In this study,a cleaner method for separation and recovery of V/W/Na in waste selective catalytic reduction(SCR)catalyst alkaline leaching solution was proposed.The method involved membrane electrolysis followed by io...In this study,a cleaner method for separation and recovery of V/W/Na in waste selective catalytic reduction(SCR)catalyst alkaline leaching solution was proposed.The method involved membrane electrolysis followed by ion morphology pretreatme nt and solvent extraction.An acidic V(Ⅴ)/W(Ⅵ)solution was obtained using the me mbrane electrolysis method without adding any other chemical reagents.In addition,Na was recovered in the form of NaOH by product,avoiding the generation of Na containing wastewater.The electrolysis parameters were investigated,the lowest power consumption of 3063 kW·h·t^(-1)NaOH was obtained at a current density of 125 A·m^(-2)and an initial NaOH concentration of 2 mol·L^(-1).After electrolysis,oxalic acid was added to the acidic V/W containing solution,converting V(Ⅴ)negative ion to V(Ⅳ)positive ion.Since W(Ⅵ)ion state remained in negative form,the generation of heteropolyacid ions(W_(x)V_(y)O_(z)^(n-))was prevented.It was found that under the condition of oxalic acid addition/theoretical consumption 1.2 and reaction temperature 75℃,100%V(Ⅴ)was co nverted to V(Ⅳ4).Using 10%N263+10%noctanol+80%sulfonated kerosene as extractant,the highest W(Ⅵ)/V(Ⅳ)separation coefficient of 7559.76was obtained at pH=1.8,O:A ratio=1:1 and extraction time 15 min.With 2 mol·L^(-1)NaOH as stripping reagent,the W stripping efficiency reached 98.50%at O:A ratio=2:1 after 4-stages of stripping.The enrichment of V remained in the solution was realized using P204 as extractant and 20%(mass)H_(2)SO_(4)as stripping reagent.The parameters of extraction/stripping process were investigated,using 10%P204+10%TBP+80%sulfonated kerosene as extractant,the V extraction efficiency reached 97.50%at O:A ratio=1:2after 4 stages of extraction.Using 20%H_(2)SO_(4)as the stripping reagent,the V stripping efficiency was 98.30%at an O:A ratio of 4:1 after five stage s of stripping.After the entire process,a high-purity VOSO_(4)and Na_(2)WO_(4)product solutions were obtained with V/W recovery efficiency 95.84%/98.50%,separately.This study examined a more effective and cleaner method for separating V/W/Na in Na_(2)WO_(4)/NaVO_(3)solution,which may serve as a reference for the separation and recovery of V/W/Na in waste SCR catalysts.展开更多
This paper examines a model that combines vortex generators and leading-edge tubercles for controlling the laminar separation bubble(LSB)over an airfoil at low Reynolds numbers(Re).This new concept of passive flow con...This paper examines a model that combines vortex generators and leading-edge tubercles for controlling the laminar separation bubble(LSB)over an airfoil at low Reynolds numbers(Re).This new concept of passive flow control technique utilizing a tubercle and vortex generator(VG)close to the leading edge was analyzed numerically for a NACA0015 airfoil.In this study,the Shear Stress Transport(SST)turbulence model was employed in the numerical modelling.Numerical modelling was completed using the ANSYS-Fluent 18.2 solver.Analyses were conducted to investigate the flow pattern and understand the underlying LSB control phenomena that enabled the new passive flow control method to provide this significant performance benefit.The findings indicated that the new concept of passive flow control technique suppressed the formation of an LSB at the suction surface of the NACA0015 airfoil,resulting in a higher lift coefficient and improved aerodynamic performance.Improvements in LSB dynamics and aerodynamic performance through the passive flow control method lead to increased energy output and enhanced stability.展开更多
The photoinduced ligand-to-metal charge transfer(LMCT)process has been extensively investigated,however,the recovery of photocatalysts has remained a persistent challenge in the field.In light of this issue,a novel ap...The photoinduced ligand-to-metal charge transfer(LMCT)process has been extensively investigated,however,the recovery of photocatalysts has remained a persistent challenge in the field.In light of this issue,a novel approach involving the development of iron-based ionic liquids as photocatalysts has been pursued for the first time,with the goal of simultaneously facilitating the LMCT process and addressing the issue of photocatalyst recovery.Remarkably,the iron-based ionic liquid 1-butyl-3-methylimidazolium tetrachloroferrate(C_(4)mim-Fe Cl_(4))demonstrates exceptional recyclability and stability for the photocatalytic hydroacylation of olefins.This study will pave the way for new approaches to photocatalytic organic synthesis using ionic liquids as recyclable photocatalysts.展开更多
Aiming at the problems of insufficient activity and selectivity of Cu-based catalysts in CO_(2)hydrogenation to methanol,Al_(2)O_(3),ZrO_(2)and CeO_(2)modified Cu-ZnO catalysts by the co-precipitation method were prep...Aiming at the problems of insufficient activity and selectivity of Cu-based catalysts in CO_(2)hydrogenation to methanol,Al_(2)O_(3),ZrO_(2)and CeO_(2)modified Cu-ZnO catalysts by the co-precipitation method were prepared,and the influence mechanism of additives on the structure-performance relationship of the catalysts was systematically explored.Through a variety of characterization methods such as XRD,N2 physical adsorption-desorption,TEM,H_(2)-TPR,CO_(2)-TPD and XPS,combined with catalytic performance evaluation experiments,the correlation between the microstructure of catalysts and the reaction performance of CO_(2)hydrogenation to methanol was analyzed in depth.The results show that metal additives significantly improve the performance of catalysts.After the introduction of additives,the specific surface area and pore volume of the catalysts increase,the grain size of Cu decreases,and its dispersion improves.The Ce-modified CZC catalyst exhibited the best performance,with the grain size of CuO as small as 11.41 nm,and the surface oxygen vacancy concentration(OⅡ/OⅠ=3.15)was significantly higher than that of other samples.The reaction performance test shows that under the conditions of 2.8 MPa,8000 h−1 and 280℃,the CO_(2)conversion of the CZC catalyst reached 18.83%,the methanol selectivity was 68.40%,and the methanol yield was 12.88%,all of which are superior to other catalysts.Its excellent performance can be attributed to the fact that CeO_(2)enhances the metal-support interaction,increases the surface basicity,promotes the adsorption and activation of CO_(2),and simultaneously inhibits the reverse water-gas shift side reaction.This study clarifies the structure-activity regulation mechanism of additive modification on Cu-ZnO catalysts,providing a theoretical basis and technical reference for the development of efficient catalysts for CO_(2)hydrogenation to methanol.展开更多
Practical application of lithium-sulfur(Li-S)batteries is hindered by the migration of lithium polysulfides(LiPSs),sluggish conversion kinetics,and anode instability.In these regards,with a novel strategy focusing on ...Practical application of lithium-sulfur(Li-S)batteries is hindered by the migration of lithium polysulfides(LiPSs),sluggish conversion kinetics,and anode instability.In these regards,with a novel strategy focusing on the selective elevation of d-orbitals,Mn/Fe dual-atom catalysts(MnFe DACs)embedded in Ndoped carbon frameworks are designed.Theoretical calculations reveal that energy levels of d_(z2),d_(zx),and d_(yz)orbitals participating in d-p hybridization are elevated closer to the Fermi level at both Mn and Fe sites,thereby reducing orbital occupancy in antibonding states.Consequently,these electronic features via the selective d-orbital elevation enable enhanced adsorption strength toward intermediate LiPSs and accelerate redox reaction during cell operation.Also,the MnFe DAC improves anode stability by regulating Li-ion flux with its lithiophilic active sites.Specifically,the cell equipped with MnFe DAC-modified separator maintains a capacity of 758.4 mAh g^(-1)after 400 cycles at 0.5 C.Notably,the cell demonstrates a high initial capacity of 822.7 mAh g^(-1)with only 0.047%decay rate over 1000 cycles at 1 C.Even under high sulfur-loading(5.0 mg cm^(-2))and low electrolyte-to-sulfur(E/S)ratio(6μL mg^(-1)),a high initial areal capacity of 4.94 m Ah cm^(-2)with 92.5%retention after 50 cycles at 0.1 C is achieved.This study provides guidelines on selective modulation of d-orbitals in DACs for high-performance Li-S batteries.展开更多
In this paper,the Ni/Al_(2)O_(3) monolithic catalyst with 15%Ni content was prepared using cordierite as a matrix,and the catalyst was modified with 10%NaOH to study the methanation performance of biomass gasification...In this paper,the Ni/Al_(2)O_(3) monolithic catalyst with 15%Ni content was prepared using cordierite as a matrix,and the catalyst was modified with 10%NaOH to study the methanation performance of biomass gasification simulated gas based on alkali-modified Ni/Al_(2)O_(3) monolithic catalyst.BET,TEM,H_(2)-TPR,XRD,CO_(2)-TPD and TG were used to characterize the physicochemical properties of the catalyst before and after modification.The results indicated that the CO conversion rate trends of unmodified and modified Ni/Al_(2)O_(3) monolithic catalysts over 2 h were fundamentally consistent.However,the Ni/Al_(2)O_(3) catalysts modified for 2 h demonstrated significantly enhanced performance compared to those modified for 1 h.Regarding CH4 selectivity,the modified Ni/Al_(2)O_(3) catalyst exhibited markedly better performance than the unmodified Ni/Al_(2)O_(3) catalyst,confirming the enhanced methane performance of the alkali-modified Ni/Al_(2)O_(3) monolithic catalyst.Under optimized conditions(H_(2)/CO volume ratio of 3∶1,space velocity of 10000 mL/(g·h),and temperature of 400℃),the methanation performance of the Ni/Al_(2)O_(3) monolithic catalyst modified for 2 h reached its peak,achieving a CO conversion rate of 97%with 100%CH4 selectivity.展开更多
Photocatalytic overall water splitting is a promising method for producing clean hydrogen energy,but faces challenges such as low light utilization efficiency and high charge carrier recombination rates.This study dem...Photocatalytic overall water splitting is a promising method for producing clean hydrogen energy,but faces challenges such as low light utilization efficiency and high charge carrier recombination rates.This study demonstrates that dielectric Mie resonance in TiO_(2)hollow nanoshells can enhance electric field intensity and increase light absorption through resonant energy transfer,compared to crushed TiO_(2)nanoparticles.The Mie resonance effect was confirmed through fluorescence spectra,photo-response current measurements,photocatalytic water splitting experiments,and Mie calculation.The incident electricfield amplitude was doubled in hollow nanoshells,allowing for increased light trapping.Additionally,the spatially separated Pt and RuO_(2)cocatalysts on the inner and outer surfaces facilitated the separation of photoinduced electrons and holes.Pt@TiO_(2)@RuO_(2)hollow nanoshells exhibited superior photocatalytic water splitting performance,with a stable H_(2)generation rate of 50.1μmol g^(−1)h^(−1)and O_(2)evolution rate of 25.1μmol g^(−1)h^(−1),outperforming other nanostructures such as TiO_(2),Pt@TiO_(2),and TiO_(2)@RuO_(2)hollow nanoshells.This study suggests that dielectric Mie resonance and spatially-separated cocatalysts offer a new approach to simultaneously enhance light absorption and charge carrier transfer in photocatalysis.展开更多
Under the backdrop of“Carbon Peak and Carbon Neutrality”(dual carbon)goal in China,the methane-carbon dioxide reforming reaction has attracted considerable attention due to its environmental benefits of converting t...Under the backdrop of“Carbon Peak and Carbon Neutrality”(dual carbon)goal in China,the methane-carbon dioxide reforming reaction has attracted considerable attention due to its environmental benefits of converting two greenhouse gases(methane and carbon dioxide)into syngas and its promising industrial applications.Nickel(Ni)-based catalysts,with high catalytic activity,low cost,and abundant resources,are considered ideal candidates for industrial applications.In this article,three reaction kinetic models were briefly introduced,namely the Power-Law(PL)model,the Eley-Rideal(ER)model,and the Langmuir-Hinshelwood-Hougen-Watson(LHHW)model.Based on the LHHW model,the reaction kinetics and mechanisms of different catalytic systems were systematically discussed,including the properties of supports,the doping of noble metals and transition metals,the role of promoters,and the influence of the geometric and electronic structures of Ni on the reaction mechanism.Furthermore,the kinetics of carbon deposition and elimination on various catalysts were analyzed.Based on the reaction rate expressions for carbon elimination,the reasons for the high activity of transition metal iron(Fe)-doped catalysts and core-shell structured catalysts in carbon elimination were explained.Based on the detailed collation and comparative analysis of the reaction mechanisms and kinetic characteristics across diverse Ni-based catalytic systems,a theoretical guidance for the designing of high-performance catalysts was provided in this work.展开更多
Electrochemical water splitting represents a sustainable technology for hydrogen(H_(2))production.However,its large-scale implementation is hindered by the high overpotentials required for both the cathodic hydrogen e...Electrochemical water splitting represents a sustainable technology for hydrogen(H_(2))production.However,its large-scale implementation is hindered by the high overpotentials required for both the cathodic hydrogen evolution reaction(HER)and the anodic oxygen evolution reaction(OER).Transition metal-based catalysts have garnered significant research interest as promising alternatives to noble-metal catalysts,owing to their low cost,tunable composition,and noble-metal-like catalytic activity.Nevertheless,systematic reviews on their application as bifunctional catalysts for overall water splitting(OWS)are still limited.This review comprehensively outlines the principal categories of bifunctional transition metal electrocatalysts derived from electrospun nanofibers(NFs),including metals,oxides,phosphides,sulfides,and carbides.Key strategies for enhancing their catalytic performance are systematically summarized,such as heterointerface engineering,heteroatom doping,metal-nonmetal-metal bridging architectures,and single-atom site design.Finally,current challenges and future research directions are discussed,aiming to provide insightful perspectives for the rational design of high-performance electrocatalysts for OWS.展开更多
CuZnAl(CZA)is a classic industrial catalyst widely used for the synthesis of methanol from syngas,but its catalytic performance is not optimal for the hydrogenation of CO_(2) to methanol.Meanwhile,understanding the ca...CuZnAl(CZA)is a classic industrial catalyst widely used for the synthesis of methanol from syngas,but its catalytic performance is not optimal for the hydrogenation of CO_(2) to methanol.Meanwhile,understanding the catalytic mechanism of Cu species in the CZA catalyst remains a great challenge.In this study,we systematically investigated the valence state change of active Cu species in CZA catalyst and their influence on catalytic performance by modifying the catalysts with varying amounts of electron donor K,thus identifying the catalytic function of Cu species with different valence states.H2-TPR,XPS and HR-TEM characterizations reveal that the highly dispersed K species supported on CZA catalysts will inhibit the reduction of CuO,resulting in a small amount of Cu_(2)O active species being produced under reaction conditions thus causing a decrease in catalytic activity.Furthermore,XRD and Cu LMM spectra show that the proportion of Cu^(0) in K-modified CZA catalysts increases with K loading,but a higher proportion of Cu^(0) species on the surface obviously promotes the reverse water gas shift(RWGS)reaction.According to the results of in situ infrared spectroscopy,CZA catalyst follows the reaction pathway mediated by HCOO^(*)in the hydrogenation of CO_(2) to methanol.展开更多
Catalysts are key for olefin polymerization reactions and are also ubiquitous in catalysis science.Multinuclear metal catalysts have witnessed enhanced performances in catalytic reactions relative to mononuclear catal...Catalysts are key for olefin polymerization reactions and are also ubiquitous in catalysis science.Multinuclear metal catalysts have witnessed enhanced performances in catalytic reactions relative to mononuclear catalysts,but which substantially involve multi-step,tedious,and difficult synthesis.Herein,this study reports an intriguing approach to construct multi-nuclear catalysts for the milestoneα-diimine nickel catalysts using an oligomeric strategy.A polymerizable norbornene unit is incorporated into theα-diimine ligand backbone,leading to the formation of the monomeric nickel catalyst Ni_(1)and its corresponding oligomeric nickel catalysts(Ni_(3)and Ni_(5))with varying degrees of polymerization(DP=3 and 5).Notably,the oligomeric catalyst Ni_(5)was facilely scaled up(50 g-level),showed enhanced thermal stability,exhibited 4.6 times higher activity,and yielded polyethylene elastomer with a 379%increased molecular weight in ethylene polymerization,compared to the monomeric catalyst Ni_(1).Catalytic performance enhancements of oligomeric catalysts were found to be DP-dependent.The kilogram-scale polyethylene,produced using Ni_(5)in a 20 L reactor,presented a highly branched all-hydrocarbon structure,which demonstrated typical elastic properties(tensile strength:4 MPa,elastic recovery:SR=72%)along with great processability(MFI=3.0 g/10 min),insulating characteristics(volume resistivity=2×10^(16)Ω/m),and hydrophobicity(water vapor permeability:0.03 g/m^(2)/day),suggesting potentially practical applications.展开更多
Against the backdrop of escalating global climate change and energy crises,the resource utilization of carbon dioxide(CO_(2)),a major greenhouse gas,has become a crucial pathway for achieving carbon peaking and carbon...Against the backdrop of escalating global climate change and energy crises,the resource utilization of carbon dioxide(CO_(2)),a major greenhouse gas,has become a crucial pathway for achieving carbon peaking and carbon neutrality goals.The hydrogenation of CO_(2)to methanol not only enables carbon sequestration and recycling,but also provides a route to produce high value-added fuels and basic chemical feedstocks,holding significant environmental and economic potential.However,this conversion process is thermodynamically and kinetically limited,and traditional catalyst systems(e.g.,Cu/ZnO/Al_(2)O_(3))exhibit inadequate activity,selectivity,and stability under mild conditions.Therefore,the development of novel high-performance catalysts with precisely tunable structures and functionalities is imperative.Metal-organic frameworks(MOFs),as crystalline porous materials with high surface area,tunable pore structures,and diverse metal-ligand compositions,have the great potential in CO_(2)hydrogenation catalysis.Their structural design flexibility allows for the construction of well-dispersed active sites,tailored electronic environments,and enhanced metal-support interactions.This review systematically summarizes the recent advances in MOF-based and MOF-derived catalysts for CO_(2)hydrogenation to methanol,focusing on four design strategies:(1)spatial confinement and in situ construction,(2)defect engineering and ion-exchange,(3)bimetallic synergy and hybrid structure design,and(4)MOF-derived nanomaterial synthesis.These approaches significantly improve CO_(2)conversion and methanol selectivity by optimizing metal dispersion,interfacial structures,and reaction pathways.The reaction mechanism is further explored by focusing on the three main reaction pathways:the formate pathway(HCOO*),the RWGS(Reverse Water Gas Shift reaction)+CO*hydrogenation pathway,and the trans-COOH pathway.In situ spectroscopic studies and density functional theory(DFT)calculations elucidate the formation and transformation of key intermediates,as well as the roles of active sites,metal-support interfaces,oxygen vacancies,and promoters.Additionally,representative catalytic performance data for MOFbased systems are compiled and compared,demonstrating their advantages over traditional catalysts in terms of CO_(2)conversion,methanol selectivity,and space-time yield.Future perspectives for MOF-based CO_(2)hydrogenation catalysts will prioritize two main directions:structural design and mechanistic understanding.The precise construction of active sites through multi-metallic synergy,defect engineering,and interfacial electronic modulation should be made to enhance catalyst selectivity and stability.In addition,advanced in situ characterization techniques combined with theoretical modeling are essential to unravel the detailed reaction mechanisms and intermediate behaviors,thereby guiding rational catalyst design.Moreover,to enable industrial application,challenges related to thermal/hydrothermal stability,catalyst recyclability,and cost-effective large-scale synthesis must be addressed.The development of green,scalable preparation methods and the integration of MOF catalysts into practical reaction systems(e.g.,flow reactors)will be crucial for bridging the gap between laboratory research and commercial deployment.Ultimately,multi-scale structure-performance optimization and catalytic system integration will be vital for accelerating the industrialization of MOF-based CO_(2)-to-methanol technologies.展开更多
To elucidate the effect of calcite-regulated activated carbon(AC)structure on low-temperature denitrification performance of SCR catalysts,this work prepared a series of Mn-Ce/De-AC-xCaCO_(3)(x is the calcite content ...To elucidate the effect of calcite-regulated activated carbon(AC)structure on low-temperature denitrification performance of SCR catalysts,this work prepared a series of Mn-Ce/De-AC-xCaCO_(3)(x is the calcite content in coal)catalysts were prepared by the incipient wetness impregnation method,followed by acid washing to remove calcium-containing minerals.Comprehensive characterization and low-temperature denitrification tests revealed that calcite-induced structural modulation of coal-derived AC significantly enhances catalytic activity.Specifically,NO conversion increased from 88.3%of Mn-Ce/De-AC to 91.7%of Mn-Ce/De-AC-1CaCO_(3)(210℃).The improved SCR denitrification activity results from the enhancement of physicochemical properties including higher Mn^(4+)content and Ce^(4+)/Ce^(3+)ratio,an abundance of chemisorbed oxygen and acidic sites,which could strengthen the SCR reaction pathways(richer NH_(3)activated species and bidentate nitrate active species).Therefore,NO removal is enhanced.展开更多
Seawater zinc-air batteries are promising energy storage devices due to their high energy density and utilization of seawater electrolytes.However,their efficiency is hindered by the sluggish oxygen reduction reaction...Seawater zinc-air batteries are promising energy storage devices due to their high energy density and utilization of seawater electrolytes.However,their efficiency is hindered by the sluggish oxygen reduction reaction(ORR)and chlorideinduced degradation over conventional catalysts.In this study,we proposed a universal synthetic strategy to construct heteroatom axially coordinated Fe–N_(4) single-atom seawater catalyst materials(Cl–Fe–N_(4) and S–Fe–N_(4)).X-ray absorption spectroscopy confirmed their five-coordinated square pyramidal structure.Systematic evaluation of catalytic activities revealed that compared with S–Fe–N_(4),Cl–Fe–N_(4) exhibits smaller electrochemical active surface area and specific surface area,yet demonstrates higher limiting current density(5.8 mA cm^(−2)).The assembled zinc-air batteries using Cl–Fe–N_(4) showed superior power density(187.7 mW cm^(−2) at 245.1 mA cm^(−2)),indicating that Cl axial coordination more effectively enhances the intrinsic ORR activity.Moreover,Cl–Fe–N_(4) demonstrates stronger Cl−poisoning resistance in seawater environments.Chronoamperometry tests and zinc-air battery cycling performance evaluations confirmed its enhanced stability.Density functional theory calculations revealed that the introduction of heteroatoms in the axial direction regulates the electron center of Fe single atom,leading to more active reaction intermediates and increased electron density of Fe single sites,thereby enhancing the reduction in adsorbed intermediates and hence the overall ORR catalytic activity.展开更多
The oxygen evolution reaction(OER)suffers from sluggish kinetics,necessitating efficient electrocatalysts to reduce overpotentials in water splitting.Currently recognized OER mechanisms primarily include the adsorbate...The oxygen evolution reaction(OER)suffers from sluggish kinetics,necessitating efficient electrocatalysts to reduce overpotentials in water splitting.Currently recognized OER mechanisms primarily include the adsorbate evolution mechanism(AEM),lattice oxygen mechanism(LOM),and oxide path mechanism(OPM).Compared to AEM,limited by scaling relationships,and LOM,constrained by stability issues,the OPM offers a promising alternative by enabling direct O-O bond formation via dual active sites,thus bypassing^(*)OOH intermediates and lattice O involvement and achieving a balance between activity and durability.However,activating the OPM process requires precise control over the spatial and electronic structure of active sites,making the design of OPM-based catalysts challenging.While previous reviews have focused on homo/heteronuclear diatomic perspectives of OPM-based catalysts,it is urgent to systematically summarize design strategies to provide a rational reference for their development.Herein,a review of design strategies for OPM-based OER catalysts across three scales is comprehensively presented,including in-situ engineering,doping-enabled sites reconstruction,and introducing new sites for nanoparticles,direct synthesis or post-treatments for molecular catalysts,and doping or template strategies for atom pairs or arrays.The unique advantage of atom arrays is also highlighted,and their future research directions and possible strategies are discussed.This review provides a systematic summary and forward-looking perspectives for rationally designing high-performance OPM-based OER catalysts.展开更多
Under the context of global energy transition and carbon neutrality,controlling nitrogen oxide(NO_(x))emissions from biomass combustion is of great significance,and the development of high-efficiency low-temperature c...Under the context of global energy transition and carbon neutrality,controlling nitrogen oxide(NO_(x))emissions from biomass combustion is of great significance,and the development of high-efficiency low-temperature catalysts has become a current research focus.In this study,Nb was used to dope and modify the Mn_(7)-Cu_(3)/BCN catalyst to construct the Mn_(7)-Cu_(3)-Nb_(x)/BCN system.The doping amount was optimized through selective catalytic reduction(SCR)activity tests.The reaction mechanism was explored by combining in situ DRIFTS and density functional theory(DFT)simulations.Experimental findings revealed that the catalyst doped with 0.05%Nb achieved the optimal performance,sustaining a NO conversion efficiency of≥94%within the temperature window of 150−275℃while demonstrating improved resistance to alkali metal K poisoning.Mechanistic analyses showed that at low temperatures,the catalyst facilitated the SCR reaction via both the Eley-Rideal(E-R)and Langmuir-Hinshelwood(L-H)pathways,with the synergistic interaction between multiple active sites driving the efficient conversion of NH3 and NO.DFT calculations further confirmed that both pathways had the characteristics of low reaction energy barriers and significant exothermicity,ensuring the high activity and feasibility of the low-temperature reaction.The findings provided foundational theoretical support for the design of Nb-doped Mn-Cu-supported catalysts and the exploration of the underlying working mechanisms.展开更多
Microporous polyimides(PIM-PIs)have emerged as promising high-performance membranes for gas separation.However,achieving an optimal balance between permeability and selectivity remains a major challenge.In this study,...Microporous polyimides(PIM-PIs)have emerged as promising high-performance membranes for gas separation.However,achieving an optimal balance between permeability and selectivity remains a major challenge.In this study,we designed and synthesized a series of PIM-PIs by combining rigid dianhydrides 9-bis(trifluoromethyl)-2,3,6,7-xanthenetetracarboxylic dianhydride(6FCDA)and 4,4′-(hexafluoroisopropylidene)diphthalic anhydride(6FDA)with contorted diamines,including 9,9-bis(4-aminophenyl)fluorene(FDA),9,9′-spirobifluorene-2,2′-diamine(SBFDA),and 3,3,3′,3′-tetramethyl-1,1′-spirobiindane-5,5′-diamine-6,6′-diol(TSDA),to systematically elucidate the relationship between hierarchical microstructure and gas transport behavior.Comprehensive characterization revealed that the 6FCDA-based polymers exhibited a higher microporosity(V_(micro)/V_(total)up to 54.7%)and fractional free volume compared to their 6FDA counterparts.Gas permeation measurements showed that the 6FCDA/SBFDA membrane delivered a CO_(2)permeability of 386 Barrer and CO_(2)/CH_(4)selectivity of 30.2,exceeding the 2008 Robeson upper bound.Structure-property correlation analyses indicated that diffusion selectivity predominantly governed gas separation performance,with rigid,spirocyclic architectures suppressing chain packing to generate sub-5Åmicropores,as further validated by molecular simulations.The optimized 6FCDA/FDA membrane achieved a BET surface area of 423 m^(2)·g^(−1),while maintaining excellent mechanical strength and high thermal stability.This work establishes an effective monomer design strategy to overcome the permeability-selectivity trade-off through backbone rigidification,thereby advancing PIM-PIs for practical applications in natural gas purification and carbon capture.展开更多
With the legislative development,the organic and inorganic composition separation has become the primary requirement for sewer sediment disposal,however the relevant technology has been rarely reported and the driving...With the legislative development,the organic and inorganic composition separation has become the primary requirement for sewer sediment disposal,however the relevant technology has been rarely reported and the driving mechanism was still unclear.In this study,direct disintegration of biopolymers and indirect broken of connection point were investigated on the hydrolysis and component separation.Three typical sewer sediment treatment approaches,i.e.,alkaline,thermal and cation exchange treatments were proposed,which represented the hydrolysis-driving forces of chemical hydrolysis,physical hydrolysis and innovative cation bridging break-age.The results showed that the organic and inorganic separation rates of sewer sediment driven by alkaline,thermal and cation exchange treatments reached 21.26%,23.80%,and 19.56%-48.0%,respectively,compared to 4.43%in control.The secondary structure of proteins was disrupted,transitioning from𝛼α-helix to𝛽β-turn and random coil.Meanwhile,much biopolymers were released from solid to the liquid phase.From thermody-namic perspective,sewer sediment deposition was controlled by short-range interfacial interactions described by extended Derjaguin-Landau-Verwey-Overbeek theory.Additionally,the separation of organic and inorganic components was positively correlated with the thermodynamic parameters(Corr=0.87),highlighted the robust-ness of various driving forces.And the flocculation energy barriers were 2.40(alkaline),1.60 times(thermal),and 4.02–4.97 times(cation exchange)compared to control group.The findings revealed the contrition differ-ence of direct disintegration of gelatinous biopolymers and indirect breakage of composition connection sites in sediment composition separation,filling the critical gaps in understanding the specific mechanisms of sediment biopolymer disintegration and intermolecular connection breakage.展开更多
The efficient flotation separation of rare earth elements(REEs)from gangue minerals is crucial in mineral processing.This study synthesized a quaternary ammonium salt ionic liquid collector,tetrabutylammonium salicylh...The efficient flotation separation of rare earth elements(REEs)from gangue minerals is crucial in mineral processing.This study synthesized a quaternary ammonium salt ionic liquid collector,tetrabutylammonium salicylhydroxamate(T-S),and investigated its performance in separating bastnaesite and fluorite.T-S was synthesized from salicylhydroxamic acid(SHA)and tetrabutylammonium chloride(TBAC),and its molecular structure was characterized using Fourier transform infrared(FTIR)spectroscopy.Microflotation tests indicate that T-S outperforms SHA and TBAC in both collecting ability and selectivity for bastnaesite.Adsorption,zeta potential,and infrared spectroscopy measurements reveal that T-S exhibits stronger adsorption on bastnaesite compared to SHA and TBAC.X-ray photoelectron spectroscopy(XPS)and molecular dynamics simulations(MDS)results confirm that chemical adsorption occurs between Ce on the bastnaesite surface and the-C(=O)NHOH groups of T-S.Moreover,the interaction between T-S and the bastnaesite surface is stronger than that with the fluorite surface.This work provides valuable insights for designing ionic liquid collectors for the flotation separation of bastnaesite and fluorite.展开更多
Single-atom catalysts(SACs)have demonstrated excellent performance in heterogeneous catalytic reactions owing to their maximized atomic efficiency,distinctive geometric,and electronic configurations.However,the effica...Single-atom catalysts(SACs)have demonstrated excellent performance in heterogeneous catalytic reactions owing to their maximized atomic efficiency,distinctive geometric,and electronic configurations.However,the efficacy of SACs remains limited for certain reactions requiring simultaneous activation of multiple reactants over metallic active sites.Herein,we report an atomically dispersed Pt1Ru1 dual-atom pair site anchored on nanodiamond@graphene(ND@G)for CO oxidation.The Pt1Ru1 dual-atom catalyst shows an exceptional turnover frequency(TOF)of 17.6.10^(-2)s^(-1)at significantly lower temperature(30℃),achieving a tenfold increase in TOF compared to singleatom Pt1/ND@G catalyst(1.5.10^(-2)s^(-1))and surpassing to previously reported Pt-based catalysts under similar conditions.Moreover,the catalyst demonstrates excellent stability,maintaining its activity for 40 h at 80℃without significant deactivation.The superior catalytic performance of Pt-Ru dual-atom catalysts is attributed to the synergistic effect between Pt and Ru atoms with enhanced metallicity for improving simultaneous adsorption and activation of CO and O_(2),and the tuning of conventional competitive reactant adsorption into a non-competitive pathway over dual-atom pair sites.The present work manifests the advantages of dual-atom pair sites in heterogeneous catalysis and paves the way for precise design of catalysts at the atomic scale.展开更多
基金the support the National Natural Science Foundation of China(5210440)S&T Program of Hebei(23311501D)Program of HBIS Group under HG2023222。
文摘In this study,a cleaner method for separation and recovery of V/W/Na in waste selective catalytic reduction(SCR)catalyst alkaline leaching solution was proposed.The method involved membrane electrolysis followed by ion morphology pretreatme nt and solvent extraction.An acidic V(Ⅴ)/W(Ⅵ)solution was obtained using the me mbrane electrolysis method without adding any other chemical reagents.In addition,Na was recovered in the form of NaOH by product,avoiding the generation of Na containing wastewater.The electrolysis parameters were investigated,the lowest power consumption of 3063 kW·h·t^(-1)NaOH was obtained at a current density of 125 A·m^(-2)and an initial NaOH concentration of 2 mol·L^(-1).After electrolysis,oxalic acid was added to the acidic V/W containing solution,converting V(Ⅴ)negative ion to V(Ⅳ)positive ion.Since W(Ⅵ)ion state remained in negative form,the generation of heteropolyacid ions(W_(x)V_(y)O_(z)^(n-))was prevented.It was found that under the condition of oxalic acid addition/theoretical consumption 1.2 and reaction temperature 75℃,100%V(Ⅴ)was co nverted to V(Ⅳ4).Using 10%N263+10%noctanol+80%sulfonated kerosene as extractant,the highest W(Ⅵ)/V(Ⅳ)separation coefficient of 7559.76was obtained at pH=1.8,O:A ratio=1:1 and extraction time 15 min.With 2 mol·L^(-1)NaOH as stripping reagent,the W stripping efficiency reached 98.50%at O:A ratio=2:1 after 4-stages of stripping.The enrichment of V remained in the solution was realized using P204 as extractant and 20%(mass)H_(2)SO_(4)as stripping reagent.The parameters of extraction/stripping process were investigated,using 10%P204+10%TBP+80%sulfonated kerosene as extractant,the V extraction efficiency reached 97.50%at O:A ratio=1:2after 4 stages of extraction.Using 20%H_(2)SO_(4)as the stripping reagent,the V stripping efficiency was 98.30%at an O:A ratio of 4:1 after five stage s of stripping.After the entire process,a high-purity VOSO_(4)and Na_(2)WO_(4)product solutions were obtained with V/W recovery efficiency 95.84%/98.50%,separately.This study examined a more effective and cleaner method for separating V/W/Na in Na_(2)WO_(4)/NaVO_(3)solution,which may serve as a reference for the separation and recovery of V/W/Na in waste SCR catalysts.
基金the Scientific Research Projects Unit of Erciyes University under contract no:FDS-2022-11532 and FOA-2025-14773.
文摘This paper examines a model that combines vortex generators and leading-edge tubercles for controlling the laminar separation bubble(LSB)over an airfoil at low Reynolds numbers(Re).This new concept of passive flow control technique utilizing a tubercle and vortex generator(VG)close to the leading edge was analyzed numerically for a NACA0015 airfoil.In this study,the Shear Stress Transport(SST)turbulence model was employed in the numerical modelling.Numerical modelling was completed using the ANSYS-Fluent 18.2 solver.Analyses were conducted to investigate the flow pattern and understand the underlying LSB control phenomena that enabled the new passive flow control method to provide this significant performance benefit.The findings indicated that the new concept of passive flow control technique suppressed the formation of an LSB at the suction surface of the NACA0015 airfoil,resulting in a higher lift coefficient and improved aerodynamic performance.Improvements in LSB dynamics and aerodynamic performance through the passive flow control method lead to increased energy output and enhanced stability.
基金financial support from the National Natural Science Foundation of China(Nos.22071222,22171249)the Natural Science Foundation of Henan Province(Nos.232300421363,242300420526)+2 种基金Key Research Projects of Universities in Henan Province(No.23A180010)Science&Technology Innovation Talents in Universities of Henan Province(No.23HASTIT003)Science and Technology Research and Development Plan Joint Fund of Henan Province(No.242301420006)。
文摘The photoinduced ligand-to-metal charge transfer(LMCT)process has been extensively investigated,however,the recovery of photocatalysts has remained a persistent challenge in the field.In light of this issue,a novel approach involving the development of iron-based ionic liquids as photocatalysts has been pursued for the first time,with the goal of simultaneously facilitating the LMCT process and addressing the issue of photocatalyst recovery.Remarkably,the iron-based ionic liquid 1-butyl-3-methylimidazolium tetrachloroferrate(C_(4)mim-Fe Cl_(4))demonstrates exceptional recyclability and stability for the photocatalytic hydroacylation of olefins.This study will pave the way for new approaches to photocatalytic organic synthesis using ionic liquids as recyclable photocatalysts.
基金Supported by National Key R&D Program of China(2022YFA1503400)。
文摘Aiming at the problems of insufficient activity and selectivity of Cu-based catalysts in CO_(2)hydrogenation to methanol,Al_(2)O_(3),ZrO_(2)and CeO_(2)modified Cu-ZnO catalysts by the co-precipitation method were prepared,and the influence mechanism of additives on the structure-performance relationship of the catalysts was systematically explored.Through a variety of characterization methods such as XRD,N2 physical adsorption-desorption,TEM,H_(2)-TPR,CO_(2)-TPD and XPS,combined with catalytic performance evaluation experiments,the correlation between the microstructure of catalysts and the reaction performance of CO_(2)hydrogenation to methanol was analyzed in depth.The results show that metal additives significantly improve the performance of catalysts.After the introduction of additives,the specific surface area and pore volume of the catalysts increase,the grain size of Cu decreases,and its dispersion improves.The Ce-modified CZC catalyst exhibited the best performance,with the grain size of CuO as small as 11.41 nm,and the surface oxygen vacancy concentration(OⅡ/OⅠ=3.15)was significantly higher than that of other samples.The reaction performance test shows that under the conditions of 2.8 MPa,8000 h−1 and 280℃,the CO_(2)conversion of the CZC catalyst reached 18.83%,the methanol selectivity was 68.40%,and the methanol yield was 12.88%,all of which are superior to other catalysts.Its excellent performance can be attributed to the fact that CeO_(2)enhances the metal-support interaction,increases the surface basicity,promotes the adsorption and activation of CO_(2),and simultaneously inhibits the reverse water-gas shift side reaction.This study clarifies the structure-activity regulation mechanism of additive modification on Cu-ZnO catalysts,providing a theoretical basis and technical reference for the development of efficient catalysts for CO_(2)hydrogenation to methanol.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korea government(MSIT)(RS-2024-00355916)by the NRF grant funded by the Korea government(MSIT)(RS-2021-NR060090)by the Korea Institute for Advancement of Technology(KIAT)grant funded by the Korea Government(MOTIE)(RS-2024-00419413,HRD Program for Industrial Innovation)。
文摘Practical application of lithium-sulfur(Li-S)batteries is hindered by the migration of lithium polysulfides(LiPSs),sluggish conversion kinetics,and anode instability.In these regards,with a novel strategy focusing on the selective elevation of d-orbitals,Mn/Fe dual-atom catalysts(MnFe DACs)embedded in Ndoped carbon frameworks are designed.Theoretical calculations reveal that energy levels of d_(z2),d_(zx),and d_(yz)orbitals participating in d-p hybridization are elevated closer to the Fermi level at both Mn and Fe sites,thereby reducing orbital occupancy in antibonding states.Consequently,these electronic features via the selective d-orbital elevation enable enhanced adsorption strength toward intermediate LiPSs and accelerate redox reaction during cell operation.Also,the MnFe DAC improves anode stability by regulating Li-ion flux with its lithiophilic active sites.Specifically,the cell equipped with MnFe DAC-modified separator maintains a capacity of 758.4 mAh g^(-1)after 400 cycles at 0.5 C.Notably,the cell demonstrates a high initial capacity of 822.7 mAh g^(-1)with only 0.047%decay rate over 1000 cycles at 1 C.Even under high sulfur-loading(5.0 mg cm^(-2))and low electrolyte-to-sulfur(E/S)ratio(6μL mg^(-1)),a high initial areal capacity of 4.94 m Ah cm^(-2)with 92.5%retention after 50 cycles at 0.1 C is achieved.This study provides guidelines on selective modulation of d-orbitals in DACs for high-performance Li-S batteries.
基金Supported by the National Natural Science Foundation of China(52506188,52476215)Natural Science Foundation of Liaoning Province(2024-MS-139,2024JH3/10200047)Scientific Research Program of Department of Education of Liaoning Province(310125042,LJ212410143033)。
文摘In this paper,the Ni/Al_(2)O_(3) monolithic catalyst with 15%Ni content was prepared using cordierite as a matrix,and the catalyst was modified with 10%NaOH to study the methanation performance of biomass gasification simulated gas based on alkali-modified Ni/Al_(2)O_(3) monolithic catalyst.BET,TEM,H_(2)-TPR,XRD,CO_(2)-TPD and TG were used to characterize the physicochemical properties of the catalyst before and after modification.The results indicated that the CO conversion rate trends of unmodified and modified Ni/Al_(2)O_(3) monolithic catalysts over 2 h were fundamentally consistent.However,the Ni/Al_(2)O_(3) catalysts modified for 2 h demonstrated significantly enhanced performance compared to those modified for 1 h.Regarding CH4 selectivity,the modified Ni/Al_(2)O_(3) catalyst exhibited markedly better performance than the unmodified Ni/Al_(2)O_(3) catalyst,confirming the enhanced methane performance of the alkali-modified Ni/Al_(2)O_(3) monolithic catalyst.Under optimized conditions(H_(2)/CO volume ratio of 3∶1,space velocity of 10000 mL/(g·h),and temperature of 400℃),the methanation performance of the Ni/Al_(2)O_(3) monolithic catalyst modified for 2 h reached its peak,achieving a CO conversion rate of 97%with 100%CH4 selectivity.
基金supported by the National Natural Science Foundation of China(Nos.51702023,62274017)Natural Science Foundation of Jiangsu Province(No.BK20231224)China Postdoctoral Science Foundation(No.2022M711138).
文摘Photocatalytic overall water splitting is a promising method for producing clean hydrogen energy,but faces challenges such as low light utilization efficiency and high charge carrier recombination rates.This study demonstrates that dielectric Mie resonance in TiO_(2)hollow nanoshells can enhance electric field intensity and increase light absorption through resonant energy transfer,compared to crushed TiO_(2)nanoparticles.The Mie resonance effect was confirmed through fluorescence spectra,photo-response current measurements,photocatalytic water splitting experiments,and Mie calculation.The incident electricfield amplitude was doubled in hollow nanoshells,allowing for increased light trapping.Additionally,the spatially separated Pt and RuO_(2)cocatalysts on the inner and outer surfaces facilitated the separation of photoinduced electrons and holes.Pt@TiO_(2)@RuO_(2)hollow nanoshells exhibited superior photocatalytic water splitting performance,with a stable H_(2)generation rate of 50.1μmol g^(−1)h^(−1)and O_(2)evolution rate of 25.1μmol g^(−1)h^(−1),outperforming other nanostructures such as TiO_(2),Pt@TiO_(2),and TiO_(2)@RuO_(2)hollow nanoshells.This study suggests that dielectric Mie resonance and spatially-separated cocatalysts offer a new approach to simultaneously enhance light absorption and charge carrier transfer in photocatalysis.
基金Supported by Innovation Capability Support Program of Shaanxi(2024RS-CXTD-53,2024ZC-KJXX-096)the Key R&D Program of Shaanxi Province(2022QCY-LL-69)Xi’an Science and Technology Project(24GXFW0089)。
文摘Under the backdrop of“Carbon Peak and Carbon Neutrality”(dual carbon)goal in China,the methane-carbon dioxide reforming reaction has attracted considerable attention due to its environmental benefits of converting two greenhouse gases(methane and carbon dioxide)into syngas and its promising industrial applications.Nickel(Ni)-based catalysts,with high catalytic activity,low cost,and abundant resources,are considered ideal candidates for industrial applications.In this article,three reaction kinetic models were briefly introduced,namely the Power-Law(PL)model,the Eley-Rideal(ER)model,and the Langmuir-Hinshelwood-Hougen-Watson(LHHW)model.Based on the LHHW model,the reaction kinetics and mechanisms of different catalytic systems were systematically discussed,including the properties of supports,the doping of noble metals and transition metals,the role of promoters,and the influence of the geometric and electronic structures of Ni on the reaction mechanism.Furthermore,the kinetics of carbon deposition and elimination on various catalysts were analyzed.Based on the reaction rate expressions for carbon elimination,the reasons for the high activity of transition metal iron(Fe)-doped catalysts and core-shell structured catalysts in carbon elimination were explained.Based on the detailed collation and comparative analysis of the reaction mechanisms and kinetic characteristics across diverse Ni-based catalytic systems,a theoretical guidance for the designing of high-performance catalysts was provided in this work.
基金Supported by the National Natural Science Foundation of China(No.52273056)the Science and Technology Development Program of Jilin Province,China(No.YDZJ202501ZYTS305)。
文摘Electrochemical water splitting represents a sustainable technology for hydrogen(H_(2))production.However,its large-scale implementation is hindered by the high overpotentials required for both the cathodic hydrogen evolution reaction(HER)and the anodic oxygen evolution reaction(OER).Transition metal-based catalysts have garnered significant research interest as promising alternatives to noble-metal catalysts,owing to their low cost,tunable composition,and noble-metal-like catalytic activity.Nevertheless,systematic reviews on their application as bifunctional catalysts for overall water splitting(OWS)are still limited.This review comprehensively outlines the principal categories of bifunctional transition metal electrocatalysts derived from electrospun nanofibers(NFs),including metals,oxides,phosphides,sulfides,and carbides.Key strategies for enhancing their catalytic performance are systematically summarized,such as heterointerface engineering,heteroatom doping,metal-nonmetal-metal bridging architectures,and single-atom site design.Finally,current challenges and future research directions are discussed,aiming to provide insightful perspectives for the rational design of high-performance electrocatalysts for OWS.
基金Supported by the National Key Research and Development Program of China(2022YFB4101800)the National Natural Science Foundation of China(22172032,U22A20431)。
文摘CuZnAl(CZA)is a classic industrial catalyst widely used for the synthesis of methanol from syngas,but its catalytic performance is not optimal for the hydrogenation of CO_(2) to methanol.Meanwhile,understanding the catalytic mechanism of Cu species in the CZA catalyst remains a great challenge.In this study,we systematically investigated the valence state change of active Cu species in CZA catalyst and their influence on catalytic performance by modifying the catalysts with varying amounts of electron donor K,thus identifying the catalytic function of Cu species with different valence states.H2-TPR,XPS and HR-TEM characterizations reveal that the highly dispersed K species supported on CZA catalysts will inhibit the reduction of CuO,resulting in a small amount of Cu_(2)O active species being produced under reaction conditions thus causing a decrease in catalytic activity.Furthermore,XRD and Cu LMM spectra show that the proportion of Cu^(0) in K-modified CZA catalysts increases with K loading,but a higher proportion of Cu^(0) species on the surface obviously promotes the reverse water gas shift(RWGS)reaction.According to the results of in situ infrared spectroscopy,CZA catalyst follows the reaction pathway mediated by HCOO^(*)in the hydrogenation of CO_(2) to methanol.
基金financial support from the National Natural Science Foundation of China(Nos.22401274,U23B6011)the Jilin Provincial Science and Technology Department Program(No.20250102070JC)。
文摘Catalysts are key for olefin polymerization reactions and are also ubiquitous in catalysis science.Multinuclear metal catalysts have witnessed enhanced performances in catalytic reactions relative to mononuclear catalysts,but which substantially involve multi-step,tedious,and difficult synthesis.Herein,this study reports an intriguing approach to construct multi-nuclear catalysts for the milestoneα-diimine nickel catalysts using an oligomeric strategy.A polymerizable norbornene unit is incorporated into theα-diimine ligand backbone,leading to the formation of the monomeric nickel catalyst Ni_(1)and its corresponding oligomeric nickel catalysts(Ni_(3)and Ni_(5))with varying degrees of polymerization(DP=3 and 5).Notably,the oligomeric catalyst Ni_(5)was facilely scaled up(50 g-level),showed enhanced thermal stability,exhibited 4.6 times higher activity,and yielded polyethylene elastomer with a 379%increased molecular weight in ethylene polymerization,compared to the monomeric catalyst Ni_(1).Catalytic performance enhancements of oligomeric catalysts were found to be DP-dependent.The kilogram-scale polyethylene,produced using Ni_(5)in a 20 L reactor,presented a highly branched all-hydrocarbon structure,which demonstrated typical elastic properties(tensile strength:4 MPa,elastic recovery:SR=72%)along with great processability(MFI=3.0 g/10 min),insulating characteristics(volume resistivity=2×10^(16)Ω/m),and hydrophobicity(water vapor permeability:0.03 g/m^(2)/day),suggesting potentially practical applications.
基金Supported by the National Key Research and Development Program of China(2023YFB4104500,2023YFB4104502)the National Natural Science Foundation of China(22138013)the Taishan Scholar Project(ts201712020).
文摘Against the backdrop of escalating global climate change and energy crises,the resource utilization of carbon dioxide(CO_(2)),a major greenhouse gas,has become a crucial pathway for achieving carbon peaking and carbon neutrality goals.The hydrogenation of CO_(2)to methanol not only enables carbon sequestration and recycling,but also provides a route to produce high value-added fuels and basic chemical feedstocks,holding significant environmental and economic potential.However,this conversion process is thermodynamically and kinetically limited,and traditional catalyst systems(e.g.,Cu/ZnO/Al_(2)O_(3))exhibit inadequate activity,selectivity,and stability under mild conditions.Therefore,the development of novel high-performance catalysts with precisely tunable structures and functionalities is imperative.Metal-organic frameworks(MOFs),as crystalline porous materials with high surface area,tunable pore structures,and diverse metal-ligand compositions,have the great potential in CO_(2)hydrogenation catalysis.Their structural design flexibility allows for the construction of well-dispersed active sites,tailored electronic environments,and enhanced metal-support interactions.This review systematically summarizes the recent advances in MOF-based and MOF-derived catalysts for CO_(2)hydrogenation to methanol,focusing on four design strategies:(1)spatial confinement and in situ construction,(2)defect engineering and ion-exchange,(3)bimetallic synergy and hybrid structure design,and(4)MOF-derived nanomaterial synthesis.These approaches significantly improve CO_(2)conversion and methanol selectivity by optimizing metal dispersion,interfacial structures,and reaction pathways.The reaction mechanism is further explored by focusing on the three main reaction pathways:the formate pathway(HCOO*),the RWGS(Reverse Water Gas Shift reaction)+CO*hydrogenation pathway,and the trans-COOH pathway.In situ spectroscopic studies and density functional theory(DFT)calculations elucidate the formation and transformation of key intermediates,as well as the roles of active sites,metal-support interfaces,oxygen vacancies,and promoters.Additionally,representative catalytic performance data for MOFbased systems are compiled and compared,demonstrating their advantages over traditional catalysts in terms of CO_(2)conversion,methanol selectivity,and space-time yield.Future perspectives for MOF-based CO_(2)hydrogenation catalysts will prioritize two main directions:structural design and mechanistic understanding.The precise construction of active sites through multi-metallic synergy,defect engineering,and interfacial electronic modulation should be made to enhance catalyst selectivity and stability.In addition,advanced in situ characterization techniques combined with theoretical modeling are essential to unravel the detailed reaction mechanisms and intermediate behaviors,thereby guiding rational catalyst design.Moreover,to enable industrial application,challenges related to thermal/hydrothermal stability,catalyst recyclability,and cost-effective large-scale synthesis must be addressed.The development of green,scalable preparation methods and the integration of MOF catalysts into practical reaction systems(e.g.,flow reactors)will be crucial for bridging the gap between laboratory research and commercial deployment.Ultimately,multi-scale structure-performance optimization and catalytic system integration will be vital for accelerating the industrialization of MOF-based CO_(2)-to-methanol technologies.
基金Supported by the Science and Technology Cooperation and Exchange special project of Cooperation of Shanxi Province(202404041101014)the Fundamental Research Program of Shanxi Province(202403021212333)+3 种基金the Joint Funds of the National Natural Science Foundation of China(U24A20555)the Lvliang Key R&D of University-Local Cooperation(2023XDHZ10)the Initiation Fund for Doctoral Research of Taiyuan University of Science and Technology(20242026)the Outstanding Doctor Funding Award of Shanxi Province(20242080).
文摘To elucidate the effect of calcite-regulated activated carbon(AC)structure on low-temperature denitrification performance of SCR catalysts,this work prepared a series of Mn-Ce/De-AC-xCaCO_(3)(x is the calcite content in coal)catalysts were prepared by the incipient wetness impregnation method,followed by acid washing to remove calcium-containing minerals.Comprehensive characterization and low-temperature denitrification tests revealed that calcite-induced structural modulation of coal-derived AC significantly enhances catalytic activity.Specifically,NO conversion increased from 88.3%of Mn-Ce/De-AC to 91.7%of Mn-Ce/De-AC-1CaCO_(3)(210℃).The improved SCR denitrification activity results from the enhancement of physicochemical properties including higher Mn^(4+)content and Ce^(4+)/Ce^(3+)ratio,an abundance of chemisorbed oxygen and acidic sites,which could strengthen the SCR reaction pathways(richer NH_(3)activated species and bidentate nitrate active species).Therefore,NO removal is enhanced.
基金funded by the Innovative Research Group Project of the National Natural Science Foundation of China(52121004)the Research Development Fund(No.RDF-21-02-060)by Xi’an Jiaotong-Liverpool University+1 种基金support received from the Suzhou Industrial Park High Quality Innovation Platform of Functional Molecular Materials and Devices(YZCXPT2023105)the XJTLU Advanced Materials Research Center(AMRC).
文摘Seawater zinc-air batteries are promising energy storage devices due to their high energy density and utilization of seawater electrolytes.However,their efficiency is hindered by the sluggish oxygen reduction reaction(ORR)and chlorideinduced degradation over conventional catalysts.In this study,we proposed a universal synthetic strategy to construct heteroatom axially coordinated Fe–N_(4) single-atom seawater catalyst materials(Cl–Fe–N_(4) and S–Fe–N_(4)).X-ray absorption spectroscopy confirmed their five-coordinated square pyramidal structure.Systematic evaluation of catalytic activities revealed that compared with S–Fe–N_(4),Cl–Fe–N_(4) exhibits smaller electrochemical active surface area and specific surface area,yet demonstrates higher limiting current density(5.8 mA cm^(−2)).The assembled zinc-air batteries using Cl–Fe–N_(4) showed superior power density(187.7 mW cm^(−2) at 245.1 mA cm^(−2)),indicating that Cl axial coordination more effectively enhances the intrinsic ORR activity.Moreover,Cl–Fe–N_(4) demonstrates stronger Cl−poisoning resistance in seawater environments.Chronoamperometry tests and zinc-air battery cycling performance evaluations confirmed its enhanced stability.Density functional theory calculations revealed that the introduction of heteroatoms in the axial direction regulates the electron center of Fe single atom,leading to more active reaction intermediates and increased electron density of Fe single sites,thereby enhancing the reduction in adsorbed intermediates and hence the overall ORR catalytic activity.
基金funding from the National Natural Science Foundation of China(22378289)the Key Central Government Guides Local Funds for Science and Technology Development(YDZJSX2022A021)the special fund for Science and Technology Innovation Teams of Shanxi Province(202304051001026)。
文摘The oxygen evolution reaction(OER)suffers from sluggish kinetics,necessitating efficient electrocatalysts to reduce overpotentials in water splitting.Currently recognized OER mechanisms primarily include the adsorbate evolution mechanism(AEM),lattice oxygen mechanism(LOM),and oxide path mechanism(OPM).Compared to AEM,limited by scaling relationships,and LOM,constrained by stability issues,the OPM offers a promising alternative by enabling direct O-O bond formation via dual active sites,thus bypassing^(*)OOH intermediates and lattice O involvement and achieving a balance between activity and durability.However,activating the OPM process requires precise control over the spatial and electronic structure of active sites,making the design of OPM-based catalysts challenging.While previous reviews have focused on homo/heteronuclear diatomic perspectives of OPM-based catalysts,it is urgent to systematically summarize design strategies to provide a rational reference for their development.Herein,a review of design strategies for OPM-based OER catalysts across three scales is comprehensively presented,including in-situ engineering,doping-enabled sites reconstruction,and introducing new sites for nanoparticles,direct synthesis or post-treatments for molecular catalysts,and doping or template strategies for atom pairs or arrays.The unique advantage of atom arrays is also highlighted,and their future research directions and possible strategies are discussed.This review provides a systematic summary and forward-looking perspectives for rationally designing high-performance OPM-based OER catalysts.
基金Supported by National Key Research and Development Program of China(2020YFD1100302)。
文摘Under the context of global energy transition and carbon neutrality,controlling nitrogen oxide(NO_(x))emissions from biomass combustion is of great significance,and the development of high-efficiency low-temperature catalysts has become a current research focus.In this study,Nb was used to dope and modify the Mn_(7)-Cu_(3)/BCN catalyst to construct the Mn_(7)-Cu_(3)-Nb_(x)/BCN system.The doping amount was optimized through selective catalytic reduction(SCR)activity tests.The reaction mechanism was explored by combining in situ DRIFTS and density functional theory(DFT)simulations.Experimental findings revealed that the catalyst doped with 0.05%Nb achieved the optimal performance,sustaining a NO conversion efficiency of≥94%within the temperature window of 150−275℃while demonstrating improved resistance to alkali metal K poisoning.Mechanistic analyses showed that at low temperatures,the catalyst facilitated the SCR reaction via both the Eley-Rideal(E-R)and Langmuir-Hinshelwood(L-H)pathways,with the synergistic interaction between multiple active sites driving the efficient conversion of NH3 and NO.DFT calculations further confirmed that both pathways had the characteristics of low reaction energy barriers and significant exothermicity,ensuring the high activity and feasibility of the low-temperature reaction.The findings provided foundational theoretical support for the design of Nb-doped Mn-Cu-supported catalysts and the exploration of the underlying working mechanisms.
基金financially supported by the Sinopec Seed Program Project(No.223281)State Key Laboratory of Advanced Papermaking and Paper-based Materials(No.2024ZD06)+3 种基金Guangdong Basic and Applied Basic Research Foundation(Nos.2022A1515110543 and 2023A1515110170)the Natural Science Foundation of Guangdong Province(No.2024B1515040023)Guangjuyingcai program of Guangzhou(No.2024D03J0002)111 Project(No.B18023).
文摘Microporous polyimides(PIM-PIs)have emerged as promising high-performance membranes for gas separation.However,achieving an optimal balance between permeability and selectivity remains a major challenge.In this study,we designed and synthesized a series of PIM-PIs by combining rigid dianhydrides 9-bis(trifluoromethyl)-2,3,6,7-xanthenetetracarboxylic dianhydride(6FCDA)and 4,4′-(hexafluoroisopropylidene)diphthalic anhydride(6FDA)with contorted diamines,including 9,9-bis(4-aminophenyl)fluorene(FDA),9,9′-spirobifluorene-2,2′-diamine(SBFDA),and 3,3,3′,3′-tetramethyl-1,1′-spirobiindane-5,5′-diamine-6,6′-diol(TSDA),to systematically elucidate the relationship between hierarchical microstructure and gas transport behavior.Comprehensive characterization revealed that the 6FCDA-based polymers exhibited a higher microporosity(V_(micro)/V_(total)up to 54.7%)and fractional free volume compared to their 6FDA counterparts.Gas permeation measurements showed that the 6FCDA/SBFDA membrane delivered a CO_(2)permeability of 386 Barrer and CO_(2)/CH_(4)selectivity of 30.2,exceeding the 2008 Robeson upper bound.Structure-property correlation analyses indicated that diffusion selectivity predominantly governed gas separation performance,with rigid,spirocyclic architectures suppressing chain packing to generate sub-5Åmicropores,as further validated by molecular simulations.The optimized 6FCDA/FDA membrane achieved a BET surface area of 423 m^(2)·g^(−1),while maintaining excellent mechanical strength and high thermal stability.This work establishes an effective monomer design strategy to overcome the permeability-selectivity trade-off through backbone rigidification,thereby advancing PIM-PIs for practical applications in natural gas purification and carbon capture.
基金supported by Shaanxi Key Research and Development Program(No.2024SF-YBXM-546)the National Natural Science Foundation of China(No.52470161)the State Key Laboratory of Pollution Control and Resource Reuse Foundation(No.PCRRF21007).
文摘With the legislative development,the organic and inorganic composition separation has become the primary requirement for sewer sediment disposal,however the relevant technology has been rarely reported and the driving mechanism was still unclear.In this study,direct disintegration of biopolymers and indirect broken of connection point were investigated on the hydrolysis and component separation.Three typical sewer sediment treatment approaches,i.e.,alkaline,thermal and cation exchange treatments were proposed,which represented the hydrolysis-driving forces of chemical hydrolysis,physical hydrolysis and innovative cation bridging break-age.The results showed that the organic and inorganic separation rates of sewer sediment driven by alkaline,thermal and cation exchange treatments reached 21.26%,23.80%,and 19.56%-48.0%,respectively,compared to 4.43%in control.The secondary structure of proteins was disrupted,transitioning from𝛼α-helix to𝛽β-turn and random coil.Meanwhile,much biopolymers were released from solid to the liquid phase.From thermody-namic perspective,sewer sediment deposition was controlled by short-range interfacial interactions described by extended Derjaguin-Landau-Verwey-Overbeek theory.Additionally,the separation of organic and inorganic components was positively correlated with the thermodynamic parameters(Corr=0.87),highlighted the robust-ness of various driving forces.And the flocculation energy barriers were 2.40(alkaline),1.60 times(thermal),and 4.02–4.97 times(cation exchange)compared to control group.The findings revealed the contrition differ-ence of direct disintegration of gelatinous biopolymers and indirect breakage of composition connection sites in sediment composition separation,filling the critical gaps in understanding the specific mechanisms of sediment biopolymer disintegration and intermolecular connection breakage.
基金Project supported by the National Key Research and Development Program of China(2022YFC2905800)National Natural Science Foundation of China(52374276,52274269)+2 种基金Yunnan Fundamental Re search Projects(202401AS070051)the Natural Science Foundation of Hubei Province of China(2024AFD123)Young Elite Scientists Sponsorship Program by CAST(YESS20200276)。
文摘The efficient flotation separation of rare earth elements(REEs)from gangue minerals is crucial in mineral processing.This study synthesized a quaternary ammonium salt ionic liquid collector,tetrabutylammonium salicylhydroxamate(T-S),and investigated its performance in separating bastnaesite and fluorite.T-S was synthesized from salicylhydroxamic acid(SHA)and tetrabutylammonium chloride(TBAC),and its molecular structure was characterized using Fourier transform infrared(FTIR)spectroscopy.Microflotation tests indicate that T-S outperforms SHA and TBAC in both collecting ability and selectivity for bastnaesite.Adsorption,zeta potential,and infrared spectroscopy measurements reveal that T-S exhibits stronger adsorption on bastnaesite compared to SHA and TBAC.X-ray photoelectron spectroscopy(XPS)and molecular dynamics simulations(MDS)results confirm that chemical adsorption occurs between Ce on the bastnaesite surface and the-C(=O)NHOH groups of T-S.Moreover,the interaction between T-S and the bastnaesite surface is stronger than that with the fluorite surface.This work provides valuable insights for designing ionic liquid collectors for the flotation separation of bastnaesite and fluorite.
基金supported by the National Key R&D Program of China (2021YFA1502802)the National Natural Science Foundation of China (U21B2092, 22202213, 22402210, 22502215, 22502214, 22572200, and 22579171)+3 种基金the International Partnership Program of Chinese Academy of Sciences (172GJHZ2022028MI)the Shenyang Bureau of Science and Technology (24-213-3-25)the Natural Science Foundation of Liaoning Province (2025BS0153)Zhongke Technology Achievement Transfer and Transformation Center of Henan Province 2025119
文摘Single-atom catalysts(SACs)have demonstrated excellent performance in heterogeneous catalytic reactions owing to their maximized atomic efficiency,distinctive geometric,and electronic configurations.However,the efficacy of SACs remains limited for certain reactions requiring simultaneous activation of multiple reactants over metallic active sites.Herein,we report an atomically dispersed Pt1Ru1 dual-atom pair site anchored on nanodiamond@graphene(ND@G)for CO oxidation.The Pt1Ru1 dual-atom catalyst shows an exceptional turnover frequency(TOF)of 17.6.10^(-2)s^(-1)at significantly lower temperature(30℃),achieving a tenfold increase in TOF compared to singleatom Pt1/ND@G catalyst(1.5.10^(-2)s^(-1))and surpassing to previously reported Pt-based catalysts under similar conditions.Moreover,the catalyst demonstrates excellent stability,maintaining its activity for 40 h at 80℃without significant deactivation.The superior catalytic performance of Pt-Ru dual-atom catalysts is attributed to the synergistic effect between Pt and Ru atoms with enhanced metallicity for improving simultaneous adsorption and activation of CO and O_(2),and the tuning of conventional competitive reactant adsorption into a non-competitive pathway over dual-atom pair sites.The present work manifests the advantages of dual-atom pair sites in heterogeneous catalysis and paves the way for precise design of catalysts at the atomic scale.
