NiFe-layered double hydroxides(NiFe-LDHs)are among the most promising earth-abundant electrocatalysts for the oxygen evolution reaction(OER)in alkaline media.However,their practical application is hindered by intrinsi...NiFe-layered double hydroxides(NiFe-LDHs)are among the most promising earth-abundant electrocatalysts for the oxygen evolution reaction(OER)in alkaline media.However,their practical application is hindered by intrinsic activity limitations and poor stability,primarily due to the asymmetric adsorption of oxygen intermediates.To overcome this,the binding strength must be synergistically tuned to a moderate level to optimize catalytic performance.Here,we engineered NiFeCoCr LDH through Co doping to enhance electrical conductivity and controlled Cr leaching to introduce cationic vacancies for modulating intermediate binding strength in NiFe LDH.X-ray absorption near-edge structure and extended X-ray absorption fine structure analyses reveal that NiFe-LDH with Co doping and Cr vacancies modulates the Ni oxidation state and local coordination environment,leading to a balanced electronic structure and enhanced structural complexity around the Ni sites.Additionally,these vacancies can trap OH^(-)/H_(2)O species,which can serve as a reservoir for OH^(-) transfer,facilitating the rapid formation of OER intermediates and enhancing catalytic performance at high current densities.As a result,V_(Cr)-NiFeCo LDH achieves 1.6 A cm^(-2)current density at 1.7 V vs.RHE while maintaining stable operation for over 1000 h at 500 mA cm^(-2).Density functional theory(DFT)calculations validate the synergistic effects of Co doping and Cr-induced vacancies on intermediate binding energies and improved OER kinetics.Overall,this work presents a rational design strategy to simultaneously enhance the activity and durability of NiFe-based OER catalysts for their application in high-performance alkaline water electrolysis.展开更多
Artificial photosynthesis of hydrogen peroxide(H_(2)O_(2))from earth-abundant water and oxygen is a sustainable approach,however current photocatalysts suffer from low production rate and solar-to-chemical conversion ...Artificial photosynthesis of hydrogen peroxide(H_(2)O_(2))from earth-abundant water and oxygen is a sustainable approach,however current photocatalysts suffer from low production rate and solar-to-chemical conversion efficiency(<1.5%).Herein,we report that nickelchromium layered double hydroxide with intercalated nitrate(NiCrOOH-NO_(3))and a thickness of~4.4 nm is an efficient photocatalyst,enabling a H_(2)O_(2)production yield of 28.7 mmol g^(-1)h^(-1)under visible light irradiation with3.92%solar-to-chemical conversion efficiency.Experimental and computational studies have revealed an inherent facet-dependent reduction-oxidation reaction behavior and spatial separation of photogenerated electrons and holes.An unexpected role of intercalated nitrate is demonstrated,which promotes excited electron—hole spatial separation and facilitates the electron transfer to oxygen intermediate via delocalization.This work provides understandings in the impact of nanostructure and anion in the design of advanced photocatalysts,paving the way toward practical synthesis of H_(2)O_(2)using fully solar-driven renewable energy.展开更多
Owing to its excellent eco-friendliness and facile water elution properties,aluminum-based lithium adsorbents have attracted a surge of interest for selectively extracting Li^(+)from Salt Lake brines,which account for...Owing to its excellent eco-friendliness and facile water elution properties,aluminum-based lithium adsorbents have attracted a surge of interest for selectively extracting Li^(+)from Salt Lake brines,which account for more than 60%of the global lithium resources.However,structural collapse,facile deactivation during desorption process,and ultra-low actual adsorption capacity limit its further large-scale application,particularly in low-grade sulfate-type brines.Herein,considering its advantages,limitations,and structural features,the structural collapse of the aluminum-based lithium adsorbent was effectively suppressed by the in situ intercalation of VO_(3)^(-)and V_(2)O_(7)^(4-)into the interlayer of[LiAl_(2)(OH)_(6)]^(+).Evidently,the initial adsorption capacity andα_(Mg)^(Li)of as-configured adsorbents powder are 14.96 mg g^(-1) and 192.42 in real sulfate-type West Taijinar Salt Lake brines following NaCl salts removal with 800 mg L^(-1) Li^(+)and 9.56 g L^(-1) SO_(4)^(2-).Furthermore,the initial and retained adsorption capacities of these novel adsorbents granulate in brines after 100 adsorption/desorption cycles are 26.68 and 10.36 mg g^(-1),respectively,which are almost 10 times higher than those of industrially utilized products.Based on experiments and density functional theory calculations,the process and mechanism of anion intercalation control were preliminarily elucidated.Furthermore,research findings indicate that intercalated anions can influence not only interlayer interactions but also the backbone strength of LDH-type adsorbents.This work significantly overcomes the major utilization challenges of aluminum-based lithium adsorbents,thereby enabling the high-efficiency and stable extraction of Li^(+)from low-grade brines,including sulfate-type brines.展开更多
High-entropy layered hydroxides(HELHs),an emerging frontier in entropy-stabilized materials derived from layered double hydroxides(LDHs),have captivated attention with their unparalleled tunability,thermodynamic stabi...High-entropy layered hydroxides(HELHs),an emerging frontier in entropy-stabilized materials derived from layered double hydroxides(LDHs),have captivated attention with their unparalleled tunability,thermodynamic stability,and electrochemical performance.The integration of the high-entropy concept into LDHs empowers HELHs to surmount the constraints of conventional materials through compositional diversity,structurally disordered configurations,and synergistic multi-element interactions.This review systematically embarks on their synthesis methodologies,functional mechanisms,and applications in energy conversion/storage and biomedicine.Advanced synthesis strategies,such as plasma-assisted hydrothermal methods,facilitate precise control over HELH architectures while supporting scalable production.HELHs demonstrate superior electrochemical performance in critical reactions,including oxygen evolution reaction,water oxidation,hydrogen evolution,and glucose electrooxidation.Future directions encompass integrating in situ characterization with simulations,leveraging machine learning for composition screening,and expanding HELHs application through interdisciplinary collaborations.This work establishes a comprehensive roadmap for advancing HELHs as next-generation multifunctional platforms for sustainable energy and biomedical technologies.展开更多
NiFe layered double hydroxide(NiFe LDH)has emerged as a promising catalyst for the oxygen evolution reaction(OER);however,its hydrogen evolution reaction(HER)activity remains suboptimal due to unfavorable electronic s...NiFe layered double hydroxide(NiFe LDH)has emerged as a promising catalyst for the oxygen evolution reaction(OER);however,its hydrogen evolution reaction(HER)activity remains suboptimal due to unfavorable electronic structures,particularly the d-electron density of metal sites,which impede water dissociation and lead to poor hydrogen adsorption/desorption capabilities.Herein,we introduce an efficient cooperative d-electron density regulation(CDDR)engineering to comprehensively optimize the delectron density of NiFe LDH by grafting MoO_(x) -modified NiFe LDH nanosheets onto porous nickel particles(PNPs).The PNPs facilitate d-electron density modulation along the edges of the nanosheets,while the MoO_(x) species enable d-electron density modulation across the plane of the nanosheets,thus cooperatively constructing enriched d-electron density in NiFe LDH.Theoretical studies validate the CDDR process and reveal that the enriched d-electron density accelerates water dissociation and optimizes the hydrogen adsorption behavior of NiFe LDH.As a result,the engineered catalyst exhibits significantly improved HER activity,achieving an ultra-low overpotential of 38 mV at 10 mA cm^(-2)in 1 M KOH.Additionally,the CDDR-optimized catalyst also exhibits good OER performance,demonstrating excellent bifunctional performance for overall water splitting in both alkaline freshwater and seawater electrolytes.This work presents a novel CDDR strategy for engineering NiFe LDH into efficient HER catalysts without compromising its OER activity,potentially paving the way for the development of active and robust electrocatalysts for sustainable energy applications.展开更多
A method for the effective in-situ formation of boron-containing Mg-Al layered double hydroxides(LDHs)was developed for boron removal and stabilization.The influence of the B/Al molar ratio and pH on the formation of ...A method for the effective in-situ formation of boron-containing Mg-Al layered double hydroxides(LDHs)was developed for boron removal and stabilization.The influence of the B/Al molar ratio and pH on the formation of Mg-Al-B–LDHs was investigated.Compared with the adsorption method,under a high B/Al ratio,the coprecipitation method increased the boron sorption density from 0.256 to 0.472 of Al.The Toxicity Characteristic Leaching Procedure showed that the boron-coprecipitated LDHs exhibited higher stability than the boron-adsorption LDHs.The synthesized LDH samples were characterized by X-ray diffraction,X-ray photoelectron spectroscopy,and solid-state 11B-NMR.The results showed that boron was effectively incorporated into the LDH structure for the coprecipitation method.Combined with the experimental results,a potential in-situ formation pathway for Mg-Al-B–LDHs was elucidated through density functional theory calculations.The boron tended to directly incorporate into the LDH structure in the coprecipitation method,whereas it was predominantly adsorbed on the LDH surface in the adsorption method.The adsorption energy demonstrated that boron preferentially bonded to Mg^(2+)sites on the surface.The mechanism of boron incorporation in the LDHs for the coprecipitation method involved precipitation of amorphous aluminum hydroxide,layered boehmite transformation,nucleation,and layer stacking.During these processes,boron formed complexes to enhance its stability.Residual boron underwent further reactions with the LDHs,including surface adsorption and ion exchange.These findings provide theoretical insight into the effective removal and long-term immobilization of boron in landfill leachate self-remediation processes.展开更多
Large-scale hydrogen production via water electrolysis faces a freshwater shortage.Direct seawater electrolysis offers a solution but encounters new challenges.Herein,we report a feasible strategy to both prevent meta...Large-scale hydrogen production via water electrolysis faces a freshwater shortage.Direct seawater electrolysis offers a solution but encounters new challenges.Herein,we report a feasible strategy to both prevent metal hydroxides deposition and boost the hydrogen evolution reaction by adding a chelating agent,EDTA-Na_(4),that chelates with Mg^(2+)/Ca^(2+),thus inhibiting their deposition and gathering them near the cathode surface,resulting in breaking the ordered hydrogen bond networks of interfacial water and reducing the activation energy of water dissociation.Furthermore,hydrolysis of–COO^(-) also promoted water dissociation to produce more active*H and*OH near the electrode surface that in turn serves as a diffusion medium for*OH,accelerating mass transfer and enabling seawater electrolysis to exhibit a stable performance,which operates continuously at 100 mA cm^(-2)@2.20 V and 200 mA cm^(-2)@2.58 V for 400 h in the symmetric electrolyzer and 500 mA cm^(-2)@2.29 V for over 500 h in the asymmetric electrolyzer.This study provides a new perspective to address the issues of stable and scalable direct seawater electrolysis for practical green hydrogen production.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
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
Layered double hydroxides(LDHs)have emerged as a promising class of photocatalysts with remarkable properties for diverse energy and environmental-related applications.This review offers insights into recent advances ...Layered double hydroxides(LDHs)have emerged as a promising class of photocatalysts with remarkable properties for diverse energy and environmental-related applications.This review offers insights into recent advances in LDH-based photocatalysts,focusing on their synthesis methods,structural properties,and photocatalytic performance.The unique structure of LDHs,characterized by positively charged metal hydroxide layers and intercalated anions,presents opportunities for tailoring their properties to enhance photocatalytic performance.The mechanisms for pollutant degradation,water splitting,and CO_(2) reduction are discussed,along with strategies to enhance the efficacy and stability of LDH-based photocatalysts.The photocatalytic mechanisms of LDHs for various reactions,including pollutant degradation,water splitting,and CO_(2) reduction,are discussed.Additionally,strategies for enriching the efficacy and stability of LDH-based photocatalysts are explored.This review underscores the significant potential of LDHs as versatile and efficient photocatalysts for addressing current environmental and energy challenges.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
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
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
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
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
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
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
基金supported by the Natural Science Foundation of China Grant No.52272289 and 5240223,and JSPS(Japan Society for the Promotion of Science)of Grant No.22K19088,23H00313,24H02202,and 24H02205。
文摘NiFe-layered double hydroxides(NiFe-LDHs)are among the most promising earth-abundant electrocatalysts for the oxygen evolution reaction(OER)in alkaline media.However,their practical application is hindered by intrinsic activity limitations and poor stability,primarily due to the asymmetric adsorption of oxygen intermediates.To overcome this,the binding strength must be synergistically tuned to a moderate level to optimize catalytic performance.Here,we engineered NiFeCoCr LDH through Co doping to enhance electrical conductivity and controlled Cr leaching to introduce cationic vacancies for modulating intermediate binding strength in NiFe LDH.X-ray absorption near-edge structure and extended X-ray absorption fine structure analyses reveal that NiFe-LDH with Co doping and Cr vacancies modulates the Ni oxidation state and local coordination environment,leading to a balanced electronic structure and enhanced structural complexity around the Ni sites.Additionally,these vacancies can trap OH^(-)/H_(2)O species,which can serve as a reservoir for OH^(-) transfer,facilitating the rapid formation of OER intermediates and enhancing catalytic performance at high current densities.As a result,V_(Cr)-NiFeCo LDH achieves 1.6 A cm^(-2)current density at 1.7 V vs.RHE while maintaining stable operation for over 1000 h at 500 mA cm^(-2).Density functional theory(DFT)calculations validate the synergistic effects of Co doping and Cr-induced vacancies on intermediate binding energies and improved OER kinetics.Overall,this work presents a rational design strategy to simultaneously enhance the activity and durability of NiFe-based OER catalysts for their application in high-performance alkaline water electrolysis.
基金support from the National Natural Science Foundation of China(NSFC 21905092,22475072 and 22075085)the Fundamental Research Funds for the Central Universities+1 种基金supported by the Shanghai Frontiers Science Center of Molecule Intelligent SynthesesEast China Normal University Multifunctional Platform for Innovation(004)。
文摘Artificial photosynthesis of hydrogen peroxide(H_(2)O_(2))from earth-abundant water and oxygen is a sustainable approach,however current photocatalysts suffer from low production rate and solar-to-chemical conversion efficiency(<1.5%).Herein,we report that nickelchromium layered double hydroxide with intercalated nitrate(NiCrOOH-NO_(3))and a thickness of~4.4 nm is an efficient photocatalyst,enabling a H_(2)O_(2)production yield of 28.7 mmol g^(-1)h^(-1)under visible light irradiation with3.92%solar-to-chemical conversion efficiency.Experimental and computational studies have revealed an inherent facet-dependent reduction-oxidation reaction behavior and spatial separation of photogenerated electrons and holes.An unexpected role of intercalated nitrate is demonstrated,which promotes excited electron—hole spatial separation and facilitates the electron transfer to oxygen intermediate via delocalization.This work provides understandings in the impact of nanostructure and anion in the design of advanced photocatalysts,paving the way toward practical synthesis of H_(2)O_(2)using fully solar-driven renewable energy.
基金supported by the Sichuan Provincial Department of Science and Technology Project (2025YFHZ0271).
文摘Owing to its excellent eco-friendliness and facile water elution properties,aluminum-based lithium adsorbents have attracted a surge of interest for selectively extracting Li^(+)from Salt Lake brines,which account for more than 60%of the global lithium resources.However,structural collapse,facile deactivation during desorption process,and ultra-low actual adsorption capacity limit its further large-scale application,particularly in low-grade sulfate-type brines.Herein,considering its advantages,limitations,and structural features,the structural collapse of the aluminum-based lithium adsorbent was effectively suppressed by the in situ intercalation of VO_(3)^(-)and V_(2)O_(7)^(4-)into the interlayer of[LiAl_(2)(OH)_(6)]^(+).Evidently,the initial adsorption capacity andα_(Mg)^(Li)of as-configured adsorbents powder are 14.96 mg g^(-1) and 192.42 in real sulfate-type West Taijinar Salt Lake brines following NaCl salts removal with 800 mg L^(-1) Li^(+)and 9.56 g L^(-1) SO_(4)^(2-).Furthermore,the initial and retained adsorption capacities of these novel adsorbents granulate in brines after 100 adsorption/desorption cycles are 26.68 and 10.36 mg g^(-1),respectively,which are almost 10 times higher than those of industrially utilized products.Based on experiments and density functional theory calculations,the process and mechanism of anion intercalation control were preliminarily elucidated.Furthermore,research findings indicate that intercalated anions can influence not only interlayer interactions but also the backbone strength of LDH-type adsorbents.This work significantly overcomes the major utilization challenges of aluminum-based lithium adsorbents,thereby enabling the high-efficiency and stable extraction of Li^(+)from low-grade brines,including sulfate-type brines.
基金the financial support by Advanced Materials-National Science and Technology Major Project(2024ZD0607400)the National Natural Science Foundation of China(No.52402305)+4 种基金the high-level innovation and entrepreneurship talent project of Qinchuangyuan(No.QCYRCXM-2023-084)the Postdoctoral Fellowship Program of CPSF under Grant Number GZB20230570 and 2024M752552Key projects of Shaanxi Province,China(2023GXLH-001)Natural Science Basic Research Program of Shaanxi(Program No.2024JCYBQN-0494,No.2022TD-27)the State Key Laboratory for Electrical Insulation and Power Equipment(No.EIPE23125)。
文摘High-entropy layered hydroxides(HELHs),an emerging frontier in entropy-stabilized materials derived from layered double hydroxides(LDHs),have captivated attention with their unparalleled tunability,thermodynamic stability,and electrochemical performance.The integration of the high-entropy concept into LDHs empowers HELHs to surmount the constraints of conventional materials through compositional diversity,structurally disordered configurations,and synergistic multi-element interactions.This review systematically embarks on their synthesis methodologies,functional mechanisms,and applications in energy conversion/storage and biomedicine.Advanced synthesis strategies,such as plasma-assisted hydrothermal methods,facilitate precise control over HELH architectures while supporting scalable production.HELHs demonstrate superior electrochemical performance in critical reactions,including oxygen evolution reaction,water oxidation,hydrogen evolution,and glucose electrooxidation.Future directions encompass integrating in situ characterization with simulations,leveraging machine learning for composition screening,and expanding HELHs application through interdisciplinary collaborations.This work establishes a comprehensive roadmap for advancing HELHs as next-generation multifunctional platforms for sustainable energy and biomedical technologies.
基金financially supported from the National Key Research and Development Program of China(2022YFB3803600)the National Natural Science Foundation of China(52301272,22309168,12564025,and 52472205)+7 种基金the Fundamental Research Funds for the Central Universities(CCNU25ZH006)the National College Student Innovation and Entrepreneurship Training Project(202510513082)the Research Program of HBNU(2025X082 and2025Y145)the Foundation of Hubei Key Laboratory of Photoelectric Materials and Devices(PMD202404)the General Program of Open Project of the State Key Laboratory of Precision Welding and Joining of Materials Structures(MSWJ-25M-18)the Key Research Project of Hubei Provincial Department of Education(No.D20252503)the Key Project of Hubei Provincial Natural Science Foundation of China(2025AFD002)the Foundation of National Laboratory of Solid State Microstructures(M37087)。
文摘NiFe layered double hydroxide(NiFe LDH)has emerged as a promising catalyst for the oxygen evolution reaction(OER);however,its hydrogen evolution reaction(HER)activity remains suboptimal due to unfavorable electronic structures,particularly the d-electron density of metal sites,which impede water dissociation and lead to poor hydrogen adsorption/desorption capabilities.Herein,we introduce an efficient cooperative d-electron density regulation(CDDR)engineering to comprehensively optimize the delectron density of NiFe LDH by grafting MoO_(x) -modified NiFe LDH nanosheets onto porous nickel particles(PNPs).The PNPs facilitate d-electron density modulation along the edges of the nanosheets,while the MoO_(x) species enable d-electron density modulation across the plane of the nanosheets,thus cooperatively constructing enriched d-electron density in NiFe LDH.Theoretical studies validate the CDDR process and reveal that the enriched d-electron density accelerates water dissociation and optimizes the hydrogen adsorption behavior of NiFe LDH.As a result,the engineered catalyst exhibits significantly improved HER activity,achieving an ultra-low overpotential of 38 mV at 10 mA cm^(-2)in 1 M KOH.Additionally,the CDDR-optimized catalyst also exhibits good OER performance,demonstrating excellent bifunctional performance for overall water splitting in both alkaline freshwater and seawater electrolytes.This work presents a novel CDDR strategy for engineering NiFe LDH into efficient HER catalysts without compromising its OER activity,potentially paving the way for the development of active and robust electrocatalysts for sustainable energy applications.
基金supported by the research equipment (Nos. G1006,G1010 and G1018) shared in MEXT Project for promoting public utilization of advanced research infrastructure (Program for supporting construction of core facilities)(No. JPMXS0440500023)financial support of the China Scholarship Council.
文摘A method for the effective in-situ formation of boron-containing Mg-Al layered double hydroxides(LDHs)was developed for boron removal and stabilization.The influence of the B/Al molar ratio and pH on the formation of Mg-Al-B–LDHs was investigated.Compared with the adsorption method,under a high B/Al ratio,the coprecipitation method increased the boron sorption density from 0.256 to 0.472 of Al.The Toxicity Characteristic Leaching Procedure showed that the boron-coprecipitated LDHs exhibited higher stability than the boron-adsorption LDHs.The synthesized LDH samples were characterized by X-ray diffraction,X-ray photoelectron spectroscopy,and solid-state 11B-NMR.The results showed that boron was effectively incorporated into the LDH structure for the coprecipitation method.Combined with the experimental results,a potential in-situ formation pathway for Mg-Al-B–LDHs was elucidated through density functional theory calculations.The boron tended to directly incorporate into the LDH structure in the coprecipitation method,whereas it was predominantly adsorbed on the LDH surface in the adsorption method.The adsorption energy demonstrated that boron preferentially bonded to Mg^(2+)sites on the surface.The mechanism of boron incorporation in the LDHs for the coprecipitation method involved precipitation of amorphous aluminum hydroxide,layered boehmite transformation,nucleation,and layer stacking.During these processes,boron formed complexes to enhance its stability.Residual boron underwent further reactions with the LDHs,including surface adsorption and ion exchange.These findings provide theoretical insight into the effective removal and long-term immobilization of boron in landfill leachate self-remediation processes.
基金the support from the National Key Research and Development Program of China(2023YFB4005000)the Joint Fund of Liaoning Binhai Laboratory(LBLF-2023-04)+3 种基金Dalian Science and Technology Talent Innovation Support Plan(2022RY09)Innovation Research Fund of Dalian Institute of Chemical Physics(DICP I202318)National Natural Science Foundation of China(22478384)the UK EPSRC(EP/W03784X/1)。
文摘Large-scale hydrogen production via water electrolysis faces a freshwater shortage.Direct seawater electrolysis offers a solution but encounters new challenges.Herein,we report a feasible strategy to both prevent metal hydroxides deposition and boost the hydrogen evolution reaction by adding a chelating agent,EDTA-Na_(4),that chelates with Mg^(2+)/Ca^(2+),thus inhibiting their deposition and gathering them near the cathode surface,resulting in breaking the ordered hydrogen bond networks of interfacial water and reducing the activation energy of water dissociation.Furthermore,hydrolysis of–COO^(-) also promoted water dissociation to produce more active*H and*OH near the electrode surface that in turn serves as a diffusion medium for*OH,accelerating mass transfer and enabling seawater electrolysis to exhibit a stable performance,which operates continuously at 100 mA cm^(-2)@2.20 V and 200 mA cm^(-2)@2.58 V for 400 h in the symmetric electrolyzer and 500 mA cm^(-2)@2.29 V for over 500 h in the asymmetric electrolyzer.This study provides a new perspective to address the issues of stable and scalable direct seawater electrolysis for practical green hydrogen production.
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supported by Karpagam Academy of Higher Education,India(No.KAHE/R-Acad/A1/Seed Money/024/2981)。
文摘Layered double hydroxides(LDHs)have emerged as a promising class of photocatalysts with remarkable properties for diverse energy and environmental-related applications.This review offers insights into recent advances in LDH-based photocatalysts,focusing on their synthesis methods,structural properties,and photocatalytic performance.The unique structure of LDHs,characterized by positively charged metal hydroxide layers and intercalated anions,presents opportunities for tailoring their properties to enhance photocatalytic performance.The mechanisms for pollutant degradation,water splitting,and CO_(2) reduction are discussed,along with strategies to enhance the efficacy and stability of LDH-based photocatalysts.The photocatalytic mechanisms of LDHs for various reactions,including pollutant degradation,water splitting,and CO_(2) reduction,are discussed.Additionally,strategies for enriching the efficacy and stability of LDH-based photocatalysts are explored.This review underscores the significant potential of LDHs as versatile and efficient photocatalysts for addressing current environmental and energy challenges.
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.
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.
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.
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.
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.
