Developing acid-stable manganesebased catalysts for the oxygen evolution reaction(OER)is pivotal for advancing proton exchange membrane water electrolysis(PEMWE).Here,we present a selenium-doped MnO_(2) catalyst,where...Developing acid-stable manganesebased catalysts for the oxygen evolution reaction(OER)is pivotal for advancing proton exchange membrane water electrolysis(PEMWE).Here,we present a selenium-doped MnO_(2) catalyst,where the synergistic effects of Se and oxygen defects stabilize Mn^(3+)species and regulate*OH adsorption dynamics.In situ spectroscopic studies and density functional theory(DFT)calculations confirm that Se doping modulates the electronic structure of Mn centers,lowering the energy barrier for*OH deprotonation and accelerating OER kinetics.In 0.5 M H_(2)SO_(4),Se-MnO_(2) achieves current densities of 10 and 100 mA·cm^(-2) with overpotentials of 345±5 and 398±5 mV,respectively,outperforming commercial RuO_()2.Integrated into PEM electrolyzers,the catalyst demonstrates exceptional stability over 400 h under dynamic current densities(100–500 mA·cm^(-2)),showcasing structural integrity and negligible activity decay.The strategic doping of selenium significantly enhances catalytic performance,thereby offering a promising pathway toward the development of cost-effective electrocatalysts for applications under acidic conditions.展开更多
With the development of renewable energy,electrochemical carbon dioxide reduction reaction(CO_(2)RR)has become a potential solution for achieving carbon neutrality.However,until now,due to issues with salt precipitate...With the development of renewable energy,electrochemical carbon dioxide reduction reaction(CO_(2)RR)has become a potential solution for achieving carbon neutrality.However,until now,due to issues with salt precipitate and regeneration of the electrolyte,this technology faces challenges such as difficulty in maintaining long-term stable operation and excessive costs.The pure water CO_(2)electrolyzers are believed to be the ultimate solution to eliminate the salt depreciation and electrolyte issues.This study develops an in-situ method tailored for CO_(2)reduction in pure water.By employing distribution of relaxation times(DRT)analysis and in-situ electrochemical active surface area(ECSA)measurements,we carried out a comprehensive investigation into the mass transport and electrochemical active surface area of gas diffusion electrodes(GDE)under pure water conditions.The maximum 89%CO selectivity and high selectivity(>80%)in the range of 0-300 mA/cm^(2)were achieved using commercial Ag nanoparticles by rational design of catalyst layer.We found that ionomers influence the CO_(2)electrolyzers performance via affecting local pH,GDE-membrane interface,and CO_(2)transport,while catalyst loading mainly influences the active area and CO_(2)transport.This work provides benchmark and insights for future pure water CO_(2)electrolyzers development.展开更多
Electrocatalytic CO_(2)reduction(CO_(2)RR)is spurring intensive research interest,where many attentions have been paid to catalyst design and mechanism study.Electrode near-surface microenvironment matters fundamental...Electrocatalytic CO_(2)reduction(CO_(2)RR)is spurring intensive research interest,where many attentions have been paid to catalyst design and mechanism study.Electrode near-surface microenvironment matters fundamentally for reactant mass transfer,water molecule interference,catalyst exposure,and others,yet it has been rarely investigated.In the latest issue of Angew.Chem.Int.Ed.,Han,Kang and coauthors reported a method to regulate the microenvironment on the catalyst surface by adding polyethylene glycol,which remarkably improves the yield of multicarbon products.This strategy of controlling multiple proton-electron coupling processes through molecular chemistry-driven microenvironmental regulation is thought to inspire new idea for addressing the low efficiency challenge of CO_(2)RR.展开更多
Electrocatalysis is a promising approach to clean energy conversion due to its high efficiency and low environmental pollution. Noble metal materials have been studied to show high activity toward electrocatalyltic re...Electrocatalysis is a promising approach to clean energy conversion due to its high efficiency and low environmental pollution. Noble metal materials have been studied to show high activity toward electrocatalyltic reactions, although such applications remain restricted by the high cost and poor durability of the noble metals. By precisely adjusting the catalyst composition, size, and structure, electrocatalysts with excellent performance can be obtained. Atomic layer deposition(ALD) is a technique used to produce ultrathin films and ultrafine nanoparticles at the atomic level. It possesses unique advantages for the controllable design and synthesis of electrocatalysts. Furthermore, the homogenous composition and structure of the electrocatalysts prepared by ALD favor the exploration of structure-reactivity relationships and catalytic mechanisms. In this review, the mechanism, characteristics, and advantages of ALD in fabricating nanostructures are introduced first. Subsequently, the problems associated with existing electrocatalysts and a series of recently developed ALD strategies to enhance the activity and durability of electrocatalysts are presented. For example, the deposition of ultrafine Pt nanoparticles to increase the utilization and activity of Pt, fabrication of core–shell, overcoat, nanotrap, and other novel structures to protect the noble-metal nanoparticles and enhance the catalyst stability. In addition, ALD developments in synthesizing non-noble metallic electrocatalysts are summarized and discussed. Finally, based on the current studies, an outlook for the ALD application in the design and synthesis of electrocatalysts is presented.展开更多
Piezocatalytic materials have been widely used for catalytic hydrogen evolution and purification of organic contaminants.However,most studies focus on nano-size and/or polycrystalline catalysts,suffering from aggregat...Piezocatalytic materials have been widely used for catalytic hydrogen evolution and purification of organic contaminants.However,most studies focus on nano-size and/or polycrystalline catalysts,suffering from aggregation and neutralization of internal piezoelectric field caused by polydomains.Here we report a single crystal ZnO of large size and few bulk defects crafted by a hydrothermal method for piezocatalytic hydrogen generation from pure water.It is noteworthy that single-side surface areas of both original as-prepared ZnO and Ga-doped ZnO bulk crystals are larger than 30 cm^(2).The high quality of ZnO and Ga-doped ZnO bulks are further uncovered by high-resolution transmission electron microscope(HRTEM),photoluminescence(PL)and X-ray diffraction(XRD).Remarkably,an outstanding hydrogen production rate of co-catalyst-free Ga-doped ZnO bulk crystal(i.e.,a maximum rate of 5915μmol h^(-1) m^(-2))is observed in pure water triggered by ultrasound in dark,which is over 100 times higher than that of its powder counterpart(i.e.,52.54μmol h^(-1) m^(-2)).The piezocatalytic performance of ZnO bulk crystal is systematically studied in terms of varied exposed crystal facet,thickness and conductivity.Different piezocatalytic performances are attributed to magnitude and distribution of piezoelectric potential,revealed by the finite element method(FEM)simulation.The density functional theory(DFT)calculations are employed to investigate the piezocatalytic hydrogen evolution process,indicating a strong H_(2)O adsorption and a low energy barrier for both H_(2)O dissociation and H2 generation on the stressed Znterminated(0001)ZnO surface.展开更多
The facile designs and fabrication of noble metal-free electrocatalysts are highly required to achieve multifunctional catalytic activity with excellent stability in Zn-air batteries,fuel cells and water splitting sys...The facile designs and fabrication of noble metal-free electrocatalysts are highly required to achieve multifunctional catalytic activity with excellent stability in Zn-air batteries,fuel cells and water splitting systems.Herein,a heterostructure engineering is applied to construct the high performance Co,Ncontaining carbon-based multifunctional electrocatalysts with the feature of isotype(i.e.n-n type Co_(2)N_(0.67)-BHPC)and anisotype(i.e.p-n type Co_(2)O_(3)-BHPC)heterojunctions for ORR,OER and HER.The nn type Co_(2)N_(0.67)-BHPC,in which biomass(e.g.mushroom)-derived hierarchical porous carbon(BHPC)incorporated with nonstoichiometric active species Co_(2)N_(0.67),is fabricated by using an in situ protective strategy of macrocyclic central Co-N_(4) from CoTPP(5,10,15,20-tetrakis(phenyl)porphyrinato cobalt)precursor through the intermolecularπ-πinteractions between CoTPP and its metal-free analogue H_(2) TPP.Meanwhile,an unprotected strategy of macrocyclic central Co-N_(4) from CoTPP can afford the anisotype Co_(2)O_(3)-BHPC p-n heterojunction.The as-prepared n-n type Co_(2)N_(0.67)-BHPC heterojunction exhibited a higher density of Co-based active sites with outstanding stability and more efficient charge transfer at the isotype heterojunction interface in comparison with p-n type Co_(2)O_(3)-BHPC heterojunction.Consequently,for ORR,Co_(2)N_(0.67)-BHPC exhibits the more positive onset and half-wave potentials of 0.93 and 0.86 V vs.RHE,respectively,superior to those of the commercial 20 wt%Pt/C and most of Cobased catalysts reported so far.To drive a current density of 10 mA cm^(-2),Co_(2)N_(0.67)-BHPC also shows the lower overpotentials of 0.34 and 0.21 V vs.RHE for OER and HER,respectively.Furthermore,the Zn-air battery equipped with Co_(2)N_(0.67)-BHPC displays higher maximum power density(109 mW cm^(-2))and charge-discharge cycle stability.Interestingly,the anisotype heterojunction Co_(2)O_(3)-BHPC as trifunctional electrocatalyst reveals evidently photoelectrochemical enhancement compared with the photostable Co_(2)N_(0.67)-BHPC.That is to say,isotype heterojunction material(n-n type Co^(2)N_(0.67)-BHPC)is equipped with better electrocatalytic performance than anisotype one(p-n type Co_(2)O_(3)-BHPC),but the opposite is true in photoelectrochemical catalysis.Meanwhile,the possible mechanism is proposed based on the energy band structures of the Co_(2)N_(0.67)-BHPC and Co_(2)O_(3)-BHPC and the cocatalyst effects.The present work provides much more possibilities to tune the electrocatalytic and photoelectrochemical properties of catalysts through a facile combination of heterostructure engineering protocol and macrocyclic central metal protective strategy.展开更多
The high cost,scarcity,and poor stability of precious-metal-based catalysts have hindered their extensive application in energy conversion and storage.This stimulates the search for earth-abundant alternatives to repl...The high cost,scarcity,and poor stability of precious-metal-based catalysts have hindered their extensive application in energy conversion and storage.This stimulates the search for earth-abundant alternatives to replace noble metal electrocatalysts.Hence,in this study,we investigate a novel and low-cost bifunctional electrocatalyst consisting of ZnCoMnO_(4) anchored on nitrogen-doped graphene oxide(ZnCoMnO_(4)/N-rGO).Benefiting from the strong Co-N interaction in ZnCoMnO_(4) and the coupled conductive N-rGO,the catalysts exhibit high electrocatalytic activity.Moreover,density functional theory calculations support the dominant role of the strong Co-N electronic interaction,which leads to ZnCoMnO_(4)/N-rGO having more favorable binding energies with O2 and H_(2) O,resulting in fast reaction kinetics.The obtained ZnCoMnO_(4)/N-rGO electrocatalyst exhibits superb bifunctional activity,with a half-wave potential of 0.83 V for the oxygen reduction reaction and a low onset potential of 1.57 V for the oxygen evolution reaction in 0.1 M KOH solution.Furthermore,a Zn-air battery driven by the ZnCoMnO_(4)/N-rGO catalyst shows remarkable discharge/charge performance,with a power density of 138.52 mW cm^(-2) and longterm cycling stability for 48 h.This work provides a promising multifunctional electrocatalyst based on non-noble metals for the storage and conversion of renewable energy.展开更多
Based on the basic principle and mechanism of flue gas denitrification,the commonly used catalysts for flue gas denitrification were introduced firstly,and then the catalytic performance,stability and reaction mechani...Based on the basic principle and mechanism of flue gas denitrification,the commonly used catalysts for flue gas denitrification were introduced firstly,and then the catalytic performance,stability and reaction mechanism of catalysts in the market were analyzed.Different types of catalysts were studied to look for green catalysts with high activity,sulfur resistance,water vapor resistance and other advantages.The mechanism of denitration reaction of green catalysts was discussed,and the laws of formation,propagation and consumption of active species in the reaction process were revealed to provide theoretical basis for optimizing catalyst design and improving reaction conditions.Then the research status and problems of new catalysts for flue gas denitrification were described.Finally,the future development direction of green catalysts for flue gas denitration was discussed to improve the performance and stability of catalysts and meet the performance requirements of denitration catalysts in different industries.展开更多
Graphene,owing to its exceptional electronic,optical,thermal,and mechanical properties,has emerged as a highly promising material.Currently,the synthesis of large-area graphene films on metal substrates via chemical v...Graphene,owing to its exceptional electronic,optical,thermal,and mechanical properties,has emerged as a highly promising material.Currently,the synthesis of large-area graphene films on metal substrates via chemical vapor deposition remains the predominant approach for producing high-quality graphene.To realize the potential applications of graphene,it is essential to transfer graphene films to target substrates in a manner that is non-destructive,clean,and efficient,as this significantly affects the performance of graphene devices.This review examines the current methods for graphene transfer from three perspectives:non-destructive transfer,clean transfer,and high-efficiency transfer.It analyzes and compares the advancements and limitations of various transfer techniques.Finally,the review identifies the key challenges faced by current graphene transfer methods and anticipates future developmental prospects.展开更多
Through literature analysis and case study, the introduction history, variety selection (high bush, half high bush, low bush) and regional cultivation techniques of blueberry in China were summarized, and the practica...Through literature analysis and case study, the introduction history, variety selection (high bush, half high bush, low bush) and regional cultivation techniques of blueberry in China were summarized, and the practical effects of precision cultivation (water and fertilizer integration, wild planting) and under-forest economic model (forest-blueberry-fungus system, ecological tourism) were evaluated. It provided a technical reference for expanding the planting scale of blueberry and improving the fruit quality.展开更多
The addition of cold flow improvers(CFIs)is considered as the optimum strategy to improve the cold flow properties(CFPs)of diesel fuels,but this strategy is always limited by the required large dosage.To obtain low-do...The addition of cold flow improvers(CFIs)is considered as the optimum strategy to improve the cold flow properties(CFPs)of diesel fuels,but this strategy is always limited by the required large dosage.To obtain low-dosage and high-efficiency CFIs for diesel,1,2,3,6-tetrahydrophthalic anhydride(THPA)was introduced as a third and polar monomer to enhance the depressive effects of alkyl methacrylatetrans anethole copolymers(C_(14)MC-TA).The terpolymers of alkyl methacrylate-trans anethole-1,2,3,6-tetrahydrophthalic anhydride(C_(14)MC-TA-THPA)were synthesized and compared with the binary copolymers of C_(14)MC-TA and alkyl methacrylate-1,2,3,6-tetrahydrophthalic anhydride(C_(14)MC-THPA).Results showed that C_(14)MC-THPA achieved the best depressive effects on the cold filter plugging point(CFPP)and solid point(SP)by 11℃and 16℃at a dosage of 1250 mg/L and monomer ratio of 6:1,while 1500mg/L C_(14)MC-TA(1:1)reached the optimal depressive effects on the CFPP and SP by 12℃and 18℃.THPA introduction significantly improved the depressive effects of C_(14)MC-TA.Lower dosages of C_(14)MCTA-THPA in diesel exerted better improvement effects on the CFPP and SP than that of C_(14)MC-TA and C_(14)MC-THPA.When the monomer ratio and dosage were 6:0.6:0.4 and 1000 mg/L,the improvement effect of C_(14)MC-TA-THPA on diesel reached the optimum level,and the CFPP and SP were reduced by 13℃and 19℃,respectively.A 3D nonlinear surface diagram fitted by a mathematical model was also used for the first time to better understand the relationships of monomer ratios,dosages,and depressive effects of CFIs in diesel.Surface analysis results showed that C_(14)MC-TA-THPA achieved the optimum depressive effects at a monomer ratio of 6:0.66:0.34 and dosage of 1000 mg/L,and the CFPP and SP decreased by 14℃ and 19℃,respectively.The predicted results were consistent with the actual ones.Additionally,the improvement mechanism of these copolymers in diesel was also explored.展开更多
The preparation of Pd-based catalysts with rich electrons and a high atom dispersion rate is of great significance for improving the reactivity of cross-coupling reactions,which is a powerful tool for pharmaceutical a...The preparation of Pd-based catalysts with rich electrons and a high atom dispersion rate is of great significance for improving the reactivity of cross-coupling reactions,which is a powerful tool for pharmaceutical and fine chemical synthesis.Here,we report a PdNi single-atom alloy(SAA)catalyst in which isolated Pd single atoms are anchored onto the surface of Ni nanoparticles(NPs)applied for Suzuki coupling reactions and Heck coupling reactions.The 0.1%PdNi SAA exhibits extraordinary catalytic activity(reaction rate:17,032.25 mmol h^(-1)gPd^(-1))toward the Suzuki cross-coupling reaction between 4-bromoanisole and phenylboronic acid at 80℃for 1 h.The excellent activity is supposed to attribute to the 100 percent utilization rate of Pd atoms and the highly stable surface zero-valance Pd atoms,which provides abundant sites and electrons for the adsorption and fracture of the C-X(X=Cl,Br,I)bond.Moreover,our work demonstrates the excellent application prospect of SAAs for cross-coupling reactions.展开更多
The development of atomically dispersed platinum-based catalysts with high performance and welldefined active site structures is crucial for the commercialization of water electrolysis for hydrogen production.Herein,w...The development of atomically dispersed platinum-based catalysts with high performance and welldefined active site structures is crucial for the commercialization of water electrolysis for hydrogen production.Herein,we propose a coordination dual-shell synergistic regulation mechanism of coal pitchderived carbon-supported single atom Pt-N_(x)O_(y)-S_(1)catalytic sites by a self-assembly-pyrolysis strategy for promoting hydrogen evolution reaction(HER).The Pt-N_(3)O1-S_(1)sites exhibited the highest HER performance,with an overpotential of 92 mV at a current density of 400 mA cm^(-2).At 50 mV,the turnover frequency was 34.04 s^(-1)and the mass activity was 22.83 A mg_(Pt)^(-l),which is 63.4 times that of the 20%Pt/C catalyst.Theoretical calculations revealed that the coordination dual-shell impacts the electronic structure of the Pt atoms and the adsorption strength towards reactants synergistically.The S atoms in the second coordination shell weakened the strength of Pt-N first shell,resulting the more surface valence electrons around Pt atoms,exhibiting the most suitable adsorption free energy and enhancing the adsorption of H^(+)on Pt-N_(3)O_(1)-S_(1)sites,thus enhancing the electrocatalytic HER process by promoting Volmer step.This work reveals that coordination dual-shell synergistic regulation is an effective strategy for enhancing the electrocatalytic reaction process.展开更多
Efficient catalysis of the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)is essential for the rechargeable zinc-air batteries(R-ZABs).However,challenges remain due to the scarcity of effective bifunc...Efficient catalysis of the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)is essential for the rechargeable zinc-air batteries(R-ZABs).However,challenges remain due to the scarcity of effective bifunctional electrocatalysts and limited understanding of the structure-activity relationships.Pyrrole-type single-atom catalysts(SACs)with unique electronic structures have emerged as promising electrocatalysts.In this work,we combine density functional theory(DFT)calculations and experimental studies to systematically explore the structure-activity relationships and potential of pyrrole-type transition metal-N_(3)(TM-po-N_(3))as bifunctional catalysts.DFT calculations reveal that differences in the dependence of ORR and OER activities on the free energy of adsorption of reaction intermediates significantly affect the TM-po-N_(3)bifunctional activity and identify magnetic Cu-po-N_(3)as the best candidate.The bifunctional activity of Cu-po-N_(3)originates from interactions between spin-polarized out-of-plane Cu_3d and O_2s+2p orbitals.Theoretical predictions are validated experimentally,showing that the synthesized Cu-SAC/NC exhibits excellent bifunctional performance with a small potential gap of 0.666 V.Additionally,the assembled R-ZABs display a high-power density of 170 mW cm^(-2)and long-term stability,with the charge-discharge voltage gap increasing by only 0.01 V over 240 h.This work provides new insights into the design of efficient bifunctional catalysts.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
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
Sluggish sulfur redox kinetics remain a critical bottleneck in the advancement of high-performance lithiumsulfur batteries(LSBs).Single-atom catalysts(SACs)offer a promising solution to this limitation,particularly wh...Sluggish sulfur redox kinetics remain a critical bottleneck in the advancement of high-performance lithiumsulfur batteries(LSBs).Single-atom catalysts(SACs)offer a promising solution to this limitation,particularly when their coordination structures are carefully engineered.Here,we develop a chromium-based SAC featuring a unique undercoordinated CrN_(3) configuration to boost sulfur electrochemistry.Compared with conventional CrN_(4),the CrN_(3) motif lowers 3d orbital occupancy and meanwhile activates the in-plane hybridizations with S 3p orbitals upon interaction with polysulfides,contributing to moderate adsorption strength and reduced energy barriers for bidirectional sulfur conversions.Additionally,the integration of the two-dimensional(2D)porous framework ensures abundant electrochemically active surfaces and efficiently exposed active sites.As a result,CrN_(3)-based cells demonstrate fast and durable sulfur redox reactions,enabling an ultralow capacity decay of 0.0075%per cycle over 1000 cycles and a high-rate capability of 651.9 mAh·g^(-1)at 5 C.The CrN_(3) catalyst retains robust catalytic efficiency under demanding conditions,delivering a high areal capacity of 5.53 mAh·cm^(-2) at high sulfur loading and lean electrolyte.This work establishes a compelling paradigm of SAC coordination engineering for designing advanced sulfur electrocatalysts for next-generation LSBs.展开更多
High‐entropy amorphous catalysts(HEACs)integrate multielement synergy with structural disorder,making them promising candidates for water splitting.Their distinctive features—including flexible coordination environm...High‐entropy amorphous catalysts(HEACs)integrate multielement synergy with structural disorder,making them promising candidates for water splitting.Their distinctive features—including flexible coordination environments,tunable electronic structures,abundant unsaturated active sites,and dynamic structural reassembly—collectively enhance electrochemical activity and durability under operating conditions.This review summarizes recent advances in HEACs for hydrogen evolution,oxygen evolution,and overall water splitting,highlighting their disorder-driven advantages over crystalline counterparts.Catalytic performance benchmarks are presented,and mechanistic insights are discussed,focusing on how multimetallic synergy,amorphization effect,and in‐situ reconstruction cooperatively regulate reaction pathways.These insights provide guidance for the rational design of next‐generation amorphous high‐entropy electrocatalysts with improved efficiency and durability.展开更多
基金supported by the National Natural Science Foundation of China(No.52403363)the Hebei Natural Science Foundation(No.E2024203006)+2 种基金the Chunhui Program Cooperative Research Project of the Ministry of Education(No.202200266)the Science Research Project of Hebei Education Department(No.BJ2025007)the S&T Program of Qinhuangdao(No.202401A131).
文摘Developing acid-stable manganesebased catalysts for the oxygen evolution reaction(OER)is pivotal for advancing proton exchange membrane water electrolysis(PEMWE).Here,we present a selenium-doped MnO_(2) catalyst,where the synergistic effects of Se and oxygen defects stabilize Mn^(3+)species and regulate*OH adsorption dynamics.In situ spectroscopic studies and density functional theory(DFT)calculations confirm that Se doping modulates the electronic structure of Mn centers,lowering the energy barrier for*OH deprotonation and accelerating OER kinetics.In 0.5 M H_(2)SO_(4),Se-MnO_(2) achieves current densities of 10 and 100 mA·cm^(-2) with overpotentials of 345±5 and 398±5 mV,respectively,outperforming commercial RuO_()2.Integrated into PEM electrolyzers,the catalyst demonstrates exceptional stability over 400 h under dynamic current densities(100–500 mA·cm^(-2)),showcasing structural integrity and negligible activity decay.The strategic doping of selenium significantly enhances catalytic performance,thereby offering a promising pathway toward the development of cost-effective electrocatalysts for applications under acidic conditions.
基金supported by the National Natural Science Foundation of China(No.52394204)by the Shanghai Municipal Science and Technology Major Project。
文摘With the development of renewable energy,electrochemical carbon dioxide reduction reaction(CO_(2)RR)has become a potential solution for achieving carbon neutrality.However,until now,due to issues with salt precipitate and regeneration of the electrolyte,this technology faces challenges such as difficulty in maintaining long-term stable operation and excessive costs.The pure water CO_(2)electrolyzers are believed to be the ultimate solution to eliminate the salt depreciation and electrolyte issues.This study develops an in-situ method tailored for CO_(2)reduction in pure water.By employing distribution of relaxation times(DRT)analysis and in-situ electrochemical active surface area(ECSA)measurements,we carried out a comprehensive investigation into the mass transport and electrochemical active surface area of gas diffusion electrodes(GDE)under pure water conditions.The maximum 89%CO selectivity and high selectivity(>80%)in the range of 0-300 mA/cm^(2)were achieved using commercial Ag nanoparticles by rational design of catalyst layer.We found that ionomers influence the CO_(2)electrolyzers performance via affecting local pH,GDE-membrane interface,and CO_(2)transport,while catalyst loading mainly influences the active area and CO_(2)transport.This work provides benchmark and insights for future pure water CO_(2)electrolyzers development.
基金supported by the National Natural Science Foundation of China(22393961,U23A20132,22209007)the Beijing Natural Science Foundation(2232016)+1 种基金the Beijing Nova Program(20240484611)the Fundamental Research Funds for the Central Universities,China(buctrc202029,buctrc202129).
文摘Electrocatalytic CO_(2)reduction(CO_(2)RR)is spurring intensive research interest,where many attentions have been paid to catalyst design and mechanism study.Electrode near-surface microenvironment matters fundamentally for reactant mass transfer,water molecule interference,catalyst exposure,and others,yet it has been rarely investigated.In the latest issue of Angew.Chem.Int.Ed.,Han,Kang and coauthors reported a method to regulate the microenvironment on the catalyst surface by adding polyethylene glycol,which remarkably improves the yield of multicarbon products.This strategy of controlling multiple proton-electron coupling processes through molecular chemistry-driven microenvironmental regulation is thought to inspire new idea for addressing the low efficiency challenge of CO_(2)RR.
基金supported by the National Natural Science Foundation of China(21872160,21802094,21673269)the National Science Fund for Distinguished Young Scholars(21825204)+1 种基金the National Key R&D Program of China(2017YFA0700101)the Natural Science Basic Research Plan in Shaanxi Province of China(2018JQ2038)~~
文摘Electrocatalysis is a promising approach to clean energy conversion due to its high efficiency and low environmental pollution. Noble metal materials have been studied to show high activity toward electrocatalyltic reactions, although such applications remain restricted by the high cost and poor durability of the noble metals. By precisely adjusting the catalyst composition, size, and structure, electrocatalysts with excellent performance can be obtained. Atomic layer deposition(ALD) is a technique used to produce ultrathin films and ultrafine nanoparticles at the atomic level. It possesses unique advantages for the controllable design and synthesis of electrocatalysts. Furthermore, the homogenous composition and structure of the electrocatalysts prepared by ALD favor the exploration of structure-reactivity relationships and catalytic mechanisms. In this review, the mechanism, characteristics, and advantages of ALD in fabricating nanostructures are introduced first. Subsequently, the problems associated with existing electrocatalysts and a series of recently developed ALD strategies to enhance the activity and durability of electrocatalysts are presented. For example, the deposition of ultrafine Pt nanoparticles to increase the utilization and activity of Pt, fabrication of core–shell, overcoat, nanotrap, and other novel structures to protect the noble-metal nanoparticles and enhance the catalyst stability. In addition, ALD developments in synthesizing non-noble metallic electrocatalysts are summarized and discussed. Finally, based on the current studies, an outlook for the ALD application in the design and synthesis of electrocatalysts is presented.
基金the financial support from the National Natural Science Foundation of China(No.21905317)the financial support from the National Natural Science Foundation of China(No.91833301)the Youth Talent Promotion Project from China Association for Science and Technology。
文摘Piezocatalytic materials have been widely used for catalytic hydrogen evolution and purification of organic contaminants.However,most studies focus on nano-size and/or polycrystalline catalysts,suffering from aggregation and neutralization of internal piezoelectric field caused by polydomains.Here we report a single crystal ZnO of large size and few bulk defects crafted by a hydrothermal method for piezocatalytic hydrogen generation from pure water.It is noteworthy that single-side surface areas of both original as-prepared ZnO and Ga-doped ZnO bulk crystals are larger than 30 cm^(2).The high quality of ZnO and Ga-doped ZnO bulks are further uncovered by high-resolution transmission electron microscope(HRTEM),photoluminescence(PL)and X-ray diffraction(XRD).Remarkably,an outstanding hydrogen production rate of co-catalyst-free Ga-doped ZnO bulk crystal(i.e.,a maximum rate of 5915μmol h^(-1) m^(-2))is observed in pure water triggered by ultrasound in dark,which is over 100 times higher than that of its powder counterpart(i.e.,52.54μmol h^(-1) m^(-2)).The piezocatalytic performance of ZnO bulk crystal is systematically studied in terms of varied exposed crystal facet,thickness and conductivity.Different piezocatalytic performances are attributed to magnitude and distribution of piezoelectric potential,revealed by the finite element method(FEM)simulation.The density functional theory(DFT)calculations are employed to investigate the piezocatalytic hydrogen evolution process,indicating a strong H_(2)O adsorption and a low energy barrier for both H_(2)O dissociation and H2 generation on the stressed Znterminated(0001)ZnO surface.
基金financially supported by the National Natural Science Foundation of China(21771192)Major Program of Shandong Province Natural Science Foundation(ZR2017ZB0315)+3 种基金Program for Taishan Scholar of Shandong Province(ts201712019)the Fundamental Research Funds for the Central Universities(19CX05001A,18CX02053A)Qingdao Applied Basic Research Project(19-6-2-20-cg)Yankuang Group 2019 Science and Technology Program。
文摘The facile designs and fabrication of noble metal-free electrocatalysts are highly required to achieve multifunctional catalytic activity with excellent stability in Zn-air batteries,fuel cells and water splitting systems.Herein,a heterostructure engineering is applied to construct the high performance Co,Ncontaining carbon-based multifunctional electrocatalysts with the feature of isotype(i.e.n-n type Co_(2)N_(0.67)-BHPC)and anisotype(i.e.p-n type Co_(2)O_(3)-BHPC)heterojunctions for ORR,OER and HER.The nn type Co_(2)N_(0.67)-BHPC,in which biomass(e.g.mushroom)-derived hierarchical porous carbon(BHPC)incorporated with nonstoichiometric active species Co_(2)N_(0.67),is fabricated by using an in situ protective strategy of macrocyclic central Co-N_(4) from CoTPP(5,10,15,20-tetrakis(phenyl)porphyrinato cobalt)precursor through the intermolecularπ-πinteractions between CoTPP and its metal-free analogue H_(2) TPP.Meanwhile,an unprotected strategy of macrocyclic central Co-N_(4) from CoTPP can afford the anisotype Co_(2)O_(3)-BHPC p-n heterojunction.The as-prepared n-n type Co_(2)N_(0.67)-BHPC heterojunction exhibited a higher density of Co-based active sites with outstanding stability and more efficient charge transfer at the isotype heterojunction interface in comparison with p-n type Co_(2)O_(3)-BHPC heterojunction.Consequently,for ORR,Co_(2)N_(0.67)-BHPC exhibits the more positive onset and half-wave potentials of 0.93 and 0.86 V vs.RHE,respectively,superior to those of the commercial 20 wt%Pt/C and most of Cobased catalysts reported so far.To drive a current density of 10 mA cm^(-2),Co_(2)N_(0.67)-BHPC also shows the lower overpotentials of 0.34 and 0.21 V vs.RHE for OER and HER,respectively.Furthermore,the Zn-air battery equipped with Co_(2)N_(0.67)-BHPC displays higher maximum power density(109 mW cm^(-2))and charge-discharge cycle stability.Interestingly,the anisotype heterojunction Co_(2)O_(3)-BHPC as trifunctional electrocatalyst reveals evidently photoelectrochemical enhancement compared with the photostable Co_(2)N_(0.67)-BHPC.That is to say,isotype heterojunction material(n-n type Co^(2)N_(0.67)-BHPC)is equipped with better electrocatalytic performance than anisotype one(p-n type Co_(2)O_(3)-BHPC),but the opposite is true in photoelectrochemical catalysis.Meanwhile,the possible mechanism is proposed based on the energy band structures of the Co_(2)N_(0.67)-BHPC and Co_(2)O_(3)-BHPC and the cocatalyst effects.The present work provides much more possibilities to tune the electrocatalytic and photoelectrochemical properties of catalysts through a facile combination of heterostructure engineering protocol and macrocyclic central metal protective strategy.
基金financially supported by the National Natural Science Foundation of China for Youths(No.21601067,21701057)the China Postdoctoral Science Foundation(No.2020 M673037)a project funded by the Priority Academic Program Development of the Jiangsu Higher Education Institutions。
文摘The high cost,scarcity,and poor stability of precious-metal-based catalysts have hindered their extensive application in energy conversion and storage.This stimulates the search for earth-abundant alternatives to replace noble metal electrocatalysts.Hence,in this study,we investigate a novel and low-cost bifunctional electrocatalyst consisting of ZnCoMnO_(4) anchored on nitrogen-doped graphene oxide(ZnCoMnO_(4)/N-rGO).Benefiting from the strong Co-N interaction in ZnCoMnO_(4) and the coupled conductive N-rGO,the catalysts exhibit high electrocatalytic activity.Moreover,density functional theory calculations support the dominant role of the strong Co-N electronic interaction,which leads to ZnCoMnO_(4)/N-rGO having more favorable binding energies with O2 and H_(2) O,resulting in fast reaction kinetics.The obtained ZnCoMnO_(4)/N-rGO electrocatalyst exhibits superb bifunctional activity,with a half-wave potential of 0.83 V for the oxygen reduction reaction and a low onset potential of 1.57 V for the oxygen evolution reaction in 0.1 M KOH solution.Furthermore,a Zn-air battery driven by the ZnCoMnO_(4)/N-rGO catalyst shows remarkable discharge/charge performance,with a power density of 138.52 mW cm^(-2) and longterm cycling stability for 48 h.This work provides a promising multifunctional electrocatalyst based on non-noble metals for the storage and conversion of renewable energy.
基金Supported by the Interdisciplinary Team Project of Shenyang University of Technology in 2021:Green and Low-carbon(Technology and Evaluation)of Typical Industries of Carbon Peak(2021-70-06)"Double First-class"Construction Project of Liaoning Province in 2020(Scientific Research)(FWDFGD2020041).
文摘Based on the basic principle and mechanism of flue gas denitrification,the commonly used catalysts for flue gas denitrification were introduced firstly,and then the catalytic performance,stability and reaction mechanism of catalysts in the market were analyzed.Different types of catalysts were studied to look for green catalysts with high activity,sulfur resistance,water vapor resistance and other advantages.The mechanism of denitration reaction of green catalysts was discussed,and the laws of formation,propagation and consumption of active species in the reaction process were revealed to provide theoretical basis for optimizing catalyst design and improving reaction conditions.Then the research status and problems of new catalysts for flue gas denitrification were described.Finally,the future development direction of green catalysts for flue gas denitration was discussed to improve the performance and stability of catalysts and meet the performance requirements of denitration catalysts in different industries.
基金supported by the National Key R&D Program of China(2020YFB2009002).
文摘Graphene,owing to its exceptional electronic,optical,thermal,and mechanical properties,has emerged as a highly promising material.Currently,the synthesis of large-area graphene films on metal substrates via chemical vapor deposition remains the predominant approach for producing high-quality graphene.To realize the potential applications of graphene,it is essential to transfer graphene films to target substrates in a manner that is non-destructive,clean,and efficient,as this significantly affects the performance of graphene devices.This review examines the current methods for graphene transfer from three perspectives:non-destructive transfer,clean transfer,and high-efficiency transfer.It analyzes and compares the advancements and limitations of various transfer techniques.Finally,the review identifies the key challenges faced by current graphene transfer methods and anticipates future developmental prospects.
文摘Through literature analysis and case study, the introduction history, variety selection (high bush, half high bush, low bush) and regional cultivation techniques of blueberry in China were summarized, and the practical effects of precision cultivation (water and fertilizer integration, wild planting) and under-forest economic model (forest-blueberry-fungus system, ecological tourism) were evaluated. It provided a technical reference for expanding the planting scale of blueberry and improving the fruit quality.
基金supported from the Natural Science Foundation Project of Shanghai(Nos.23ZR1425300 and 22ZR1426100)Experimental Technical Team Construction Project of Shanghai Education Commission(No.10110N230080)+1 种基金National Natural Science Foundation of China(No.22075183)Research and Innovation Project of Shanghai Municipal Education Commission(No.2023ZKZD54).
文摘The addition of cold flow improvers(CFIs)is considered as the optimum strategy to improve the cold flow properties(CFPs)of diesel fuels,but this strategy is always limited by the required large dosage.To obtain low-dosage and high-efficiency CFIs for diesel,1,2,3,6-tetrahydrophthalic anhydride(THPA)was introduced as a third and polar monomer to enhance the depressive effects of alkyl methacrylatetrans anethole copolymers(C_(14)MC-TA).The terpolymers of alkyl methacrylate-trans anethole-1,2,3,6-tetrahydrophthalic anhydride(C_(14)MC-TA-THPA)were synthesized and compared with the binary copolymers of C_(14)MC-TA and alkyl methacrylate-1,2,3,6-tetrahydrophthalic anhydride(C_(14)MC-THPA).Results showed that C_(14)MC-THPA achieved the best depressive effects on the cold filter plugging point(CFPP)and solid point(SP)by 11℃and 16℃at a dosage of 1250 mg/L and monomer ratio of 6:1,while 1500mg/L C_(14)MC-TA(1:1)reached the optimal depressive effects on the CFPP and SP by 12℃and 18℃.THPA introduction significantly improved the depressive effects of C_(14)MC-TA.Lower dosages of C_(14)MCTA-THPA in diesel exerted better improvement effects on the CFPP and SP than that of C_(14)MC-TA and C_(14)MC-THPA.When the monomer ratio and dosage were 6:0.6:0.4 and 1000 mg/L,the improvement effect of C_(14)MC-TA-THPA on diesel reached the optimum level,and the CFPP and SP were reduced by 13℃and 19℃,respectively.A 3D nonlinear surface diagram fitted by a mathematical model was also used for the first time to better understand the relationships of monomer ratios,dosages,and depressive effects of CFIs in diesel.Surface analysis results showed that C_(14)MC-TA-THPA achieved the optimum depressive effects at a monomer ratio of 6:0.66:0.34 and dosage of 1000 mg/L,and the CFPP and SP decreased by 14℃ and 19℃,respectively.The predicted results were consistent with the actual ones.Additionally,the improvement mechanism of these copolymers in diesel was also explored.
基金supported by the financial aid from National Science and Technology Major Project of China(No.2021YFB3500700)National Natural Science Foundation of China(Nos.22020102003,22025506 and 22271274)Program of Science and Technology Development Plan of Jilin Province of China(Nos.20230101035JC and 20230101022JC)。
文摘The preparation of Pd-based catalysts with rich electrons and a high atom dispersion rate is of great significance for improving the reactivity of cross-coupling reactions,which is a powerful tool for pharmaceutical and fine chemical synthesis.Here,we report a PdNi single-atom alloy(SAA)catalyst in which isolated Pd single atoms are anchored onto the surface of Ni nanoparticles(NPs)applied for Suzuki coupling reactions and Heck coupling reactions.The 0.1%PdNi SAA exhibits extraordinary catalytic activity(reaction rate:17,032.25 mmol h^(-1)gPd^(-1))toward the Suzuki cross-coupling reaction between 4-bromoanisole and phenylboronic acid at 80℃for 1 h.The excellent activity is supposed to attribute to the 100 percent utilization rate of Pd atoms and the highly stable surface zero-valance Pd atoms,which provides abundant sites and electrons for the adsorption and fracture of the C-X(X=Cl,Br,I)bond.Moreover,our work demonstrates the excellent application prospect of SAAs for cross-coupling reactions.
基金supported by the National Natural Science Foundation of China(22108306,22478432 and 22406191)Taishan Scholars Program of Shandong Province(tsqn201909065)the Natural Science Foundation of Shandong Province(ZR2024JQ004,ZR2021YQ15)。
文摘The development of atomically dispersed platinum-based catalysts with high performance and welldefined active site structures is crucial for the commercialization of water electrolysis for hydrogen production.Herein,we propose a coordination dual-shell synergistic regulation mechanism of coal pitchderived carbon-supported single atom Pt-N_(x)O_(y)-S_(1)catalytic sites by a self-assembly-pyrolysis strategy for promoting hydrogen evolution reaction(HER).The Pt-N_(3)O1-S_(1)sites exhibited the highest HER performance,with an overpotential of 92 mV at a current density of 400 mA cm^(-2).At 50 mV,the turnover frequency was 34.04 s^(-1)and the mass activity was 22.83 A mg_(Pt)^(-l),which is 63.4 times that of the 20%Pt/C catalyst.Theoretical calculations revealed that the coordination dual-shell impacts the electronic structure of the Pt atoms and the adsorption strength towards reactants synergistically.The S atoms in the second coordination shell weakened the strength of Pt-N first shell,resulting the more surface valence electrons around Pt atoms,exhibiting the most suitable adsorption free energy and enhancing the adsorption of H^(+)on Pt-N_(3)O_(1)-S_(1)sites,thus enhancing the electrocatalytic HER process by promoting Volmer step.This work reveals that coordination dual-shell synergistic regulation is an effective strategy for enhancing the electrocatalytic reaction process.
基金supported by the Hainan Province Science and Technology Special Fund(ZDYF2020037)the National Natural Science Foundation of China(22109035,52164028,52274297,22462006)+3 种基金the Postdoctoral Science Foundation of Hainan Province(RZ2100007123)the Basic and Applied Basic Research Foundation of Guangdong Province(2019A1515110558)the Start-up Research Foundation of Hainan University(KYQD(ZR)-20008,20083,20084,21125)Hainan University(XTCX2022HYC05)。
文摘Efficient catalysis of the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)is essential for the rechargeable zinc-air batteries(R-ZABs).However,challenges remain due to the scarcity of effective bifunctional electrocatalysts and limited understanding of the structure-activity relationships.Pyrrole-type single-atom catalysts(SACs)with unique electronic structures have emerged as promising electrocatalysts.In this work,we combine density functional theory(DFT)calculations and experimental studies to systematically explore the structure-activity relationships and potential of pyrrole-type transition metal-N_(3)(TM-po-N_(3))as bifunctional catalysts.DFT calculations reveal that differences in the dependence of ORR and OER activities on the free energy of adsorption of reaction intermediates significantly affect the TM-po-N_(3)bifunctional activity and identify magnetic Cu-po-N_(3)as the best candidate.The bifunctional activity of Cu-po-N_(3)originates from interactions between spin-polarized out-of-plane Cu_3d and O_2s+2p orbitals.Theoretical predictions are validated experimentally,showing that the synthesized Cu-SAC/NC exhibits excellent bifunctional performance with a small potential gap of 0.666 V.Additionally,the assembled R-ZABs display a high-power density of 170 mW cm^(-2)and long-term stability,with the charge-discharge voltage gap increasing by only 0.01 V over 240 h.This work provides new insights into the design of efficient bifunctional catalysts.
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(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the National Natural Science Foundation of China(No.22379069)Fundamental Research Funds for the Central Universities(No.30922010304).
文摘Sluggish sulfur redox kinetics remain a critical bottleneck in the advancement of high-performance lithiumsulfur batteries(LSBs).Single-atom catalysts(SACs)offer a promising solution to this limitation,particularly when their coordination structures are carefully engineered.Here,we develop a chromium-based SAC featuring a unique undercoordinated CrN_(3) configuration to boost sulfur electrochemistry.Compared with conventional CrN_(4),the CrN_(3) motif lowers 3d orbital occupancy and meanwhile activates the in-plane hybridizations with S 3p orbitals upon interaction with polysulfides,contributing to moderate adsorption strength and reduced energy barriers for bidirectional sulfur conversions.Additionally,the integration of the two-dimensional(2D)porous framework ensures abundant electrochemically active surfaces and efficiently exposed active sites.As a result,CrN_(3)-based cells demonstrate fast and durable sulfur redox reactions,enabling an ultralow capacity decay of 0.0075%per cycle over 1000 cycles and a high-rate capability of 651.9 mAh·g^(-1)at 5 C.The CrN_(3) catalyst retains robust catalytic efficiency under demanding conditions,delivering a high areal capacity of 5.53 mAh·cm^(-2) at high sulfur loading and lean electrolyte.This work establishes a compelling paradigm of SAC coordination engineering for designing advanced sulfur electrocatalysts for next-generation LSBs.
基金supported by the Australian Research Council(ARC)Projects(DP220101139,DP220101142,and LP240100542).
文摘High‐entropy amorphous catalysts(HEACs)integrate multielement synergy with structural disorder,making them promising candidates for water splitting.Their distinctive features—including flexible coordination environments,tunable electronic structures,abundant unsaturated active sites,and dynamic structural reassembly—collectively enhance electrochemical activity and durability under operating conditions.This review summarizes recent advances in HEACs for hydrogen evolution,oxygen evolution,and overall water splitting,highlighting their disorder-driven advantages over crystalline counterparts.Catalytic performance benchmarks are presented,and mechanistic insights are discussed,focusing on how multimetallic synergy,amorphization effect,and in‐situ reconstruction cooperatively regulate reaction pathways.These insights provide guidance for the rational design of next‐generation amorphous high‐entropy electrocatalysts with improved efficiency and durability.
