The surface properties of catalysts determine the intrinsic activity and adaptability.Ruthenium is regarded as a potential candidate to substitute platinum for water electrolysis due to the low cost and analogous elec...The surface properties of catalysts determine the intrinsic activity and adaptability.Ruthenium is regarded as a potential candidate to substitute platinum for water electrolysis due to the low cost and analogous electronic structures while it suffers from severe dissolution and stability problems.Herein,the modification of Ru/C with atomically dispersed cobalt atoms is achieved via a simple thermal doping method.The newly formed amorphous shell with Ru-Co sites on the Ru/C catalyst improved the hydrogen evolution reaction activity and stability significantly.Impressively,the obtained Co1Ru@Ru/CN_(x)catalyst exhibited an overpotential as low as 30 mV at 10 mA cm^(-2)in an alkaline medium,which is among the best HER catalysts reported so far.The oxygen oxophile Co prevents the fast oxidation and dissolution of Ru species,ensuring outstanding long-term durability up to 70 h.Theoretical calculations reveal that the Ru-Co coordination acts as a more active site for water dissociation than the Ru-Ru.Meanwhile,the"Ru-Co shell/Ru core"structures show high adaptability for the reaction conditions.This simple doping strategy offers prospects for scalable preparation of highly active electrocatalysts.展开更多
The method to combine thermoelectric(TE)and magnetocaloric(MC)cooling techniques lies in developing a new material that simultaneously possesses a large TE and good MC cooling performance.In this work,using n-type Bi_...The method to combine thermoelectric(TE)and magnetocaloric(MC)cooling techniques lies in developing a new material that simultaneously possesses a large TE and good MC cooling performance.In this work,using n-type Bi_(2)Te_(2.7)Se_(0.3)(BTS)as the TE base material and Gd as the second-phase MC material,Gd/BTS composites were prepared by the spark plasma sintering method.In the composites,interfacial reaction between Gd and BTS was identified,resulting in the formation of Gd Te,which has a large impact on the electron concentration through the adjustment of defect concentration.The MC/TE composite containing 2.5 wt%Gd exhibited a ZT value of 0.6 at 300 K,essentially retaining the original TE performance,while all the composites largely maintained the excellent MC performance of Gd.This work provides a potential pathway to achieving high performance in MC/TE composites.展开更多
Multi-orifice cross-flow jet mixers(MOCJMs)are used in various industrial applications due to their excellent mixing efficiency,but few studies have focused on the micromixing performance of MOCJMs.Herein,the flow cha...Multi-orifice cross-flow jet mixers(MOCJMs)are used in various industrial applications due to their excellent mixing efficiency,but few studies have focused on the micromixing performance of MOCJMs.Herein,the flow characteristics and micromixing performance inside the MOCJM were investigated using experiments and computational fluid dynamics(CFD)simulations based on the Villermaux/Dushman system and the finite-rate/modified eddy-dissipation model.The optimal A value was correlated with the characteristic parameters of MOCJMs to develop a CFD calculation method applicable to the study of the micromixing performance of the MOCJMs.Then the micromixing efficiency was evaluated using the segregation index XS,and the effects of operational and geometric parameters such as mixing flow Reynolds number(ReM),flow ratio(RF),total jet area(ST),the number of jet orifices(n),and outlet configuration on the micromixing efficiency were investigated.It was found that the intensive turbulent region generated by interactions between jets,as well as between jets and crossflows,facilitated rapid reactions.XS decreased with increasing ReM and decreasing RF.Furthermore,MOCJMs with lower ST,four jet orifices,and the narrower outlet configuration demonstrated a better micromixing efficiency.This study contributes to a deeper understanding of the micromixing performance of MOCJMs and provides valuable guidance for their design,optimization,and industrial application.展开更多
A systematic study was conducted to comprehend the mechanism of thermal activation of silica-alumina materials by using ^29Si and ^27Al magnetic angle spinning nuclear magnetic resonance （MAS NMR） spectroscopy. The ...A systematic study was conducted to comprehend the mechanism of thermal activation of silica-alumina materials by using ^29Si and ^27Al magnetic angle spinning nuclear magnetic resonance （MAS NMR） spectroscopy. The reaction performance of silica-alumina-based materials with different molar ratios of Si/Al, which were thermally activated, was also investigated. With the increase in calcining temperature, the coordination of Al in metakaolin becomes four, five, and six firstly, and then transforms completely to four and six. It is indicated by identical coupled plasma optical emission spectroscopy （ICP） and NMR that, the reaction performance of monomeric silicate anions is better than that of polymeric silicate anions which are primarily cross-linked in the alkali solution. Moreover, it also shows that the thermal activation temperature, cooling method, and the molar ratio of Na/Ca have remarkable effects on the reaction performance.展开更多
Oxygen reduction reaction(ORR)is the key reaction at the cathode of proton exchange membrane fuel cells(PEMFCs)and metal-air batteries(1)To address the challenges associated with Pt-based electrocatalysts having promi...Oxygen reduction reaction(ORR)is the key reaction at the cathode of proton exchange membrane fuel cells(PEMFCs)and metal-air batteries(1)To address the challenges associated with Pt-based electrocatalysts having prominent activity for ORR,e.g.scarce abundance,prohibitive cost,poor stability,and vulnerability to reaction intermediates,it is necessary to explore other cost-effective ORR electrocatalysts with competitive or even superior performance to promote the commercialization of the energy conversion devices.展开更多
Ag3PO4 microcrystals with highly enhanced visible light photocatalytic activity are prepared by a facile and simple solid state reaction at room temperature. The composition, morphology and optical properties of the a...Ag3PO4 microcrystals with highly enhanced visible light photocatalytic activity are prepared by a facile and simple solid state reaction at room temperature. The composition, morphology and optical properties of the asprepared Ag3PO4 microcrystMs are characterized by x-ray diffraction, scanning electron microscopy and UV-vis diffuse reflectance spectra. The photocatalytie properties of Ag3PO4 are investigated by the degradation of both methylene blue and methyl orange dyes under visible light irradiation. The as-prepared Ag3PO4 microcrystals possess high photocatalytic oxygen production with the rate of 673μmolh-1g-1. Moreover, the as-prepared Ag3PO4 microcrystals show an enhanced photoelectrochemistry performance under irradiation of visible light.展开更多
Reducing the cost and improving the electrocatalytic activity are the key to developing high efficiency electrocatalysts for oxygen evolution reaction(OER).Here,bimetallic NiFe-based metal-organic framework(MOF)was pr...Reducing the cost and improving the electrocatalytic activity are the key to developing high efficiency electrocatalysts for oxygen evolution reaction(OER).Here,bimetallic NiFe-based metal-organic framework(MOF)was prepared by solvothermal method,and then used as precursor to prepare NiFe-based MOF-derived materials by pyrolysis.The effects of different metal ratios and pyrolysis temperatures on the sample structure and OER electrocatalytic performance were investigated and compared.The experimental results showed that when the metal molar ratio was Fe:Ni=1:5 and the pyrolysis temperature was 450℃,the sample(FeNi_(5)-MOF-450)exhibits a composite structure of Ni Fe_(2)O_(4)/FeNi_(3)/C and owns the superior electrocatalytic activity in OER.When the current density is 100 mA·cm^(-2),the overpotential of the sample was 377 mV with Tafel slope of 56.2 mV·dec^(-1),which indicates that FeNi_(5)-MOF-450 exhibits superior electrocatalytic performance than the commercial RuO_(2).Moreover,the long-term stability of FeNi_(5)-MOF-450 further promotes its development in OER.This work demonstrated that the regulatory methods such as component optimization can effectively improve the OER catalytic performance of NiFe-based MOF-derived materials.展开更多
Replacing fossil fuels with fuel cells is a feasible way to reduce global energy shortages and environmental pollution.However,the oxygen reduction reaction(ORR)at the cathode has sluggish kinetics,which limits the de...Replacing fossil fuels with fuel cells is a feasible way to reduce global energy shortages and environmental pollution.However,the oxygen reduction reaction(ORR)at the cathode has sluggish kinetics,which limits the development of fuel cells.It is significant to develop catalysts with high catalytic activity of ORR.The single-atom catalysts(SACs)of Pt supported on heteroatom-doped graphene are potential candidates for ORR.Here we studied the SACs of Pt with different heteroatoms doping and screened out Pt-C_(4) and Pt-C_(3)O_(1) structures with only 0.13 V overpotential for ORR.Meanwhile,it is found that B atoms doping could weaken the adsorption capacity of Pt,while N or O atoms doping could enhance it.This regularity was verified on Fe SACs.Through the electronic interaction analysis between Pt and adsorbate,we explained the mechanism of this regularity and further proposed a new descriptor named corrected d-band center(ε_(d-corr))to describe it.This descriptor is an appropriate reflection of the number of free electrons of the SACs,which could evaluate its adsorption capacity.Our work provides a purposeful regulatory strategy for the design of ORR catalysts.展开更多
The global practical implementation of proton exchange membrane fuel cells(PEMFCs)heavily relies on the advancement of highly effective platinum(Pt)-based electrocatalysts for the oxygen reduction reaction(ORR).To ach...The global practical implementation of proton exchange membrane fuel cells(PEMFCs)heavily relies on the advancement of highly effective platinum(Pt)-based electrocatalysts for the oxygen reduction reaction(ORR).To achieve high ORR performance,electrocatalysts with highly accessible reactive surfaces are needed to promote the uncovering of active positions for easy mass transportation.In this critical review,we introduce different approaches for the emerging development of effective ORR electrocatalysts,which offer high activity and durability.The strategies,including morphological engineering,geometric configuration modification via supporting materials,alloys regulation,core-shell,and confinement engineering of single atom electrocatalysts(SAEs),are discussed in line with the goals and requirements of ORR performance enhancement.We review the ongoing development of Pt electrocatalysts based on the syntheses,nanoarchitecture,electrochemical performances,and stability.We eventually explore the obstacles and research directions on further developing more effective electrocatalysts.展开更多
基金support from the National Natural Science Foundation of China(21802120,21872121,and 21908189)the National Key R&D Program of China(2016YFA0202900)+3 种基金the Key R&D Project of Zhejiang Province(2020C01133)the Fundamental Research Funds for the Central Universities(G2019KY05119)the China Postdoctoral Science Foundation(2021 M692634)the Natural Science Basic Research Program of Shaanxi Province(2022JQ-118)are greatly appreciated.
文摘The surface properties of catalysts determine the intrinsic activity and adaptability.Ruthenium is regarded as a potential candidate to substitute platinum for water electrolysis due to the low cost and analogous electronic structures while it suffers from severe dissolution and stability problems.Herein,the modification of Ru/C with atomically dispersed cobalt atoms is achieved via a simple thermal doping method.The newly formed amorphous shell with Ru-Co sites on the Ru/C catalyst improved the hydrogen evolution reaction activity and stability significantly.Impressively,the obtained Co1Ru@Ru/CN_(x)catalyst exhibited an overpotential as low as 30 mV at 10 mA cm^(-2)in an alkaline medium,which is among the best HER catalysts reported so far.The oxygen oxophile Co prevents the fast oxidation and dissolution of Ru species,ensuring outstanding long-term durability up to 70 h.Theoretical calculations reveal that the Ru-Co coordination acts as a more active site for water dissociation than the Ru-Ru.Meanwhile,the"Ru-Co shell/Ru core"structures show high adaptability for the reaction conditions.This simple doping strategy offers prospects for scalable preparation of highly active electrocatalysts.
基金Project supported by the National Key Research and Development Program of China (Grant Nos.2019YFA0704900 and 2023YFB3809400)the National Natural Science Foundation of China (Grant Nos.52130203 and 52172232)the Basic and Applied Basic Research Foundation of Guangdong Province (Grant No.2022B1515120005)。
文摘The method to combine thermoelectric(TE)and magnetocaloric(MC)cooling techniques lies in developing a new material that simultaneously possesses a large TE and good MC cooling performance.In this work,using n-type Bi_(2)Te_(2.7)Se_(0.3)(BTS)as the TE base material and Gd as the second-phase MC material,Gd/BTS composites were prepared by the spark plasma sintering method.In the composites,interfacial reaction between Gd and BTS was identified,resulting in the formation of Gd Te,which has a large impact on the electron concentration through the adjustment of defect concentration.The MC/TE composite containing 2.5 wt%Gd exhibited a ZT value of 0.6 at 300 K,essentially retaining the original TE performance,while all the composites largely maintained the excellent MC performance of Gd.This work provides a potential pathway to achieving high performance in MC/TE composites.
基金the financial support from the Shanghai Sailing Program,China(21YF1409500)the National Natural Science Foundation of China(22308100,22308105)+1 种基金the State Key Laboratory of Chemical Engineering(SKL-ChE-23Z01)the National Science Fund for Distinguished Young Scholars of China(22225804).
文摘Multi-orifice cross-flow jet mixers(MOCJMs)are used in various industrial applications due to their excellent mixing efficiency,but few studies have focused on the micromixing performance of MOCJMs.Herein,the flow characteristics and micromixing performance inside the MOCJM were investigated using experiments and computational fluid dynamics(CFD)simulations based on the Villermaux/Dushman system and the finite-rate/modified eddy-dissipation model.The optimal A value was correlated with the characteristic parameters of MOCJMs to develop a CFD calculation method applicable to the study of the micromixing performance of the MOCJMs.Then the micromixing efficiency was evaluated using the segregation index XS,and the effects of operational and geometric parameters such as mixing flow Reynolds number(ReM),flow ratio(RF),total jet area(ST),the number of jet orifices(n),and outlet configuration on the micromixing efficiency were investigated.It was found that the intensive turbulent region generated by interactions between jets,as well as between jets and crossflows,facilitated rapid reactions.XS decreased with increasing ReM and decreasing RF.Furthermore,MOCJMs with lower ST,four jet orifices,and the narrower outlet configuration demonstrated a better micromixing efficiency.This study contributes to a deeper understanding of the micromixing performance of MOCJMs and provides valuable guidance for their design,optimization,and industrial application.
基金supported by the National Key Technologies R&D Program of China (No.2006BAC21B03)the National Natural Science Foundation of China (No.50674062)
文摘A systematic study was conducted to comprehend the mechanism of thermal activation of silica-alumina materials by using ^29Si and ^27Al magnetic angle spinning nuclear magnetic resonance （MAS NMR） spectroscopy. The reaction performance of silica-alumina-based materials with different molar ratios of Si/Al, which were thermally activated, was also investigated. With the increase in calcining temperature, the coordination of Al in metakaolin becomes four, five, and six firstly, and then transforms completely to four and six. It is indicated by identical coupled plasma optical emission spectroscopy （ICP） and NMR that, the reaction performance of monomeric silicate anions is better than that of polymeric silicate anions which are primarily cross-linked in the alkali solution. Moreover, it also shows that the thermal activation temperature, cooling method, and the molar ratio of Na/Ca have remarkable effects on the reaction performance.
文摘Oxygen reduction reaction(ORR)is the key reaction at the cathode of proton exchange membrane fuel cells(PEMFCs)and metal-air batteries(1)To address the challenges associated with Pt-based electrocatalysts having prominent activity for ORR,e.g.scarce abundance,prohibitive cost,poor stability,and vulnerability to reaction intermediates,it is necessary to explore other cost-effective ORR electrocatalysts with competitive or even superior performance to promote the commercialization of the energy conversion devices.
基金Supported by the Beijing Higher Education Young Elite Teacher Project under Grant No YETP1297the Fundamental Research Funds for the Central Universities under Grant No 2014MDLXYZY05+1 种基金the Undergraduate Innovative Test Program of China under Grant Nos GCCX2015110009 and BEIJ2015110024the National Natural Science Foundation of China under Grant Nos11074312 and 11374377
文摘Ag3PO4 microcrystals with highly enhanced visible light photocatalytic activity are prepared by a facile and simple solid state reaction at room temperature. The composition, morphology and optical properties of the asprepared Ag3PO4 microcrystMs are characterized by x-ray diffraction, scanning electron microscopy and UV-vis diffuse reflectance spectra. The photocatalytie properties of Ag3PO4 are investigated by the degradation of both methylene blue and methyl orange dyes under visible light irradiation. The as-prepared Ag3PO4 microcrystals possess high photocatalytic oxygen production with the rate of 673μmolh-1g-1. Moreover, the as-prepared Ag3PO4 microcrystals show an enhanced photoelectrochemistry performance under irradiation of visible light.
基金supported by the Shandong Natural Science Fund (No.ZR2020KB010)the Fundamental Research Funds for the Central Universities (No.22CX 07010A)。
文摘Reducing the cost and improving the electrocatalytic activity are the key to developing high efficiency electrocatalysts for oxygen evolution reaction(OER).Here,bimetallic NiFe-based metal-organic framework(MOF)was prepared by solvothermal method,and then used as precursor to prepare NiFe-based MOF-derived materials by pyrolysis.The effects of different metal ratios and pyrolysis temperatures on the sample structure and OER electrocatalytic performance were investigated and compared.The experimental results showed that when the metal molar ratio was Fe:Ni=1:5 and the pyrolysis temperature was 450℃,the sample(FeNi_(5)-MOF-450)exhibits a composite structure of Ni Fe_(2)O_(4)/FeNi_(3)/C and owns the superior electrocatalytic activity in OER.When the current density is 100 mA·cm^(-2),the overpotential of the sample was 377 mV with Tafel slope of 56.2 mV·dec^(-1),which indicates that FeNi_(5)-MOF-450 exhibits superior electrocatalytic performance than the commercial RuO_(2).Moreover,the long-term stability of FeNi_(5)-MOF-450 further promotes its development in OER.This work demonstrated that the regulatory methods such as component optimization can effectively improve the OER catalytic performance of NiFe-based MOF-derived materials.
基金supported by the National Key R&D Program of China(Nos.2022YFA1503100 and 2022YFA1503102)the National Natural Science Foundation of China(No.22273050)the Natural Science Foundation of Shandong Province(Nos.YDZX2021001 and ZR2022MB098).
文摘Replacing fossil fuels with fuel cells is a feasible way to reduce global energy shortages and environmental pollution.However,the oxygen reduction reaction(ORR)at the cathode has sluggish kinetics,which limits the development of fuel cells.It is significant to develop catalysts with high catalytic activity of ORR.The single-atom catalysts(SACs)of Pt supported on heteroatom-doped graphene are potential candidates for ORR.Here we studied the SACs of Pt with different heteroatoms doping and screened out Pt-C_(4) and Pt-C_(3)O_(1) structures with only 0.13 V overpotential for ORR.Meanwhile,it is found that B atoms doping could weaken the adsorption capacity of Pt,while N or O atoms doping could enhance it.This regularity was verified on Fe SACs.Through the electronic interaction analysis between Pt and adsorbate,we explained the mechanism of this regularity and further proposed a new descriptor named corrected d-band center(ε_(d-corr))to describe it.This descriptor is an appropriate reflection of the number of free electrons of the SACs,which could evaluate its adsorption capacity.Our work provides a purposeful regulatory strategy for the design of ORR catalysts.
基金A.A.,G.H.,S.H.,A.L.,and X.Y.J.thank the financial support from Kempe Foundation(SMK21-0011,SMK21-0020)A.L.acknowledges Swedish Research Council(2019-03865)European Union’s Horizon Europe research and innovation program under grant agreement No.101086667.X.Y.J.thanks the financial support from Horizon-EIC and Pathfinder challenges,Grant Number:101070976.
文摘The global practical implementation of proton exchange membrane fuel cells(PEMFCs)heavily relies on the advancement of highly effective platinum(Pt)-based electrocatalysts for the oxygen reduction reaction(ORR).To achieve high ORR performance,electrocatalysts with highly accessible reactive surfaces are needed to promote the uncovering of active positions for easy mass transportation.In this critical review,we introduce different approaches for the emerging development of effective ORR electrocatalysts,which offer high activity and durability.The strategies,including morphological engineering,geometric configuration modification via supporting materials,alloys regulation,core-shell,and confinement engineering of single atom electrocatalysts(SAEs),are discussed in line with the goals and requirements of ORR performance enhancement.We review the ongoing development of Pt electrocatalysts based on the syntheses,nanoarchitecture,electrochemical performances,and stability.We eventually explore the obstacles and research directions on further developing more effective electrocatalysts.
