Copper-based catalysts exhibit excellent three-way catalytic activity but tend to undergo agglomeration at high temperatures,resulting in inadequate thermal stability.This study focuses on construction of strong metal...Copper-based catalysts exhibit excellent three-way catalytic activity but tend to undergo agglomeration at high temperatures,resulting in inadequate thermal stability.This study focuses on construction of strong metal-support interactions through La doping to improve the thermal stability and resistance to thermal aging of the catalysts.Cu/CeZrLaO_(2)demonstrates superior thermal aging resistance even after thermal aged at 1000℃for 3 h,which still maintains 88%and 100%for CO and HC conversion,and more than 65%NO conversion at the simulated vehicle exhaust atmosphere.The introduction of La into the CeZrO_(2)support forms Ce-Zr-La-O ternary solid solution,enhancing the structural stability and suppressing grain growth at elevated temperatures.Meanwhile,the doping of this trivalent generates a large number of oxygen vacancies in the catalyst,which improves the dispersion of copper through the anchoring effect.Crucially,La substantially strengthens the metal-support interaction,preventing sintering and agglomeration of copper under harsh conditions,ultimately maintaining the dispersion of copper on the catalyst surface.The present work effectively improves the thermal stability of the Cu/CeZrO_(2)catalyst,establishing a foundation for the further industrial application of the copper-based three-way catalyst.展开更多
Ce-Zr-Al-Nd2O3 （CZAN） support materials were prepared by co-precipitation and impregnation methods, respectively. They were characterized by X-ray diffTaction （XRD）, low temperature nitrogen adsorption-desorption,...Ce-Zr-Al-Nd2O3 （CZAN） support materials were prepared by co-precipitation and impregnation methods, respectively. They were characterized by X-ray diffTaction （XRD）, low temperature nitrogen adsorption-desorption, oxygen pulsing technique, H2-temperamre programmed reduction （H2-TPR） and X-ray photoelectron spectroscopy （XPS）. The Pd-only three-way catalysts （Pd-TWC） supported on these materials were prepared by incipient wetness method and studied by activity tests. The results demonstrated that the CZAN supports obtained by the two methods showed better structural, textural and redox properties than the CZA without Nd2O3, and the addition of Nd203 improved the catalytic activity of TWC. Especially, the CZAN-i support prepared by impregnation method had better thermal stability and redox property. Meanwhile, the Pd/CZAN-i catalyst exhibited the best catalytic performance. XPS measurements indicated that the Nd-modified samples possessed more Ce3＋ and oxygen vacancies on the surface of samples, which led to a better redox property. The excellent redox property of support materials helped to improve the catalytic activity of TWC.展开更多
In the purification process of automobile exhaust,existing water plays an important role as an oxidant,which converts CO and hydrocarbons（HCs） by the water-gas shift（WGS） and the steam reforming（SR） reactions,re...In the purification process of automobile exhaust,existing water plays an important role as an oxidant,which converts CO and hydrocarbons（HCs） by the water-gas shift（WGS） and the steam reforming（SR） reactions,respectively,especially at high temperatures.Meanwhile it is major component of the exhaust which can affect significantly the thermal stability of the three-way catalyst.Activity experiments were carried out close to the real operation conditions（GHSV,concentration,etc.） with a Pd/Ce0.67Zr0.33O2 catalyst supplying information on the CO and C3H8 oxidation reactions in feedstream formed by different reactant combinations.The obtained results showed that the activity of the CO and C3H8 oxidation was promoted by the addition of steam due to the WGS and SR reactions.The WGS and SR reaction were competitive under oxygen-lean conditions.The kinetic analysis was considered for WGS and SR reactions.展开更多
Oxygen storage-capacity （OSC）, oxygen buffer capacity （OBC）, X-my diffraction and electron diffraction pattern, high resolution electron microscopy were used to study the quaternary oxides, i .e., of Ce, Tb, Pr an...Oxygen storage-capacity （OSC）, oxygen buffer capacity （OBC）, X-my diffraction and electron diffraction pattern, high resolution electron microscopy were used to study the quaternary oxides, i .e., of Ce, Tb, Pr and Zr. （Ce0.6 Tb0.2Zr0.2O2- δ and Ce0.6Pr0.2Zr0.2O2-δ ）. OSC and OBC data indicate that these oxides have very good oxygen transfer capacity （OTC） and their pseudo-solid solutions exhibit fluorite-type structure. These oxides may act as a good candidate for three-way catalysts （TWC）.展开更多
The next-generation Euro 7 standard proposed much lower pollutant limits from gasoline vehicles,specifically for CO and NO_(x),which would be challenging for the three-way catalysts(TWCs)utilized commercially to elimi...The next-generation Euro 7 standard proposed much lower pollutant limits from gasoline vehicles,specifically for CO and NO_(x),which would be challenging for the three-way catalysts(TWCs)utilized commercially to eliminate these pollutants.TWCs with reductive(Rh)and oxidative(Pd)active components on gasoline particulate filters(TWC on GPF)play importantly auxiliary roles in the remediation of CO and NO_(x)downstream the close coupled TWCs to meet their emission targets.Here,a low-content Rh-based TWC(0.17 wt%)zoned with a less expensive Pd-based TWC(0.29 wt%)for GPF applications(cGPF)is reported using improved colloidal deposition method.The supporting of Rh on Y-stabilized ZrO_(2)rather than on CeO_(2)-ZrO_(2)inhibits the formation of inactive Ce rhodate species,while Pd on CeO_(2)-ZrO_(2)not only guarantees the high oxygen storage capacity(OSC)but also enhances catalytic activity.The layout of the front one-fifth in volume being 0.29 wt%Pd on Ce_(0.43)Zr_(0.5)7O_(2)and the rear four-fifths being 0.17 wt%Rh on Zr_(0.85)Y_(0.15)O_(2)prevents the possible alloying of Rh with Pd.The highly effective zoned Rh and Pd TWCs show synergistic three-way activity before and after severe hydrothermal aging at 1000℃with 10%water for24 h,which could be potential choices for close coupled GPF application to satisfy the upcoming stringent emission standards,such as Euro 7 and China 6b.展开更多
A series of catalysts with (Ce-Zr-La-Pr)O contents range from 0 to 50% in coating and single-palladium loads on substrates were prepared to study effects of (Ce-Zr-La-Pr)O contents on catalytic activities and durabili...A series of catalysts with (Ce-Zr-La-Pr)O contents range from 0 to 50% in coating and single-palladium loads on substrates were prepared to study effects of (Ce-Zr-La-Pr)O contents on catalytic activities and durability by contrasting the characteristics of light-off, A/F and catalytic conversions of the fresh catalysts with that of the aged catalysts. The results show that (Ce-Zr-La-Pr)O can enhance the catalysts light-off characteristics, widen A/F windows and increase catalytic conversions at a certain extent through optimizing physical structural and chemical property of the mixed coating. However, (Ce-Zr-La-Pr)O contents influence greatly on the catalysts activities and durability, and the catalysts with contents ranging from 10% to 30% exhibited better integrative properties in all samples, and 10% was the optical content to make the catalyst performance highest in this thesis. It is indicated that an suitable content of (Ce-Zr-La-Pr)O plays an important role in assisting catalysis, enhancing durability and increasing oxygen storage capability.展开更多
The regulated pollutants （CO,HC and NOx） and unregulated pollutants （volatile organic compounds and carbonyl compounds）,emitted from a dual fuel vehicle fueled with gasoline and E10 fuel,are measured under a trans...The regulated pollutants （CO,HC and NOx） and unregulated pollutants （volatile organic compounds and carbonyl compounds）,emitted from a dual fuel vehicle fueled with gasoline and E10 fuel,are measured under a transient cycle and steady modes.The impacts of a three-way catalyst （TWC） are investigated for the two types of fuels.The measured results show that NOx and acetaldehyde emitted from the E10-fueled car are much more than that from the gasoline-fueled car under the same modes.On the basis of maximum incremental reactivity （MIR） factors and emissions of organic gases,the ozone specific reactivity of the tailpipe gases are evaluated.展开更多
Ce0.35Zr0.55Y0. 10 solid solution was prepared by co-precipitation technique and characterized by specific surface area measurements （BET） and X-ray diffraction （XRD）. Ce0.35Zr0.55Y0.10 was used to prepare low Pt-...Ce0.35Zr0.55Y0. 10 solid solution was prepared by co-precipitation technique and characterized by specific surface area measurements （BET） and X-ray diffraction （XRD）. Ce0.35Zr0.55Y0.10 was used to prepare low Pt-Rh threeway catalyst （TWC）, and its influence on the performance of TWC was investigated. The results revealed that Ce0.35 Zr0.55Y0.10 had a cubic structure similar to Ce0.50Zr0.50O2 and its specific surface area can maintain higher than Ce0.50 Zr0.50O2 after 1000 ℃ calcination for 5 h. Being hydrothermal aged at 1000 ℃ for 5 h, the catalyst containing Ce0.35 Zr0.55Y0.10 still exhibited higher conversion of C3H8, CO and NO and lower light-off temperature in comparison with Ce0.50Zr0.50O2 TWC.展开更多
Three-way catalysts are widely used to control criterion pollutant emissions fromthe increasing gasoline engines.With the stringent requirements of automotivepollutant emission standards in various countries,Rh has be...Three-way catalysts are widely used to control criterion pollutant emissions fromthe increasing gasoline engines.With the stringent requirements of automotivepollutant emission standards in various countries,Rh has become an irreplaceablecomponent of three-way catalysts due to its superior NOx elimination,high N2selectivity,and simultaneous elimination of CO and hydrocarbons.In this review,we systematically review the recent development of Rh-based three-way catalystsin terms of potential supports and effective active center construction strategies.We further summarize the key role of Rh metal in the three-way catalytic mechanismand reaction kinetics.Finally,we conclude the current challenges and futureopportunities facing Rh-based catalysts.It is believed that based on the deep understandingof Rh-based three-way catalysts,the design of Rh-based catalysts withgood low-temperature catalytic performance and low cost is expected to be realizedin the future.展开更多
Sulfur content is one of the fuel properties to be monitored. Sulfur dioxide, the major product derived from organic sulfur compounds in the exhaust gas emissions, is a poison to the three-way catalysts (TWC). A gas m...Sulfur content is one of the fuel properties to be monitored. Sulfur dioxide, the major product derived from organic sulfur compounds in the exhaust gas emissions, is a poison to the three-way catalysts (TWC). A gas mixture was applied to simulate the exhaust gases used in the TWC aging procedure tests. Two types of the TWC, REX-IIC and REX-IID, were tested in this study. The performance of both TWC's before and after the 100-hour sulfur aging program was compared. It was concluded that the Pt component in the TWC was apt to be poisoned by sulfur much easily than Rh. The performance of the REX-IID catalyst was generally better than that of the REX-IIC catalyst.展开更多
FeOx-CeO2 mixed oxides with increasing Fe/（Ce＋Fe） atomic ratio （1-20 mol%） were prepared by sol-gel method and characterized by X-ray powder diffraction （XRD）, Brunauer-Emrnett-Teller （BET） and Hydrogen tempe...FeOx-CeO2 mixed oxides with increasing Fe/（Ce＋Fe） atomic ratio （1-20 mol%） were prepared by sol-gel method and characterized by X-ray powder diffraction （XRD）, Brunauer-Emrnett-Teller （BET） and Hydrogen temperature-programmed reduction （H2-TPR） techniques. The dynamic oxygen storage capacity （DOSC） was investigated by mass spectrometry with CO/O2 transient pulses. The powder XRD data following Rietveld refinement revealed that the solubility limit of iron oxides in the CeO2 was 5 mol% based on Fe/（Ce＋Fe）. The lattice parameters experienced a decrease followed by an increase due to the influence of the maximum solubility limit of iron oxides in the CeO2. TPR analysis revealed that Fe introduction into ceria strongly modified the textual and structural properties, which influenced the oxygen handling properties. DOSC results revealed that Ce-based materials containing Fe oxides with multiple valences contribute to the majority of DOSC. The kinetic analysis indicated that the calculated apparent kinetic parameters obey the compensation effect. The three-way catalytic performance for Pd-only catalysts based on the Fe doping support exhibited the redundant iron species separated out of the CeO2 and interacted with the ceria and Pd species on the surface, which seriously influenced the catalytic properties, especially after hydrothermal aging treatment.展开更多
The 0.7 wt% Pt ＋ 0.3 wt% Rh/Ce0.6Zr0.4O2 catalysts were fabricated via different methods, including ultrasonic-assisted membrane reduction （UAMR） co-precipitation, UAMR separation precipitation, co-impregnation, an...The 0.7 wt% Pt ＋ 0.3 wt% Rh/Ce0.6Zr0.4O2 catalysts were fabricated via different methods, including ultrasonic-assisted membrane reduction （UAMR） co-precipitation, UAMR separation precipitation, co-impregnation, and sequential impregnation. The catalysts were physico-chemically characterized by N2 adsorption, XRD, TEM, and Hz-TPR techniques, and evaluated for three-way catalytic activities with simulated automobile exhaust. UAMR co-precipitation- and UAMR separation precipitation- prepared catalysts exhibited a high surface area and metal dispersion, wide λ window and excellent conversion for NOx reduction under lean conditions. Both fresh and aged catalysts from UAMR- precipitation showed the high surface areas of ca. 60-67 m^2/g and 18-22 m^2/g, respectively, high metal dispersion of 41%-55%, and small active particle diameters of 2.1-2.7 nm. When these catalysts were aged, the catalysts prepared by the UAMR method exhibited a wider working window （△λ = 0.284--0.287） than impregnated ones （△λ = 0.065-0.115） as well as excellent three-way catalytic performance, and showed lower/so （169℃） and T90 （195℃） for NO reduction than the aged catalysts from impregnation processes, which were at 265 and 309℃, respectively. This implied that the UAMR-separation precipitation has important potential for industrial applications to improve catalytic performance and thermal stability. The fresh and aged 0.7 wt% Pt ＋ 0.3 wt% Rh/Ce0.6Zr0.4O2 catalysts prepared by the UAMR-separation precipitation method exhibited better catalytic performance than the corresponding catalysts prepared by conventional impregnation routes.展开更多
As the oxygen redox ability shows great effects on the catalytic performances of ceria-zirconia based materials,many strategies have been utilized to improve the oxygen storage capacity.Here in this study,we report a ...As the oxygen redox ability shows great effects on the catalytic performances of ceria-zirconia based materials,many strategies have been utilized to improve the oxygen storage capacity.Here in this study,we report a simple and facile approach to prepare a SO_(4)^(2-)-modified La,Y-doped ceria-zirconia material(SO/CZLY-f)with high oxygen storage capacity.Due to the additional redox process between SO_(4)^(2-)and S^(2-),oxygen storage capacity of SO/CZLY-f(745.3μmol O_(2)/g)is about 1.6 times higher than that of La,Ydoped ceria-zirconia material without SO_(4)^(2-)modification.Moreover,the catalytic activities and stability of the corresponding Pd-only three-way catalyst were measured.Compared to that of Pd@CZLY-f,the operation window of CO,full conversion temperature of HC and NO over Pd@SO/CZLY-f are obviously widened and lowered,respectively.After aging treatment at 1100℃for 4 h,the superiority of aged Pdloading composite is still maintained.展开更多
The three way catalysts (TWCs) promoters (Ce Zr)O 2, (Pr Ce Zr)O 2 and (Pr Zr)O 2 were prepared by sol gel like method. They were characterized by XRD, EXAFS and BET surface area determination. The reduction ...The three way catalysts (TWCs) promoters (Ce Zr)O 2, (Pr Ce Zr)O 2 and (Pr Zr)O 2 were prepared by sol gel like method. They were characterized by XRD, EXAFS and BET surface area determination. The reduction features of the promoters were measured by temperature programmed reduction (TPR) of H 2 to access the potential for the promoters containing praseodymia as oxygen storage component in three way catalyst. The (Pr Zr)O 2 cubic solid solution is formed at high temperature up to 800 ℃, which makes it more reducible than the (Ce Zr)O 2 solid solution. For the (Pr Ce Zr)O 2 samples, the ternary solid solution plays an important role in the reduction process. The performance of the three way catalysts with fully formulated Pt, Pd and Rh is proceeded by using both light off temperature under a stoichiometric gas composition and the conversion of CO, C 3H 6 and NO under changing air/fuel ratio at a constant reaction temperature 400 ℃ . The results indicate that a small amount of praseodymia doping into (Ce Zr)O 2 favors the light off temperature of C 3H 6 and NO, and all the catalysts containing praseodymia obviously exhibits enhanced width of S value for NO conversion at lean region ( S ≥1.00).展开更多
Ceria-zirconia-alumina （CZA） solid solution was prepared by sol-gel method in the present study. 0.5 wt.% Pd supported on CZA was prepared by incipient wetness impregnation. The steam effects for CO and C3H8 oxidati...Ceria-zirconia-alumina （CZA） solid solution was prepared by sol-gel method in the present study. 0.5 wt.% Pd supported on CZA was prepared by incipient wetness impregnation. The steam effects for CO and C3H8 oxidation, three-way catalytic activity and stoichiometric window property were studied. The light-off temperature of the CO oxidation reaction shifted to a lower temperature due to the water-gas shift （WGS） reactions. The oxidation of C3H8 was enhanced due to the steam reforming （SR） reactions. The steam promoted the C3H8 oxidation and NO reduction in three-way catalytic reaction. The amplitude of stoichiometric window was amplified by the addition of water to the feed stream.展开更多
The activity and hydrothermal stability of the Rh/Ce_(x)Zr_(1-x)O_(2)(x=0,0.05,0.3,0.5) model three-way catalysts for gasoline vehicle emissions control were investigated in this work.Among the Rh/Ce_(x)Zr_(1-x)O_(2) ...The activity and hydrothermal stability of the Rh/Ce_(x)Zr_(1-x)O_(2)(x=0,0.05,0.3,0.5) model three-way catalysts for gasoline vehicle emissions control were investigated in this work.Among the Rh/Ce_(x)Zr_(1-x)O_(2) samples with different Ce/Zr ratios,the Rh/ZrO_(2) sample exhibits a significantly better activity and hydrothermal stability than the rest of the samples.The impacts of having more Ce components in the Rh/Ce_(x)Zr_(1-x)O_(2) catalysts are associated with the strong Rh-O-Ce interaction that tends to over stabilize the rhodium species.A significant amount of such rhodium atoms can be found in the bulk of the support oxides after a hydrothermal aging at 1050℃ with 10% H_(2)O in air for 12 h.Differently,the sintering of rhodium on the surface of Rh/ZrO_(2) catalysts is the main reason for the catalyst deactivation during the hydrothermal aging.These findings provide an example where high dispersion of supported metal induced by strong metal-support interactions does not necessarily lead to high catalytic activity.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
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
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
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
基金Project supported by Taiyuan Ecological Environment Bureau(RH2400000291)the Natural Science Foundation of Shanxi(202203021211140,20210302124131)。
文摘Copper-based catalysts exhibit excellent three-way catalytic activity but tend to undergo agglomeration at high temperatures,resulting in inadequate thermal stability.This study focuses on construction of strong metal-support interactions through La doping to improve the thermal stability and resistance to thermal aging of the catalysts.Cu/CeZrLaO_(2)demonstrates superior thermal aging resistance even after thermal aged at 1000℃for 3 h,which still maintains 88%and 100%for CO and HC conversion,and more than 65%NO conversion at the simulated vehicle exhaust atmosphere.The introduction of La into the CeZrO_(2)support forms Ce-Zr-La-O ternary solid solution,enhancing the structural stability and suppressing grain growth at elevated temperatures.Meanwhile,the doping of this trivalent generates a large number of oxygen vacancies in the catalyst,which improves the dispersion of copper through the anchoring effect.Crucially,La substantially strengthens the metal-support interaction,preventing sintering and agglomeration of copper under harsh conditions,ultimately maintaining the dispersion of copper on the catalyst surface.The present work effectively improves the thermal stability of the Cu/CeZrO_(2)catalyst,establishing a foundation for the further industrial application of the copper-based three-way catalyst.
基金Project supported by National Natural Science Foundation of China (20773090, 20803049)the Specialized Research Fund for the Doctoral Program of Higher Education (20070610026, 200806100009)
文摘Ce-Zr-Al-Nd2O3 （CZAN） support materials were prepared by co-precipitation and impregnation methods, respectively. They were characterized by X-ray diffTaction （XRD）, low temperature nitrogen adsorption-desorption, oxygen pulsing technique, H2-temperamre programmed reduction （H2-TPR） and X-ray photoelectron spectroscopy （XPS）. The Pd-only three-way catalysts （Pd-TWC） supported on these materials were prepared by incipient wetness method and studied by activity tests. The results demonstrated that the CZAN supports obtained by the two methods showed better structural, textural and redox properties than the CZA without Nd2O3, and the addition of Nd203 improved the catalytic activity of TWC. Especially, the CZAN-i support prepared by impregnation method had better thermal stability and redox property. Meanwhile, the Pd/CZAN-i catalyst exhibited the best catalytic performance. XPS measurements indicated that the Nd-modified samples possessed more Ce3＋ and oxygen vacancies on the surface of samples, which led to a better redox property. The excellent redox property of support materials helped to improve the catalytic activity of TWC.
基金supported by the National High-Tech Research and Development Program of China(2009AA064803)
文摘In the purification process of automobile exhaust,existing water plays an important role as an oxidant,which converts CO and hydrocarbons（HCs） by the water-gas shift（WGS） and the steam reforming（SR） reactions,respectively,especially at high temperatures.Meanwhile it is major component of the exhaust which can affect significantly the thermal stability of the three-way catalyst.Activity experiments were carried out close to the real operation conditions（GHSV,concentration,etc.） with a Pd/Ce0.67Zr0.33O2 catalyst supplying information on the CO and C3H8 oxidation reactions in feedstream formed by different reactant combinations.The obtained results showed that the activity of the CO and C3H8 oxidation was promoted by the addition of steam due to the WGS and SR reactions.The WGS and SR reaction were competitive under oxygen-lean conditions.The kinetic analysis was considered for WGS and SR reactions.
文摘Oxygen storage-capacity （OSC）, oxygen buffer capacity （OBC）, X-my diffraction and electron diffraction pattern, high resolution electron microscopy were used to study the quaternary oxides, i .e., of Ce, Tb, Pr and Zr. （Ce0.6 Tb0.2Zr0.2O2- δ and Ce0.6Pr0.2Zr0.2O2-δ ）. OSC and OBC data indicate that these oxides have very good oxygen transfer capacity （OTC） and their pseudo-solid solutions exhibit fluorite-type structure. These oxides may act as a good candidate for three-way catalysts （TWC）.
基金Project supported by the National Natural Science Foundation of China(22076062,22276070)China Postdoctoral Science Foundation(2022M711957)+1 种基金National Engineering Laboratory for Mobile Source Emission Control Technology(NELMS2019A14)Project of Jinan Municipal Bureau of Science and Technology(2020GXRC021).
文摘The next-generation Euro 7 standard proposed much lower pollutant limits from gasoline vehicles,specifically for CO and NO_(x),which would be challenging for the three-way catalysts(TWCs)utilized commercially to eliminate these pollutants.TWCs with reductive(Rh)and oxidative(Pd)active components on gasoline particulate filters(TWC on GPF)play importantly auxiliary roles in the remediation of CO and NO_(x)downstream the close coupled TWCs to meet their emission targets.Here,a low-content Rh-based TWC(0.17 wt%)zoned with a less expensive Pd-based TWC(0.29 wt%)for GPF applications(cGPF)is reported using improved colloidal deposition method.The supporting of Rh on Y-stabilized ZrO_(2)rather than on CeO_(2)-ZrO_(2)inhibits the formation of inactive Ce rhodate species,while Pd on CeO_(2)-ZrO_(2)not only guarantees the high oxygen storage capacity(OSC)but also enhances catalytic activity.The layout of the front one-fifth in volume being 0.29 wt%Pd on Ce_(0.43)Zr_(0.5)7O_(2)and the rear four-fifths being 0.17 wt%Rh on Zr_(0.85)Y_(0.15)O_(2)prevents the possible alloying of Rh with Pd.The highly effective zoned Rh and Pd TWCs show synergistic three-way activity before and after severe hydrothermal aging at 1000℃with 10%water for24 h,which could be potential choices for close coupled GPF application to satisfy the upcoming stringent emission standards,such as Euro 7 and China 6b.
文摘A series of catalysts with (Ce-Zr-La-Pr)O contents range from 0 to 50% in coating and single-palladium loads on substrates were prepared to study effects of (Ce-Zr-La-Pr)O contents on catalytic activities and durability by contrasting the characteristics of light-off, A/F and catalytic conversions of the fresh catalysts with that of the aged catalysts. The results show that (Ce-Zr-La-Pr)O can enhance the catalysts light-off characteristics, widen A/F windows and increase catalytic conversions at a certain extent through optimizing physical structural and chemical property of the mixed coating. However, (Ce-Zr-La-Pr)O contents influence greatly on the catalysts activities and durability, and the catalysts with contents ranging from 10% to 30% exhibited better integrative properties in all samples, and 10% was the optical content to make the catalyst performance highest in this thesis. It is indicated that an suitable content of (Ce-Zr-La-Pr)O plays an important role in assisting catalysis, enhancing durability and increasing oxygen storage capability.
基金Sponsored by the National Natural Science Foundation of China (40805053)
文摘The regulated pollutants （CO,HC and NOx） and unregulated pollutants （volatile organic compounds and carbonyl compounds）,emitted from a dual fuel vehicle fueled with gasoline and E10 fuel,are measured under a transient cycle and steady modes.The impacts of a three-way catalyst （TWC） are investigated for the two types of fuels.The measured results show that NOx and acetaldehyde emitted from the E10-fueled car are much more than that from the gasoline-fueled car under the same modes.On the basis of maximum incremental reactivity （MIR） factors and emissions of organic gases,the ozone specific reactivity of the tailpipe gases are evaluated.
基金Project supported by the National Natural Science Foundation of China (20273043)the National Natural Science KeyFoundation of China (20333030)
文摘Ce0.35Zr0.55Y0. 10 solid solution was prepared by co-precipitation technique and characterized by specific surface area measurements （BET） and X-ray diffraction （XRD）. Ce0.35Zr0.55Y0.10 was used to prepare low Pt-Rh threeway catalyst （TWC）, and its influence on the performance of TWC was investigated. The results revealed that Ce0.35 Zr0.55Y0.10 had a cubic structure similar to Ce0.50Zr0.50O2 and its specific surface area can maintain higher than Ce0.50 Zr0.50O2 after 1000 ℃ calcination for 5 h. Being hydrothermal aged at 1000 ℃ for 5 h, the catalyst containing Ce0.35 Zr0.55Y0.10 still exhibited higher conversion of C3H8, CO and NO and lower light-off temperature in comparison with Ce0.50Zr0.50O2 TWC.
基金supported by the financial aid from National Science and Technology Major Project of China(2021YFB3500700)National Natural Science Foundation of China(22020102003,22025506,22271274 and U23A20140)Program of Science and Technology Development Plan of Jilin Province of China(20230101035JC and 20230101022JC).
文摘Three-way catalysts are widely used to control criterion pollutant emissions fromthe increasing gasoline engines.With the stringent requirements of automotivepollutant emission standards in various countries,Rh has become an irreplaceablecomponent of three-way catalysts due to its superior NOx elimination,high N2selectivity,and simultaneous elimination of CO and hydrocarbons.In this review,we systematically review the recent development of Rh-based three-way catalystsin terms of potential supports and effective active center construction strategies.We further summarize the key role of Rh metal in the three-way catalytic mechanismand reaction kinetics.Finally,we conclude the current challenges and futureopportunities facing Rh-based catalysts.It is believed that based on the deep understandingof Rh-based three-way catalysts,the design of Rh-based catalysts withgood low-temperature catalytic performance and low cost is expected to be realizedin the future.
文摘Sulfur content is one of the fuel properties to be monitored. Sulfur dioxide, the major product derived from organic sulfur compounds in the exhaust gas emissions, is a poison to the three-way catalysts (TWC). A gas mixture was applied to simulate the exhaust gases used in the TWC aging procedure tests. Two types of the TWC, REX-IIC and REX-IID, were tested in this study. The performance of both TWC's before and after the 100-hour sulfur aging program was compared. It was concluded that the Pt component in the TWC was apt to be poisoned by sulfur much easily than Rh. The performance of the REX-IID catalyst was generally better than that of the REX-IIC catalyst.
基金support the National HighTech Research and Development Program of China (No.2011AA03A405)
文摘FeOx-CeO2 mixed oxides with increasing Fe/（Ce＋Fe） atomic ratio （1-20 mol%） were prepared by sol-gel method and characterized by X-ray powder diffraction （XRD）, Brunauer-Emrnett-Teller （BET） and Hydrogen temperature-programmed reduction （H2-TPR） techniques. The dynamic oxygen storage capacity （DOSC） was investigated by mass spectrometry with CO/O2 transient pulses. The powder XRD data following Rietveld refinement revealed that the solubility limit of iron oxides in the CeO2 was 5 mol% based on Fe/（Ce＋Fe）. The lattice parameters experienced a decrease followed by an increase due to the influence of the maximum solubility limit of iron oxides in the CeO2. TPR analysis revealed that Fe introduction into ceria strongly modified the textual and structural properties, which influenced the oxygen handling properties. DOSC results revealed that Ce-based materials containing Fe oxides with multiple valences contribute to the majority of DOSC. The kinetic analysis indicated that the calculated apparent kinetic parameters obey the compensation effect. The three-way catalytic performance for Pd-only catalysts based on the Fe doping support exhibited the redundant iron species separated out of the CeO2 and interacted with the ceria and Pd species on the surface, which seriously influenced the catalytic properties, especially after hydrothermal aging treatment.
基金supported by the National Nature Foundation of China(No.21277009)the Beijing National Nature Foundation(No.2101002)+2 种基金the Funding Project for Academic Human Resources Development in Institutions of Higher Learning under the Jurisdiction of Beijing Municipality(No.PHR201107104,PHR200907105)the National Research and Development Program(863)of China(No.2011AA03A406)the National Industrial Project of New Rare Earth Materials
文摘The 0.7 wt% Pt ＋ 0.3 wt% Rh/Ce0.6Zr0.4O2 catalysts were fabricated via different methods, including ultrasonic-assisted membrane reduction （UAMR） co-precipitation, UAMR separation precipitation, co-impregnation, and sequential impregnation. The catalysts were physico-chemically characterized by N2 adsorption, XRD, TEM, and Hz-TPR techniques, and evaluated for three-way catalytic activities with simulated automobile exhaust. UAMR co-precipitation- and UAMR separation precipitation- prepared catalysts exhibited a high surface area and metal dispersion, wide λ window and excellent conversion for NOx reduction under lean conditions. Both fresh and aged catalysts from UAMR- precipitation showed the high surface areas of ca. 60-67 m^2/g and 18-22 m^2/g, respectively, high metal dispersion of 41%-55%, and small active particle diameters of 2.1-2.7 nm. When these catalysts were aged, the catalysts prepared by the UAMR method exhibited a wider working window （△λ = 0.284--0.287） than impregnated ones （△λ = 0.065-0.115） as well as excellent three-way catalytic performance, and showed lower/so （169℃） and T90 （195℃） for NO reduction than the aged catalysts from impregnation processes, which were at 265 and 309℃, respectively. This implied that the UAMR-separation precipitation has important potential for industrial applications to improve catalytic performance and thermal stability. The fresh and aged 0.7 wt% Pt ＋ 0.3 wt% Rh/Ce0.6Zr0.4O2 catalysts prepared by the UAMR-separation precipitation method exhibited better catalytic performance than the corresponding catalysts prepared by conventional impregnation routes.
基金Project supported by the Beijing Nova Program(Z181100006218030)Major State Research Development Program of Hebei province(20374202D)。
文摘As the oxygen redox ability shows great effects on the catalytic performances of ceria-zirconia based materials,many strategies have been utilized to improve the oxygen storage capacity.Here in this study,we report a simple and facile approach to prepare a SO_(4)^(2-)-modified La,Y-doped ceria-zirconia material(SO/CZLY-f)with high oxygen storage capacity.Due to the additional redox process between SO_(4)^(2-)and S^(2-),oxygen storage capacity of SO/CZLY-f(745.3μmol O_(2)/g)is about 1.6 times higher than that of La,Ydoped ceria-zirconia material without SO_(4)^(2-)modification.Moreover,the catalytic activities and stability of the corresponding Pd-only three-way catalyst were measured.Compared to that of Pd@CZLY-f,the operation window of CO,full conversion temperature of HC and NO over Pd@SO/CZLY-f are obviously widened and lowered,respectively.After aging treatment at 1100℃for 4 h,the superiority of aged Pdloading composite is still maintained.
文摘The three way catalysts (TWCs) promoters (Ce Zr)O 2, (Pr Ce Zr)O 2 and (Pr Zr)O 2 were prepared by sol gel like method. They were characterized by XRD, EXAFS and BET surface area determination. The reduction features of the promoters were measured by temperature programmed reduction (TPR) of H 2 to access the potential for the promoters containing praseodymia as oxygen storage component in three way catalyst. The (Pr Zr)O 2 cubic solid solution is formed at high temperature up to 800 ℃, which makes it more reducible than the (Ce Zr)O 2 solid solution. For the (Pr Ce Zr)O 2 samples, the ternary solid solution plays an important role in the reduction process. The performance of the three way catalysts with fully formulated Pt, Pd and Rh is proceeded by using both light off temperature under a stoichiometric gas composition and the conversion of CO, C 3H 6 and NO under changing air/fuel ratio at a constant reaction temperature 400 ℃ . The results indicate that a small amount of praseodymia doping into (Ce Zr)O 2 favors the light off temperature of C 3H 6 and NO, and all the catalysts containing praseodymia obviously exhibits enhanced width of S value for NO conversion at lean region ( S ≥1.00).
基金Project supported by National High-Tech Research and Development Program of China(2011AA03A405)the Key Program of TianjinNatural Science Foundation(09JCZDJC26600)
文摘Ceria-zirconia-alumina （CZA） solid solution was prepared by sol-gel method in the present study. 0.5 wt.% Pd supported on CZA was prepared by incipient wetness impregnation. The steam effects for CO and C3H8 oxidation, three-way catalytic activity and stoichiometric window property were studied. The light-off temperature of the CO oxidation reaction shifted to a lower temperature due to the water-gas shift （WGS） reactions. The oxidation of C3H8 was enhanced due to the steam reforming （SR） reactions. The steam promoted the C3H8 oxidation and NO reduction in three-way catalytic reaction. The amplitude of stoichiometric window was amplified by the addition of water to the feed stream.
基金Project supported by the National Key Research and Development Program(2017YFC0211003)GM Global Research and Development(GAC 2696)。
文摘The activity and hydrothermal stability of the Rh/Ce_(x)Zr_(1-x)O_(2)(x=0,0.05,0.3,0.5) model three-way catalysts for gasoline vehicle emissions control were investigated in this work.Among the Rh/Ce_(x)Zr_(1-x)O_(2) samples with different Ce/Zr ratios,the Rh/ZrO_(2) sample exhibits a significantly better activity and hydrothermal stability than the rest of the samples.The impacts of having more Ce components in the Rh/Ce_(x)Zr_(1-x)O_(2) catalysts are associated with the strong Rh-O-Ce interaction that tends to over stabilize the rhodium species.A significant amount of such rhodium atoms can be found in the bulk of the support oxides after a hydrothermal aging at 1050℃ with 10% H_(2)O in air for 12 h.Differently,the sintering of rhodium on the surface of Rh/ZrO_(2) catalysts is the main reason for the catalyst deactivation during the hydrothermal aging.These findings provide an example where high dispersion of supported metal induced by strong metal-support interactions does not necessarily lead to high catalytic activity.
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 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.
