (No. 20224000000320)。
文摘The conversion of solar energy to produce clean hydrogen fuel through water splitting is an emerging strategy for efficiently storing solar energy in the form of solar fuel.This aligns with the increasing global demand for the development of an ideal energy alternative to fossil fuels that does not emit greenhouse gases.Electrochemical(EC) and photoelectrochemical(PEC) water splitting technologies have garnered significant attention worldwide for advanced hydrogen solar fuel production in recent decades.To achieve sustainable green H_(2) production,it is essential to create efficient catalyst materials that are low-cost and can replace expensive noble metal-based catalysts.These characteristics make them an ideal catalyst material for the process.Two-dimensional MXenes with M_(n+1)X_(n) structure have been identified as a promising option for EC and PEC water splitting due to their superior hydrophilicity,metal-like conductivity,large surface area,and adjustable surface chemistry.Here,we present a summary of recent advancements in the synthesis and performance enhancement methods for MXene hybrid materials in hydrogen production through EC and PEC water splitting.Furthermore,we examine the challenges and insights associated with the rational design of MXene-based hybrid materials to facilitate efficient water splitting for sustainable solar fuel production.
基金supported by the Natural Science Foundation of China(61901142)the Key Research and Development Project of Hainan Province(ZDYF2022SHFZ093).
文摘Traditional garnet solid electrolyte(Li_(7)La_(3)Zr_(2)O_(12))suffers from low room temperature ionic conductivity,poor air stability,high sintering temperature and energy consumption.Considering the development prospects of high-entropy materials with high structural disorder and strong component controllability in the field of electrochemical energy storage,herein,a novel high-entropy garnet-type oxide solid electrolyte,Li_(5.75)Ga_(0.25)La_(3)Zr_(0.5)Ti_(0.5)Sn_(0.5)Nb_(0.5)O_(12)(LGLZTSNO)was constructed by partially replacing the Li and Zr sites in Li_(7)La_(3)Zr_(2)O_(12)with Ga and Ti/Sn/Nb elements,respectively.The experimental and density functional theory(DFT)calculation results show that the high-entropy LGLZTSNO electrolyte has preferable room temperature ion conductivity,air stability,interface contact performance with lithium anode,and the ability to suppress lithium dendrites.Thanks to the improvement of electrolyte performance,the critical current density of Li/Ag@LGLZTSNO/Li symmetric cell was increased from 0.42 to 1.57 mA cm^(−2),and the interface area specific impedance(IASR)was reduced from 765.2 to 42.3Ωcm^(2).Meanwhile,the Li/Ag@LGLZTSNO/LFP full cell also exhibits excellent rate performance and cycling performance(148 mA h g^(−1)at 0.1 C and 124 mA h g^(−1)at 0.5 C,capacity retention up to 84.8%after 100 cycles at 0.1 C),showing the application prospects of high-entropy LGLZTSNO solid electrolyte in high-performance all solid state lithium batteries.
基金Outsourced R&D Project of Korea Electric Power Corporation(KEPCO),Grant/Award Number:R23XO04National Research Foundation of Korea(NRF)+7 种基金Korean government(MSIT),Grant/Award Numbers:NRF-2021M3H4A6A01045764,2020M3H4A3106313,2021R1C1C1004264,2021R1A4A1032114Korea Institute for Advancement of Technology(KIAT)Ministry of Trade,Industry,and Energy(MOTIE),Korea,Grant/Award Number:P0025273Korea Institute of Energy Technology Evaluation and Planning(KETEP)and the Ministry of Trade,Industry&Energy(MOTIE)of the Republic of Korea,Grant/Award Number:20224000000320KENTECH Research GrantKorea Institute of Energy Technology,Republic of Korea,Grant/Award Number:KRG2022-01-016Regional Innovation Strategy(RIS)through the National Research Foundation of Korea(NRF)Ministry of Education(MOE),Grant/Award Number:2021RIS-002。
文摘Efficient and cost-effective electrocatalysts that can operate across a wide range of pH conditions are essential for green hydrogen production.Inspired by biological systems,Fe_(7)S_(8)nanoparticles incorporated on polydopamine matrix electrocatalyst were synthesized by co-precipitation and annealing process.The resulting Fe_(7)S_(8)/C electrocatalyst possesses a three-dimensional structure and exhibits enhanced electrocatalytic performance for hydrogen production across various pH conditions.Notably,the Fe_(7)S_(8)/C electrocatalyst demonstrates exceptional activity,achieving low overpotentials of 90.6,45.9,and 107.4 mV in acidic,neutral,and alkaline environments,respectively.Electrochemical impedance spectroscopy reveals that Fe_(7)S_(8)/C exhibits the lowest charge transfer resistance under neutral conditions,indicating an improved proton-coupled electron transfer process.Continuous-wave electron paramagnetic resonance results confirm a change in the valence state of Fe from 3+to 1+during the hydrogen evolution reaction(HER).These findings closely resemble the behavior of natural[FeFe]-hydrogenase,known for its superior hydrogen production in neutral conditions.The remarkable performance of our Fe_(7)S_(8)/C electrocatalyst opens up new possibilities for utilizing bioinspired materials as catalysts for the HER.
文摘Over the last decade’s magnesium and magnesium based compounds have been intensively investigated as potential hydrogen storage as well as thermal energy storage materials due to their abundance and availability as well as their extraordinary high gravimetric and volumetric storage densities.This review work provides a broad overview of the most appealing systems and of their hydrogenation/dehydrogenation properties.Special emphasis is placed on reviewing the efforts made by the scientific community in improving the material’s thermodynamic and kinetic properties while maintaining a high hydrogen storage capacity.
文摘With the increased use of renewable energy sources,the need to store large amounts of energy will become increasingly important in the near future.A cost efficient possibility is to use the reaction of recycled Mg waste with hydrogen as thermo-chemical energy storage.Owing to the high reaction enthalpy,the moderate pressure and appropriate temperature conditions,the broad abundance and the recyclability,the Mg/Al alloy is perfectly suitable for this purpose.As further development of a previous work,in which the performance of recycled Mg/Al waste was presented,a kinetic model for hydro-and dehydrogenation is derived in this study.Temperature and pressure dependencies are determined,as well as the rate limiting step of the reaction.First experiments are carried out in an autoclave with a scaled-up powder mass,which is also used to validate the model by simulating the geometry with the scaled-up experiments at different conditions.
基金supported by the Basic Science Research Program of the National Research Foundation of Korea(NRF2021R1A2C4001777,NRF-2021R1A2C2007823)the Carbon to X Project(NRF-2020M3H7A1098231)funded by the Ministry of Science and ICT,Republic of Koreasupported by the Technology Innovation Program(20013794,Center for Composite Materials and Concurrent Design)funded by the Ministry of Trade,Industry&Energy(MOTIE),Republic of Korea。
文摘Copper(Cu)provides a cost-effective means of producing value-added fuels through the electrochemical reduction of carbon dioxide(CO_(2)RR).However,we observed the production of hydrocarbons via CO_(2)RR on commercial Cu films is less efficient because of the surface impurities,i.e.,Fe.Carbon monoxide(CO),a reaction intermediate of CO_(2)RR to hydrocarbons,binds strongly to the Fe sites and interrupts the production of hydrocarbons,resulting in an active hydrogen evolution reaction(HER).Herein,we report a method of blocking the effect of Fe impurities on the Cu surface through the preferential growth of nano-sized metal-organic frameworks(MOFs)on Fe site.When zirconium(Zr)-based MOFs(UiO-66)forms a compensating layer on Cu film via the terephthalic acid(TPA)-Fe coordination bond,the Ui O-66 coated Cu film(UiO-66@Cu)presents significantly improved hydrocarbon Faradaic efficiency(FE)of 37.59%compared to 14.68%FE on commercial Cu film(99.9%purity)by suppressing HER.According to X-ray photoelectron spectroscopy(XPS)analysis,the UiO-66 ligand binds to entire metallic Fe site on the Cu surface,while metallic Cu is retained.Thus,UiO-66@Cu provides active sites of Cu for CO_(2)RR and leads to highly efficient and selective production of hydrocarbons.
文摘The purpose of this study is to point out the dominant factor of heat and mass distribution in single-cell PEFC (polymer electrolyte fuel cell). The numerical simulation by simple 3D model to clarify the influence of cell components structure on heat and mass transfer phenomena as well as power generation experiment and measurement of in-plane temperature distribution by thermograph was carried out. From the simulation, the gas channel pitch of separator was the key factor to unify in-plane distribution of temperature and gas concentration on reaction surface in cell. The compression of GDL (gas diffusion layer) by cell binding caused wider distribution of mass concentration in GDL. From the experiment, the power generation performance was promoted with decreasing gas channel pitch. The temperature range in observation area was reduced with decreasing gas channel pitch. It can be concluded that the power generation performance is promoted by decreasing gas channel pitch.
文摘1.Introduction Controlled combustion is perhaps the oldest human invention,providing food,warmth,protection,and power over millennia.In the last century,for example,it has enabled the United Kingdom to cut its agricultural labor force to near 1% of the population,replacing the horse and muscle power that dominated the 19th and earlier centuries[1].
基金the financial support from the National Natural Science Foundation of China (22197121)Knowledge Innovation Program of Wuhan-Basic Research (2022010801010202)Research Fund Program of Guangdong Provincial Key Laboratory of Fuel Cell Technology (FC202201)。
文摘Nucleophile oxidation reaction(NOR), represented by ethanol oxidation reaction(EOR), is a promising pathway to replace oxygen evolution reaction(OER). EOR can effectively reduce the driving voltage of hydrogen production in direct water splitting. In this work, large current and high efficiency of EOR on a Ni, Fe layered double hydroxide(NiFe-LDH) catalyst were simultaneously achieved by a facile fluorination strategy. F in NiFe-LDH can reduce the activation energy of the dehydrogenation reaction, thus promoting the deprotonation process of NiFe-LDH to achieve a lower EOR onset potential. It also weakens the absorption of OH-and nucleophile electrooxidation products on the surface of NiFe-LDH at a higher potential, achieving a high current density and EOR selectivity, according to density functional theory calculations. Based on our experiment results, the optimized fluorinated NiFe-LDH catalyst achieves a low potential of 1.386 V to deliver a 10 mA cm^(-2)EOR. Moreover, the Faraday efficiency is greater than 95%, with a current density ranging from 10 to 250 mA cm^(-2). This work provides a promising pathway for an efficient and cost-effective NOR catalyst design for economic hydrogen production.
基金This study was financially supported by the National Natural Science Foundation of China(Nos.U21A20332,52103226,52202275,52203314 and 12204253)the Distinguished Young Scholars Fund of Jiangsu Province(No.BK20220061).
文摘The engineering of the electronic configurations of active sites,together with the production of more accessible active sites through heterostructure design,has been established as a forceful methodology for boosting water electrolysis performance.Herein,a facile approach is developed to fabricate well-dispersed MoO_(2) and WO_(2) nanoparticles with abundant heterointerfaces entrapped in N,P-doped carbon nanofibers(referred to as MoO_(2)/WO_(2)@N,P-CNFs hereafter)as hydrogen evolution reaction(HER)electrocatalysts in alkaline and acidic electrolytes.Extensive spectroscopic analyses and theoretical findings manifest that the heterointerface formed by the work function modulation of MoO_(2)/WO_(2) triggers the spontaneous electron redistribution from MoO_(2)to WO_(2) and a built-in electric field,which is essential to promote water adsorption,optimize the H-intermediate adsorption energy,result in the enhanced charge transfer efficiency,and ultimately increase the intrinsic HER activity.Simultaneously,the intimate confinement of MoO_(2)/WO_(2) heterostructures in the porous carbon substrate can restrain the active sites from unfavorable coarsening and detachment,thus ensuring facilitated HER kinetics and outstanding structural robustness.As a result,MoO_(2)/WO_(2)@N,P-CNFs exhibit superior catalytic HER performance in acidic and basic solutions,requiring 118 and 95 mV overpotentials to achieve 10 mA·cm^(−2),respectively,surpassing a number of reported non-noble metal-based electrocatalysts.This work provides guidelines for the rational design and construction of special metallic heterocomponents with optimized interfacial electronic structure for various electrochemical technologies.
基金supported by the National Key Research and Development Program of China(No.2022YFE0110400)the National Natural Science Foundation of China(Nos.52122207,52173245,52130206,U20A20337,and 52221006)the Fundamental Research Funds for the Central Universities(No.CLYY2022).
文摘Ruthenium(Ru)is an attractive potential alternative to platinum as an electrocatalyst for the oxygen reduction reaction(ORR),in virtue of its high catalytic selectivity and relatively low price.In this work,a series of well-dispersed nitrogen-coordinated Ru-clusters on carbon black(Ru_(x)N_(y)/C)were prepared by pyrolyzing different Ru-containing sandwich compounds as the Ru sources.The higher thermal stability of these complexed sandwich precursors(bis(1,2,3,4,5-pentamethylcyclopentadienyl)Ru(II)monomer,dichloro(p-cymene)Ru(II)dimer,and chloro(1,2,3,4,5-pentamethylcyclopentadienyl)Ru(II)tetramer)affords the control of coordinated state for the resulting Ru-clusters,in comparison of that derived from ruthenium chlorides.After the pyrolysis treatment,the Ru coordinated state in Ru_(x)N_(y)/C,with the Ru–N and Ru–Ru bonds,still showed the structural inheritance from the Ru(II)monomer,dimer,and tetramer,but using ruthenium chlorides as the Ru source resulted in the nanoscale Ru agglomerations.The ORR testing exhibited that the Ru_(x)N_(y)/C sample derived from the Ru(II)tetramer(Ru_(x)N_(y)/C-T)presents the higher catalytic activity than the other obtained samples in either alkaline or acidic electrolytes.Even in the acidic electrolyte,Ru_(x)N_(y)/C-T shows the comparable ORR activity to that of Pt/C catalysts,and it shows the superior tolerance against methanol and CO.The X-ray absorption spectroscopy and density functional theory calculations demonstrate that these tetra-nuclear Ru-clusters could be the most active site due to their broadened d-orbital bands and lower energy d-band center than those of other subnano species and nanocrystals,and their favorable Yeager-type adsorption of O_(2)-molecules is also contributed to promoting O–O bond cleavage and accelerating the ORR process.