In recent years,photocatalytic N_(2) reduction for ammonia synthesis at room temperature and atmospheric pressure has gradually become a research hotspot,exhibiting extremely high development potential.However,the low...In recent years,photocatalytic N_(2) reduction for ammonia synthesis at room temperature and atmospheric pressure has gradually become a research hotspot,exhibiting extremely high development potential.However,the low photogenerated charge separation efficiency and the lack of effective active sites seriously constrain the reaction efficiencies of semiconductor photocatalysts for N_(2) reduction of ammonia synthesis.Therefore,the rational design of catalytic materials is the key to enhance the photocatalytic N_(2) reduction reaction of ammonia synthesis.Transition metal Ru as the active center not only accelerates the adsorption and activation of N_(2) molecules,but also has good selectivity for N_(2) reduction.Moreover,the interaction between the metal and the support can effectively regulate the electronic structure of the active site,accelerate the photogenerated electron transfer,and significantly enhance the photocatalytic activity.Based on this,this review systematically investigates the Ru co-semiconductors to realize efficient photocatalytic N_(2) reduction for ammonia synthesis,and introduces its basic principles.Specifically,the Ru co-semiconductor photocatalytic material systems are introduced,such as TiO2-based,g-C3N4-based,and metal oxide materials,including the design of catalysts,crystal structures,and other characteristics.In addition,the modification strategies of photocatalytic N_(2) reduction ammonia synthesis materials are also presented,including loading/doping,defect engineering,construction of heterojunctions,and crystal surface modulation.Furthermore,the progress and shortcomings of the application of Ru co-semiconductors in these processes are summarized and comprehensively discussed,and the future outlook of Ru co-semiconductors in photocatalytic N_(2) reduction ammonia synthesis applications is proposed.展开更多
Alloying transition metals with Pt is an effective strategy for optimizing Pt-based catalysts toward the oxygen reduction reaction(ORR).Atomic ordered intermetallic compounds(IMC)provide unique electronic and geometri...Alloying transition metals with Pt is an effective strategy for optimizing Pt-based catalysts toward the oxygen reduction reaction(ORR).Atomic ordered intermetallic compounds(IMC)provide unique electronic and geometrical effects as well as stronger intermetallic interactions due to the ordered arrangement of metal atoms,thus exhibiting superior electrocata-lytic activity and durability.However,quantitatively analyzing the ordering degree of IMC and exploring the correlation between the ordering degree and ORR activity remains extremely challenging.Herein,a series of ternary Pt_(2)NiCo interme-tallic catalysts(o-Pt_(2)NiCo)with different ordering degree were synthesized by annealing temperature modulation.Among them,the o-Pt_(2)NiCo which annealed at 800℃for two hours exhibits the highest ordering degree and the optimal ORR ac-tivity,which the mass activity of o-Pt_(2)NiCo is 1.8 times and 2.8 times higher than that of disordered Pt_(2)NiCo alloy and Pt/C.Furthermore,the o-Pt_(2)NiCo still maintains 70.8%mass activity after 30,000 potential cycles.Additionally,the ORR activity test results for Pt_(2)NiCo IMC with different ordering degree also provide a positive correlation between the ordering degree and ORR activity.This work provides a prospective design direction for ternary Pt-based electrocatalysts.展开更多
A gold catalyst of Au/pyrenyl‑graphdiyne(Pyr‑GDY)was prepared by anchoring small size of gold nanoparticles(Au NPs)on the surface of Pyr‑GDY for electrocatalytic nitrogen reduction reaction(eNRR),in which Au NPs with ...A gold catalyst of Au/pyrenyl‑graphdiyne(Pyr‑GDY)was prepared by anchoring small size of gold nanoparticles(Au NPs)on the surface of Pyr‑GDY for electrocatalytic nitrogen reduction reaction(eNRR),in which Au NPs with a size of approximately 3.69 nm was evenly distributed on spongy‑like porous Pyr‑GDY.The catalyst exhibited a good electrocatalytic activity for N_(2)reduction in a nitrogen‑saturated electrolyte,with an ammonia yield of 32.1μg·h^(-1)·mg_(cat)^(-1)at-0.3 V(vs RHE),3.5 times higher than that of Au/C(Au NPs anchored on carbon black).In addition,Au/Pyr‑GDY showed a Faraday efficiency(FE)of 26.9%for eNRR,and a good catalysis durability for over 22 h.展开更多
The poor electronic conductivity of metal-organic framework(MOF)materials hinders their direct application in the field of electrocatalysis in fuel cells.Herein,we proposed a strategy of embedding carbon nanotubes(CNT...The poor electronic conductivity of metal-organic framework(MOF)materials hinders their direct application in the field of electrocatalysis in fuel cells.Herein,we proposed a strategy of embedding carbon nanotubes(CNTs)during the growth process of MOF crystals,synthesizing a metalloporphyrin-based MOF catalyst TCPPCo-MOF-CNT with a unique CNT-intercalated MOF structure.Physical characterization revealed that the CNTs enhance the overall conductivity while retaining the original characteristics of the MOF and metalloporphyrin.Simultaneously,the insertion of CNTs generated adequate mesopores and created a hierarchical porous structure that enhances mass transfer efficiency.X-ray photoelectron spectroscopic analysis confirmed that the C atom in CNT changed the electron cloud density on the catalytic active center Co,optimizing the electronic structure.Consequently,the E_(1/2) of the TCPPCo-MOF-CNT catalyst under neutral conditions reached 0.77 V(vs.RHE),outperforming the catalyst without CNTs.When the TCPPCo-MOF-CNT was employed as the cathode catalyst in assembling microbial fuel cells(MFCs)with Nafion-117 as the proton exchange membrane,the maxi-mum power density of MFCs reached approximately 500 mW·m^(-2).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
Nitric oxide(NO),which generally originates from vehicle exhaust and industrial flue gases,is one of the most serious air pollutants.In this case,the electrochemical NO reduction reaction(NORR)not only removes the atm...Nitric oxide(NO),which generally originates from vehicle exhaust and industrial flue gases,is one of the most serious air pollutants.In this case,the electrochemical NO reduction reaction(NORR)not only removes the atmospheric pollutant NO but also produces valuable ammonia(NH_(3)).Hence,through the synthesis and modification of Fe_(3)C nanocrystal cata-lysts,the as-obtained optimal sample of Fe_(3)C/C-900 was adopted as the NORR catalyst at ambient conditions.As a result,the Fe_(3)C/C-900 catalyst showed an NH_(3)Faraday efficiency of 76.5%and an NH_(3)yield rate of 177.5μmol·h^(-1)·cm^(-2)at the working potentials of-0.8 and-1.2 V versus reversible hydrogen electrode(vs.RHE),respectively.And it delivered a stable NORR activity during the electrolysis.Moreover,we attribute the high NORR properties of Fe_(3)C/C-900 to two aspects:one is the enhanced intrinsic activity of Fe_(3)C nanocrystals,including the lowering of the energy barrier of rate-limiting step(*NOH→*N)and the inhibition of hydrogen evolution;on the other hand,the favorable dispersion of active components,the effective adsorption of gaseous NO,and the release of liquid NH_(3)products facilitated by the porous carbon substrate.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
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
The selective reduction of carbon dioxide(CO_(2))into high-value-added chemicals is one of the most effective means to solve the current energy and environmental problems,which could realize the utilization of CO_(2) ...The selective reduction of carbon dioxide(CO_(2))into high-value-added chemicals is one of the most effective means to solve the current energy and environmental problems,which could realize the utilization of CO_(2) and promote the balance of the carbon cycle.Formate is one of the most economical and practical products of all the electrochemical CO_(2) reduction products.Among the many metal-based electrocatalysts that can convert CO_(2) into formate,Sn-based catalysts have received a lot of attention because of their low-cost,non-toxic characteristics and high selectivity for formate.In this article,the most recent development of Sn-based electrocatalysts is comprehensively summarized by giving examples,which are mainly divided into monometallic Sn,alloyed Sn,Sn-based compounds and Sn composite catalysts.Finally,the current performance enhancement strategies and future directions of the field are summarized.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
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
Copper-based catalysts have garnered wide attention in the field of electrocatalytic nitrate reduction for ammonia production due to their low hydrogen precipitation activity and high ammonia selectivity.However,they ...Copper-based catalysts have garnered wide attention in the field of electrocatalytic nitrate reduction for ammonia production due to their low hydrogen precipitation activity and high ammonia selectivity.However,they still face challenges pertaining of poor stability and low activity,which hinder their further application.Herein,we present a Cu_(2)O/Cu heterojunction catalyst supported on nitrogen-doped porous carbon for nitrate reduction.High resolution transmission electron microscopy(HRTEM)and X-ray Diffraction(XRD)results confirm the presence of Cu_(2)O/Cu heterojunctions,which serve as an active phase in catalysis.The nitrogen-doped porous carbon as a carrier not only enhances the catalyst’s stability,but also facilitates the exposure and dispersion of active sites.At-1.29 V(vs.RHE),the maximum production rate of ammonia reaches 8.8 mg/(mg·h)with a Faradaic efficiency of 92.8%.This study also elucidates the effect of Cu_(2)O-to-Cu ratio in the heterojunction on catalytic performance,thereby providing valuable insights for designing efficient nitrate reduction catalysts for ammonia production.展开更多
The complex structure of the bottom of a high-speed train is an important source of train aerodynamic drag.Thus,improving the bottom structure is of great significance to reduce the aerodynamic drag of the train.In th...The complex structure of the bottom of a high-speed train is an important source of train aerodynamic drag.Thus,improving the bottom structure is of great significance to reduce the aerodynamic drag of the train.In this study,computational fluid dynamics(CFD)based on three-dimensional steady incompressible Reynolds-average Naiver-Stokes(RANS)equations and Realizable k-εturbulence model were utilized for numerical simulations.Inspired by the concept of streamlined design and the idea of bottom flow field control,this study iteratively designed the bogies in a streamlined shape and combined them with the bottom deflectors to investigate the joint drag reduction mechanism.Three models,i.e.,single-bogie model,simplified train model,and eight-car high-speed train model,were created and their aerodynamic characteristics were analyzed.The results show that the single-bogie model with streamlined design shows a noticeable drag reduction,whose power bogie and trailer bogie experience 13.92%and 7.63%drag reduction,respectively.The range of positive pressure area on the bogie is reduced.The aerodynamic drag can be further reduced to 15.01%by installing both the streamlined bogie and the deflector on the simplified train model.When the streamlined bogies and deflectors are used on the eight-car model together,the total drag reduction rate reaches 2.90%.Therefore,the proposed aerodynamic kit for the high-speed train bottom is capable to improve the flow structure around the bogie regions,reduce the bottom flow velocity,and narrow the scope of the train’s influence on the surrounding environment,achieving the appreciable reduction of aerodynamic drag.This paper can provide a new idea for the drag reduction of high-speed trains.展开更多
Fluidized reduction roasting is an efficient metallurgical technique.However,its application to nickel laterite ore has rarely been reported.In this paper,the effects of reduction temperature,reduction time,CO concent...Fluidized reduction roasting is an efficient metallurgical technique.However,its application to nickel laterite ore has rarely been reported.In this paper,the effects of reduction temperature,reduction time,CO concentration,and material particle size on the roasting characteristics of ferronickel fluidization reduction were investigated.Combined with X-ray diffraction,scanning electron microscopy-energy dispersive spectrometry(SEM-EDS)characterization,the mineral phases and microscopic morphology of nickel laterite ore and its roasted ores were analyzed in depth.The results indicated that under the condition of a CO/CO_(2)ratio of 1:1,a reduction temperature of 800℃,and a reduction roasting time of 60 min,a nickel-iron concentrate with a nickel grade of 2.10%and an iron content of 45.96%was produced from a raw material with a nickel grade of 1.45%,achieving a remarkable nickel recovery rate of 46.26%.XRD and SEM-EDS analysis indicated that nickel in the concentrate mainly exists in the form of[Fe,Ni],while the unrecovered nickel in the tailings is primarily present in the form of[Fe,Ni]and Ni_(2)SiO_(4)in forsterite.This study established a theoretical foundation for further exploration of fluidized reduction roasting technology.展开更多
Modern conflicts demand substantial physical and psychological exertion,often resulting in fatigue and diminished combat or operational readiness.Several exoskeletons have been developed recently to address these chal...Modern conflicts demand substantial physical and psychological exertion,often resulting in fatigue and diminished combat or operational readiness.Several exoskeletons have been developed recently to address these challenges,presenting various limitations that affect their operational or everyday usability.This article evaluates the performance of a dual-purpose passive ankle exoskeleton developed for the reduction of metabolic costs during walking,seeking to identify a force element that could be applied to the target population.Based on the 6-min walk test,twenty-nine subjects participated in the study using three different force elements.The results indicate that it is possible to reduce metabolic expenditure while using the developed exoskeleton.Additionally,the comfort and range of motion results verify the exoskeleton's suitability for use in uneven terrain and during extended periods.Nevertheless,the choice of the force element should be tailored to each user,and the control system should be adjustable to optimise the exoskeleton's performance.展开更多
To replace precious metal oxygen reduction reaction(ORR)electrocatalysts,many transition metals and N-doped car-bon composites have been proposed in the last decade resulting in their rapid development as promising no...To replace precious metal oxygen reduction reaction(ORR)electrocatalysts,many transition metals and N-doped car-bon composites have been proposed in the last decade resulting in their rapid development as promising non-precious metal catalysts.We used Ketjenblack carbon as the precursor and mixed it with a polymeric ionic liquid(PIL)of[Hvim]NO_(3) and Fe(NO_(3))_(3),which was thermally calcined at 900℃ to produce a porous FeO_(x),N co-doped carbon material denoted FeO_(x)-N/C.Because the PIL of[Hvim]NO_(3) strongly combines with and disperses Fe^(3+)ions,and NO_(3)−is thermally pyrolyzed to form the porous structure,the FeO_(x)-N/C catalyst has a high electrocatalytic activity for the ORR in both 0.1 mol L^(−1) KOH and 0.5 mol L^(−1) H_(2)SO_(4) electrolytes.It was used as the catalyst to assemble a zinc-air battery,which had a peak power density of 185 mW·cm^(−2).Its superior electrocatalytic activity,wide pH range,and easy preparation make FeO_(x)-N/C a promising electrocatalyst for fuel cells and metal-air batteries.展开更多
This paper is aimed to present a clean,inexpensive and sustainable method to synthesize high purity lithium sulfide(Li_(2)S)powder through hydrogen reduction of lithium sulfate(Li_(2)SO_(4)).A three-step reduction pro...This paper is aimed to present a clean,inexpensive and sustainable method to synthesize high purity lithium sulfide(Li_(2)S)powder through hydrogen reduction of lithium sulfate(Li_(2)SO_(4)).A three-step reduction process has been successfully developed to synthesize well-crystallized and single-phase Li_(2)S powder by investigating the melting,sintering and reduction behavior of the mixtures of Li_(2)SO_(4)-Li_(2)S.High purity alumina was found to be the most suitable crucible material for producing high purity Li_(2)S,because it was not attacked by the Li_(2)SO_(4)-Li_(2)S melt during heating,as compared with other materials,such as carbon,mullite,quartz,boron nitride and stainless steel.The use of synthesized LizS resulted in higher purity and substantially higher room temperature ionic conductivity(2.77 mS·cm^(-1))for the argyrodite sulfide electrolyte Li_(6)PS_(5)Cl than commercial Li_(2)S(1.12 mS·cm^(-1)).This novel method offers a great opportunity to produce battery grade Li_(2)S for sulfide solid electrolyte applications.展开更多
In recent years,magnetic fields have been widely applied in catalysis to increase the performance of electrocatalysis,photocatalysis,and thermocatalysis through an important noncontact way.This work demonstrated that ...In recent years,magnetic fields have been widely applied in catalysis to increase the performance of electrocatalysis,photocatalysis,and thermocatalysis through an important noncontact way.This work demonstrated that doping CsPbCl_(3) halide perovskite nanocrystals with nickel ions(Ni^(2+))and applying an external magnetic field can significantly enhance the performance of the photocatalytic carbon dioxide reduction reaction(CO_(2)RR).Compared with its counterpart,Ni-doped CsPbCl_(3) exhibits a sixfold increase in CO_(2)RR efficiency under a 500 mT magnetic field.Insights into the mechanism of this enhancement effect were obtained through photogenerated current density measurements and X-ray magnetic circular dichroism.The results illustrate that the significant enhancement in catalytic performance by the magnetic field is attributed to the synergistic effects of magnetic element doping and the external magnetic field,leading to reduced electron‒hole recombination and extended carrier lifetimes.This study provides an effective strategy for enhancing the efficiency of the photocatalytic CO_(2)RR by manipulating spin-polarized electrons in photocatalytic semiconductors via a noncontact external magnetic field.展开更多
This study developed a direct reduction route to smelt refractory high-phosphorus iron ores by using hydrogen rich gas.The effects of temperature,gas composition,and gangue on the reduction behavior of iron ore pellet...This study developed a direct reduction route to smelt refractory high-phosphorus iron ores by using hydrogen rich gas.The effects of temperature,gas composition,and gangue on the reduction behavior of iron ore pellets were investigated.Additionally,the migration behavior of phosphorus throughout the reduction-smelting process was examined.The apparent activation energy of the reduction process increased from 64.2 to 194.2 kJ/mol.Increasing the basicity from 0.5 to 0.9 increased the metallization rate from 85.9%to 89.2%.During the reduction process,phosphorus remained in the gangue phase.Carbon deposition and phosphorus removal behaviors of the pellets were investigated and correlated with the gas composition,temperature,pressure,metallization rate,and basicity.Increasing the FeO and CaO contents led to an increase in the liquidus temperature.A high metallization rate of the pellets reduced the phosphorus removal rate but increased the carbon content of the final iron product.Increasing basicity restricted the migration of phosphorus and improved the rate of phosphorus removal.The optimum dephosphorization parameters were separation temperature of 1823 K,basicity of 2.0,and metallization rate of 82.3%.This study presents a high-efficiency and low carbon method for smelting high-phosphorus iron ores.展开更多
Zinc indium sulfide(ZnIn_(2)S_(4),ZIS),a novel photocatalyst with layered nanostructure,has drawn significant attention in the field of photocatalytic CO_(2) reduction in recent years due to various advantages,includi...Zinc indium sulfide(ZnIn_(2)S_(4),ZIS),a novel photocatalyst with layered nanostructure,has drawn significant attention in the field of photocatalytic CO_(2) reduction in recent years due to various advantages,including non-toxicity,structural stability,easy availability,and suitable band gap.We introduced the types of ZISbased nanomaterials and their action mechanism in photocatalytic CO_(2) reduction.Moreover,we put forward prospects in the future development directions of ZIS-based nanomaterials for photocatalytic CO_(2) reduction.展开更多
基金supported by Taishan Scholars Foundation of Shandong province(tsqn 201909058)。
文摘In recent years,photocatalytic N_(2) reduction for ammonia synthesis at room temperature and atmospheric pressure has gradually become a research hotspot,exhibiting extremely high development potential.However,the low photogenerated charge separation efficiency and the lack of effective active sites seriously constrain the reaction efficiencies of semiconductor photocatalysts for N_(2) reduction of ammonia synthesis.Therefore,the rational design of catalytic materials is the key to enhance the photocatalytic N_(2) reduction reaction of ammonia synthesis.Transition metal Ru as the active center not only accelerates the adsorption and activation of N_(2) molecules,but also has good selectivity for N_(2) reduction.Moreover,the interaction between the metal and the support can effectively regulate the electronic structure of the active site,accelerate the photogenerated electron transfer,and significantly enhance the photocatalytic activity.Based on this,this review systematically investigates the Ru co-semiconductors to realize efficient photocatalytic N_(2) reduction for ammonia synthesis,and introduces its basic principles.Specifically,the Ru co-semiconductor photocatalytic material systems are introduced,such as TiO2-based,g-C3N4-based,and metal oxide materials,including the design of catalysts,crystal structures,and other characteristics.In addition,the modification strategies of photocatalytic N_(2) reduction ammonia synthesis materials are also presented,including loading/doping,defect engineering,construction of heterojunctions,and crystal surface modulation.Furthermore,the progress and shortcomings of the application of Ru co-semiconductors in these processes are summarized and comprehensively discussed,and the future outlook of Ru co-semiconductors in photocatalytic N_(2) reduction ammonia synthesis applications is proposed.
基金supported by the National Natural Science Foundation(22279036)the Innovation and Talent Recruitment Base of New Energy Chemistry and Device(B21003).
文摘Alloying transition metals with Pt is an effective strategy for optimizing Pt-based catalysts toward the oxygen reduction reaction(ORR).Atomic ordered intermetallic compounds(IMC)provide unique electronic and geometrical effects as well as stronger intermetallic interactions due to the ordered arrangement of metal atoms,thus exhibiting superior electrocata-lytic activity and durability.However,quantitatively analyzing the ordering degree of IMC and exploring the correlation between the ordering degree and ORR activity remains extremely challenging.Herein,a series of ternary Pt_(2)NiCo interme-tallic catalysts(o-Pt_(2)NiCo)with different ordering degree were synthesized by annealing temperature modulation.Among them,the o-Pt_(2)NiCo which annealed at 800℃for two hours exhibits the highest ordering degree and the optimal ORR ac-tivity,which the mass activity of o-Pt_(2)NiCo is 1.8 times and 2.8 times higher than that of disordered Pt_(2)NiCo alloy and Pt/C.Furthermore,the o-Pt_(2)NiCo still maintains 70.8%mass activity after 30,000 potential cycles.Additionally,the ORR activity test results for Pt_(2)NiCo IMC with different ordering degree also provide a positive correlation between the ordering degree and ORR activity.This work provides a prospective design direction for ternary Pt-based electrocatalysts.
文摘A gold catalyst of Au/pyrenyl‑graphdiyne(Pyr‑GDY)was prepared by anchoring small size of gold nanoparticles(Au NPs)on the surface of Pyr‑GDY for electrocatalytic nitrogen reduction reaction(eNRR),in which Au NPs with a size of approximately 3.69 nm was evenly distributed on spongy‑like porous Pyr‑GDY.The catalyst exhibited a good electrocatalytic activity for N_(2)reduction in a nitrogen‑saturated electrolyte,with an ammonia yield of 32.1μg·h^(-1)·mg_(cat)^(-1)at-0.3 V(vs RHE),3.5 times higher than that of Au/C(Au NPs anchored on carbon black).In addition,Au/Pyr‑GDY showed a Faraday efficiency(FE)of 26.9%for eNRR,and a good catalysis durability for over 22 h.
基金the financial support from the National Natural Science Foundation of China(No.22178307)China Southern Power Grid(Grant Nos.0470002022030103HX00002-01).
文摘The poor electronic conductivity of metal-organic framework(MOF)materials hinders their direct application in the field of electrocatalysis in fuel cells.Herein,we proposed a strategy of embedding carbon nanotubes(CNTs)during the growth process of MOF crystals,synthesizing a metalloporphyrin-based MOF catalyst TCPPCo-MOF-CNT with a unique CNT-intercalated MOF structure.Physical characterization revealed that the CNTs enhance the overall conductivity while retaining the original characteristics of the MOF and metalloporphyrin.Simultaneously,the insertion of CNTs generated adequate mesopores and created a hierarchical porous structure that enhances mass transfer efficiency.X-ray photoelectron spectroscopic analysis confirmed that the C atom in CNT changed the electron cloud density on the catalytic active center Co,optimizing the electronic structure.Consequently,the E_(1/2) of the TCPPCo-MOF-CNT catalyst under neutral conditions reached 0.77 V(vs.RHE),outperforming the catalyst without CNTs.When the TCPPCo-MOF-CNT was employed as the cathode catalyst in assembling microbial fuel cells(MFCs)with Nafion-117 as the proton exchange membrane,the maxi-mum power density of MFCs reached approximately 500 mW·m^(-2).
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 the Guangxi Natural Science Fund for Distinguished Young Scholars(2024GXNSFFA010008)Shenzhen Science and Technology Program(JCYJ20230807112503008).
文摘Nitric oxide(NO),which generally originates from vehicle exhaust and industrial flue gases,is one of the most serious air pollutants.In this case,the electrochemical NO reduction reaction(NORR)not only removes the atmospheric pollutant NO but also produces valuable ammonia(NH_(3)).Hence,through the synthesis and modification of Fe_(3)C nanocrystal cata-lysts,the as-obtained optimal sample of Fe_(3)C/C-900 was adopted as the NORR catalyst at ambient conditions.As a result,the Fe_(3)C/C-900 catalyst showed an NH_(3)Faraday efficiency of 76.5%and an NH_(3)yield rate of 177.5μmol·h^(-1)·cm^(-2)at the working potentials of-0.8 and-1.2 V versus reversible hydrogen electrode(vs.RHE),respectively.And it delivered a stable NORR activity during the electrolysis.Moreover,we attribute the high NORR properties of Fe_(3)C/C-900 to two aspects:one is the enhanced intrinsic activity of Fe_(3)C nanocrystals,including the lowering of the energy barrier of rate-limiting step(*NOH→*N)and the inhibition of hydrogen evolution;on the other hand,the favorable dispersion of active components,the effective adsorption of gaseous NO,and the release of liquid NH_(3)products facilitated by the porous carbon substrate.
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.
基金Project(52204378)supported by the National Natural Science Foundation of China。
文摘The selective reduction of carbon dioxide(CO_(2))into high-value-added chemicals is one of the most effective means to solve the current energy and environmental problems,which could realize the utilization of CO_(2) and promote the balance of the carbon cycle.Formate is one of the most economical and practical products of all the electrochemical CO_(2) reduction products.Among the many metal-based electrocatalysts that can convert CO_(2) into formate,Sn-based catalysts have received a lot of attention because of their low-cost,non-toxic characteristics and high selectivity for formate.In this article,the most recent development of Sn-based electrocatalysts is comprehensively summarized by giving examples,which are mainly divided into monometallic Sn,alloyed Sn,Sn-based compounds and Sn composite catalysts.Finally,the current performance enhancement strategies and future directions of the field are summarized.
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.
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.
基金supported by the Fundamental Research Funds for the Central Universities(DUT22LAB601)the Technology Development Contract of Sinopec(123038).
文摘Copper-based catalysts have garnered wide attention in the field of electrocatalytic nitrate reduction for ammonia production due to their low hydrogen precipitation activity and high ammonia selectivity.However,they still face challenges pertaining of poor stability and low activity,which hinder their further application.Herein,we present a Cu_(2)O/Cu heterojunction catalyst supported on nitrogen-doped porous carbon for nitrate reduction.High resolution transmission electron microscopy(HRTEM)and X-ray Diffraction(XRD)results confirm the presence of Cu_(2)O/Cu heterojunctions,which serve as an active phase in catalysis.The nitrogen-doped porous carbon as a carrier not only enhances the catalyst’s stability,but also facilitates the exposure and dispersion of active sites.At-1.29 V(vs.RHE),the maximum production rate of ammonia reaches 8.8 mg/(mg·h)with a Faradaic efficiency of 92.8%.This study also elucidates the effect of Cu_(2)O-to-Cu ratio in the heterojunction on catalytic performance,thereby providing valuable insights for designing efficient nitrate reduction catalysts for ammonia production.
基金Project(2020YFA0710901)supported by the National Key Research and Development Program of ChinaProject(2023JJ30643)supported by the Natural Science Foundation of Hunan Province,China+1 种基金Project(12372204)supported by the National Natural Science Foundation of ChinaProject(2022ZZTS0725)supported by the Self-exploration and Innovation Project for Postgraduates of Central South University,China。
文摘The complex structure of the bottom of a high-speed train is an important source of train aerodynamic drag.Thus,improving the bottom structure is of great significance to reduce the aerodynamic drag of the train.In this study,computational fluid dynamics(CFD)based on three-dimensional steady incompressible Reynolds-average Naiver-Stokes(RANS)equations and Realizable k-εturbulence model were utilized for numerical simulations.Inspired by the concept of streamlined design and the idea of bottom flow field control,this study iteratively designed the bogies in a streamlined shape and combined them with the bottom deflectors to investigate the joint drag reduction mechanism.Three models,i.e.,single-bogie model,simplified train model,and eight-car high-speed train model,were created and their aerodynamic characteristics were analyzed.The results show that the single-bogie model with streamlined design shows a noticeable drag reduction,whose power bogie and trailer bogie experience 13.92%and 7.63%drag reduction,respectively.The range of positive pressure area on the bogie is reduced.The aerodynamic drag can be further reduced to 15.01%by installing both the streamlined bogie and the deflector on the simplified train model.When the streamlined bogies and deflectors are used on the eight-car model together,the total drag reduction rate reaches 2.90%.Therefore,the proposed aerodynamic kit for the high-speed train bottom is capable to improve the flow structure around the bogie regions,reduce the bottom flow velocity,and narrow the scope of the train’s influence on the surrounding environment,achieving the appreciable reduction of aerodynamic drag.This paper can provide a new idea for the drag reduction of high-speed trains.
基金Project(XDA 29020100)supported by the Strategic Priority Research Program of the Chinese Academy of SciencesProject(2022YFE0206600)supported by National Key R&D Program of China。
文摘Fluidized reduction roasting is an efficient metallurgical technique.However,its application to nickel laterite ore has rarely been reported.In this paper,the effects of reduction temperature,reduction time,CO concentration,and material particle size on the roasting characteristics of ferronickel fluidization reduction were investigated.Combined with X-ray diffraction,scanning electron microscopy-energy dispersive spectrometry(SEM-EDS)characterization,the mineral phases and microscopic morphology of nickel laterite ore and its roasted ores were analyzed in depth.The results indicated that under the condition of a CO/CO_(2)ratio of 1:1,a reduction temperature of 800℃,and a reduction roasting time of 60 min,a nickel-iron concentrate with a nickel grade of 2.10%and an iron content of 45.96%was produced from a raw material with a nickel grade of 1.45%,achieving a remarkable nickel recovery rate of 46.26%.XRD and SEM-EDS analysis indicated that nickel in the concentrate mainly exists in the form of[Fe,Ni],while the unrecovered nickel in the tailings is primarily present in the form of[Fe,Ni]and Ni_(2)SiO_(4)in forsterite.This study established a theoretical foundation for further exploration of fluidized reduction roasting technology.
基金the Portuguese Army,through CINAMIL,within project ELITE2-Enhancement LITe ExoskeletonFoundation for Science and Technology (FCT),through IDMEC,under LAETA,project UIDB/50022/2020 for supporting this research。
文摘Modern conflicts demand substantial physical and psychological exertion,often resulting in fatigue and diminished combat or operational readiness.Several exoskeletons have been developed recently to address these challenges,presenting various limitations that affect their operational or everyday usability.This article evaluates the performance of a dual-purpose passive ankle exoskeleton developed for the reduction of metabolic costs during walking,seeking to identify a force element that could be applied to the target population.Based on the 6-min walk test,twenty-nine subjects participated in the study using three different force elements.The results indicate that it is possible to reduce metabolic expenditure while using the developed exoskeleton.Additionally,the comfort and range of motion results verify the exoskeleton's suitability for use in uneven terrain and during extended periods.Nevertheless,the choice of the force element should be tailored to each user,and the control system should be adjustable to optimise the exoskeleton's performance.
文摘To replace precious metal oxygen reduction reaction(ORR)electrocatalysts,many transition metals and N-doped car-bon composites have been proposed in the last decade resulting in their rapid development as promising non-precious metal catalysts.We used Ketjenblack carbon as the precursor and mixed it with a polymeric ionic liquid(PIL)of[Hvim]NO_(3) and Fe(NO_(3))_(3),which was thermally calcined at 900℃ to produce a porous FeO_(x),N co-doped carbon material denoted FeO_(x)-N/C.Because the PIL of[Hvim]NO_(3) strongly combines with and disperses Fe^(3+)ions,and NO_(3)−is thermally pyrolyzed to form the porous structure,the FeO_(x)-N/C catalyst has a high electrocatalytic activity for the ORR in both 0.1 mol L^(−1) KOH and 0.5 mol L^(−1) H_(2)SO_(4) electrolytes.It was used as the catalyst to assemble a zinc-air battery,which had a peak power density of 185 mW·cm^(−2).Its superior electrocatalytic activity,wide pH range,and easy preparation make FeO_(x)-N/C a promising electrocatalyst for fuel cells and metal-air batteries.
基金Fiscal Year 2023-2024 High-Level and Growth Research and Development Subsidy for supporting the research and development activities for small and medium-size enterprise(SMEs),which is administered by Chiba Industry Advancement Center(Grant No.2066 and 2027)。
文摘This paper is aimed to present a clean,inexpensive and sustainable method to synthesize high purity lithium sulfide(Li_(2)S)powder through hydrogen reduction of lithium sulfate(Li_(2)SO_(4)).A three-step reduction process has been successfully developed to synthesize well-crystallized and single-phase Li_(2)S powder by investigating the melting,sintering and reduction behavior of the mixtures of Li_(2)SO_(4)-Li_(2)S.High purity alumina was found to be the most suitable crucible material for producing high purity Li_(2)S,because it was not attacked by the Li_(2)SO_(4)-Li_(2)S melt during heating,as compared with other materials,such as carbon,mullite,quartz,boron nitride and stainless steel.The use of synthesized LizS resulted in higher purity and substantially higher room temperature ionic conductivity(2.77 mS·cm^(-1))for the argyrodite sulfide electrolyte Li_(6)PS_(5)Cl than commercial Li_(2)S(1.12 mS·cm^(-1)).This novel method offers a great opportunity to produce battery grade Li_(2)S for sulfide solid electrolyte applications.
基金supported by the National Key R&D Program of China(2021YFA1501003)the Joint Funds of the National Natural Science Foundation of China(U23A2081)+5 种基金the National Natural Science Foundation of China(92261105,22221003)the Anhui Provincial Key Research and Development Project(2023z04020010,2022a05020053)the Anhui Provincial Natural Science Foundation(2108085UD06,2208085UD04)the USTC Research Funds of the Double First Class Initiative(YD2060002029,YD2060006005)the Fundamental Research Funds for the Central Universities(WK2060000004,WK2060000021,WK2060000025,WK9990000155)the Joint Funds from Hefei National Synchrotron Radiation Laboratory(KY2060000180,KY2060000195).
文摘In recent years,magnetic fields have been widely applied in catalysis to increase the performance of electrocatalysis,photocatalysis,and thermocatalysis through an important noncontact way.This work demonstrated that doping CsPbCl_(3) halide perovskite nanocrystals with nickel ions(Ni^(2+))and applying an external magnetic field can significantly enhance the performance of the photocatalytic carbon dioxide reduction reaction(CO_(2)RR).Compared with its counterpart,Ni-doped CsPbCl_(3) exhibits a sixfold increase in CO_(2)RR efficiency under a 500 mT magnetic field.Insights into the mechanism of this enhancement effect were obtained through photogenerated current density measurements and X-ray magnetic circular dichroism.The results illustrate that the significant enhancement in catalytic performance by the magnetic field is attributed to the synergistic effects of magnetic element doping and the external magnetic field,leading to reduced electron‒hole recombination and extended carrier lifetimes.This study provides an effective strategy for enhancing the efficiency of the photocatalytic CO_(2)RR by manipulating spin-polarized electrons in photocatalytic semiconductors via a noncontact external magnetic field.
基金Project(U1960205)supported by the National Natural Science Foundation of ChinaProject(2020ZXA01)supported by China Minmetals Science and Technology Special Plan Foundation。
文摘This study developed a direct reduction route to smelt refractory high-phosphorus iron ores by using hydrogen rich gas.The effects of temperature,gas composition,and gangue on the reduction behavior of iron ore pellets were investigated.Additionally,the migration behavior of phosphorus throughout the reduction-smelting process was examined.The apparent activation energy of the reduction process increased from 64.2 to 194.2 kJ/mol.Increasing the basicity from 0.5 to 0.9 increased the metallization rate from 85.9%to 89.2%.During the reduction process,phosphorus remained in the gangue phase.Carbon deposition and phosphorus removal behaviors of the pellets were investigated and correlated with the gas composition,temperature,pressure,metallization rate,and basicity.Increasing the FeO and CaO contents led to an increase in the liquidus temperature.A high metallization rate of the pellets reduced the phosphorus removal rate but increased the carbon content of the final iron product.Increasing basicity restricted the migration of phosphorus and improved the rate of phosphorus removal.The optimum dephosphorization parameters were separation temperature of 1823 K,basicity of 2.0,and metallization rate of 82.3%.This study presents a high-efficiency and low carbon method for smelting high-phosphorus iron ores.
文摘Zinc indium sulfide(ZnIn_(2)S_(4),ZIS),a novel photocatalyst with layered nanostructure,has drawn significant attention in the field of photocatalytic CO_(2) reduction in recent years due to various advantages,including non-toxicity,structural stability,easy availability,and suitable band gap.We introduced the types of ZISbased nanomaterials and their action mechanism in photocatalytic CO_(2) reduction.Moreover,we put forward prospects in the future development directions of ZIS-based nanomaterials for photocatalytic CO_(2) reduction.
