3D printing technology enhances the combustion characteristics of hybrid rocket fuels by enabling complex geometries. However, improvements in regression rates and energy properties of monotonous 3D printed fuels have...3D printing technology enhances the combustion characteristics of hybrid rocket fuels by enabling complex geometries. However, improvements in regression rates and energy properties of monotonous 3D printed fuels have been limited. This study explores the impact of poly(vinylidene fluoride) and polydopamine-coated aluminum particles on the thermal and combustion properties of 3D printed hybrid rocket fuels. Physical self-assembly and anti-solvent methods were employed for constructing composite μAl particles. Characterization using SEM, XRD, XPS, FTIR, and μCT revealed a core-shell structure and homogeneous elemental distribution. Thermal analysis showed that PVDF coatings significantly increased the heat of combustion for aluminum particles, with maximum enhancement observed in μAl@PDA@PVDF(denoted as μAl@PF) at 6.20 k J/g. Subsequently, 3D printed fuels with varying pure and composite μAl particle contents were prepared using 3D printing. Combustion tests indicated higher regression rates for Al@PF/Resin composites compared to pure resin, positively correlating with particle content. The fluorocarbon-alumina reaction during the combustion stage intensified Al particle combustion, reducing residue size. A comprehensive model based on experiments provides insights into the combustion process of PDA and PVDF-coated droplets. This study advances the design of 3D-printed hybrid rocket fuels, offering strategies to improve regression rates and energy release, crucial for enhancing solid fuel performance for hybrid propulsion.展开更多
Aluminum(Al)powder is widely applied in thermobaric explosives due to its high energy density and favorable reaction kinetics.However,the inert oxide layer(Al_(2)O_(3))on Al particles limits combustion reactivity and ...Aluminum(Al)powder is widely applied in thermobaric explosives due to its high energy density and favorable reaction kinetics.However,the inert oxide layer(Al_(2)O_(3))on Al particles limits combustion reactivity and energy efficiency.Fluoride-based surface modification has been developed as an effective approach to address this issue.Here,four classical fluoropolymers(F11,F14,PVDF,PTFE)are employed as coatings to prepare core-shell Al/Fluoropolymer.The combustion experimental results demonstrate that the core-shell Al/PTFE exhibits the highest flame propagation rate(52.88 mm·ms^(-1))and pressure output(109.02 k Pa)performance.Consequently,core-shell Al/PTFE is selected as a high-energy fuel to prepare RDX/Al/PTFE microspheres via the emulsion and solvent evaporation method,which can enhance the energy performance of RDX.The effects of the core-shell Al/PTFE ratio and RDX content on the combustion heat and pressure output are systematically investigated.The peak pressure reaches a maximum of 187.8 k Pa when the mass ratio of RDX,Al,and PTFE is 60:25:10.Additionally,RDX/Al/PTFE microspheres exhibit significantly higher laser-induced air shock velocities,detonation heat,and detonation pressure than those of pure RDX and RDX/Al.The mechanism underlying the enhanced reactivity and energetic performance is attributed to the ability of PTFE to etch the inert Al_(2)O_(3)shell on the surface of Al particles,thereby improving post-combustion reactions and significantly increasing the overall energy output of RDX explosives.This work offers a novel design strategy for high-energy structural thermobaric explosives for the practical applications.展开更多
The weak interface interaction and solid-solid phase transition have long been a conundrum for 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane(HMX)-based polymer-bonded explosives(PBX).A two-step strategy that involves...The weak interface interaction and solid-solid phase transition have long been a conundrum for 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane(HMX)-based polymer-bonded explosives(PBX).A two-step strategy that involves the pretreatment of HMX to endow—OH groups on the surface via polyalcohol bonding agent modification and in situ coating with nitrate ester-containing polymer,was proposed to address the problem.Two types of energetic polyether—glycidyl azide polymer(GAP)and nitrate modified GAP(GNP)were grafted onto HMX crystal based on isocyanate addition reaction bridged through neutral polymeric bonding agent(NPBA)layer.The morphology and structure of the HMX-based composites were characterized in detail and the core-shell structure was validated.The grafted polymers obviously enhanced the adhesion force between HMX crystals and fluoropolymer(F2314)binder.Due to the interfacial reinforcement among the components,the two HMX-based composites exhibited a remarkable increment of phase transition peak temperature by 10.2°C and 19.6°C with no more than 1.5%shell content,respectively.Furthermore,the impact and friction sensitivity of the composites decreased significantly as a result of the barrier produced by the grafted polymers.These findings will enhance the future prospects for the interface design of energetic composites aiming to solve the weak interface and safety concerns.展开更多
Transformation of urea and glycerol to glycerol carbonate is an environmental friendly and economical process.Catalysts play an indispensable role in the process.Although many catalysts have been developed,the perform...Transformation of urea and glycerol to glycerol carbonate is an environmental friendly and economical process.Catalysts play an indispensable role in the process.Although many catalysts have been developed,the performance of the catalysts still cannot meet the needs of industrialization.In this paper,research progress of the homogeneous and heterogeneous catalysts of the reaction over the past 20 years were reviewed systematically.According to the types and active centers of catalysts,the catalysts were classified systematically and analyzed in detail.The typical reaction mechanisms were also summarized.The research and development direction of catalysts is made more explicit through systematic classification and mechanism analysis.The article reveals more novel catalysts have been designed and used for the reaction,such as mixed metal oxides with special structures,solid wastes and non-metallic materials.This work summarized the current state of research and prospected possible routes for design of novel catalysts.It is hoped that this review can provide some references for developing efficient catalysts.展开更多
Carbon nanotubes(CNTs)supported CoB and CoBSn catalysts were synthesized for hydrogen production via NaBH4 hydrolysis.The roles of Sn-promoter and the effect of CNTs treatment on CoB catalysts were evaluated and discu...Carbon nanotubes(CNTs)supported CoB and CoBSn catalysts were synthesized for hydrogen production via NaBH4 hydrolysis.The roles of Sn-promoter and the effect of CNTs treatment on CoB catalysts were evaluated and discussed.It is found that after the addition of Sn promoter,the specific surface area and the generation of active CoB phase are increased,while the oxidation treatment of CNTs results in more loading amounts of active components and enrichment of electron at active sites as well as large surface area.Consequently,the Sn-doped CoB catalysts supported on CNTs with oxidation treatment exhibits a significantly improved activity with a high H_(2)generation rate of 2640 mL/(min·g).Meanwhile,this catalyst shows a low activation energy of 43.7 kJ/mol and relatively high reusability.展开更多
By simplifying catalyst-product separation and reducing phosphorus waste,heterogeneous hydroformylation offers a more sustainable alternative to homogeneous processes.However,heterogeneous hydroformylation catalysts d...By simplifying catalyst-product separation and reducing phosphorus waste,heterogeneous hydroformylation offers a more sustainable alternative to homogeneous processes.However,heterogeneous hydroformylation catalysts developed thus far still suffer from the issues of much lower activity and metal leaching,which severely hinder their practical application.Here,we demonstrate that incorporating phosphorus(P)atoms into graphitic carbon nitride(PCN)supports facilitates charge transfer from Rh to the PCN support,thus largely enhancing electronic metal-support interactions(EMSIs).In the styrene hydroformylation reaction,the activity of Rh_(1)/PCN single-atom catalysts(SACs)with varying P contents exhibited a volcano-shaped relationship with P doping,where the Rh_(1)/PCN SAC with optimal P doping showed exceptional activity,approximately 5.8-and 3.3-fold greater than that of the Rh_(1)/g-C_(3)N_(4)SAC without P doping and the industrial homogeneous catalyst HRh(CO)(PPh_(3))_(3),respectively.In addition,the optimal Rh_(1)/PCN SAC catalyst also demonstrated largely enhanced multicycle stability without any visible metal aggregation owing to the increased EMSIs,which sharply differed from the severe metal aggregation of large nanoparticles on the Rh_(1)/g-C_(3)N_(4)SAC.Mechan-istic studies revealed that the enhanced catalytic performance could be attributed to electron-deficient Rh species,which reduced CO adsorption while simultaneously promoting alkene adsorption through increased EMSIs.These findings suggest that tuning EMSIs is an effective way to achieve SACs with high activity and durability.展开更多
Electrocatalytic reduction of carbon dioxide(CO_(2))to carbon monoxide(CO)is an effective strategy to achieve carbon neutrality.High selective and low-cost catalysts for the electrocatalytic reduction of CO_(2)have re...Electrocatalytic reduction of carbon dioxide(CO_(2))to carbon monoxide(CO)is an effective strategy to achieve carbon neutrality.High selective and low-cost catalysts for the electrocatalytic reduction of CO_(2)have received increasing attention.In contrast to the conventional tube furnace method,the high-temperature shock(HTS)method enables ultra-fast thermal processing,superior atomic efficiency,and a streamlined synthesis protocol,offering a simplified method for the preparation of high-performance single-atom catalysts(SACs).The reports have shown that nickel-based SACs can be synthesized quickly and conveniently using the HTS method,making their application in CO_(2)reduction reactions(CO_(2)RR)a viable and promising avenue for further exploration.In this study,the effect of heating temperature,metal loading and different nitrogen(N)sources on the catalyst morphology,coordination environment and electrocatalytic performance were investigated.Under optimal conditions,0.05Ni-DCD-C-1050 showed excellent performance in reducing CO_(2)to CO,with CO selectivity close to 100%(−0.7 to−1.0 V vs RHE)and current density as high as 130 mA/cm^(2)(−1.1 V vs RHE)in a flow cell under alkaline environment.展开更多
The nitrogen-coordinated metal single-atom catalysts(M−N−C SACs)with an ultra-high metal loading synthetized by direct high-temperature pyrolysis have been widely reported.However,most of metal single atoms in these c...The nitrogen-coordinated metal single-atom catalysts(M−N−C SACs)with an ultra-high metal loading synthetized by direct high-temperature pyrolysis have been widely reported.However,most of metal single atoms in these catalysts were buried in the carbon matrix,resulting in a low metal utilization and inaccessibility for adsorption of reactants during the catalytic process.Herein,we reported a facile synthesis based on the hard-soft acid-base(HSAB)theory to fabricate Co single-atom catalysts with highly exposed metal atoms ligated to the external pyridinic-N sites of a nitrogen-doped carbon support.Benefiting from the highly accessible Co active sites,the prepared Co−N−C SAC exhibited a superior oxygen reduction reactivity comparable to that of the commercial Pt/C catalyst,showing a high turnover frequency(TOF)of 0.93 e^(−)·s^(-1)·site^(-1)at 0.85 V vs.RHE,far exceeding those of some representative SACs with a ultra-high metal content.This work provides a rational strategy to design and prepare M−N−C single-atom catalysts featured with high site-accessibility and site-density.展开更多
Hanyu Xu 1,Xuedan Song 1,*,Qing Zhang 1,Chang Yu 1,Jieshan Qiu 1,2,*1 Liaoning Key Lab for Energy Materials and Chemical Engineering,State Key Laboratory of Fine Chemicals,School of Chemical Engineering,Dalian Univers...Hanyu Xu 1,Xuedan Song 1,*,Qing Zhang 1,Chang Yu 1,Jieshan Qiu 1,2,*1 Liaoning Key Lab for Energy Materials and Chemical Engineering,State Key Laboratory of Fine Chemicals,School of Chemical Engineering,Dalian University of Technology,Dalian 116024,Liaoning Province,China.展开更多
Owing to outstanding hydrophilicity and ionic interaction,layered double hydroxides(LDHs)have emerged as a promising carrier for high performance catalysts.However,the synthesis of new specialized catalytic LDHs for d...Owing to outstanding hydrophilicity and ionic interaction,layered double hydroxides(LDHs)have emerged as a promising carrier for high performance catalysts.However,the synthesis of new specialized catalytic LDHs for degradation of antibiotics still faces some challenges.In this study,a CoFe_(2)O_(4)/MgAl-LDH composite catalyst was synthesized using a hydrothermal coprecipitation method.Comprehensive characterization reveals that the surface of MgAl-LDH is covered with nanometer CoFe_(2)O_(4) particles.The specific surface area of CoFe_(2)O_(4)/MgAl-LDH is 82.84 m^(2)·g^(-)1,which is 2.34 times that of CoFe_(2)O_(4).CoFe_(2)O_(4)/MgAl-LDH has a saturation magnetic strength of 22.24 A·m^(2)·kg^(-1) facilitating efficient solid-liquid separation.The composite catalyst was employed to activate peroxymonosulfate(PMS)for the efficient degradation of tetracycline hydrochloride(TCH).It is found that the catalytic performance of CoFe_(2)O_(4)/MgAl-LDH significantly exceeds that of CoFe_(2)O_(4).The maximum TCH removal reaches 98.2%under the optimal conditions([TCH]=25 mg/L,[PMS]=1.5 mmol/L,CoFe_(2)O_(4)/MgAl-LDH=0.20 g/L,pH 7,and T=25℃).Coexisting ions in the solution,such as SO_(4)^(2-),Cl-,H_(2)PO_(4)^(-),and CO_(3)^(2-),have a negligible effect on catalytic performance.Cyclic tests demonstrate that the catalytic performance of CoFe_(2)O_(4)/MgAl-LDH remains 67.2%after five cycles.Mechanism investigations suggest that O_(2)^(•-)and ^(1)O_(2) produced by CoFe_(2)O_(4)/MgAl-LDH play a critical role in the catalytic degradation.展开更多
With ongoing global warming and increasing energy demands,the CH_(4)-CO_(2)reforming reaction(dry reforming of methane,DRM)has garnered significant attention as a promising carbon capture and utilization technology.Ni...With ongoing global warming and increasing energy demands,the CH_(4)-CO_(2)reforming reaction(dry reforming of methane,DRM)has garnered significant attention as a promising carbon capture and utilization technology.Nickel-based catalysts are renowned for their outstanding activity and selectivity in this process.The impact of metal-support interaction(MSI),on Ni-based catalyst performance has been extensively researched and debated recently.This paper reviews the recent research progress of MSI on Ni-based catalysts and their characterization and modulation strategies in catalytic reactions.From the perspective of MSI,the effects of different carriers(metal oxides,carbon materials and molecular sieves,etc.)are introduced on the dispersion and surface structure of Ni active metal particles,and the effect of MSI on the activity and stability of DRM reactions on Ni-based catalysts is discussed in detail.Future research should focus on better understanding and controlling MSI to improve the performance and durability of nickel-based catalysts in CH_(4)-CO_(2)reforming,advancing cleaner energy technologies.展开更多
Combustion catalyst is a key modifier for the performance of composite solid propellant.To exploit highefficiency combustion catalyst,a fascinating bimetallic metal-organic framework[MnCo(EIM)_(2)(DCA)_(2)]n(1)was con...Combustion catalyst is a key modifier for the performance of composite solid propellant.To exploit highefficiency combustion catalyst,a fascinating bimetallic metal-organic framework[MnCo(EIM)_(2)(DCA)_(2)]n(1)was constructed by an active dicyandiamide(DCA)linker,Mn^(2+),Co^(2+)centers,and an 1-ethylimidazole(EIM)ligand.1 possesses good thermal stability(Tp=205℃),high energy density(Eg=24.34 kJ/g,Ev=35.93 kJ/cm^(3)),and insensitivity to impact and frictional stimulus.The catalytic effects of 1 contrasted to monometallic coordination compounds Mn(EIM)_(4)(DCA)_(2)(2)and Co(EIM)_(4)(DCA)_(2)(3)on the thermal decomposition of AP/RDX composite were investigated by a DSC method.The decomposition peak temperatures of AP and RDX of the composite decreased to 335.8℃ and 206.4℃,respectively,and the corresponding activation energy decreased by 27.3%and 43.6%,respectively,which are better than the performances of monometallic complexes 2 and 3.The gas products in the whole thermal decomposition stage of the sample were measured by TG-MS and TG-IR,and the catalytic mechanism of 1 to AP/RDX was further analyzed.This work reveal potential application of bimetallic MOFs in the composite solid propellants.展开更多
Single-atom catalysts(SACs)are promising for oxygen reduction reaction(ORR)on account of their excellent catalytic activity and maximum utilization of atoms.However,due to the complicated preparation processes and exp...Single-atom catalysts(SACs)are promising for oxygen reduction reaction(ORR)on account of their excellent catalytic activity and maximum utilization of atoms.However,due to the complicated preparation processes and expensive reagents used,the cost of SACs is usually too high to put into practical application.The development of cost-effective and sustainable SACs remains a great challenge.Herein,a low-cost method employing biomass is designed to prepare efficient single-atom Fe-N-C catalysts(SA-Fe-N-C).Benefiting from the confinement effect of porous carbon support and the coordination effect of glucose,SA-Fe-N-C is derived from cheap flour by the two-step pyrolysis.Atomically dispersed Fe atoms exist in the form of Fe-N_(x),which acts as active sites for ORR.The catalyst shows outstanding activity with a half-wave potential(E_(1/2))of 0.86 V,which is better than that of Pt/C(0.84 V).Additionally,the catalyst also exhibits superior stability.The ORR catalyzed by SA-Fe-N-C proceeds via an efficient 4e transfer pathway.The high performance of SA-Fe-N-C also benefits from its porous structure,extremely high specific surface area(1450.1 m^(2)/g),and abundant micropores,which are conducive to increasing the density of active sites and fully exposing them.This work provides a cost-effective strategy to synthesize SACs from cheap biomass,achieving a balance between performance and cost.展开更多
The core-shell 2,4,6,8,10,12-Hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane/2,4,6-Trinitrotoluene(CL-20/TNT)composite was prepared by spray-drying method in which sensitive high energy explosive(CL-20)was coated with in...The core-shell 2,4,6,8,10,12-Hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane/2,4,6-Trinitrotoluene(CL-20/TNT)composite was prepared by spray-drying method in which sensitive high energy explosive(CL-20)was coated with insensitive explosive(TNT).The structure and properties of different formulations of CL-20/TNT composite and CL-20/TNT mixture were characterized by scanning electron microscopy(SEM),Transmission electron microscopy(TEM),Laser particle size analyzer,X-ray photoelectron spectroscopy(XPS),X-ray diffraction(XRD),differential scanning calorimetry(DSC),impact sensitivity test and detonation performance.The results of SEM,TEM,XPS and XRD show that e-CL-20 particles are coated by TNT.When the ratio of CL-20/TNT is 75/25,core-shell structure is well formed,and thickness of the shell is about 20e30 nm.And the analysis of heat and impact show that with the increase of TNT content,the TNT coating on the core-shell composite material can not only catalyze the thermal decomposition of core material(CL-20),but also greatly reduce the impact sensitivity.Compared with the CL-20/TNT mixture(75/25)at the same ratio,the characteristic drop height of core-shell CL-20/TNT composite(75/25)increased by 47.6%and the TNT coating can accelerate the nuclear decomposition in the CL-20/TNT composites.Therefore,the preparation of the core-shell composites can be regarded as a unique means,by which the composites are characterized by controllable decomposition rate,high energy and excellent mechanical sensitivity and could be applied to propellants and other fields.展开更多
A facile and economical approach was developed for the large-scale production of powdered core-shell structured PTFE/Al (CS-PA) energetic materials through ultrasonic-assisted mixing. The low-cost micrometer-sized PTF...A facile and economical approach was developed for the large-scale production of powdered core-shell structured PTFE/Al (CS-PA) energetic materials through ultrasonic-assisted mixing. The low-cost micrometer-sized PTFE and Al particles were used as starting materials. Under high-power ultrasonic waves, the PTFE powder was dispersed into nano-to sub-micrometer-sized particles and then encapsulated the Al microparticles to form the core-shell structure. The heat of combustion, burning rate, and pressurization rate of the powdered CS-PA were measured. The thermal-initiated reaction behavior was further evaluated using thermogravimetry-differential scanning calorimetry. Subsequently, the bulk CS-PA with a uniform microstructure was obtained via cold isostatic pressing of the powdered CS-PA followed by vacuum sintering. For the bulk CS-PA, the quasi-static compression behavior was characterized, and the impact-initiated reaction processes were conducted using the Split Hopkinson Pressure Bar (SHPB) and evaluated by a high-speed camera. Compared to physically mixed PTFE/Al materials, the powdered and bulk CS-PA demonstrated enhanced thermal- and impact-initiated reaction characteristics respectively, proving the effectiveness of our approach for constructing core-shell structures.展开更多
Inspired by the phenomenon of superhydrophobic plants and animals in nature,1,3,5,7-tetranitro-1,3,5,7-tetrazocane(HMX)@copper stearate(CS)core-shell composites with similar properties was prepared.A rough shell layer...Inspired by the phenomenon of superhydrophobic plants and animals in nature,1,3,5,7-tetranitro-1,3,5,7-tetrazocane(HMX)@copper stearate(CS)core-shell composites with similar properties was prepared.A rough shell layer on the surface of the HMX was observed by scanning electron microscopy(SEM),and a series of in-depth characterization confirmed the successful generation of CS and the coreshell structure of the samples.Differential scanning calorimeter(DSC)proves that the crystal transition temperature(204℃)and high temperature decomposition exothermal temperature(284℃)of HMX@CS is almost unchanged compared with pure HMX,which means HMX and CS have good compatibility.Then,the H50 of the samples also increased continuously(16.6 cm→33.7 cm)when the CS shell content increased from 1%to 5%,indicating that the CS shell has a certain buffering performance,and CS will absorb some heat and melt under the stimulation of impact due to its low melting point,which improved impact sensitivity of HMX effectively further.Moreover,HMX@CS has excellent hydrophobic and oleophilic performance,shows excellent wettability with lipid binder,and samples with appropriate CS shell content can continue to combustion stably after covering water.This waterproof and low sensitivity coating provides a new way for the development of multifunctional energetic materials.展开更多
Copper azide(CA), as a primary explosive with high energy density, has not been practically used so far because of its high electrostatic sensitivity. The Cu2O@HKUST-1 core-shell structure hybrid material was synthesi...Copper azide(CA), as a primary explosive with high energy density, has not been practically used so far because of its high electrostatic sensitivity. The Cu2O@HKUST-1 core-shell structure hybrid material was synthesized by the “bottle around ship” methodology in this research by regulating the dissolution rate of Cu2O and the generation rate of metal-organic framework(MOF) materials. Cu2O@HKUST-1 was carbonized to form a Cu O@porous carbon(CuO@PC) composite material. CuO@PC was synthesized into a copper azide(CA) @PC composite energetic material through a gas-solid phase in-situ azidation reaction.CA is encapsulated in PC framework, which acts as a nanoscale Faraday cage, and its excellent electrical conductivity prevents electrostatic charges from accumulating on the energetic material’s surface. The CA@PC composite energetic material has a CA content of 89.6%, and its electrostatic safety is nearly 30times that of pure CA(1.47 mJ compared to 0.05 mJ). CA@PC delivers an outstanding balance of safety and energy density compared to similar materials.展开更多
Ce O2@Si O2 core-shell nanoparticles were prepared by microemulsion method, and metalloporphyrins were immobilized on the Ce O2@Si O2 core-shell nanoparticles surface via amide bond. The supported metalloporphyrin cat...Ce O2@Si O2 core-shell nanoparticles were prepared by microemulsion method, and metalloporphyrins were immobilized on the Ce O2@Si O2 core-shell nanoparticles surface via amide bond. The supported metalloporphyrin catalysts were characterized by N2 adsorption-desorption isotherm(BET), scanning electron microscopy(SEM), transmission electron microscopy(TEM), X-ray diffraction(XRD), ultraviolet and visible spectroscopy(UV-Vis), and Fourier transform infrared spectroscopy(FT-IR). The results show that the morphology of Ce O2@Si O2 nanoparticles is core-shell microspheres with about 30 nm in diameter, and metalloporphyrins are immobilized on the Ce O2@Si O2 core-shell nanoparticles via amide bond. Especially, the core-shell structure contains multi Ce O2 core and thin Si O2 shell, which may benefit the synergistic effect between the Ce O2 core and the porphyrin anchored on the very thin Si O2 shell. As a result, this supported metalloporphyrin catalysts present comparably high catalytic activity and stability for oxidation of ethylbenzene with molecular oxygen, namely, ethylbenzene conversion remains around 12% with identical selectivity of about 80% for acetophenone even after six-times reuse of the catalyst.展开更多
Two major challenges,high cost and short lifespan,have been hindering the commercialization process of lowtemperature fuel cells.Professor Wei's group has been focusing on decreasing cathode Pt loadings without lo...Two major challenges,high cost and short lifespan,have been hindering the commercialization process of lowtemperature fuel cells.Professor Wei's group has been focusing on decreasing cathode Pt loadings without losses of activity and durability,and their research advances in this area over the past three decades are briefly reviewed herein.Regarding the Pt-based catalysts and the low Pt usage,they have firstly tried to clarify the degradation mechanism of Pt/C catalysts,and then demonstrated that the activity and stability could be improved by three strategies:regulating the nanostructures of the active sites,enhancing the effects of support materials,and optimizing structures of the three-phase boundary.For Pt-free catalysts,especialiy carbon-based ones,several strategies that they proposed to enhance the activity of nitrogen-/heteroatom-doped carbon catalysts are firstly presented.Then,an indepth understanding of the degradation mechanism for carbon-based catalysts is discussed,and followed by the corresponding stability enhancement strategies.Also,the carbon-based electrode at the micrometer-scale,faces the challenges such as low active-site density,thick catalytic layer,and the effect of hydrogen peroxide,which require rational structure design for the integral cathodic electrode.This review finally gives a brief conclusion and outlook about the low cost and long lifespan of cathodic oxygen reduction catalysts.展开更多
基金funded by the National Natural Science Foundation of China(Grant No.06101213)the National Natural Science Foundation of China(Grant No.22105160).
文摘3D printing technology enhances the combustion characteristics of hybrid rocket fuels by enabling complex geometries. However, improvements in regression rates and energy properties of monotonous 3D printed fuels have been limited. This study explores the impact of poly(vinylidene fluoride) and polydopamine-coated aluminum particles on the thermal and combustion properties of 3D printed hybrid rocket fuels. Physical self-assembly and anti-solvent methods were employed for constructing composite μAl particles. Characterization using SEM, XRD, XPS, FTIR, and μCT revealed a core-shell structure and homogeneous elemental distribution. Thermal analysis showed that PVDF coatings significantly increased the heat of combustion for aluminum particles, with maximum enhancement observed in μAl@PDA@PVDF(denoted as μAl@PF) at 6.20 k J/g. Subsequently, 3D printed fuels with varying pure and composite μAl particle contents were prepared using 3D printing. Combustion tests indicated higher regression rates for Al@PF/Resin composites compared to pure resin, positively correlating with particle content. The fluorocarbon-alumina reaction during the combustion stage intensified Al particle combustion, reducing residue size. A comprehensive model based on experiments provides insights into the combustion process of PDA and PVDF-coated droplets. This study advances the design of 3D-printed hybrid rocket fuels, offering strategies to improve regression rates and energy release, crucial for enhancing solid fuel performance for hybrid propulsion.
基金supported by the National Natural Science Foundation of China(Grant Nos.T2222027 and 12202416)。
文摘Aluminum(Al)powder is widely applied in thermobaric explosives due to its high energy density and favorable reaction kinetics.However,the inert oxide layer(Al_(2)O_(3))on Al particles limits combustion reactivity and energy efficiency.Fluoride-based surface modification has been developed as an effective approach to address this issue.Here,four classical fluoropolymers(F11,F14,PVDF,PTFE)are employed as coatings to prepare core-shell Al/Fluoropolymer.The combustion experimental results demonstrate that the core-shell Al/PTFE exhibits the highest flame propagation rate(52.88 mm·ms^(-1))and pressure output(109.02 k Pa)performance.Consequently,core-shell Al/PTFE is selected as a high-energy fuel to prepare RDX/Al/PTFE microspheres via the emulsion and solvent evaporation method,which can enhance the energy performance of RDX.The effects of the core-shell Al/PTFE ratio and RDX content on the combustion heat and pressure output are systematically investigated.The peak pressure reaches a maximum of 187.8 k Pa when the mass ratio of RDX,Al,and PTFE is 60:25:10.Additionally,RDX/Al/PTFE microspheres exhibit significantly higher laser-induced air shock velocities,detonation heat,and detonation pressure than those of pure RDX and RDX/Al.The mechanism underlying the enhanced reactivity and energetic performance is attributed to the ability of PTFE to etch the inert Al_(2)O_(3)shell on the surface of Al particles,thereby improving post-combustion reactions and significantly increasing the overall energy output of RDX explosives.This work offers a novel design strategy for high-energy structural thermobaric explosives for the practical applications.
基金the support for this work by National Natural Science Foundation of China(Grant Nos.22175139 and 22105156)。
文摘The weak interface interaction and solid-solid phase transition have long been a conundrum for 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane(HMX)-based polymer-bonded explosives(PBX).A two-step strategy that involves the pretreatment of HMX to endow—OH groups on the surface via polyalcohol bonding agent modification and in situ coating with nitrate ester-containing polymer,was proposed to address the problem.Two types of energetic polyether—glycidyl azide polymer(GAP)and nitrate modified GAP(GNP)were grafted onto HMX crystal based on isocyanate addition reaction bridged through neutral polymeric bonding agent(NPBA)layer.The morphology and structure of the HMX-based composites were characterized in detail and the core-shell structure was validated.The grafted polymers obviously enhanced the adhesion force between HMX crystals and fluoropolymer(F2314)binder.Due to the interfacial reinforcement among the components,the two HMX-based composites exhibited a remarkable increment of phase transition peak temperature by 10.2°C and 19.6°C with no more than 1.5%shell content,respectively.Furthermore,the impact and friction sensitivity of the composites decreased significantly as a result of the barrier produced by the grafted polymers.These findings will enhance the future prospects for the interface design of energetic composites aiming to solve the weak interface and safety concerns.
基金supported by Fundamental Research Program of Shanxi Province(202203021221303)。
文摘Transformation of urea and glycerol to glycerol carbonate is an environmental friendly and economical process.Catalysts play an indispensable role in the process.Although many catalysts have been developed,the performance of the catalysts still cannot meet the needs of industrialization.In this paper,research progress of the homogeneous and heterogeneous catalysts of the reaction over the past 20 years were reviewed systematically.According to the types and active centers of catalysts,the catalysts were classified systematically and analyzed in detail.The typical reaction mechanisms were also summarized.The research and development direction of catalysts is made more explicit through systematic classification and mechanism analysis.The article reveals more novel catalysts have been designed and used for the reaction,such as mixed metal oxides with special structures,solid wastes and non-metallic materials.This work summarized the current state of research and prospected possible routes for design of novel catalysts.It is hoped that this review can provide some references for developing efficient catalysts.
基金supported by National Natural Science Foundation of China(22276144).
文摘Carbon nanotubes(CNTs)supported CoB and CoBSn catalysts were synthesized for hydrogen production via NaBH4 hydrolysis.The roles of Sn-promoter and the effect of CNTs treatment on CoB catalysts were evaluated and discussed.It is found that after the addition of Sn promoter,the specific surface area and the generation of active CoB phase are increased,while the oxidation treatment of CNTs results in more loading amounts of active components and enrichment of electron at active sites as well as large surface area.Consequently,the Sn-doped CoB catalysts supported on CNTs with oxidation treatment exhibits a significantly improved activity with a high H_(2)generation rate of 2640 mL/(min·g).Meanwhile,this catalyst shows a low activation energy of 43.7 kJ/mol and relatively high reusability.
基金supported by the Petrochemical Research Institute Foundation(21-CB-09-01)the National Natural Science Foundation of China(22302186,22025205)+1 种基金the China Postdoctoral Science Foundation(2022M713030,2023T160618)the Fundamental Research Funds for the Central Universities(WK2060000058,WK2060000038).
文摘By simplifying catalyst-product separation and reducing phosphorus waste,heterogeneous hydroformylation offers a more sustainable alternative to homogeneous processes.However,heterogeneous hydroformylation catalysts developed thus far still suffer from the issues of much lower activity and metal leaching,which severely hinder their practical application.Here,we demonstrate that incorporating phosphorus(P)atoms into graphitic carbon nitride(PCN)supports facilitates charge transfer from Rh to the PCN support,thus largely enhancing electronic metal-support interactions(EMSIs).In the styrene hydroformylation reaction,the activity of Rh_(1)/PCN single-atom catalysts(SACs)with varying P contents exhibited a volcano-shaped relationship with P doping,where the Rh_(1)/PCN SAC with optimal P doping showed exceptional activity,approximately 5.8-and 3.3-fold greater than that of the Rh_(1)/g-C_(3)N_(4)SAC without P doping and the industrial homogeneous catalyst HRh(CO)(PPh_(3))_(3),respectively.In addition,the optimal Rh_(1)/PCN SAC catalyst also demonstrated largely enhanced multicycle stability without any visible metal aggregation owing to the increased EMSIs,which sharply differed from the severe metal aggregation of large nanoparticles on the Rh_(1)/g-C_(3)N_(4)SAC.Mechan-istic studies revealed that the enhanced catalytic performance could be attributed to electron-deficient Rh species,which reduced CO adsorption while simultaneously promoting alkene adsorption through increased EMSIs.These findings suggest that tuning EMSIs is an effective way to achieve SACs with high activity and durability.
基金supported by the National Key R&D Program of China(2024YFB4106400)National Natural Science Foundation of China(22209200,52302331)。
文摘Electrocatalytic reduction of carbon dioxide(CO_(2))to carbon monoxide(CO)is an effective strategy to achieve carbon neutrality.High selective and low-cost catalysts for the electrocatalytic reduction of CO_(2)have received increasing attention.In contrast to the conventional tube furnace method,the high-temperature shock(HTS)method enables ultra-fast thermal processing,superior atomic efficiency,and a streamlined synthesis protocol,offering a simplified method for the preparation of high-performance single-atom catalysts(SACs).The reports have shown that nickel-based SACs can be synthesized quickly and conveniently using the HTS method,making their application in CO_(2)reduction reactions(CO_(2)RR)a viable and promising avenue for further exploration.In this study,the effect of heating temperature,metal loading and different nitrogen(N)sources on the catalyst morphology,coordination environment and electrocatalytic performance were investigated.Under optimal conditions,0.05Ni-DCD-C-1050 showed excellent performance in reducing CO_(2)to CO,with CO selectivity close to 100%(−0.7 to−1.0 V vs RHE)and current density as high as 130 mA/cm^(2)(−1.1 V vs RHE)in a flow cell under alkaline environment.
基金supported by Shanxi Province Science Foundation for Youths(202203021212300)Taiyuan University of Science and Technology Scientific Research Initial Funding(20212064)Outstanding Doctoral Award Fund in Shanxi Province(20222060).
文摘The nitrogen-coordinated metal single-atom catalysts(M−N−C SACs)with an ultra-high metal loading synthetized by direct high-temperature pyrolysis have been widely reported.However,most of metal single atoms in these catalysts were buried in the carbon matrix,resulting in a low metal utilization and inaccessibility for adsorption of reactants during the catalytic process.Herein,we reported a facile synthesis based on the hard-soft acid-base(HSAB)theory to fabricate Co single-atom catalysts with highly exposed metal atoms ligated to the external pyridinic-N sites of a nitrogen-doped carbon support.Benefiting from the highly accessible Co active sites,the prepared Co−N−C SAC exhibited a superior oxygen reduction reactivity comparable to that of the commercial Pt/C catalyst,showing a high turnover frequency(TOF)of 0.93 e^(−)·s^(-1)·site^(-1)at 0.85 V vs.RHE,far exceeding those of some representative SACs with a ultra-high metal content.This work provides a rational strategy to design and prepare M−N−C single-atom catalysts featured with high site-accessibility and site-density.
文摘Hanyu Xu 1,Xuedan Song 1,*,Qing Zhang 1,Chang Yu 1,Jieshan Qiu 1,2,*1 Liaoning Key Lab for Energy Materials and Chemical Engineering,State Key Laboratory of Fine Chemicals,School of Chemical Engineering,Dalian University of Technology,Dalian 116024,Liaoning Province,China.
基金University Synergy Innovation Program of Anhui Province(GXXT-2022-083)Science and Technology Plan Project of Wuhu City,China(2023kx12)Anhui Provincial Department of Education New Era Education Project(2023xscx070)。
文摘Owing to outstanding hydrophilicity and ionic interaction,layered double hydroxides(LDHs)have emerged as a promising carrier for high performance catalysts.However,the synthesis of new specialized catalytic LDHs for degradation of antibiotics still faces some challenges.In this study,a CoFe_(2)O_(4)/MgAl-LDH composite catalyst was synthesized using a hydrothermal coprecipitation method.Comprehensive characterization reveals that the surface of MgAl-LDH is covered with nanometer CoFe_(2)O_(4) particles.The specific surface area of CoFe_(2)O_(4)/MgAl-LDH is 82.84 m^(2)·g^(-)1,which is 2.34 times that of CoFe_(2)O_(4).CoFe_(2)O_(4)/MgAl-LDH has a saturation magnetic strength of 22.24 A·m^(2)·kg^(-1) facilitating efficient solid-liquid separation.The composite catalyst was employed to activate peroxymonosulfate(PMS)for the efficient degradation of tetracycline hydrochloride(TCH).It is found that the catalytic performance of CoFe_(2)O_(4)/MgAl-LDH significantly exceeds that of CoFe_(2)O_(4).The maximum TCH removal reaches 98.2%under the optimal conditions([TCH]=25 mg/L,[PMS]=1.5 mmol/L,CoFe_(2)O_(4)/MgAl-LDH=0.20 g/L,pH 7,and T=25℃).Coexisting ions in the solution,such as SO_(4)^(2-),Cl-,H_(2)PO_(4)^(-),and CO_(3)^(2-),have a negligible effect on catalytic performance.Cyclic tests demonstrate that the catalytic performance of CoFe_(2)O_(4)/MgAl-LDH remains 67.2%after five cycles.Mechanism investigations suggest that O_(2)^(•-)and ^(1)O_(2) produced by CoFe_(2)O_(4)/MgAl-LDH play a critical role in the catalytic degradation.
基金supported by the Natural Science Foundation of Shanxi Province(202203021221155)the Foundation of National Key Laboratory of High Efficiency and Low Carbon Utilization of Coal(J23-24-902)。
文摘With ongoing global warming and increasing energy demands,the CH_(4)-CO_(2)reforming reaction(dry reforming of methane,DRM)has garnered significant attention as a promising carbon capture and utilization technology.Nickel-based catalysts are renowned for their outstanding activity and selectivity in this process.The impact of metal-support interaction(MSI),on Ni-based catalyst performance has been extensively researched and debated recently.This paper reviews the recent research progress of MSI on Ni-based catalysts and their characterization and modulation strategies in catalytic reactions.From the perspective of MSI,the effects of different carriers(metal oxides,carbon materials and molecular sieves,etc.)are introduced on the dispersion and surface structure of Ni active metal particles,and the effect of MSI on the activity and stability of DRM reactions on Ni-based catalysts is discussed in detail.Future research should focus on better understanding and controlling MSI to improve the performance and durability of nickel-based catalysts in CH_(4)-CO_(2)reforming,advancing cleaner energy technologies.
基金supported by the National Natural Science Foundation of China(Grant No.22175025)State Key Laboratory of Explosion Science and Safety Protection(Grant No.YBKT22-03)+1 种基金the Natural Science Foundation of Chongqing(Grant No.CSTB2023 NSCQ-LZX0098)the Chongqing Municipal Education Commis-sion(Grant No.KJZD-M202301404).
文摘Combustion catalyst is a key modifier for the performance of composite solid propellant.To exploit highefficiency combustion catalyst,a fascinating bimetallic metal-organic framework[MnCo(EIM)_(2)(DCA)_(2)]n(1)was constructed by an active dicyandiamide(DCA)linker,Mn^(2+),Co^(2+)centers,and an 1-ethylimidazole(EIM)ligand.1 possesses good thermal stability(Tp=205℃),high energy density(Eg=24.34 kJ/g,Ev=35.93 kJ/cm^(3)),and insensitivity to impact and frictional stimulus.The catalytic effects of 1 contrasted to monometallic coordination compounds Mn(EIM)_(4)(DCA)_(2)(2)and Co(EIM)_(4)(DCA)_(2)(3)on the thermal decomposition of AP/RDX composite were investigated by a DSC method.The decomposition peak temperatures of AP and RDX of the composite decreased to 335.8℃ and 206.4℃,respectively,and the corresponding activation energy decreased by 27.3%and 43.6%,respectively,which are better than the performances of monometallic complexes 2 and 3.The gas products in the whole thermal decomposition stage of the sample were measured by TG-MS and TG-IR,and the catalytic mechanism of 1 to AP/RDX was further analyzed.This work reveal potential application of bimetallic MOFs in the composite solid propellants.
基金Project(52174338)supported by the National Natural Science Foundation of ChinaProjects(2022JJ20086,2021JJ30796)supported by the Natural Science Foundation of Hunan Province,China+1 种基金Project(2023CXQD005)supported by the Central South University Innovation-Driven Research Programme,ChinaProject(23B0841)supported by the Education Department of Hunan Provincial Government,China。
文摘Single-atom catalysts(SACs)are promising for oxygen reduction reaction(ORR)on account of their excellent catalytic activity and maximum utilization of atoms.However,due to the complicated preparation processes and expensive reagents used,the cost of SACs is usually too high to put into practical application.The development of cost-effective and sustainable SACs remains a great challenge.Herein,a low-cost method employing biomass is designed to prepare efficient single-atom Fe-N-C catalysts(SA-Fe-N-C).Benefiting from the confinement effect of porous carbon support and the coordination effect of glucose,SA-Fe-N-C is derived from cheap flour by the two-step pyrolysis.Atomically dispersed Fe atoms exist in the form of Fe-N_(x),which acts as active sites for ORR.The catalyst shows outstanding activity with a half-wave potential(E_(1/2))of 0.86 V,which is better than that of Pt/C(0.84 V).Additionally,the catalyst also exhibits superior stability.The ORR catalyzed by SA-Fe-N-C proceeds via an efficient 4e transfer pathway.The high performance of SA-Fe-N-C also benefits from its porous structure,extremely high specific surface area(1450.1 m^(2)/g),and abundant micropores,which are conducive to increasing the density of active sites and fully exposing them.This work provides a cost-effective strategy to synthesize SACs from cheap biomass,achieving a balance between performance and cost.
文摘The core-shell 2,4,6,8,10,12-Hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane/2,4,6-Trinitrotoluene(CL-20/TNT)composite was prepared by spray-drying method in which sensitive high energy explosive(CL-20)was coated with insensitive explosive(TNT).The structure and properties of different formulations of CL-20/TNT composite and CL-20/TNT mixture were characterized by scanning electron microscopy(SEM),Transmission electron microscopy(TEM),Laser particle size analyzer,X-ray photoelectron spectroscopy(XPS),X-ray diffraction(XRD),differential scanning calorimetry(DSC),impact sensitivity test and detonation performance.The results of SEM,TEM,XPS and XRD show that e-CL-20 particles are coated by TNT.When the ratio of CL-20/TNT is 75/25,core-shell structure is well formed,and thickness of the shell is about 20e30 nm.And the analysis of heat and impact show that with the increase of TNT content,the TNT coating on the core-shell composite material can not only catalyze the thermal decomposition of core material(CL-20),but also greatly reduce the impact sensitivity.Compared with the CL-20/TNT mixture(75/25)at the same ratio,the characteristic drop height of core-shell CL-20/TNT composite(75/25)increased by 47.6%and the TNT coating can accelerate the nuclear decomposition in the CL-20/TNT composites.Therefore,the preparation of the core-shell composites can be regarded as a unique means,by which the composites are characterized by controllable decomposition rate,high energy and excellent mechanical sensitivity and could be applied to propellants and other fields.
基金This work was supported by the National Natural Science Foundation of China(No.51571033,11804022)the Science and Technology on Transient Impact Laboratory Foundation(No.6142606183208).
文摘A facile and economical approach was developed for the large-scale production of powdered core-shell structured PTFE/Al (CS-PA) energetic materials through ultrasonic-assisted mixing. The low-cost micrometer-sized PTFE and Al particles were used as starting materials. Under high-power ultrasonic waves, the PTFE powder was dispersed into nano-to sub-micrometer-sized particles and then encapsulated the Al microparticles to form the core-shell structure. The heat of combustion, burning rate, and pressurization rate of the powdered CS-PA were measured. The thermal-initiated reaction behavior was further evaluated using thermogravimetry-differential scanning calorimetry. Subsequently, the bulk CS-PA with a uniform microstructure was obtained via cold isostatic pressing of the powdered CS-PA followed by vacuum sintering. For the bulk CS-PA, the quasi-static compression behavior was characterized, and the impact-initiated reaction processes were conducted using the Split Hopkinson Pressure Bar (SHPB) and evaluated by a high-speed camera. Compared to physically mixed PTFE/Al materials, the powdered and bulk CS-PA demonstrated enhanced thermal- and impact-initiated reaction characteristics respectively, proving the effectiveness of our approach for constructing core-shell structures.
基金financially supported by the National Natural Science Foundation of China (Grant NO.11702268)Sichuan provincial key S&T Special Projects (Grant NO.19DZX0106)
文摘Inspired by the phenomenon of superhydrophobic plants and animals in nature,1,3,5,7-tetranitro-1,3,5,7-tetrazocane(HMX)@copper stearate(CS)core-shell composites with similar properties was prepared.A rough shell layer on the surface of the HMX was observed by scanning electron microscopy(SEM),and a series of in-depth characterization confirmed the successful generation of CS and the coreshell structure of the samples.Differential scanning calorimeter(DSC)proves that the crystal transition temperature(204℃)and high temperature decomposition exothermal temperature(284℃)of HMX@CS is almost unchanged compared with pure HMX,which means HMX and CS have good compatibility.Then,the H50 of the samples also increased continuously(16.6 cm→33.7 cm)when the CS shell content increased from 1%to 5%,indicating that the CS shell has a certain buffering performance,and CS will absorb some heat and melt under the stimulation of impact due to its low melting point,which improved impact sensitivity of HMX effectively further.Moreover,HMX@CS has excellent hydrophobic and oleophilic performance,shows excellent wettability with lipid binder,and samples with appropriate CS shell content can continue to combustion stably after covering water.This waterproof and low sensitivity coating provides a new way for the development of multifunctional energetic materials.
基金the financial support by Postgraduate Research & Practice Innovation Program from Jiangsu Science and Technology Department under Grant number KYCX19_0320。
文摘Copper azide(CA), as a primary explosive with high energy density, has not been practically used so far because of its high electrostatic sensitivity. The Cu2O@HKUST-1 core-shell structure hybrid material was synthesized by the “bottle around ship” methodology in this research by regulating the dissolution rate of Cu2O and the generation rate of metal-organic framework(MOF) materials. Cu2O@HKUST-1 was carbonized to form a Cu O@porous carbon(CuO@PC) composite material. CuO@PC was synthesized into a copper azide(CA) @PC composite energetic material through a gas-solid phase in-situ azidation reaction.CA is encapsulated in PC framework, which acts as a nanoscale Faraday cage, and its excellent electrical conductivity prevents electrostatic charges from accumulating on the energetic material’s surface. The CA@PC composite energetic material has a CA content of 89.6%, and its electrostatic safety is nearly 30times that of pure CA(1.47 mJ compared to 0.05 mJ). CA@PC delivers an outstanding balance of safety and energy density compared to similar materials.
基金Projects(J21103045,J1210040,J1103312) supported by the National Natural Science Foundation of ChinaProject supported by the Fundamental Research Funds for the Central Universities of China
文摘Ce O2@Si O2 core-shell nanoparticles were prepared by microemulsion method, and metalloporphyrins were immobilized on the Ce O2@Si O2 core-shell nanoparticles surface via amide bond. The supported metalloporphyrin catalysts were characterized by N2 adsorption-desorption isotherm(BET), scanning electron microscopy(SEM), transmission electron microscopy(TEM), X-ray diffraction(XRD), ultraviolet and visible spectroscopy(UV-Vis), and Fourier transform infrared spectroscopy(FT-IR). The results show that the morphology of Ce O2@Si O2 nanoparticles is core-shell microspheres with about 30 nm in diameter, and metalloporphyrins are immobilized on the Ce O2@Si O2 core-shell nanoparticles via amide bond. Especially, the core-shell structure contains multi Ce O2 core and thin Si O2 shell, which may benefit the synergistic effect between the Ce O2 core and the porphyrin anchored on the very thin Si O2 shell. As a result, this supported metalloporphyrin catalysts present comparably high catalytic activity and stability for oxidation of ethylbenzene with molecular oxygen, namely, ethylbenzene conversion remains around 12% with identical selectivity of about 80% for acetophenone even after six-times reuse of the catalyst.
基金supported by the National Key Research and Development Program of China(No.2020YFB1506002,2019YFB1504503,2016YFB0101202)National 973 Program of China(No.2012CB215501)National Natural Science Foundation of China(No.52021004,22022502(2021),21822803(2019),21576031(2016),51272297(2013),20936008(2010),20676156(2007),20376088(2004),20176066(2002),29976047(2000)).
文摘Two major challenges,high cost and short lifespan,have been hindering the commercialization process of lowtemperature fuel cells.Professor Wei's group has been focusing on decreasing cathode Pt loadings without losses of activity and durability,and their research advances in this area over the past three decades are briefly reviewed herein.Regarding the Pt-based catalysts and the low Pt usage,they have firstly tried to clarify the degradation mechanism of Pt/C catalysts,and then demonstrated that the activity and stability could be improved by three strategies:regulating the nanostructures of the active sites,enhancing the effects of support materials,and optimizing structures of the three-phase boundary.For Pt-free catalysts,especialiy carbon-based ones,several strategies that they proposed to enhance the activity of nitrogen-/heteroatom-doped carbon catalysts are firstly presented.Then,an indepth understanding of the degradation mechanism for carbon-based catalysts is discussed,and followed by the corresponding stability enhancement strategies.Also,the carbon-based electrode at the micrometer-scale,faces the challenges such as low active-site density,thick catalytic layer,and the effect of hydrogen peroxide,which require rational structure design for the integral cathodic electrode.This review finally gives a brief conclusion and outlook about the low cost and long lifespan of cathodic oxygen reduction catalysts.
