The oxygen evolution reaction(OER)activity of single-atom catalysts(SACs)is closely related to the coordination environment of the active site.Oxygencoordinated atomic metal species bring about unique features beyond ...The oxygen evolution reaction(OER)activity of single-atom catalysts(SACs)is closely related to the coordination environment of the active site.Oxygencoordinated atomic metal species bring about unique features beyond nitrogen-coordinated atomic metal species due to the fact that the M-O bond is weaker than the M-N bond.Herein,a series of metal-oxygen-carbon structured low-nucleus clusters(LNCs)are successfully anchored on the surface of multiwalled carbon nanotubes(M-MWCNTs,M=Ni,Co,or Fe)through a foolproof low-temperature gas transfer(300℃)method without any further treatment.The morphology and coordination configuration of the LNCs at the atomic level were confirmed by comprehensive characterizations.The synthetic Ni-MWCNTs electrocatalyst features excellent OER activity and stability under alkaline conditions,transcending the performances of Co-MWCNTs,Fe-MWCNTs and RuO_(2).Density functional theory calculations reveal that the moderate oxidation of low-nucleus Ni clusters changes the unoccupied orbital of Ni atoms,thereby lowering the energy barrier of the OER rate-limiting step and making the OER process more energy-efficient.This study demonstrates a novel versatile platform for large-scale manufacturing of oxygen-coordinated LNC catalysts.展开更多
In extreme cold regions,a thermal insulation layer(TIL)is commonly employed to mitigate the detrimental effects of frost heaving forces in tunnels.Optimizing the laying scheme of TIL,specifically minimizing frost heav...In extreme cold regions,a thermal insulation layer(TIL)is commonly employed to mitigate the detrimental effects of frost heaving forces in tunnels.Optimizing the laying scheme of TIL,specifically minimizing frost heaving forces,holds considerable importance in the prevention of frost damage.This research developed a two-dimensional unsteady temperature field of circular tunnels by using the difference method(taking the off-wall laying method as an example)based on the law of conservation of energy.Then,the frozen circle and water migration coefficient were introduced to establish the relationship between the temperature field and frost heaving forces,and a reliable methodology for calculating these forces under the specific conditions of TIL installation was developed.Then(i)the influence of the air layer thickness of the off-wall laying method,(ii)different laying methods of TIL,(iii)the TIL thickness,(iv)the thermal conductivity of the TIL,and(v)the freeze-thaw cycles on the frost heaving force were investigated.The results showed that the frost heaving force served as a reliable and effective metric for evaluating the insulation effect in tunnels.In order to avoid frost damage in compliance with the design requirements,the insulation effects from various laying methods were established,in descending efficacy order as follows:off-wall laying,double layer laying,surface laying,and sandwich laying.Our findings revealed that the optimal thickness for the air layer in the offwall laying method was 0.10 m.The insulation effect of materials with a thermal conductivity below 0.047 W/(m·℃)was furthermore found to be good.Under freeze-thaw cycle conditions,it is concluded that to prevent frost damage,the TIL thickness should be the sum of the thickness r1 of the first freeze-thaw cycle without frost heaving forces and an additional reserve value 0.06r1 of the TIL thickness.展开更多
基金Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang,Grant/Award Number:2019R01006National Key R&D Program of China,Grant/Award Number:2018YFB0104300。
文摘The oxygen evolution reaction(OER)activity of single-atom catalysts(SACs)is closely related to the coordination environment of the active site.Oxygencoordinated atomic metal species bring about unique features beyond nitrogen-coordinated atomic metal species due to the fact that the M-O bond is weaker than the M-N bond.Herein,a series of metal-oxygen-carbon structured low-nucleus clusters(LNCs)are successfully anchored on the surface of multiwalled carbon nanotubes(M-MWCNTs,M=Ni,Co,or Fe)through a foolproof low-temperature gas transfer(300℃)method without any further treatment.The morphology and coordination configuration of the LNCs at the atomic level were confirmed by comprehensive characterizations.The synthetic Ni-MWCNTs electrocatalyst features excellent OER activity and stability under alkaline conditions,transcending the performances of Co-MWCNTs,Fe-MWCNTs and RuO_(2).Density functional theory calculations reveal that the moderate oxidation of low-nucleus Ni clusters changes the unoccupied orbital of Ni atoms,thereby lowering the energy barrier of the OER rate-limiting step and making the OER process more energy-efficient.This study demonstrates a novel versatile platform for large-scale manufacturing of oxygen-coordinated LNC catalysts.
基金the financial support provided by the National Natural Science Foundation of China(Nos.52078061,51878074)the Huaihua University Scientific Research Project,China(No.HHUY 2022-26)+1 种基金the Postgraduate Research and Innovation-funded Project of Hunan Province,China(No.CX20220885)。
文摘In extreme cold regions,a thermal insulation layer(TIL)is commonly employed to mitigate the detrimental effects of frost heaving forces in tunnels.Optimizing the laying scheme of TIL,specifically minimizing frost heaving forces,holds considerable importance in the prevention of frost damage.This research developed a two-dimensional unsteady temperature field of circular tunnels by using the difference method(taking the off-wall laying method as an example)based on the law of conservation of energy.Then,the frozen circle and water migration coefficient were introduced to establish the relationship between the temperature field and frost heaving forces,and a reliable methodology for calculating these forces under the specific conditions of TIL installation was developed.Then(i)the influence of the air layer thickness of the off-wall laying method,(ii)different laying methods of TIL,(iii)the TIL thickness,(iv)the thermal conductivity of the TIL,and(v)the freeze-thaw cycles on the frost heaving force were investigated.The results showed that the frost heaving force served as a reliable and effective metric for evaluating the insulation effect in tunnels.In order to avoid frost damage in compliance with the design requirements,the insulation effects from various laying methods were established,in descending efficacy order as follows:off-wall laying,double layer laying,surface laying,and sandwich laying.Our findings revealed that the optimal thickness for the air layer in the offwall laying method was 0.10 m.The insulation effect of materials with a thermal conductivity below 0.047 W/(m·℃)was furthermore found to be good.Under freeze-thaw cycle conditions,it is concluded that to prevent frost damage,the TIL thickness should be the sum of the thickness r1 of the first freeze-thaw cycle without frost heaving forces and an additional reserve value 0.06r1 of the TIL thickness.
