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
The weak adsorption energy of oxygen-containing intermediates on Co center leads to a considerable performance dis-parity between Co-N-C and costly Pt benchmark in catalyzing oxygen reduction reaction(ORR).In this wor...The weak adsorption energy of oxygen-containing intermediates on Co center leads to a considerable performance dis-parity between Co-N-C and costly Pt benchmark in catalyzing oxygen reduction reaction(ORR).In this work,we strategi-cally engineer the active site structure of Co-N-C via B substitution,which is accomplished by the pyrolysis of ammonium borate.During this process,the in-situ generated NH_(3)gas plays a critical role in creating surface defects and boron atoms substituting nitrogen atoms in the carbon structure.The well-designed CoB_(1)N_(3)active site endows Co with higher charge density and stronger adsorption energy toward oxygen species,potentially accelerating ORR kinetics.As expected,the resulting Co-B/N-C catalyst exhibited superior ORR performance over Co-N-C counterpart,with 40 mV,and fivefold en-hancement in half-wave potential and turnover frequency(TOF).More importantly,the excellent ORR performance could be translated into membrane electrode assembly(MEA)in a fuel cell test,delivering an impressive peak power density of 824 mW·cm^(-2),which is currently the best among Co-based catalysts under the same conditions.This work not only demon-strates an effective method for designing advanced catalysts,but also affords a highly promising non-precious metal ORR electrocatalyst for fuel cell applications.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
Development of robust electrocatalyst for oxygen reduction reaction(ORR)in a seawater electrolyte is the key to realize seawater electrolyte-based zinc-air batteries(SZABs).Herein,constructing a local electric field c...Development of robust electrocatalyst for oxygen reduction reaction(ORR)in a seawater electrolyte is the key to realize seawater electrolyte-based zinc-air batteries(SZABs).Herein,constructing a local electric field coupled with chloride ions(Cl-)fixation strategy in dual single-atom catalysts(DSACs)was proposed,and the resultant catalyst delivered considerable ORR performance in a seawater electrolyte,with a high half-wave potential(E_(1/2))of 0.868 V and a good maximum power density(Pmax)of 182 mW·cm^(−2)in the assembled SZABs,much higher than those of the Pt/C catalyst(E_(1/2):0.846 V;Pmax:150 mW·cm^(−2)).The in-situ characterization and theoretical calculations revealed that the Fe sites have a higher Cl^(−)adsorption affinity than the Co sites,and preferentially adsorbs Cl^(−)in a seawater electrolyte during the ORR process,and thus constructs a low-concentration Cl^(−)local microenvironment through the common-ion exclusion effect,which prevents Cl^(−)adsorption and corrosion in the Co active centers,achieving impressive catalytic stability.In addition,the directional charge movement between Fe and Co atomic pairs establishes a local electric field,optimizing the adsorption energy of Co sites for oxygen-containing intermediates,and further improving the ORR activity.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
A Co_(3)O_(4)/BiOBr heterojunction was synthesized via a facile one-step solvothermal method for highly selec-tive photocatalytic CO_(2)reduction.The optimized Co_(3)O_(4)/BiOBr-0.8 catalyst exhibited CO and CH_(4)evo...A Co_(3)O_(4)/BiOBr heterojunction was synthesized via a facile one-step solvothermal method for highly selec-tive photocatalytic CO_(2)reduction.The optimized Co_(3)O_(4)/BiOBr-0.8 catalyst exhibited CO and CH_(4)evolution rates of 112.2 and 5.5µmol·g^(-1)·h^(-1),respectively,representing 6.3-fold and 3.9-fold enhancements over pristine BiOBr.The heterojunction demonstrated broadened light absorption,enhanced photoelectrochemical activity,reduced charge-transfer resistance,and improved separation efficiency of photogenerated carriers(e^(-)/h^(+)).These synergistic effects were attributed to the formation of a Z-scheme heterostructure,which facilitated solar energy utilization and electron reduction capacity while suppressing carrier recombination.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
In the traditional strength reduction method,the cohesion and the friction angle adopt the same reduction parameter,resulting in equivalent proportional reduction.This method does not consider the different effects of...In the traditional strength reduction method,the cohesion and the friction angle adopt the same reduction parameter,resulting in equivalent proportional reduction.This method does not consider the different effects of the cohesion and friction angle on the stability of the same slope and is defective to some extent.Regarding this defect,a strength reduction method based on double reduction parameters,which adopts different reduction parameters,is proposed.The core of the double-parameter reduction method is the matching reduction principle of the slope with different angles.This principle is represented by the ratio of the reduction parameter of the cohesion to that of the friction angle,described as η.With the increase in the slopeangle,ηincreases; in particular,when the slope angle is 45°,tηis 1.0.Through the matching reduction principle,different safety margin factors can be calculated for the cohesion and friction angle.In combination with these two safety margin factors,a formula for calculating the overall safety factor of the slope is proposed,reflecting the different contributions of the cohesion and friction angle to the slope stability.Finally,it is shown that the strength reduction method based on double reduction parameters acquires a larger safety factor than the classic limit equilibrium method,but the calculation results are very close to those obtained by the limit equilibrium method.展开更多
Successfully developed an innovative process of direct reduction of cold bound pellets from iron ore concentrate with a coal based rotary kiln, in comparison with the traditional direct reduction of fired oxide pellet...Successfully developed an innovative process of direct reduction of cold bound pellets from iron ore concentrate with a coal based rotary kiln, in comparison with the traditional direct reduction of fired oxide pellets in coal based rotary kilns , possesses such advantages as: shorter flowsheet, lower capital investment, greater economic profit, good quality of direct reduced iron. The key technologies , such as the composite binder and corresponding feasible techniques were employed in practice. A mill utilizing this process and with an annual capacity of 50 thousand ton DRI has been put into operation.展开更多
The effect of various dosages of dolomites on the reduction swelling property of iron ore pellets was studied. Experimental results show that the reduction swelling index(RSI) decreases from 13.35% to 4.0%, while the ...The effect of various dosages of dolomites on the reduction swelling property of iron ore pellets was studied. Experimental results show that the reduction swelling index(RSI) decreases from 13.35% to 4.0%, while the porosity of roasted pellets increases from 35% to 40% with increasing the dolomite dosage from 0 to 10.5%. Meanwhile, the content of magnesium ferrite with high melting temperature, as well as the stability of magnetite(Fe3 O4) in the roasted pellets, increases with increasing the magnesium oxide(MgO) content from dolomite. The reasons for the decrease of RSI rely on the absence of crystal transformation from Fe2 O3 to Fe3 O4, the increased porosity of roasted pellet, and the suppression of phase transition of 2CaO·SiO2 resulted from the incorporation of magnesium into calcium silicate.展开更多
In the need of some real applications, such as text categorization and image classification, the multi-label learning gradually becomes a hot research point in recent years. Much attention has been paid to the researc...In the need of some real applications, such as text categorization and image classification, the multi-label learning gradually becomes a hot research point in recent years. Much attention has been paid to the research of multi-label classification algorithms. Considering the fact that the high dimensionality of the multi-label datasets may cause the curse of dimensionality and wil hamper the classification process, a dimensionality reduction algorithm, named multi-label kernel discriminant analysis （MLKDA）, is proposed to reduce the dimensionality of multi-label datasets. MLKDA, with the kernel trick, processes the multi-label integrally and realizes the nonlinear dimensionality reduction with the idea similar with linear discriminant analysis （LDA）. In the classification process of multi-label data, the extreme learning machine （ELM） is an efficient algorithm in the premise of good accuracy. MLKDA, combined with ELM, shows a good performance in multi-label learning experiments with several datasets. The experiments on both static data and data stream show that MLKDA outperforms multi-label dimensionality reduction via dependence maximization （MDDM） and multi-label linear discriminant analysis （MLDA） in cases of balanced datasets and stronger correlation between tags, and ELM is also a good choice for multi-label classification.展开更多
Improving vehicle fuel consumption,performance and aerodynamic efficiency by drag reduction especially in heavy vehicles is one of the indispensable issues of automotive industry.In this work,the effects of adding app...Improving vehicle fuel consumption,performance and aerodynamic efficiency by drag reduction especially in heavy vehicles is one of the indispensable issues of automotive industry.In this work,the effects of adding append devices like deflector and cab vane corner on heavy commercial vehicle drag reduction were investigated.For this purpose,the vehicle body structure was modeled with various supplementary parts at the first stage.Then,computational fluid dynamic(CFD) analysis was utilized for each case to enhance the optimal aerodynamic structure at different longitudinal speeds for heavy commercial vehicles.The results show that the most effective supplementary part is deflector,and by adding this part,the drag coefficient is decreased considerably at an optimum angle.By adding two cab vane corners at both frontal edges of cab,a significant drag reduction is noticed.Back vanes and base flaps are simple plates which can be added at the top and side end of container and at the bottom with specific angle respectively to direct the flow and prevent the turbulence.Through the analysis of airflow and pressure distribution,the results reveal that the cab vane reduces fuel consumption and drag coefficient by up to 20 % receptively using proper deflector angle.Finally,by adding all supplementary parts at their optimized positions,41% drag reduction is obtained compared to the simple model.展开更多
Considering the rheological properties of rock and soil body,and exploiting the merit of strength reduction technique,a theory of couple analysis is brought forward on the basis of strength reduction theory and rheolo...Considering the rheological properties of rock and soil body,and exploiting the merit of strength reduction technique,a theory of couple analysis is brought forward on the basis of strength reduction theory and rheological properties.Then,the concept and the calculation procedure of the safety factor are established at different time.Making use of finite element software ANSYS,the most dangerous sliding surface of the slope can be obtained through the strength reduction technique.According to the dynamic safety factor based on rheological mechanism,a good forecasting could be presented to prevent and cure the landslide.The result shows that the couple analysis reveals the process of the slope failure with the time and the important influence on the long-term stability due to the rheological parameters.展开更多
This paper focuses on fast algorithm for computing the assignment reduct in inconsistent incomplete decision systems. It is quite inconvenient to judge the assignment reduct directly ac-cording to its definition. We p...This paper focuses on fast algorithm for computing the assignment reduct in inconsistent incomplete decision systems. It is quite inconvenient to judge the assignment reduct directly ac-cording to its definition. We propose the judgment theorem for the assignment reduct in the inconsistent incomplete decision system, which greatly simplifies judging this type reduct. On such basis, we derive a novel attribute significance measure and construct the fast assignment reduction algorithm （F-ARA）, intended for com-puting the assignment reduct in inconsistent incomplete decision systems. Final y, we make a comparison between F-ARA and the discernibility matrix-based method by experiments on 13 Univer-sity of California at Irvine （UCI） datasets, and the experimental results prove that F-ARA is efficient and feasible.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the National Key Research and Development Program of China(2022YFB4004100)National Natural Science Foundation of China(22272161,22179126)+1 种基金the Jilin Province Science and Technology Development Program(YDZJ202202CXJD011,20240101019JC)Jilin Province major science and technology project(222648GX0105103875)for financial supports.
文摘The weak adsorption energy of oxygen-containing intermediates on Co center leads to a considerable performance dis-parity between Co-N-C and costly Pt benchmark in catalyzing oxygen reduction reaction(ORR).In this work,we strategi-cally engineer the active site structure of Co-N-C via B substitution,which is accomplished by the pyrolysis of ammonium borate.During this process,the in-situ generated NH_(3)gas plays a critical role in creating surface defects and boron atoms substituting nitrogen atoms in the carbon structure.The well-designed CoB_(1)N_(3)active site endows Co with higher charge density and stronger adsorption energy toward oxygen species,potentially accelerating ORR kinetics.As expected,the resulting Co-B/N-C catalyst exhibited superior ORR performance over Co-N-C counterpart,with 40 mV,and fivefold en-hancement in half-wave potential and turnover frequency(TOF).More importantly,the excellent ORR performance could be translated into membrane electrode assembly(MEA)in a fuel cell test,delivering an impressive peak power density of 824 mW·cm^(-2),which is currently the best among Co-based catalysts under the same conditions.This work not only demon-strates an effective method for designing advanced catalysts,but also affords a highly promising non-precious metal ORR electrocatalyst for fuel cell applications.
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 National Natural Science Foundation of China(52164028,52274297)the Start-up Research Foundation of Hainan University(KYQD(ZR)20008,KYQD(ZR)21125,KYQD(ZR)23169))+1 种基金Collaborative Innovation Center of Marine Science and Technology of Hainan University(XTCX2022HYC14)Innovative Research Project for Postgraduate Students in Hainan Province(Qhyb2024-95).
文摘Development of robust electrocatalyst for oxygen reduction reaction(ORR)in a seawater electrolyte is the key to realize seawater electrolyte-based zinc-air batteries(SZABs).Herein,constructing a local electric field coupled with chloride ions(Cl-)fixation strategy in dual single-atom catalysts(DSACs)was proposed,and the resultant catalyst delivered considerable ORR performance in a seawater electrolyte,with a high half-wave potential(E_(1/2))of 0.868 V and a good maximum power density(Pmax)of 182 mW·cm^(−2)in the assembled SZABs,much higher than those of the Pt/C catalyst(E_(1/2):0.846 V;Pmax:150 mW·cm^(−2)).The in-situ characterization and theoretical calculations revealed that the Fe sites have a higher Cl^(−)adsorption affinity than the Co sites,and preferentially adsorbs Cl^(−)in a seawater electrolyte during the ORR process,and thus constructs a low-concentration Cl^(−)local microenvironment through the common-ion exclusion effect,which prevents Cl^(−)adsorption and corrosion in the Co active centers,achieving impressive catalytic stability.In addition,the directional charge movement between Fe and Co atomic pairs establishes a local electric field,optimizing the adsorption energy of Co sites for oxygen-containing intermediates,and further improving the ORR activity.
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A Co_(3)O_(4)/BiOBr heterojunction was synthesized via a facile one-step solvothermal method for highly selec-tive photocatalytic CO_(2)reduction.The optimized Co_(3)O_(4)/BiOBr-0.8 catalyst exhibited CO and CH_(4)evolution rates of 112.2 and 5.5µmol·g^(-1)·h^(-1),respectively,representing 6.3-fold and 3.9-fold enhancements over pristine BiOBr.The heterojunction demonstrated broadened light absorption,enhanced photoelectrochemical activity,reduced charge-transfer resistance,and improved separation efficiency of photogenerated carriers(e^(-)/h^(+)).These synergistic effects were attributed to the formation of a Z-scheme heterostructure,which facilitated solar energy utilization and electron reduction capacity while suppressing carrier recombination.
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Project(KZCX2-YW-T12)supported by the Chinese Academy of Science,China
文摘In the traditional strength reduction method,the cohesion and the friction angle adopt the same reduction parameter,resulting in equivalent proportional reduction.This method does not consider the different effects of the cohesion and friction angle on the stability of the same slope and is defective to some extent.Regarding this defect,a strength reduction method based on double reduction parameters,which adopts different reduction parameters,is proposed.The core of the double-parameter reduction method is the matching reduction principle of the slope with different angles.This principle is represented by the ratio of the reduction parameter of the cohesion to that of the friction angle,described as η.With the increase in the slopeangle,ηincreases; in particular,when the slope angle is 45°,tηis 1.0.Through the matching reduction principle,different safety margin factors can be calculated for the cohesion and friction angle.In combination with these two safety margin factors,a formula for calculating the overall safety factor of the slope is proposed,reflecting the different contributions of the cohesion and friction angle to the slope stability.Finally,it is shown that the strength reduction method based on double reduction parameters acquires a larger safety factor than the classic limit equilibrium method,but the calculation results are very close to those obtained by the limit equilibrium method.
基金The Key Project of the 9th Five year Plan of Ministry of Science andTechnology!(No .960 40 2 0 2A)the Foundation for Unive
文摘Successfully developed an innovative process of direct reduction of cold bound pellets from iron ore concentrate with a coal based rotary kiln, in comparison with the traditional direct reduction of fired oxide pellets in coal based rotary kilns , possesses such advantages as: shorter flowsheet, lower capital investment, greater economic profit, good quality of direct reduced iron. The key technologies , such as the composite binder and corresponding feasible techniques were employed in practice. A mill utilizing this process and with an annual capacity of 50 thousand ton DRI has been put into operation.
基金Project(50725416) supported by the National Natural Science for Distinguished Young Scholars of China
文摘The effect of various dosages of dolomites on the reduction swelling property of iron ore pellets was studied. Experimental results show that the reduction swelling index(RSI) decreases from 13.35% to 4.0%, while the porosity of roasted pellets increases from 35% to 40% with increasing the dolomite dosage from 0 to 10.5%. Meanwhile, the content of magnesium ferrite with high melting temperature, as well as the stability of magnetite(Fe3 O4) in the roasted pellets, increases with increasing the magnesium oxide(MgO) content from dolomite. The reasons for the decrease of RSI rely on the absence of crystal transformation from Fe2 O3 to Fe3 O4, the increased porosity of roasted pellet, and the suppression of phase transition of 2CaO·SiO2 resulted from the incorporation of magnesium into calcium silicate.
基金supported by the National Natural Science Foundation of China(5110505261173163)the Liaoning Provincial Natural Science Foundation of China(201102037)
文摘In the need of some real applications, such as text categorization and image classification, the multi-label learning gradually becomes a hot research point in recent years. Much attention has been paid to the research of multi-label classification algorithms. Considering the fact that the high dimensionality of the multi-label datasets may cause the curse of dimensionality and wil hamper the classification process, a dimensionality reduction algorithm, named multi-label kernel discriminant analysis （MLKDA）, is proposed to reduce the dimensionality of multi-label datasets. MLKDA, with the kernel trick, processes the multi-label integrally and realizes the nonlinear dimensionality reduction with the idea similar with linear discriminant analysis （LDA）. In the classification process of multi-label data, the extreme learning machine （ELM） is an efficient algorithm in the premise of good accuracy. MLKDA, combined with ELM, shows a good performance in multi-label learning experiments with several datasets. The experiments on both static data and data stream show that MLKDA outperforms multi-label dimensionality reduction via dependence maximization （MDDM） and multi-label linear discriminant analysis （MLDA） in cases of balanced datasets and stronger correlation between tags, and ELM is also a good choice for multi-label classification.
文摘Improving vehicle fuel consumption,performance and aerodynamic efficiency by drag reduction especially in heavy vehicles is one of the indispensable issues of automotive industry.In this work,the effects of adding append devices like deflector and cab vane corner on heavy commercial vehicle drag reduction were investigated.For this purpose,the vehicle body structure was modeled with various supplementary parts at the first stage.Then,computational fluid dynamic(CFD) analysis was utilized for each case to enhance the optimal aerodynamic structure at different longitudinal speeds for heavy commercial vehicles.The results show that the most effective supplementary part is deflector,and by adding this part,the drag coefficient is decreased considerably at an optimum angle.By adding two cab vane corners at both frontal edges of cab,a significant drag reduction is noticed.Back vanes and base flaps are simple plates which can be added at the top and side end of container and at the bottom with specific angle respectively to direct the flow and prevent the turbulence.Through the analysis of airflow and pressure distribution,the results reveal that the cab vane reduces fuel consumption and drag coefficient by up to 20 % receptively using proper deflector angle.Finally,by adding all supplementary parts at their optimized positions,41% drag reduction is obtained compared to the simple model.
文摘Considering the rheological properties of rock and soil body,and exploiting the merit of strength reduction technique,a theory of couple analysis is brought forward on the basis of strength reduction theory and rheological properties.Then,the concept and the calculation procedure of the safety factor are established at different time.Making use of finite element software ANSYS,the most dangerous sliding surface of the slope can be obtained through the strength reduction technique.According to the dynamic safety factor based on rheological mechanism,a good forecasting could be presented to prevent and cure the landslide.The result shows that the couple analysis reveals the process of the slope failure with the time and the important influence on the long-term stability due to the rheological parameters.
基金supported by the National Natural Science Foundation of China(61363047)the Jiangxi Education Department(GJJ13760)the Science and Technology Support Foundation of Jiangxi Province(20111BBE50008)
文摘This paper focuses on fast algorithm for computing the assignment reduct in inconsistent incomplete decision systems. It is quite inconvenient to judge the assignment reduct directly ac-cording to its definition. We propose the judgment theorem for the assignment reduct in the inconsistent incomplete decision system, which greatly simplifies judging this type reduct. On such basis, we derive a novel attribute significance measure and construct the fast assignment reduction algorithm （F-ARA）, intended for com-puting the assignment reduct in inconsistent incomplete decision systems. Final y, we make a comparison between F-ARA and the discernibility matrix-based method by experiments on 13 Univer-sity of California at Irvine （UCI） datasets, and the experimental results prove that F-ARA is efficient and feasible.
