Developing earth-abundant electrocatalysts for hydrogen evolution reaction(HER)is important for the sustainable energy economy.Herein,efficient and stable heterocatalysts consisting of crystalline-amorphous M@MN_(x)(M...Developing earth-abundant electrocatalysts for hydrogen evolution reaction(HER)is important for the sustainable energy economy.Herein,efficient and stable heterocatalysts consisting of crystalline-amorphous M@MN_(x)(M=Co,Fe,Ni)encapsulated in N-doped carbon layers supported with N-doped graphene sheets(denoted as M@MN_(x)@NC-NG)are synthesized by facile hydrothermal reaction and nitridation process.During the nitriding process,metal ions in M(tzbc)_2(H_(2)O)_4(tzbc=4-(1H-1,2,4-triazol-1-yl)benzoic acid)complexes are reduced to crystalline M cores,accompanied by the formation of amorphous MN_(x)shells;the tzbc ligands are insitu carbonized to form outermost N-doped carbon(NC)layers that connect with inner MN_(x)via M-N-C motifs inherited from the complex precursors and inhibit the transition of MN_(x)from amorphous to crystalline phase.The Co@CoN_(x)@NC-NG catalyst exhibits excellent HER activity with small overpotentials of 45 and 64 mV at a cathode current density of 10 mA·cm^(-2)and low Tafel slopes of 40 and 85 mV·dec^(-1)in 0.5 mol·L^(-1)H_(2)SO_4 and1.0 mol·L^(-1)KOH electrolytes,respectively.The Co@CoN_(x)@NC-NG retains 97%of the initial overpotential after 100,000 s in both acidic and alkaline media.Such outstanding HER performance originates from the crystalline-amorphous Co@CoN_(x)that redistributes electrons around the heterointerfaces,facilitating the conversion process of H^(+)/H_(2)O to hydrogen and thereby promoting HER kinetics.The outermost NC layers serve as the armor of Co@CoN_(x),and graphene nanosheets act as carriers of egg-like Co@CoN_(x)@NC and conduction paths for electron shuttles,ensuring stable and continuous electrocatalytic hydrogen production.展开更多
The overall energy efficiency of electrochemical systems is severely hindered by the traditional anodic oxygen evolution reaction(OER).Utilizing urea oxidation reaction(UOR)with lower thermodynamic potential to replac...The overall energy efficiency of electrochemical systems is severely hindered by the traditional anodic oxygen evolution reaction(OER).Utilizing urea oxidation reaction(UOR)with lower thermodynamic potential to replace OER provides a promising strategy to enhance the energy efficiency.Amorphous and heterojunctions electrocatalysts have been aroused extensive studies owing to their unique physicochemical properties and outperformed activity.Herein,we report a simple method to construct a novel crystalline-amorphous NiO-CrO_(x)heterojunction grown on Ni foam for UOR electrocatalyst.The NiO-CrO_(x)electrocatalyst displays excellent UOR performance with an ultralow working potential of 1.32 V at 10 mA·cm^(−2)and ultra-long stability about 5 days even at 100 mA·cm^(−2).In-situ Raman analysis and temperature-programmed desorption(TPD)measurement verify that the presence of the amorphous CrO_(x)phase can boost the reconstruction from NiO to active NiOOH species and enhance adsorption ability of urea molecule.Besides,the unique crystalline-amorphous interfaces are also benefit to improving the UOR performance.展开更多
In this work,we prepared silicon nanowires(Si NWs) on both fluorine-doped SnO 2(FTO) coated glass substrate and common glass substrate by catalytic thermal chemical vapor deposition(CVD) using indium film as the catal...In this work,we prepared silicon nanowires(Si NWs) on both fluorine-doped SnO 2(FTO) coated glass substrate and common glass substrate by catalytic thermal chemical vapor deposition(CVD) using indium film as the catalyst.It is confirmed that indium can catalyze the growth of Si NWs.More importantly,we found that tin generated in situ from the reduction of SnO 2 by indium can act as catalyst,which greatly enhances the growth of Si NWs on FTO substrate.The obtained Si NWs have a uniform crystalline-amorphous core-shell structure that is formed via vapor-liquid-solid and vapor-solid growth of silicon sequentially.This work provides a strategy to prepare Si NWs in high yield by catalytic thermal CVD using the low melting point metal catalysts.展开更多
The supercapacitor electrode materials suffer from structure pulverization and sluggish electrode kinetics under high current rates.Herein,a unique NiMoO_(4)@Co-B heterostructure composed of highly conductive Co-B nan...The supercapacitor electrode materials suffer from structure pulverization and sluggish electrode kinetics under high current rates.Herein,a unique NiMoO_(4)@Co-B heterostructure composed of highly conductive Co-B nanoflakes and a semiconductive NiMoO_(4) nanorod is designed as an electrode material to exert the energy storage effect on supercapacitors.The formed Mott-Schottky heterostructure is helpful to overcome the ion diffusion barrier and charge transfer resistance during charging and discharging.Moreover,this crystalline-amorphous heterogeneous phase could provide additional ion storage sites and better strain adaptability.Remarkably,the optimized NiMoO_(4)@Co-B hierarchical nanorods(the mass ratio of NiMoO_(4)/Co-B is 3:1)present greatly enhanced electrochemical characteristics compared with other components,and show superior specific capacity of 236.2 mA h g^(-1)at the current density of 0.5 A g^(-1),as well as remarked rate capability.The present work broadens the horizons of advanced electrode design with distinct heterogeneous interface in other energy storage and conversion field.展开更多
Solid-state cooling based on caloric effects is considered a viable alternative to replace the conventional vapor-compression refrigeration systems.Regarding barocaloric materials,recent results show that elastomers a...Solid-state cooling based on caloric effects is considered a viable alternative to replace the conventional vapor-compression refrigeration systems.Regarding barocaloric materials,recent results show that elastomers are promising candidates for cooling applications around room-temperature.In the present paper,we report supergiant barocaloric effects observed in acetoxy silicone rubber—a very popular,low-cost and environmentally friendly elastomer.Huge values of adiabatic temperature change and reversible isothermal entropy change were obtained upon moderate applied pressures and relatively low strains.These huge barocaloric changes are associated both to the polymer chain rearrangements induced by confined compression and to the first-order structural transition.The results are comparable to the best barocaloric materials reported so far,opening encouraging prospects for the application of elastomers in near future solid-state cooling devices.展开更多
基金financially supported by the National Natural Science Foundation of China(No.91961201)the China Postdoctoral Science Foundation(No.2022M722344)Shanxi"1331"Project。
文摘Developing earth-abundant electrocatalysts for hydrogen evolution reaction(HER)is important for the sustainable energy economy.Herein,efficient and stable heterocatalysts consisting of crystalline-amorphous M@MN_(x)(M=Co,Fe,Ni)encapsulated in N-doped carbon layers supported with N-doped graphene sheets(denoted as M@MN_(x)@NC-NG)are synthesized by facile hydrothermal reaction and nitridation process.During the nitriding process,metal ions in M(tzbc)_2(H_(2)O)_4(tzbc=4-(1H-1,2,4-triazol-1-yl)benzoic acid)complexes are reduced to crystalline M cores,accompanied by the formation of amorphous MN_(x)shells;the tzbc ligands are insitu carbonized to form outermost N-doped carbon(NC)layers that connect with inner MN_(x)via M-N-C motifs inherited from the complex precursors and inhibit the transition of MN_(x)from amorphous to crystalline phase.The Co@CoN_(x)@NC-NG catalyst exhibits excellent HER activity with small overpotentials of 45 and 64 mV at a cathode current density of 10 mA·cm^(-2)and low Tafel slopes of 40 and 85 mV·dec^(-1)in 0.5 mol·L^(-1)H_(2)SO_4 and1.0 mol·L^(-1)KOH electrolytes,respectively.The Co@CoN_(x)@NC-NG retains 97%of the initial overpotential after 100,000 s in both acidic and alkaline media.Such outstanding HER performance originates from the crystalline-amorphous Co@CoN_(x)that redistributes electrons around the heterointerfaces,facilitating the conversion process of H^(+)/H_(2)O to hydrogen and thereby promoting HER kinetics.The outermost NC layers serve as the armor of Co@CoN_(x),and graphene nanosheets act as carriers of egg-like Co@CoN_(x)@NC and conduction paths for electron shuttles,ensuring stable and continuous electrocatalytic hydrogen production.
基金supported by the National Natural Science Foundation of China(Nos.52025013 and 22121005)the 111 Project(No.B12015),Haihe Laboratory of Sustainable Chemical Transformations,and the Fundamental Research Funds for the Central Universities.
文摘The overall energy efficiency of electrochemical systems is severely hindered by the traditional anodic oxygen evolution reaction(OER).Utilizing urea oxidation reaction(UOR)with lower thermodynamic potential to replace OER provides a promising strategy to enhance the energy efficiency.Amorphous and heterojunctions electrocatalysts have been aroused extensive studies owing to their unique physicochemical properties and outperformed activity.Herein,we report a simple method to construct a novel crystalline-amorphous NiO-CrO_(x)heterojunction grown on Ni foam for UOR electrocatalyst.The NiO-CrO_(x)electrocatalyst displays excellent UOR performance with an ultralow working potential of 1.32 V at 10 mA·cm^(−2)and ultra-long stability about 5 days even at 100 mA·cm^(−2).In-situ Raman analysis and temperature-programmed desorption(TPD)measurement verify that the presence of the amorphous CrO_(x)phase can boost the reconstruction from NiO to active NiOOH species and enhance adsorption ability of urea molecule.Besides,the unique crystalline-amorphous interfaces are also benefit to improving the UOR performance.
基金supported by Solar Energy Initiative of the Knowledge Innovation Program of the Chinese Academy of Sciences (KGCX2-YW-395-3)
文摘In this work,we prepared silicon nanowires(Si NWs) on both fluorine-doped SnO 2(FTO) coated glass substrate and common glass substrate by catalytic thermal chemical vapor deposition(CVD) using indium film as the catalyst.It is confirmed that indium can catalyze the growth of Si NWs.More importantly,we found that tin generated in situ from the reduction of SnO 2 by indium can act as catalyst,which greatly enhances the growth of Si NWs on FTO substrate.The obtained Si NWs have a uniform crystalline-amorphous core-shell structure that is formed via vapor-liquid-solid and vapor-solid growth of silicon sequentially.This work provides a strategy to prepare Si NWs in high yield by catalytic thermal CVD using the low melting point metal catalysts.
基金supported by the National Natural Science Foundation of China(52261040,51971104)the Outstanding Postgraduate Innovation Star Project of Gansu Provincial Department of Education(2022CXZX-383)。
文摘The supercapacitor electrode materials suffer from structure pulverization and sluggish electrode kinetics under high current rates.Herein,a unique NiMoO_(4)@Co-B heterostructure composed of highly conductive Co-B nanoflakes and a semiconductive NiMoO_(4) nanorod is designed as an electrode material to exert the energy storage effect on supercapacitors.The formed Mott-Schottky heterostructure is helpful to overcome the ion diffusion barrier and charge transfer resistance during charging and discharging.Moreover,this crystalline-amorphous heterogeneous phase could provide additional ion storage sites and better strain adaptability.Remarkably,the optimized NiMoO_(4)@Co-B hierarchical nanorods(the mass ratio of NiMoO_(4)/Co-B is 3:1)present greatly enhanced electrochemical characteristics compared with other components,and show superior specific capacity of 236.2 mA h g^(-1)at the current density of 0.5 A g^(-1),as well as remarked rate capability.The present work broadens the horizons of advanced electrode design with distinct heterogeneous interface in other energy storage and conversion field.
文摘Solid-state cooling based on caloric effects is considered a viable alternative to replace the conventional vapor-compression refrigeration systems.Regarding barocaloric materials,recent results show that elastomers are promising candidates for cooling applications around room-temperature.In the present paper,we report supergiant barocaloric effects observed in acetoxy silicone rubber—a very popular,low-cost and environmentally friendly elastomer.Huge values of adiabatic temperature change and reversible isothermal entropy change were obtained upon moderate applied pressures and relatively low strains.These huge barocaloric changes are associated both to the polymer chain rearrangements induced by confined compression and to the first-order structural transition.The results are comparable to the best barocaloric materials reported so far,opening encouraging prospects for the application of elastomers in near future solid-state cooling devices.
