The transition to sustainable energy systems necessitates efficient hydrogen production via water electrolysis,with anion-exchange membrane water electrolyzers(AEMWEs)emerging as a cost-effective alternative by combin...The transition to sustainable energy systems necessitates efficient hydrogen production via water electrolysis,with anion-exchange membrane water electrolyzers(AEMWEs)emerging as a cost-effective alternative by combining the merits of alkaline water electrolyzers(AWEs)and proton-exchange membrane water electrolyzers(PEMWEs).However,challenges persist in membrane stability,oxygen evolution reaction(OER)kinetics,and mass transport efficiency.This review highlights the pivotal role of transition metal-based layered double hydroxides(LDHs)as high-performance,non-precious OER catalysts for AEMWEs,emphasizing their tunable electronic structures,abundant active sites,and alkaline stability.We systematically outline LDHs synthesis strategies(top-down/bottom-up approaches,and self-supporting LDHs engineering on the conductive substrates),and AEMWE component design,including membraneelectrode assembly optimization and ionomer-free architectures.Standardized evaluation protocols-short-circuit inspection,impedance spectroscopy,and durability assessment are detailed to benchmark performance.Moreover,recent advances in LDHs modification(cation/anion doping,heterojunction design,three-dimensional(3D)electrode structuring)are discussed for alkaline-fed systems,alongside emerging applications in seawater and pure-water electrolysis.By correlating material innovations with device-level metrics,this work provides a roadmap to address scalability challenges,offering perspectives on advancing AEMWEs for sustainable,large-scale hydrogen production.展开更多
Efficient lubrication of magnesium alloys is a highly challenging topic in the field of tribology.In this study,magnesium silicate hydroxide(MSH)nanotubes with serpentine structures were synthesized.The tribological b...Efficient lubrication of magnesium alloys is a highly challenging topic in the field of tribology.In this study,magnesium silicate hydroxide(MSH)nanotubes with serpentine structures were synthesized.The tribological behavior of AZ91D magnesium alloy rubbed against GCr15 steel was studied under lubricating oil with surface-modified MSH nanotubes as additives.The effects of the concentration,applied load,and reciprocating frequency on the friction and wear of the AZ91D alloy were studied using an SRV-4 sliding wear tester.Results show a decrease of 18.7–68.5%in friction coefficient,and a reduction of 19.4–54.3%in wear volume of magnesium alloy can be achieved by applying the synthetic serpentine additive under different conditions.A suspension containing 0.3 wt.%MSH was most efficient in reducing wear and friction.High frequency and medium load were more conducive to improving the tribological properties of magnesium alloys.A series of beneficial physical and chemical processes occurring at the AZ91D alloy/steel interface can be used to explain friction and wear reduction based on the characterization of the morphology,chemical composition,chemical state,microstructure,and nanomechanical properties of the worn surface.The synthetic MSH,with serpentine structure and nanotube morphology,possesses excellent adsorbability,high chemical activity,and good self-lubrication and catalytic activity.Therefore,physical polishing,tribochemical reactions,and physicalchemical depositions can occur easily on the sliding contacts.A dense tribolayer with a complex composition and composite structure was formed on the worn surface.Its high hardness,good toughness and plasticity,and prominent lubricity resulted in the improvement of friction and wear,making the synthetic MSH a promising efficient oil additive for magnesium alloys under boundary and mixed lubrication.展开更多
Precipitation is often used for the preparation of La(OH)_(3)with precipitants of liquid alkali and ammonia.To solve the problems of high cost and wastewater pollution caused by common precipitants,the active MgO synt...Precipitation is often used for the preparation of La(OH)_(3)with precipitants of liquid alkali and ammonia.To solve the problems of high cost and wastewater pollution caused by common precipitants,the active MgO synthesized by pyrolysis was used as the precipitant to prepare La(OH)_(3).The species distribution of LaCl_(3)and LaCl_(3)-MgCl_(2)mixed system solution was calculated,and the kinetic analysis of the precipi-tation process was carried out to confirm the key factors influencing the precipitation of La(OH)_(3).The results show that La(OH)_(3)with D_(50)of 5.57μm,a specific surface area of 25.70 m^(2)/g,a rod-like shape,and MgO content of 0.044 wt%,was successfully prepared by adding active MgO.The precipitation ratio of La reaches 99.92%.The La(OH)_(3)precipitation is controlled by the diffusion process.The activity of MgO has a significant influence on MgO content in the precipitate.The preparation of La(OH)_(3)by active MgO provides a potential way for an eco-friendly preparation method of rare earth.展开更多
Fine nickel powders with a narrow particle size distribution were prepared by reducing nickel hydroxide in aqueous solution.The formation and reduction pathways of nickel powder were analyzed,as well as the effects of...Fine nickel powders with a narrow particle size distribution were prepared by reducing nickel hydroxide in aqueous solution.The formation and reduction pathways of nickel powder were analyzed,as well as the effects of the molar ratio of hydrazine hydrate to nickel hydroxide,hydrazine concentration,and the dosage of surfactant PEG6000 on particle size,surface morphology,and dispersion.Results reveal that the nickel particle nucleation occurs on the nickel hydroxide surface,and the nickel hydroxide gradually dissolves during the reaction.With the increase in molar ratio of hydrazine hydrate to nickel hydroxide,the nickel particle size is initially decreased and then increased.Higher hydrazine hydrate concentrations result in smaller particle sizes.A small amount of PEG6000 surfactant can improve dispersion of nickel particles,but a higher amount of PEG6000 surfactant results in the maintenance of the morphology of nickel hydroxide.Adjusting the surfactant dosage can control the average particle size between 1-2μm.展开更多
The oxygen evolution reaction(OER)is regarded as the bottleneck of electrolytic water splitting.Thus,developing robust earth-abundant electrocatalysts for efficient OER has received a great deal of attention and it is...The oxygen evolution reaction(OER)is regarded as the bottleneck of electrolytic water splitting.Thus,developing robust earth-abundant electrocatalysts for efficient OER has received a great deal of attention and it is an ongoing scientific challenge.Herein,hierarchical hollow nanorods assembled with ultrathin mesoporous cobalt silicate hydroxide nanosheets(denoted as CoSi)were successfully fabricated,using the silica nanotube derived from halloysite as a sacrificial template,via a simple hydrothermal method.The resulting cobalt silicate hydroxide nanosheets stack with thicknesses∼10 nm,as confirmed by transmis-sion electron microscopy.The elaborated nanoarchitecture possesses a high specific surface area(SSA)al-lowing good exposure to the cobalt active centers exhibiting superior catalytic activity vs analogs synthe-sized using sodium silicate.Among all as-prepared CoSi samples,those synthesized at 150℃(CoSi-150)exhibited the minimum overpotential of∼347 mV at a current density of 10 mA cm^(-2).In addition,CoSi-150 also exhibited superior performance against typical cobalt-based catalysts,and its surface hydroxyl groups were beneficial for the enhancement of OER performance.Furthermore,the CoSi-150 showed ex-cellent durability and stability after the 105 s chronopotentiometry test in 1 M KOH.This design concept provides a new strategy for the low-cost preparation of high-quality cobalt water splitting electrocata-lysts.展开更多
Reducing the highly toxic Cr(Ⅵ)to safe levels is a critical challenge in water treatment,essential for protecting both ecosystems and human health.In this study,we present a facile in situ polymerization approach to ...Reducing the highly toxic Cr(Ⅵ)to safe levels is a critical challenge in water treatment,essential for protecting both ecosystems and human health.In this study,we present a facile in situ polymerization approach to prepare polypyrrole-coated layered double hydroxide composites(PPy/NiFe LDHs).Compared with other LDHs and polypyrrole-based materials,the synthesized PPy/LDHs exhibit excellent adsorption performance under mildly acidic conditions,achieving a maximum Cr(Ⅵ)adsorption capacity of440.4 mg/g at pH 5.Notably,PPy/LDH effectively reduces Cr(Ⅵ)concentration from 10 mg/L to 0.028 mg/L,well below the maximum permissible level of 0.05 mg/L for drinking water.Additionally,PPy/LDH demonstrates durable stability;at pH 5,nickel and iron ions are not detected after adsorption,and trivalent chromium remains fixed on the material without re-release into the solution following reduction.The adsorption behavior and mechanistic analysis indicate that a combination of adsorption and reduction drives Cr(Ⅵ)removal by PPy/LDHs.This work offers an innovative approach to effectively remove the low concentrations of Cr(Ⅵ)from water,showing significant potential for efficient Cr(Ⅵ)remediation.展开更多
Synchronously achieving morphological and electronic engineering control is crucial but challenging for enhancing the oxygen evolution reaction(OER)performance of nickel-iron based catalysts.Herein,a ruthenium and sul...Synchronously achieving morphological and electronic engineering control is crucial but challenging for enhancing the oxygen evolution reaction(OER)performance of nickel-iron based catalysts.Herein,a ruthenium and sulfur co-modified nickel-iron hydroxide(S_(A)Ru_(T)-FeNiOH_(x)-5h)was synthesized by a distributed room-temperature impregnation method.It was found that the solubility product difference between ruthenium and nickel-iron hydroxide can promote the rapid nucleation of the catalyst and form finer nanosheet structures,thereby increasing 1.25 times for the contact area between the catalyst and the electrolyte.Meanwhile,the subsequent deposition of sulfur can act as an electronic modulator,promoting the transfer of surface charge at nickel sites and increasing the oxidation state of nickel.Theoretical calculations indicate that the combination of ruthenium and sulfur can effectively optimize the OER reaction pathway and lower the activation energy barrier of the rate-determining step,endowing S_(A)Ru_(T)-FeNiOH_(x)-5h an excellent OER performance with a low overpotential of 253 mV at 1000 mA/cm^(2) and long-term stability(500 h).In the future,it is hoped that this strategy of synergistic control of morphology and electronic structure can be applied to the development of other highly active catalysts.展开更多
Electrocatalysis has emerged as a sustainable approach for the selective oxidation of fatty alcohols to fatty acids,circumventing the environmental concerns associated with conventional routes.However,the low aqueous ...Electrocatalysis has emerged as a sustainable approach for the selective oxidation of fatty alcohols to fatty acids,circumventing the environmental concerns associated with conventional routes.However,the low aqueous solubility of hydrophobic fatty alcohols presents a major challenge.While nickel hydroxide(Ni(OH)_(2))serves as a cost-effective catalyst for alcohol oxidation,its hydrophilic nature limits substrate accessibility and mass transport,causing sluggish kinetics and competing oxygen evolution.Herein,we propose a hydrophobic interface engineering strategy via co-electrodeposition of Ni(OH)_(2)with polytetrafluoroethylene(PTFE),fabricating the composite electrode(ED-Ni(OH)_(2)-PTFE).The optimized electrode achieves 95%Faradaic efficiency for octanoic acid at 1.5 V vs.RHE,with a production rate 2–3 times higher than pristine Ni(OH)_(2).Mechanistic studies combining in situ Raman spectroscopy,fluorescence imaging,and coarse-grained molecular dynamics simulations reveal that PTFE selectively enriches octanol at the electrode-electrolyte interface by modulating interfacial hydrophobicity.A continuous-flow microreactor integrating anodic octanol oxidation with cathodic hydrogen evolution reduces cell voltage by~100 m V,achieving simultaneous fatty acid and hydrogen production.This work highlights the critical role of hydrophobic interfacial microenvironment design in organic electrosynthesis,offering a promising strategy for upgrading fatty alcohols under mild conditions.展开更多
Aluminum hydroxide adjuvant exhibits a poorly crystalline boehmite(PCB)structure,which demonstrates instability during prolonged storage.In the present study,we systematically investigated the quality alterations of t...Aluminum hydroxide adjuvant exhibits a poorly crystalline boehmite(PCB)structure,which demonstrates instability during prolonged storage.In the present study,we systematically investigated the quality alterations of the adjuvant stored at roo m temperature by analyzing its crystal structure,particle size distribution,electron microscopic characteristics,pH,isoelectric point(pI),and adsorption capacity.These assessments aimed to ensure the effectiveness and safety of vaccine production.Three batches of adjuvants were stored at room temperature for 15 months,and their changes were monitored using X-ray diffraction patterns,transmission electron microscopy(TEM),pH measurements,pI determination,and adsorption capacity analysis.X-ray diffraction revealed that the crystalline phases of aluminum hydroxide initially exhibited a PCB structure,which became progressively more ordered during storage.Notably,after 12 months,a new diffraction peak emerged at 18.2°2θ,with its intensity increasing over time.This corresponded to the formation of highly crystalline gibbsite and bayerite,which compromised the stability of the adjuvant.Furthermore,the pH and pI values decreased during storage,reflecting a decline in the chemical stability of the adjuvant.Comprising nanoparticles with a mean diameter of 130 nm,the adjuvant maintained a high surface area and excellent adsorption capacity.The adsorption rate at 8 mg BSA/mg Al3+consistently exceeded 97%,with no statistically significant differences observed between the adsorption capacities at 1 and 15 months(P>0.05).This indicated that the nanoparticle aluminum hydroxide adjuvant sustained high adsorption efficiency throughout the storage period,underscoring its reliability as a vaccine adsorbent.However,in the later stages of storage,the emergence of highly crystalline gibbsite and bayerite,coupled with declines in pH and pI,negatively impacted the adjuvant’s stability.Based on these findings,we recommended that aluminum hydroxide adjuvants should not be stored at room temperature for longer than 12 months to preserve their quality and efficacy.展开更多
Rationally design the morphology and structure of electroactive nanomaterials is an effective approach to enhance the performance of aqueous batteries.Herein,we co-engineered the hollow architecture and interlayer spa...Rationally design the morphology and structure of electroactive nanomaterials is an effective approach to enhance the performance of aqueous batteries.Herein,we co-engineered the hollow architecture and interlayer spacing of layered double hydroxides(LDH)to achieve high electrochemical activity.The hierarchical hollow LDH was prepared from bimetallic zeolitic imidazolate frameworks(ZIF)by a facile cation exchange strategy.Zn and Cu elements were selected as the second metals incorporated in Co-ZIF.The characteristics of the corresponding derivatives were studied.Besides,the transformation mechanism of CoZn-ZIF into nanosheet-assembled hollow Co Zn Ni LDH(denoted as CoZnNi-OH)was systematically investigated.Importantly,the interlayer spacing of CoZnNi-OH expands due to Zn^(2+)incorporation.The prepared CoZnNi-OH offers large surface area,exposed active sites,and rapid mass transfer/diffusion rate,which lead to a significant enhancement in the specific capacitance,rate performance,and cycle stability of CoZnNi-OH electrode.In addition,the aqueous alkaline CoZnNi-OH//Zn showed a maximum energy density/power density of 0.924 m Wh/cm^(2),8.479 m W/cm^(2).This work not only raises an insightful strategy for regulating the morphology and interlayer spacing of LDH,but also provides a reference of designing hollow nickel-based nanomaterials for aqueous batteries.展开更多
The aluminum hydroxide adjuvant possesses a poorly crystalline boehmite (PCB) structure, the stability of which is significantly affected by storage conditions. In the present study, we conducted a comprehensive inves...The aluminum hydroxide adjuvant possesses a poorly crystalline boehmite (PCB) structure, the stability of which is significantly affected by storage conditions. In the present study, we conducted a comprehensive investigation into the structural and quality alterations of aluminum hydroxide adjuvants under varying temperature conditions over time. Three batches of the adjuvant were stored at 2–8℃, 18–25℃, and 37℃, respectively, for 6 months. Key parameters, including X-ray diffraction patterns, pH, isoelectric point (pI), adsorption capacity, and average particle size, were analyzed to assess the impact of storage temperatures. X-ray diffraction analysis confirmed the PCB structure of the aluminum hydroxide adjuvant. Notably, after 1 month of storage at 37℃, new diffraction peaks emerged at 18.2 °2θ, with their intensity increasing progressively over time. Concurrently, the largest decreases in pI and pH were observed, measuring 0.78 and 1.33, respectively. In contrast, adjuvants stored at 2–8℃ for 6 months exhibited only faint diffraction peaks at 18.2 °2θ, indicating minor structural changes. Under these conditions, the reductions in pI and pH were comparatively smaller, at 0.43 and 0.80, respectively. The average particle size of the adjuvants remained within 110–140 nm across all storage conditions. Additionally, the aluminum hydroxide adjuvant consistently demonstrated a high protein adsorption capacity, approximately 8 mg BSA/mg Al^(3+), with no statistically significant differences in adsorption rates observed among the different temperature conditions (P > 0.05). These findings highlighted the remarkable adsorption efficiency of nanoparticle aluminum hydroxide adjuvants throughout storage, reinforcing their potential as superior vaccine adsorbents. However, elevated storage temperatures were shown to accelerate structural aging, promoting the formation of highly crystalline phases such as gibbsite or bayerite, which could compromise the stability and quality of the adjuvant.展开更多
Zinc-nitrate battery could produce electrical power,remove pollutant nitrate and obtain value-added ammonia,where the cathodic reaction of converting nitrate to ammonia is sluggish and complex due to the involvement o...Zinc-nitrate battery could produce electrical power,remove pollutant nitrate and obtain value-added ammonia,where the cathodic reaction of converting nitrate to ammonia is sluggish and complex due to the involvement of multi-electron transfer.Thus,highly efficient catalysts for nitrate reduction reaction(NO_(3)RR)are greatly needed.In this work,we report a high entropy hydroxide(HE-OH)as an excellent NO3RR catalyst,which could achieve high NH_(3)Faradaic efficiencies(e.g.,nearly 100%at-0.3 V versus reversible hydrogen electrode)and high yield rates(e.g.,30.4 mg h^(-1)cm^(-2)at-0.4 V).Moreover,HE-OH could also deliver a current density of 10 mA/cm^(2) at an overpotential of 260 mV for oxygen evolution reaction.The assembled zinc-nitrate battery using HE-OH as the cathode demonstrates a high power density(e.g.,3.62 mW/cm^(2)),rechargeability and stability.展开更多
Aqueous hybrid-ion batteries(AHBs)are a promising class of energy storage devices characterized by low cost,high safety,and high energy density.However,aqueous Cu-Al hybrid-ion batteries face challenges such as sluggi...Aqueous hybrid-ion batteries(AHBs)are a promising class of energy storage devices characterized by low cost,high safety,and high energy density.However,aqueous Cu-Al hybrid-ion batteries face challenges such as sluggish reaction kinetics and severe structural collapse of cathode materials,which limit their practical application.Here,a high-performance aqueous Cu-Al hybrid-ion battery is developed using aluminum pre-inserted Cu_(9)S_(5)(Al-Cu_(9)S_(5))as the cathode material,derived from CuAl-layered double hydroxide(CuAl-LDH).The Al^(3+)pre-intercalation strategy narrows the band gap,enhancing electron transport and improving electrochemical kinetics.The battery exhibits excellent rate performance(463 and 408 mA h g^(-1)at current densities of 500 and 1000 mA g^(-1),respectively)and good cycle stability(with a capacity retention ratio of 81% after 300 cycles at a current density of 1000 mA g^(-1)).Its performance surpasses that of most reported Al-ion batteries.Ex situ characterization and density functional theory(DFT)calculations reveal that the pre-intercalated Al^(3+)in Al-Cu9S5participates in the reversible embedding/removal of Al ions during charge/discharge processes.These findings provide valuable insights for designing pre-intercalated cathodes in aqueous Cu-Al hybrid-ion batteries with stable cycle life.展开更多
Layered double hydroxides(LDHs)are potential cathode materials for aqueous magnesium-ion batteries(AMIBs).However,the low capacity and sluggish kinetics significantly limit their electrochemical performance in AMIBs.H...Layered double hydroxides(LDHs)are potential cathode materials for aqueous magnesium-ion batteries(AMIBs).However,the low capacity and sluggish kinetics significantly limit their electrochemical performance in AMIBs.Herein,we find that oxygen vacancies can significantly boost the capacity,electrochemical kinetics,and structure stability of LDHs.The corresponding structure-performance relationship and energy storage mechanism are elaborated through exhaustive in/ex-situ experimental characterizations and density functional theory(DFT)calculations.Specially,in-situ Raman and DFT calculations reveal that oxygen vacancies elevate orbital energy of O 2p and electron density of O atoms,thereby enhancing the orbital hybridization of O 2p with Ni/Co 3d.This facilitates electron transfer between O and adjacent Ni/Co atoms and improves the covalency of Ni–O and Co–O bonds,which activates Ni/Co atoms to release more capacity and stabilizes the Ov-NiCo-LDH structure.Moreover,the distribution of relaxation times(DRT)and molecular dynamics(MD)simulations disclose that the enhanced d-p orbital hybridization optimizes the electronic structure of Ov-NiCo-LDH,which distinctly reduces the diffusion energy barriers of Mg^(2+)and improves the charge transfer kinetics of Ov-NiCo-LDH.Consequently,the assembled Ov-NiCo-LDH//active carbon(AC)and Ov-NiCo-LDH//perylenediimide(PTCDI)AMIBs can both deliver high specific discharge capacity(182.7 and 59.4 mAh g^(−1)at 0.5 A g^(−1),respectively)and long-term cycling stability(85.4%and 89.0%of capacity retentions after 2500 and 2400 cycles at 1.0 A g^(−1),respectively).In addition,the practical prospects for Ov-NiCo-LDH-based AMIBs have been demonstrated in different application scenarios.This work not only provides an effective strategy for obtaining high-performance cathodes of AMIBs,but also fundamentally elucidates the inherent mechanisms.展开更多
Noble metal-loaded layered hydroxides exhibit high efficiency in electrocatalyzing water splitting.However,their widespread use as bifunctional electrocatalysts is hindered by low metal loading,inefficient yield,and c...Noble metal-loaded layered hydroxides exhibit high efficiency in electrocatalyzing water splitting.However,their widespread use as bifunctional electrocatalysts is hindered by low metal loading,inefficient yield,and complex synthesis processes.In this work,platinum atoms were anchored onto nickel-iron layered double hydroxide/carbon nanotube(LDH/CNT)hybrid electrocatalysts by using a straightforward milling technique with K_(2)Pt Cl_(6)·6H_(2)O as the Pt source.By adjusting the Pt-to-Fe ratio to 1/2 and 1/10,excellent electrocatalysts—Pt_(1/6)-Ni_(2/3)Fe_(1/3)-LDH/CNT and Pt_(1/30)-Ni_(2/3)Fe_(1/3)-LDH/CNT—were achieved with superior performance in hydrogen evolution reaction(HER)and oxygen evolution reaction(OER),outperforming the corresponding commercial Pt/C(20 wt%)and Ru O_(2)electrocatalysts.The enhanced electrochemical performance is attributed to the modification of Pt's electronic structure,which exhibits electron-rich states for HER and electrondeficient states for OER,significantly boosting Pt's electrochemical activity.Furthermore,the simple milling technology for controlling Pt loading offers a promising approach for scaling up the production of electrocatalysts.展开更多
Amorphous two-dimensional transition metal oxide/(oxy)hydroxide(2D TMO/TMHO)nanomaterials(NMs)have the properties of both 2D and amorphous materials,displaying outstanding physicochemical qualities.Therefore,they demo...Amorphous two-dimensional transition metal oxide/(oxy)hydroxide(2D TMO/TMHO)nanomaterials(NMs)have the properties of both 2D and amorphous materials,displaying outstanding physicochemical qualities.Therefore,they demonstrate considerable promise for use in electrocatalytic water splitting applications.Here,the primary amorphization strategies for achieving the 2D TMO/TMHO NMs are comprehensively reviewed,including low-temperature reaction,rapid reaction,exchange/doping effect,ligand modulation,and interfacial energy confinement.By integrating these strategies with various physicochemical synthesis methods,it is feasible to control the amorphization of TMO/TMHO NMs while maintaining the distinctive benefits of their 2D structures.Furthermore,it delves into the structural advantages of amorphous 2D TMO/TMHO NMs in electrocatalytic water splitting,particularly emphasizing recent advancements in enhancing their electrocatalytic performance through interface engineering.The challenges and potential future directions for the precise synthesis and practical application of amorphous 2D TMO/TMHO NMs are also provided.This review aims to establish a theoretical foundation and offer experimental instructions for developing effective and enduring electrocatalysts for water splitting.展开更多
Developing an efficient electrocatalyst for superior electrochemical water splitting(EWS)is crucial for achieving comprehensive hydrogen production.A heterostructured electrocatalyst,free of noble metals,Ti_(3)C_(2)MX...Developing an efficient electrocatalyst for superior electrochemical water splitting(EWS)is crucial for achieving comprehensive hydrogen production.A heterostructured electrocatalyst,free of noble metals,Ti_(3)C_(2)MXene nanosheet-integrated cobalt-doped nickel hydroxide(NHCoMX)composite was synthesized via a hydrothermal method.The abundant pores in the Ti_(3)C_(2)MXene nanosheet(MX)-integrated microarchitecture increased the number of active sites and facilitated charge transfer,thus enhancing electrocatalysis.Specifically,the MXenhanced charge transfer considerably transformed the microelectronic structure of cobalt-doped Ni(OH)2(NHCo),which promoted its hydrogen evolution reaction(HER)and oxygen evolution reaction(OER).Hence,as an EWS catalyst,NHCoMX exhibited an exceptional electrocatalytic activity,demonstrating OER and HER overpotentials of 310 mV and 73 mV,respectively,with low Tafel slopes of 65 mV dec^(-1)and 85 mV dec^(-1),respectively;it exhibited a current density of 10 mV cm^(-2)in 1.0 mol L^(-1)KOH,representing the closest efficiency to the noble state-of-the-art RuO2 and Pt/C catalyst.Furthermore,the developed electrocatalyst improved the activities of both HER and OER,leading to an overall EWS current density of 10 mA cm^(-2)at 1.72 V in an alkaline electrolyte with two electrodes.This study describes an efficient heterostructured NHCoMX composite electrocatalyst.It is significantly comparable to the noble state-of-the-art electrocatalysts and can be extended to fabricate resourceful catalysts for large-scale EWS applications.展开更多
Carbon-based materials exhibit excellent dielectric absorption properties,among which graphene has received particular attention in research of electromagnetic wave absorbing materials because of its high electrical c...Carbon-based materials exhibit excellent dielectric absorption properties,among which graphene has received particular attention in research of electromagnetic wave absorbing materials because of its high electrical conductivity and unique large-area,thin-layer two-dimensional structural features.However,the electromagnetic absorption performance of the material is hindered from further improvement due to its single component composition.It is influenced by the conductive network of graphene,making it challenging to achieve a balance in impedance matching and electromagnetic loss,thereby restricting its broader application.To address these challenges,we developed a series of nickel hydroxide-modified graphene composites.Through a structural composite design,we optimized overall impedance matching,introduced diverse loss mechanisms to enhance electromagnetic loss performance,and utilized a secondary reaction control method to precisely regulate the deposition of nickel hydroxide on the graphene surface,thereby achieving regulate of the composite material's electromagnetic parameters within a defined range.Under low sample filling ratios and a thin sample thickness of 1.8 mm,the effective absorption bandwidth reaches 6.5 GHz,demonstrating excellent electromagnetic absorption performance.This study provides a controllable design approach for modulating material electromagnetic parameters by influencing the reaction process.It also offers a design method for composites with an outstanding electromagnetic loss mechanism.展开更多
The sluggish kinetics of the oxygen evolution reaction(OER)process impedes the exploration of green hydrogen via water splitting.Herein,we design and synthesize vanadium-doped CoSn(OH)_(6)perovskite hydroxide catalyst...The sluggish kinetics of the oxygen evolution reaction(OER)process impedes the exploration of green hydrogen via water splitting.Herein,we design and synthesize vanadium-doped CoSn(OH)_(6)perovskite hydroxide catalysts by Fe^(3+)etching during the hydrothermal and chemical deposition process.The as-prepared CoVSn(OH)_(6)@CoVSnFe(OH)_(x)-4 catalyst exhibits a lowoverpotential of 225 mV at 10 mA·cm^(-2)with a Tafel slope of 30.47 mV·dec^(-1).An overall water splitting electrolyzer(CoVSn(OH)_(6)@CoVSnFe(OH)_(x)-4‖Pt/C)is constructed,delivering a voltage of 1.48 V at a current density of10 mA·cm^(-2)with excellent durability.The dynamic phase evolution during the OER process is revealed by in situ Raman and XPS measurement,which represents that the introduced V and Fe ions facilitate the formation of active CoOOH as well as modify the electronic structure of the catalyst.Density functional theory(DFT)calculations further evidence that V and Fe introduction optimize the adsorption energies of oxygen intermediates*OH and*O,respectively,thereby enabling a synergistic optimization of the multi-step OER process and advancing electrocatalytic performance.展开更多
Novel and promising chloride ion batteries(CIBs)that can operate at room temperature have attracted great attentions,due to the sustainable chloride-containing resources and high theoretical energy density.To achieve ...Novel and promising chloride ion batteries(CIBs)that can operate at room temperature have attracted great attentions,due to the sustainable chloride-containing resources and high theoretical energy density.To achieve the superior electrochemical properties of CIBs,the structure design of electrode materials is essential.Herein,2D NiAl-layered double hydroxide(NiAl-LDH)nanoarrays derived from Al2O3 are in-situ grafted to graphene(G)by atomic layer deposition(ALD)and hydrothermal method.The achieved NiAl-LDH@G hybrids with 2D NiAl-LDH arrays grown perpendicularly on graphene surface,can efficiently prevent the stacking of LDHs and enlarge specific surface area to provide more active sites.The NiAl-LDH@G cathode exhibits a maximum discharge capacity of 223.3 mA h g^(-1)and an excellent reversible capacity of 107 mA h g^(-1)over 500 cycles at 100 mA g^(-1)with a high coulombic efficiency around 96%,whereas pure NiAl-LDH has a discharge capacity of only 48.8 mA h g^(-1)and a coulombic efficiency(CE)of about 78%.More importantly,the NiAl-LDH@G electrode has a stable voltage at 1.9 V and an outstanding discharge capacity of higher than 72 mA h g^(-1)after 120 days.Additionally,XRD,XPS,and EDS have been employed to unveil the electrochemical reaction and Cl-storage mechanism of the NiAlLDH@G cathode in CIBs.This work opens a facile and reasonable way for improving electrochemical performance at anion-type rechargeable batteries in terms of cathode material design and mechanism interpretation.展开更多
基金supported by the National Natural Science Foundation of China(Nos.52122308 and 22305225)the Postdoctoral Fellowship Program of CPSF(No.GZC20232391).
文摘The transition to sustainable energy systems necessitates efficient hydrogen production via water electrolysis,with anion-exchange membrane water electrolyzers(AEMWEs)emerging as a cost-effective alternative by combining the merits of alkaline water electrolyzers(AWEs)and proton-exchange membrane water electrolyzers(PEMWEs).However,challenges persist in membrane stability,oxygen evolution reaction(OER)kinetics,and mass transport efficiency.This review highlights the pivotal role of transition metal-based layered double hydroxides(LDHs)as high-performance,non-precious OER catalysts for AEMWEs,emphasizing their tunable electronic structures,abundant active sites,and alkaline stability.We systematically outline LDHs synthesis strategies(top-down/bottom-up approaches,and self-supporting LDHs engineering on the conductive substrates),and AEMWE component design,including membraneelectrode assembly optimization and ionomer-free architectures.Standardized evaluation protocols-short-circuit inspection,impedance spectroscopy,and durability assessment are detailed to benchmark performance.Moreover,recent advances in LDHs modification(cation/anion doping,heterojunction design,three-dimensional(3D)electrode structuring)are discussed for alkaline-fed systems,alongside emerging applications in seawater and pure-water electrolysis.By correlating material innovations with device-level metrics,this work provides a roadmap to address scalability challenges,offering perspectives on advancing AEMWEs for sustainable,large-scale hydrogen production.
基金support from the National Natural Science Foundation of China(grant number 52075544)Innovation Funds of Jihua Laboratory(X220971UZ230)+1 种基金Basic and Applied Basic Research Foundation of Guangdong Province(2022A1515110649)Funds from Research Platforms of Guangdong Higher Education Institutes(2022ZDJS038).
文摘Efficient lubrication of magnesium alloys is a highly challenging topic in the field of tribology.In this study,magnesium silicate hydroxide(MSH)nanotubes with serpentine structures were synthesized.The tribological behavior of AZ91D magnesium alloy rubbed against GCr15 steel was studied under lubricating oil with surface-modified MSH nanotubes as additives.The effects of the concentration,applied load,and reciprocating frequency on the friction and wear of the AZ91D alloy were studied using an SRV-4 sliding wear tester.Results show a decrease of 18.7–68.5%in friction coefficient,and a reduction of 19.4–54.3%in wear volume of magnesium alloy can be achieved by applying the synthetic serpentine additive under different conditions.A suspension containing 0.3 wt.%MSH was most efficient in reducing wear and friction.High frequency and medium load were more conducive to improving the tribological properties of magnesium alloys.A series of beneficial physical and chemical processes occurring at the AZ91D alloy/steel interface can be used to explain friction and wear reduction based on the characterization of the morphology,chemical composition,chemical state,microstructure,and nanomechanical properties of the worn surface.The synthetic MSH,with serpentine structure and nanotube morphology,possesses excellent adsorbability,high chemical activity,and good self-lubrication and catalytic activity.Therefore,physical polishing,tribochemical reactions,and physicalchemical depositions can occur easily on the sliding contacts.A dense tribolayer with a complex composition and composite structure was formed on the worn surface.Its high hardness,good toughness and plasticity,and prominent lubricity resulted in the improvement of friction and wear,making the synthetic MSH a promising efficient oil additive for magnesium alloys under boundary and mixed lubrication.
基金the National Key Research and Development Program of China(2022YFB3504503)the National Natural Science Foundation of China(52274355)the Gansu Province Science and Technology Major Special Project,China(22ZD6GD061).
文摘Precipitation is often used for the preparation of La(OH)_(3)with precipitants of liquid alkali and ammonia.To solve the problems of high cost and wastewater pollution caused by common precipitants,the active MgO synthesized by pyrolysis was used as the precipitant to prepare La(OH)_(3).The species distribution of LaCl_(3)and LaCl_(3)-MgCl_(2)mixed system solution was calculated,and the kinetic analysis of the precipi-tation process was carried out to confirm the key factors influencing the precipitation of La(OH)_(3).The results show that La(OH)_(3)with D_(50)of 5.57μm,a specific surface area of 25.70 m^(2)/g,a rod-like shape,and MgO content of 0.044 wt%,was successfully prepared by adding active MgO.The precipitation ratio of La reaches 99.92%.The La(OH)_(3)precipitation is controlled by the diffusion process.The activity of MgO has a significant influence on MgO content in the precipitate.The preparation of La(OH)_(3)by active MgO provides a potential way for an eco-friendly preparation method of rare earth.
基金National Natural Science Foundation of China(51704257,52174350)Hunan Provincial Science and Technology Innovation Program(2024AQ2039)。
文摘Fine nickel powders with a narrow particle size distribution were prepared by reducing nickel hydroxide in aqueous solution.The formation and reduction pathways of nickel powder were analyzed,as well as the effects of the molar ratio of hydrazine hydrate to nickel hydroxide,hydrazine concentration,and the dosage of surfactant PEG6000 on particle size,surface morphology,and dispersion.Results reveal that the nickel particle nucleation occurs on the nickel hydroxide surface,and the nickel hydroxide gradually dissolves during the reaction.With the increase in molar ratio of hydrazine hydrate to nickel hydroxide,the nickel particle size is initially decreased and then increased.Higher hydrazine hydrate concentrations result in smaller particle sizes.A small amount of PEG6000 surfactant can improve dispersion of nickel particles,but a higher amount of PEG6000 surfactant results in the maintenance of the morphology of nickel hydroxide.Adjusting the surfactant dosage can control the average particle size between 1-2μm.
基金supported by the Central Government Guiding Local Science and Technology Development Fund Projects(No.236Z4108G)China Scholarship Council,the National Natu-ral Science Foundation of China(No.51874115)+2 种基金the Open Project of State Key Laboratory of Environment-friendly Energy Materials(No.22kfhg09)the Open Project of Key Laboratory of Solid Waste Treatment and Resource Recycle of Ministry of Education(No.22kfgk01)the Youth Talent Support Program of Hebei Province,the Giant Plan Innovation Team Project of Hebei Province,and the Excellent Young Scientist Foundation of Hebei province,China(No.E2018202241).
文摘The oxygen evolution reaction(OER)is regarded as the bottleneck of electrolytic water splitting.Thus,developing robust earth-abundant electrocatalysts for efficient OER has received a great deal of attention and it is an ongoing scientific challenge.Herein,hierarchical hollow nanorods assembled with ultrathin mesoporous cobalt silicate hydroxide nanosheets(denoted as CoSi)were successfully fabricated,using the silica nanotube derived from halloysite as a sacrificial template,via a simple hydrothermal method.The resulting cobalt silicate hydroxide nanosheets stack with thicknesses∼10 nm,as confirmed by transmis-sion electron microscopy.The elaborated nanoarchitecture possesses a high specific surface area(SSA)al-lowing good exposure to the cobalt active centers exhibiting superior catalytic activity vs analogs synthe-sized using sodium silicate.Among all as-prepared CoSi samples,those synthesized at 150℃(CoSi-150)exhibited the minimum overpotential of∼347 mV at a current density of 10 mA cm^(-2).In addition,CoSi-150 also exhibited superior performance against typical cobalt-based catalysts,and its surface hydroxyl groups were beneficial for the enhancement of OER performance.Furthermore,the CoSi-150 showed ex-cellent durability and stability after the 105 s chronopotentiometry test in 1 M KOH.This design concept provides a new strategy for the low-cost preparation of high-quality cobalt water splitting electrocata-lysts.
基金supported by the National Natural Science Foundation of China(Nos.52370070,and 52070047)。
文摘Reducing the highly toxic Cr(Ⅵ)to safe levels is a critical challenge in water treatment,essential for protecting both ecosystems and human health.In this study,we present a facile in situ polymerization approach to prepare polypyrrole-coated layered double hydroxide composites(PPy/NiFe LDHs).Compared with other LDHs and polypyrrole-based materials,the synthesized PPy/LDHs exhibit excellent adsorption performance under mildly acidic conditions,achieving a maximum Cr(Ⅵ)adsorption capacity of440.4 mg/g at pH 5.Notably,PPy/LDH effectively reduces Cr(Ⅵ)concentration from 10 mg/L to 0.028 mg/L,well below the maximum permissible level of 0.05 mg/L for drinking water.Additionally,PPy/LDH demonstrates durable stability;at pH 5,nickel and iron ions are not detected after adsorption,and trivalent chromium remains fixed on the material without re-release into the solution following reduction.The adsorption behavior and mechanistic analysis indicate that a combination of adsorption and reduction drives Cr(Ⅵ)removal by PPy/LDHs.This work offers an innovative approach to effectively remove the low concentrations of Cr(Ⅵ)from water,showing significant potential for efficient Cr(Ⅵ)remediation.
基金financially supported by Shandong Provincial Natural Science Foundation(No.ZR2024QB021)Qingdao Natural Science Foundation(No.24–4-4-zrjj-21-jch)National Natural Science Foundation of China(Nos.62204098,62304124,22309107)。
文摘Synchronously achieving morphological and electronic engineering control is crucial but challenging for enhancing the oxygen evolution reaction(OER)performance of nickel-iron based catalysts.Herein,a ruthenium and sulfur co-modified nickel-iron hydroxide(S_(A)Ru_(T)-FeNiOH_(x)-5h)was synthesized by a distributed room-temperature impregnation method.It was found that the solubility product difference between ruthenium and nickel-iron hydroxide can promote the rapid nucleation of the catalyst and form finer nanosheet structures,thereby increasing 1.25 times for the contact area between the catalyst and the electrolyte.Meanwhile,the subsequent deposition of sulfur can act as an electronic modulator,promoting the transfer of surface charge at nickel sites and increasing the oxidation state of nickel.Theoretical calculations indicate that the combination of ruthenium and sulfur can effectively optimize the OER reaction pathway and lower the activation energy barrier of the rate-determining step,endowing S_(A)Ru_(T)-FeNiOH_(x)-5h an excellent OER performance with a low overpotential of 253 mV at 1000 mA/cm^(2) and long-term stability(500 h).In the future,it is hoped that this strategy of synergistic control of morphology and electronic structure can be applied to the development of other highly active catalysts.
基金Financial supports from the National Natural Science Foundation(No.21991104 and No.22,278,235)。
文摘Electrocatalysis has emerged as a sustainable approach for the selective oxidation of fatty alcohols to fatty acids,circumventing the environmental concerns associated with conventional routes.However,the low aqueous solubility of hydrophobic fatty alcohols presents a major challenge.While nickel hydroxide(Ni(OH)_(2))serves as a cost-effective catalyst for alcohol oxidation,its hydrophilic nature limits substrate accessibility and mass transport,causing sluggish kinetics and competing oxygen evolution.Herein,we propose a hydrophobic interface engineering strategy via co-electrodeposition of Ni(OH)_(2)with polytetrafluoroethylene(PTFE),fabricating the composite electrode(ED-Ni(OH)_(2)-PTFE).The optimized electrode achieves 95%Faradaic efficiency for octanoic acid at 1.5 V vs.RHE,with a production rate 2–3 times higher than pristine Ni(OH)_(2).Mechanistic studies combining in situ Raman spectroscopy,fluorescence imaging,and coarse-grained molecular dynamics simulations reveal that PTFE selectively enriches octanol at the electrode-electrolyte interface by modulating interfacial hydrophobicity.A continuous-flow microreactor integrating anodic octanol oxidation with cathodic hydrogen evolution reduces cell voltage by~100 m V,achieving simultaneous fatty acid and hydrogen production.This work highlights the critical role of hydrophobic interfacial microenvironment design in organic electrosynthesis,offering a promising strategy for upgrading fatty alcohols under mild conditions.
文摘Aluminum hydroxide adjuvant exhibits a poorly crystalline boehmite(PCB)structure,which demonstrates instability during prolonged storage.In the present study,we systematically investigated the quality alterations of the adjuvant stored at roo m temperature by analyzing its crystal structure,particle size distribution,electron microscopic characteristics,pH,isoelectric point(pI),and adsorption capacity.These assessments aimed to ensure the effectiveness and safety of vaccine production.Three batches of adjuvants were stored at room temperature for 15 months,and their changes were monitored using X-ray diffraction patterns,transmission electron microscopy(TEM),pH measurements,pI determination,and adsorption capacity analysis.X-ray diffraction revealed that the crystalline phases of aluminum hydroxide initially exhibited a PCB structure,which became progressively more ordered during storage.Notably,after 12 months,a new diffraction peak emerged at 18.2°2θ,with its intensity increasing over time.This corresponded to the formation of highly crystalline gibbsite and bayerite,which compromised the stability of the adjuvant.Furthermore,the pH and pI values decreased during storage,reflecting a decline in the chemical stability of the adjuvant.Comprising nanoparticles with a mean diameter of 130 nm,the adjuvant maintained a high surface area and excellent adsorption capacity.The adsorption rate at 8 mg BSA/mg Al3+consistently exceeded 97%,with no statistically significant differences observed between the adsorption capacities at 1 and 15 months(P>0.05).This indicated that the nanoparticle aluminum hydroxide adjuvant sustained high adsorption efficiency throughout the storage period,underscoring its reliability as a vaccine adsorbent.However,in the later stages of storage,the emergence of highly crystalline gibbsite and bayerite,coupled with declines in pH and pI,negatively impacted the adjuvant’s stability.Based on these findings,we recommended that aluminum hydroxide adjuvants should not be stored at room temperature for longer than 12 months to preserve their quality and efficacy.
基金supported by the National Natural Science Foundation of China(Nos.52371240,U1904215)Natural Science Foundation of Jiangsu Province(No.BK20200044)Changjiang scholars’program of the Ministry of Education(No.Q2018270)。
文摘Rationally design the morphology and structure of electroactive nanomaterials is an effective approach to enhance the performance of aqueous batteries.Herein,we co-engineered the hollow architecture and interlayer spacing of layered double hydroxides(LDH)to achieve high electrochemical activity.The hierarchical hollow LDH was prepared from bimetallic zeolitic imidazolate frameworks(ZIF)by a facile cation exchange strategy.Zn and Cu elements were selected as the second metals incorporated in Co-ZIF.The characteristics of the corresponding derivatives were studied.Besides,the transformation mechanism of CoZn-ZIF into nanosheet-assembled hollow Co Zn Ni LDH(denoted as CoZnNi-OH)was systematically investigated.Importantly,the interlayer spacing of CoZnNi-OH expands due to Zn^(2+)incorporation.The prepared CoZnNi-OH offers large surface area,exposed active sites,and rapid mass transfer/diffusion rate,which lead to a significant enhancement in the specific capacitance,rate performance,and cycle stability of CoZnNi-OH electrode.In addition,the aqueous alkaline CoZnNi-OH//Zn showed a maximum energy density/power density of 0.924 m Wh/cm^(2),8.479 m W/cm^(2).This work not only raises an insightful strategy for regulating the morphology and interlayer spacing of LDH,but also provides a reference of designing hollow nickel-based nanomaterials for aqueous batteries.
文摘The aluminum hydroxide adjuvant possesses a poorly crystalline boehmite (PCB) structure, the stability of which is significantly affected by storage conditions. In the present study, we conducted a comprehensive investigation into the structural and quality alterations of aluminum hydroxide adjuvants under varying temperature conditions over time. Three batches of the adjuvant were stored at 2–8℃, 18–25℃, and 37℃, respectively, for 6 months. Key parameters, including X-ray diffraction patterns, pH, isoelectric point (pI), adsorption capacity, and average particle size, were analyzed to assess the impact of storage temperatures. X-ray diffraction analysis confirmed the PCB structure of the aluminum hydroxide adjuvant. Notably, after 1 month of storage at 37℃, new diffraction peaks emerged at 18.2 °2θ, with their intensity increasing progressively over time. Concurrently, the largest decreases in pI and pH were observed, measuring 0.78 and 1.33, respectively. In contrast, adjuvants stored at 2–8℃ for 6 months exhibited only faint diffraction peaks at 18.2 °2θ, indicating minor structural changes. Under these conditions, the reductions in pI and pH were comparatively smaller, at 0.43 and 0.80, respectively. The average particle size of the adjuvants remained within 110–140 nm across all storage conditions. Additionally, the aluminum hydroxide adjuvant consistently demonstrated a high protein adsorption capacity, approximately 8 mg BSA/mg Al^(3+), with no statistically significant differences in adsorption rates observed among the different temperature conditions (P > 0.05). These findings highlighted the remarkable adsorption efficiency of nanoparticle aluminum hydroxide adjuvants throughout storage, reinforcing their potential as superior vaccine adsorbents. However, elevated storage temperatures were shown to accelerate structural aging, promoting the formation of highly crystalline phases such as gibbsite or bayerite, which could compromise the stability and quality of the adjuvant.
基金financially supported by the National Natural Science Foundation of China(Nos.22209040 and 22202063)。
文摘Zinc-nitrate battery could produce electrical power,remove pollutant nitrate and obtain value-added ammonia,where the cathodic reaction of converting nitrate to ammonia is sluggish and complex due to the involvement of multi-electron transfer.Thus,highly efficient catalysts for nitrate reduction reaction(NO_(3)RR)are greatly needed.In this work,we report a high entropy hydroxide(HE-OH)as an excellent NO3RR catalyst,which could achieve high NH_(3)Faradaic efficiencies(e.g.,nearly 100%at-0.3 V versus reversible hydrogen electrode)and high yield rates(e.g.,30.4 mg h^(-1)cm^(-2)at-0.4 V).Moreover,HE-OH could also deliver a current density of 10 mA/cm^(2) at an overpotential of 260 mV for oxygen evolution reaction.The assembled zinc-nitrate battery using HE-OH as the cathode demonstrates a high power density(e.g.,3.62 mW/cm^(2)),rechargeability and stability.
基金supported by the National Natural Science Foundation of China(Nos.22278020 and 2177060378)the Fundamental Research Funds for the Central Universities(Nos.12060093063 and XK1803-05)the Program for Changjiang Scholars and Innovative Research Teams in University(No.IRT1205)。
文摘Aqueous hybrid-ion batteries(AHBs)are a promising class of energy storage devices characterized by low cost,high safety,and high energy density.However,aqueous Cu-Al hybrid-ion batteries face challenges such as sluggish reaction kinetics and severe structural collapse of cathode materials,which limit their practical application.Here,a high-performance aqueous Cu-Al hybrid-ion battery is developed using aluminum pre-inserted Cu_(9)S_(5)(Al-Cu_(9)S_(5))as the cathode material,derived from CuAl-layered double hydroxide(CuAl-LDH).The Al^(3+)pre-intercalation strategy narrows the band gap,enhancing electron transport and improving electrochemical kinetics.The battery exhibits excellent rate performance(463 and 408 mA h g^(-1)at current densities of 500 and 1000 mA g^(-1),respectively)and good cycle stability(with a capacity retention ratio of 81% after 300 cycles at a current density of 1000 mA g^(-1)).Its performance surpasses that of most reported Al-ion batteries.Ex situ characterization and density functional theory(DFT)calculations reveal that the pre-intercalated Al^(3+)in Al-Cu9S5participates in the reversible embedding/removal of Al ions during charge/discharge processes.These findings provide valuable insights for designing pre-intercalated cathodes in aqueous Cu-Al hybrid-ion batteries with stable cycle life.
基金financial support of the National Natural Science Foundation of China (22379063)
文摘Layered double hydroxides(LDHs)are potential cathode materials for aqueous magnesium-ion batteries(AMIBs).However,the low capacity and sluggish kinetics significantly limit their electrochemical performance in AMIBs.Herein,we find that oxygen vacancies can significantly boost the capacity,electrochemical kinetics,and structure stability of LDHs.The corresponding structure-performance relationship and energy storage mechanism are elaborated through exhaustive in/ex-situ experimental characterizations and density functional theory(DFT)calculations.Specially,in-situ Raman and DFT calculations reveal that oxygen vacancies elevate orbital energy of O 2p and electron density of O atoms,thereby enhancing the orbital hybridization of O 2p with Ni/Co 3d.This facilitates electron transfer between O and adjacent Ni/Co atoms and improves the covalency of Ni–O and Co–O bonds,which activates Ni/Co atoms to release more capacity and stabilizes the Ov-NiCo-LDH structure.Moreover,the distribution of relaxation times(DRT)and molecular dynamics(MD)simulations disclose that the enhanced d-p orbital hybridization optimizes the electronic structure of Ov-NiCo-LDH,which distinctly reduces the diffusion energy barriers of Mg^(2+)and improves the charge transfer kinetics of Ov-NiCo-LDH.Consequently,the assembled Ov-NiCo-LDH//active carbon(AC)and Ov-NiCo-LDH//perylenediimide(PTCDI)AMIBs can both deliver high specific discharge capacity(182.7 and 59.4 mAh g^(−1)at 0.5 A g^(−1),respectively)and long-term cycling stability(85.4%and 89.0%of capacity retentions after 2500 and 2400 cycles at 1.0 A g^(−1),respectively).In addition,the practical prospects for Ov-NiCo-LDH-based AMIBs have been demonstrated in different application scenarios.This work not only provides an effective strategy for obtaining high-performance cathodes of AMIBs,but also fundamentally elucidates the inherent mechanisms.
基金supported by the Natural Science Foundation of Henan(242300421230)the Young Teacher Fundamental Research Cultivation Program of Zhengzhou University(JC23557030)the National Natural Science Foundation of China(U21A20281 and 22208322)。
文摘Noble metal-loaded layered hydroxides exhibit high efficiency in electrocatalyzing water splitting.However,their widespread use as bifunctional electrocatalysts is hindered by low metal loading,inefficient yield,and complex synthesis processes.In this work,platinum atoms were anchored onto nickel-iron layered double hydroxide/carbon nanotube(LDH/CNT)hybrid electrocatalysts by using a straightforward milling technique with K_(2)Pt Cl_(6)·6H_(2)O as the Pt source.By adjusting the Pt-to-Fe ratio to 1/2 and 1/10,excellent electrocatalysts—Pt_(1/6)-Ni_(2/3)Fe_(1/3)-LDH/CNT and Pt_(1/30)-Ni_(2/3)Fe_(1/3)-LDH/CNT—were achieved with superior performance in hydrogen evolution reaction(HER)and oxygen evolution reaction(OER),outperforming the corresponding commercial Pt/C(20 wt%)and Ru O_(2)electrocatalysts.The enhanced electrochemical performance is attributed to the modification of Pt's electronic structure,which exhibits electron-rich states for HER and electrondeficient states for OER,significantly boosting Pt's electrochemical activity.Furthermore,the simple milling technology for controlling Pt loading offers a promising approach for scaling up the production of electrocatalysts.
基金supported by the National Key Research and Development Program of China(No.2018YFA0703700)the National Natural Science Foundation of China(No.12034002)the Interdisciplinary Research Project for Young Teachers of USTB(Fundamental Research Funds for the Central Universities,No.FRF-IDRY-23-033)。
文摘Amorphous two-dimensional transition metal oxide/(oxy)hydroxide(2D TMO/TMHO)nanomaterials(NMs)have the properties of both 2D and amorphous materials,displaying outstanding physicochemical qualities.Therefore,they demonstrate considerable promise for use in electrocatalytic water splitting applications.Here,the primary amorphization strategies for achieving the 2D TMO/TMHO NMs are comprehensively reviewed,including low-temperature reaction,rapid reaction,exchange/doping effect,ligand modulation,and interfacial energy confinement.By integrating these strategies with various physicochemical synthesis methods,it is feasible to control the amorphization of TMO/TMHO NMs while maintaining the distinctive benefits of their 2D structures.Furthermore,it delves into the structural advantages of amorphous 2D TMO/TMHO NMs in electrocatalytic water splitting,particularly emphasizing recent advancements in enhancing their electrocatalytic performance through interface engineering.The challenges and potential future directions for the precise synthesis and practical application of amorphous 2D TMO/TMHO NMs are also provided.This review aims to establish a theoretical foundation and offer experimental instructions for developing effective and enduring electrocatalysts for water splitting.
基金supported by the Basic Science Research Program through the National Research Foundation of Korea(NRF),funded by the Ministry of Education(NRF-2018R1A6A1A03024962)the Ministry of Science and ICT(NRF-2020R1A2C2100746).
文摘Developing an efficient electrocatalyst for superior electrochemical water splitting(EWS)is crucial for achieving comprehensive hydrogen production.A heterostructured electrocatalyst,free of noble metals,Ti_(3)C_(2)MXene nanosheet-integrated cobalt-doped nickel hydroxide(NHCoMX)composite was synthesized via a hydrothermal method.The abundant pores in the Ti_(3)C_(2)MXene nanosheet(MX)-integrated microarchitecture increased the number of active sites and facilitated charge transfer,thus enhancing electrocatalysis.Specifically,the MXenhanced charge transfer considerably transformed the microelectronic structure of cobalt-doped Ni(OH)2(NHCo),which promoted its hydrogen evolution reaction(HER)and oxygen evolution reaction(OER).Hence,as an EWS catalyst,NHCoMX exhibited an exceptional electrocatalytic activity,demonstrating OER and HER overpotentials of 310 mV and 73 mV,respectively,with low Tafel slopes of 65 mV dec^(-1)and 85 mV dec^(-1),respectively;it exhibited a current density of 10 mV cm^(-2)in 1.0 mol L^(-1)KOH,representing the closest efficiency to the noble state-of-the-art RuO2 and Pt/C catalyst.Furthermore,the developed electrocatalyst improved the activities of both HER and OER,leading to an overall EWS current density of 10 mA cm^(-2)at 1.72 V in an alkaline electrolyte with two electrodes.This study describes an efficient heterostructured NHCoMX composite electrocatalyst.It is significantly comparable to the noble state-of-the-art electrocatalysts and can be extended to fabricate resourceful catalysts for large-scale EWS applications.
基金supported by the Research Funds of the State Key Laboratory for Marine Corrosion and Protection(No.JS220903).
文摘Carbon-based materials exhibit excellent dielectric absorption properties,among which graphene has received particular attention in research of electromagnetic wave absorbing materials because of its high electrical conductivity and unique large-area,thin-layer two-dimensional structural features.However,the electromagnetic absorption performance of the material is hindered from further improvement due to its single component composition.It is influenced by the conductive network of graphene,making it challenging to achieve a balance in impedance matching and electromagnetic loss,thereby restricting its broader application.To address these challenges,we developed a series of nickel hydroxide-modified graphene composites.Through a structural composite design,we optimized overall impedance matching,introduced diverse loss mechanisms to enhance electromagnetic loss performance,and utilized a secondary reaction control method to precisely regulate the deposition of nickel hydroxide on the graphene surface,thereby achieving regulate of the composite material's electromagnetic parameters within a defined range.Under low sample filling ratios and a thin sample thickness of 1.8 mm,the effective absorption bandwidth reaches 6.5 GHz,demonstrating excellent electromagnetic absorption performance.This study provides a controllable design approach for modulating material electromagnetic parameters by influencing the reaction process.It also offers a design method for composites with an outstanding electromagnetic loss mechanism.
基金financially supported by Yunnan Major Scientific and Technological Projects(No.202202AG050017-02)Yunnan Fundamental Research Projects(No.202101BE070001-017)the National Natural Science Foundation of China(Nos.52101258 and 52272202)
文摘The sluggish kinetics of the oxygen evolution reaction(OER)process impedes the exploration of green hydrogen via water splitting.Herein,we design and synthesize vanadium-doped CoSn(OH)_(6)perovskite hydroxide catalysts by Fe^(3+)etching during the hydrothermal and chemical deposition process.The as-prepared CoVSn(OH)_(6)@CoVSnFe(OH)_(x)-4 catalyst exhibits a lowoverpotential of 225 mV at 10 mA·cm^(-2)with a Tafel slope of 30.47 mV·dec^(-1).An overall water splitting electrolyzer(CoVSn(OH)_(6)@CoVSnFe(OH)_(x)-4‖Pt/C)is constructed,delivering a voltage of 1.48 V at a current density of10 mA·cm^(-2)with excellent durability.The dynamic phase evolution during the OER process is revealed by in situ Raman and XPS measurement,which represents that the introduced V and Fe ions facilitate the formation of active CoOOH as well as modify the electronic structure of the catalyst.Density functional theory(DFT)calculations further evidence that V and Fe introduction optimize the adsorption energies of oxygen intermediates*OH and*O,respectively,thereby enabling a synergistic optimization of the multi-step OER process and advancing electrocatalytic performance.
基金supported by the National Natural Science Foundation of China(Grant Nos.22278101,22068010,22168016,and 52365044)the Natural Science Foundation of Hainan Province(Grant Nos.2019RC142 and 519QN176)the Finance Science and Technology Project of Hainan Province(Grant No.ZDYF2020009).
文摘Novel and promising chloride ion batteries(CIBs)that can operate at room temperature have attracted great attentions,due to the sustainable chloride-containing resources and high theoretical energy density.To achieve the superior electrochemical properties of CIBs,the structure design of electrode materials is essential.Herein,2D NiAl-layered double hydroxide(NiAl-LDH)nanoarrays derived from Al2O3 are in-situ grafted to graphene(G)by atomic layer deposition(ALD)and hydrothermal method.The achieved NiAl-LDH@G hybrids with 2D NiAl-LDH arrays grown perpendicularly on graphene surface,can efficiently prevent the stacking of LDHs and enlarge specific surface area to provide more active sites.The NiAl-LDH@G cathode exhibits a maximum discharge capacity of 223.3 mA h g^(-1)and an excellent reversible capacity of 107 mA h g^(-1)over 500 cycles at 100 mA g^(-1)with a high coulombic efficiency around 96%,whereas pure NiAl-LDH has a discharge capacity of only 48.8 mA h g^(-1)and a coulombic efficiency(CE)of about 78%.More importantly,the NiAl-LDH@G electrode has a stable voltage at 1.9 V and an outstanding discharge capacity of higher than 72 mA h g^(-1)after 120 days.Additionally,XRD,XPS,and EDS have been employed to unveil the electrochemical reaction and Cl-storage mechanism of the NiAlLDH@G cathode in CIBs.This work opens a facile and reasonable way for improving electrochemical performance at anion-type rechargeable batteries in terms of cathode material design and mechanism interpretation.
