Heteroatom doping is a promising approach to enhance catalytic activity by modulating physical properties,electronic structure,and reaction pathway.Herein,we demonstrate that appropriate Ni-doping could trigger a pref...Heteroatom doping is a promising approach to enhance catalytic activity by modulating physical properties,electronic structure,and reaction pathway.Herein,we demonstrate that appropriate Ni-doping could trigger a preferential transition of the basal plane from 2H(trigonal prismatic)to 1T′(clustered Mo)by inducing lattice distortion and S vacancy(SV)and thus dramatically facilitate its catalytic hydrogen evolution activity.It is noteworthy that the unique catalysts did possess superior catalytic performance of hydrogen evolution reaction(HER).The rate of photocatalytic hydrogen evolution could reach 20.45 mmol·g^(−1)·h^(−1) and reduced only slightly in the long period of the photocatalytic process.First-principles calculations reveal that the distorted Ni-1T′-MoS_(2) with SV could generate favorable water adsorption energy(Ead(H_(2)O))and Gibbs free energy of hydrogen adsorption(∆GH).This work exhibits a facile and promising pathway for synergistically regulating physical properties,electronic structure,or wettability based on the doping strategy for designing HER electrocatalysts.展开更多
Hierarchical nanostructure construction and electronic structure engineering are commonly employed to increase the electrocatalytic activity of HER electrocatalysts.Herein,Ni doped Co_(3)S_(4) hierarchical nanosheets ...Hierarchical nanostructure construction and electronic structure engineering are commonly employed to increase the electrocatalytic activity of HER electrocatalysts.Herein,Ni doped Co_(3)S_(4) hierarchical nanosheets on Ti mesh(Ni doped Co_(3)S_(4) HNS/TM)were successfully prepared by using metal organic framework(MOF)as precursor which was synthesized under ambient condition.Characterization results confirmed this structure and Ni incorporation into Co_(3)S_(4) lattice as well as the modified electronic structure of Co_(3)S_(4) by Ni doping.Alkaline HER performance showed that Ni doped Co_(3)S_(4) HNS/TM presented outstanding HER activity with 173 m V overpotential at-10 m A·cm^(-2),surpassing most of metal sulfide-based electrocatalysts.The hierarchical structure,superior electrical conductivity and electronic structure modulation contributed to the accelerated water dissociation and enhanced intrinsic activity.This work provides a new avenue for synthesizing hierarchical nanostructure and simultaneously tuning the electronic structure to promote HER performance,which has potential application in designing highly efficient and cost-effective HER nanostructured electrocatalyst.展开更多
Chemical bath deposition technique has been used to deposit Ni-doped Sb2S3 thin films onto glass substrate. Doping was carried out by adding 1, 3 and 5 wt% of Ni. Bath temperature was kept as 10℃ and films were annea...Chemical bath deposition technique has been used to deposit Ni-doped Sb2S3 thin films onto glass substrate. Doping was carried out by adding 1, 3 and 5 wt% of Ni. Bath temperature was kept as 10℃ and films were annealed at 250℃ under vacuum. Polycrystalline nature of films with an orthorhombic phase was analyzed by X-ray diffraction technique. Scanning electron microscopy was used for morphological study which shows that grains are spherical. Optical measurements using transmittance data indicated that films have a direct band gap of 1.00 - 2.60 eV with an absorption coefficient of ~104 cm<sup>-1</sup> in visible range. The average value of electrical conductivity was calculated as 1.66, 1.11 and 1.06 (Ω·cm)<sup>-1</sup> for as-deposited films and 1.90, 2.08 and 1.15 (Ω·cm)<sup>-1</sup> for annealed films while refractive indices were found as 2.18 - 3.38 and 1.91 - 3.74 respectively. The obtained films can be used for solar cell applications due to their good absorbing properties like higher absorption coefficient and refractive index values.展开更多
Thanks to tunable physical and chemical properties,two-dimensional(2D)materials have received intensive interest,endowing their excellent electrocatalytic performances for applications in energy conversion.However,the...Thanks to tunable physical and chemical properties,two-dimensional(2D)materials have received intensive interest,endowing their excellent electrocatalytic performances for applications in energy conversion.However,their catalytic activities are largely determined by poor adsorption energy and limited active edge sites.Herein,a one-step electrochemical exfoliation strategy was developed to fabricate 2D Ni-doped MoS_(2)nanosheets(Ni-EX-MoS_(2))with a lateral size of500 nm and thickness of3.5 nm.Profiting from high electrical conductivity and abundant exposing active sites,Ni-EX-MoS_(2)catalyst displayed an admirable performance for electrochemical hydrogen evolution reaction(HER)with a low overpotential of 145 m V at 10 m A/cm^(2)as well as a small Tafel slope of 89 m V/dec in alkaline media,which are superior to those of the most reported MoS_(2)-based electrocatalysts.The formed Ni species with tuning electronic structure played a crucial role as primary active center of Ni-EX-MoS_(2),as well as the forming stable 1T/2H phase MoS_(2)interface demonstrated a synergistic effect on electrocatalytic HER performance.Further,Ni-EX-MoS_(2)was employed as a cathode electrode for alkaline Zn-H_(2)O battery,which displayed a high power density of 3.3 m W/cm^(2)with excellent stability.This work will provide a simple and effective guideline for design of electrochemically exfoliated transition metal-doped MoS_(2)nanosheets to inspire their practical applications in energy catalytic and storage.展开更多
Simultaneously integrating heterogeneous interface,element doping,and metal decorating was a promising strategy to promote the visible-light-driven photocatalytic activity.Herein,we demonstrated a facile solvothermal ...Simultaneously integrating heterogeneous interface,element doping,and metal decorating was a promising strategy to promote the visible-light-driven photocatalytic activity.Herein,we demonstrated a facile solvothermal route for Ni-doped BiOBr/Bi^(0) with ZnO 3D hierarchical heterojunction(denoted as Z@B/BiNi).The optimal photocatalysts of Z@B/Bi-Ni sample presented a remarkable catalytic performance of high concentrations of tetracycline solution(40 mg/L)than those of the Z@B/Bi,Z@B,BOB and ZnO photocatalysts toward the visible-light-driven degradation.The enhanced photocatalytic mechanism can be proposed as follows:(ⅰ)3D hierarchical heterojunction provided more active sites and accelerated the separation of charge carriers for photocatalytic TC;(ⅱ)formation of oxygen vacancies on the surface over Z@B/Bi-Ni by in-situ reduction of Bi^(0) and Ni doping could serve as the active sites for oxygen activation to adsorb free O_(2) and generate more superoxide radicals;(ⅲ)SPR effect of Bi metal were beneficial to carrier separation and also act as the active site to trap O_(2) molecules.This work clarified the role of unique morphologies,surface plasmonic resonance(SPR)effect of metal Bi,and Ni doping in Z@B/Bi-Ni,and its photocatalytic reaction mechanism was proposed by a series of experiments,characterization and DFT calculations,arousing a new perspective to design hierarchical heterojunction photocatalysts.展开更多
A novel Ni doped carbon quantum dots(Ni-CQDs)fluorescence probe was synthesized by facile electrolysis of monoatomic Ni dispersed porous carbon(Ni–N–C).The obtained Ni-CQDs showed a high quantum yield of 6.3%with th...A novel Ni doped carbon quantum dots(Ni-CQDs)fluorescence probe was synthesized by facile electrolysis of monoatomic Ni dispersed porous carbon(Ni–N–C).The obtained Ni-CQDs showed a high quantum yield of 6.3%with the strongest excitation and emission peaks of 360 nm and 460 nm,and maintained over 90%of the maximum fluorescence intensity in a wide p H range of 3–12.The metal ions detectability of Ni-CQDs was enhanced by Ni doping and functional groups modification,and the rapid and selective detection of Fe^(3+)and Cu^(2+)ions was achieved with Ni-CQDs through dynamic and static quenching mechanism,respectively.On one hand,the energy band gap of Ni-CQDs was regulated by Ni doping,so that excited electrons in Ni-CQDs were able to transfer to Fe^(3+)easily.On the other hand,the abundant functional groups promoted the generation of static quenching complexation between Cu^(2+)and Ni-CQDs.In metal ions detection,the linear quantitation range of Fe^(3+)and Cu^(2+)were 100–1000μM(R^(2)=0.9955)and 300–900μM(R^(2)=0.9978),respectively.The limits of detection(LOD)were calculated as 10.17 and 7.88μM,respectively.Moreover,the fluorescence quenched by Cu^(2+)could be recovered by EDTA2-due to the destruction of the static quenching complexation.In this way,NiCQDs showed the ability to identify the two metal ions to a certain degree under the condition of Fe^(3+)and Cu^(2+)coexistent.This work paves the way of facile multiple metal ion detection with high sensitivity.展开更多
In this work,pure SnO_(2) and Ni-doped SnO_(2) nanorods were synthesized through a one-step template-free hydrothermal method and then used to detect isopropanol.Sensors fabricated with the Ni-doped SnO_(2) nanocompos...In this work,pure SnO_(2) and Ni-doped SnO_(2) nanorods were synthesized through a one-step template-free hydrothermal method and then used to detect isopropanol.Sensors fabricated with the Ni-doped SnO_(2) nanocomposites showed the best gas sensing performance when the Ni doping amount was 1.5 mol.%.The response reached 250 at 225℃,which was approximately 8.3 times higher than that of the pure SnO_(2) nanorods.The limit of detection for isopropanol was as low as 10 ppb at the optimum working temperature.In addition,it also displayed good selectivity and excellent reproducibility.It is believed that the enhanced isopropanol sensing behavior benefit from the increased oxygen defects and larger specific surface area by Ni doping.展开更多
Developing highly efficient and stable non-precious metal catalysts for water splitting is urgently required.In this work,we report a facile one-step molten salt method for the preparation of self-supporting Ni-doped ...Developing highly efficient and stable non-precious metal catalysts for water splitting is urgently required.In this work,we report a facile one-step molten salt method for the preparation of self-supporting Ni-doped Mo_(2)C on carbon fiber paper(Ni–Mo_(2)CCB/CFP)for hydrogen evolution reaction(HER).The effects of nickel nitrate concentration on the phase composition,morphology,and electrocatalytic HER performance of Ni-doped Mo_(2)C@CFP electrocatalysts was investigated.With the continuous increase of Ni(NO_(3))_(2)concentration,the morphology of Mo_(2)C gradually changes from granular to flower-like,providing larger specific surface area and more active sites.Doping nickel(Ni)into the crystal lattice of Mo_(2)C largely reduces the impedance of the electrocatalysts and enhances their electrocatalytic activity.The as-developed Mo_(2)C–3 M Ni(NO_(3))_(2)/CFP electrocatalyst exhibits high catalytic activity with a small overpotential of 56 mV at a current density of 10 mA·cm^(-2).This catalyst has a fast HER kinetics,as demonstrated by a very small Tafel slope of 27.4 mV·dec^(-1),and persistent long-term stability.A further higher Ni concentration had an adverse effect on the electrocatalytic performance.Density functional theory(DFT)calculations further verified the experimental results.Ni doping could reduce the binding energy of Mo–H,facilitating the desorption of the adsorbed hydrogen(Hads)on the surface,thereby improving the intrinsic catalytic activity of Ni-doped Mo_(2)C-based catalysts.Nevertheless,excessive Ni doping would inhibit the catalytic activity of the electrocatalysts.This work not only provides a simple strategy for the facile preparation of non-precious metal electrocatalysts with high catalytic activity,but also unveils the influence mechanism of the Ni doping concentration on the HER performance of the electrocatalysts from the theoretical perspective.展开更多
Hierarchical hollow-structured magnetic–dielectric materials are considered to be promising and competitive functional absorbers for microwave absorption(MA).Herein,a hierarchical hollow hydrangea multicomponent meta...Hierarchical hollow-structured magnetic–dielectric materials are considered to be promising and competitive functional absorbers for microwave absorption(MA).Herein,a hierarchical hollow hydrangea multicomponent metal oxides/metal-carbon was designed and successfully produced via a facile self-assembly method and calcination process.Adequate magnetic NiO and Ni nanoparticles were suspended within the hollow hydrangea-like nitrogen-doped carbon matrix(HH N-NiO/Ni/C),constructing a unique hierarchical hollow structured multicomponent magnetic–dielectric MA composite.The annealing temperature and oxidation time were carefully regulated to investigate the complex permittivity and permeability.HH N-NiO/Ni/C delivers exceptional MA properties with maximum reflection loss of–45.8 dB at 1.7 mm thickness and displays a wide effective absorption frequency range of 5.6 GHz.The superior MA performance can be attributed to the following aspects:(1)The hierarchical hollow multicomponent structure offers plentiful of heterojunction interfaces triggering interfacial polarization;(2)nitrogen doped-carbon(N-C)facilitates the conductive loss by the unique electron migration path in the graphitized C and NiO/Ni;(3)magnetic NiO/Ni nanoparticles homogeneously dispersed within N-C form extensive C skeleton and strengthen the magnetic response ability;(4)hierarchical hollow wrinkled structures possess a large interspace and heterogeneous interface improving polarization loss and enhancing multireflection process and the unique structure satisfies magnetic and dielectric loss simultaneously resulting from synergistic effects of different components within the composites.展开更多
The enhancements in thermoelectric(TE)performances of p-type skutterudites are usually limited due to the relatively low Seebeck coefficients owing to the higher carrier concentration and more impurity phases induced ...The enhancements in thermoelectric(TE)performances of p-type skutterudites are usually limited due to the relatively low Seebeck coefficients owing to the higher carrier concentration and more impurity phases induced by inherent structural instability of a Fe-based skutterudite.As shown in this study,alloying engineering of Ni doping at Fe sites in a p-type CeFe_(3.8)Co_(0.2)Sb_(12)skutterudite can not only reduce the impurity phases with high thermal conductivity but also regulate the carrier concentration,and thus significantly increase the Seebeck coefficient.The thermal conductivity was largely suppressed due to the enhanced point defect phonon scattering and decreased hole concentration.As a result,a TE figure of merit ZT of the CeFe_(3.5)Ni_(0.3)Co_(0.2)Sb_(12)sample reached 0.8,which is approximately 50%higher than that of a Ni-free sample.Appropriate Ni doping can maintain a high ZT at a high temperature by controlling the reduction in a band gap.Therefore,a high average ZT close to 0.8 at 650–800 K for CeFe_(3.5)Ni_(0.3)Co_(0.2)Sb_(12)was obtained,which was comparable to or even higher than those of the reported Ce-filled Fe-based skutterudites due to the synergistic optimization of electrical and thermal performances.This study provides a strategy to synergistically optimize electrical–thermal performances of the p-type skutterudites by alloying engineering.展开更多
基金supported by the National Funds for Distinguished Young Scientists(No.61825503)the National Natural Science Foundation of China(Nos.51902101,61775101,and 61804082)+2 种基金the Natural Science Foundation of Jiangsu Province(Nos.BK20201381 and BK20210577)the Science Foundation of Nanjing University of Posts and Telecommunications(No.NY219144)the National College Student Innovation and Entrepreneurship Training Program.
文摘Heteroatom doping is a promising approach to enhance catalytic activity by modulating physical properties,electronic structure,and reaction pathway.Herein,we demonstrate that appropriate Ni-doping could trigger a preferential transition of the basal plane from 2H(trigonal prismatic)to 1T′(clustered Mo)by inducing lattice distortion and S vacancy(SV)and thus dramatically facilitate its catalytic hydrogen evolution activity.It is noteworthy that the unique catalysts did possess superior catalytic performance of hydrogen evolution reaction(HER).The rate of photocatalytic hydrogen evolution could reach 20.45 mmol·g^(−1)·h^(−1) and reduced only slightly in the long period of the photocatalytic process.First-principles calculations reveal that the distorted Ni-1T′-MoS_(2) with SV could generate favorable water adsorption energy(Ead(H_(2)O))and Gibbs free energy of hydrogen adsorption(∆GH).This work exhibits a facile and promising pathway for synergistically regulating physical properties,electronic structure,or wettability based on the doping strategy for designing HER electrocatalysts.
基金funded by National Natural Science Foundation of China(Nos.21906008 and 51571076)Open Project of State Key Laboratory of Urban Water Resource and Environment of Har-bin Institute of Technology(No.HCK201716)+1 种基金Chongqing Basic and Frontier Research Program(cstc2018jcyjAX0774)Science and Technology Research Program of Chongqing Municipal Education Commission(Nos.KJQN201901420 and KJQN202001413).
文摘Hierarchical nanostructure construction and electronic structure engineering are commonly employed to increase the electrocatalytic activity of HER electrocatalysts.Herein,Ni doped Co_(3)S_(4) hierarchical nanosheets on Ti mesh(Ni doped Co_(3)S_(4) HNS/TM)were successfully prepared by using metal organic framework(MOF)as precursor which was synthesized under ambient condition.Characterization results confirmed this structure and Ni incorporation into Co_(3)S_(4) lattice as well as the modified electronic structure of Co_(3)S_(4) by Ni doping.Alkaline HER performance showed that Ni doped Co_(3)S_(4) HNS/TM presented outstanding HER activity with 173 m V overpotential at-10 m A·cm^(-2),surpassing most of metal sulfide-based electrocatalysts.The hierarchical structure,superior electrical conductivity and electronic structure modulation contributed to the accelerated water dissociation and enhanced intrinsic activity.This work provides a new avenue for synthesizing hierarchical nanostructure and simultaneously tuning the electronic structure to promote HER performance,which has potential application in designing highly efficient and cost-effective HER nanostructured electrocatalyst.
文摘Chemical bath deposition technique has been used to deposit Ni-doped Sb2S3 thin films onto glass substrate. Doping was carried out by adding 1, 3 and 5 wt% of Ni. Bath temperature was kept as 10℃ and films were annealed at 250℃ under vacuum. Polycrystalline nature of films with an orthorhombic phase was analyzed by X-ray diffraction technique. Scanning electron microscopy was used for morphological study which shows that grains are spherical. Optical measurements using transmittance data indicated that films have a direct band gap of 1.00 - 2.60 eV with an absorption coefficient of ~104 cm<sup>-1</sup> in visible range. The average value of electrical conductivity was calculated as 1.66, 1.11 and 1.06 (Ω·cm)<sup>-1</sup> for as-deposited films and 1.90, 2.08 and 1.15 (Ω·cm)<sup>-1</sup> for annealed films while refractive indices were found as 2.18 - 3.38 and 1.91 - 3.74 respectively. The obtained films can be used for solar cell applications due to their good absorbing properties like higher absorption coefficient and refractive index values.
基金financially supported by the National Natural Science Foundation of China(Nos.21805244,51776188)the financial support from National Natural Science Foundation of China(Nos.21922811,21878270,21961160742)+1 种基金the Zhejiang Provincial Natural Science Foundation of China(No.LR19B060002)the Startup Foundation for HundredTalent Program of Zhejiang University,Jiangxi Province"Double Thousand Plan"Project(No.205201000020)。
文摘Thanks to tunable physical and chemical properties,two-dimensional(2D)materials have received intensive interest,endowing their excellent electrocatalytic performances for applications in energy conversion.However,their catalytic activities are largely determined by poor adsorption energy and limited active edge sites.Herein,a one-step electrochemical exfoliation strategy was developed to fabricate 2D Ni-doped MoS_(2)nanosheets(Ni-EX-MoS_(2))with a lateral size of500 nm and thickness of3.5 nm.Profiting from high electrical conductivity and abundant exposing active sites,Ni-EX-MoS_(2)catalyst displayed an admirable performance for electrochemical hydrogen evolution reaction(HER)with a low overpotential of 145 m V at 10 m A/cm^(2)as well as a small Tafel slope of 89 m V/dec in alkaline media,which are superior to those of the most reported MoS_(2)-based electrocatalysts.The formed Ni species with tuning electronic structure played a crucial role as primary active center of Ni-EX-MoS_(2),as well as the forming stable 1T/2H phase MoS_(2)interface demonstrated a synergistic effect on electrocatalytic HER performance.Further,Ni-EX-MoS_(2)was employed as a cathode electrode for alkaline Zn-H_(2)O battery,which displayed a high power density of 3.3 m W/cm^(2)with excellent stability.This work will provide a simple and effective guideline for design of electrochemically exfoliated transition metal-doped MoS_(2)nanosheets to inspire their practical applications in energy catalytic and storage.
基金supported by the National Natural Science Foundation of China(No.21576211)Tianjin Program of Science and Technology(No.21ZYJDJC00100)+1 种基金Tianjin Innovative Research Team in Universities(No.TD13-5031)Tianjin 131 Research Team of Innovative Talents。
文摘Simultaneously integrating heterogeneous interface,element doping,and metal decorating was a promising strategy to promote the visible-light-driven photocatalytic activity.Herein,we demonstrated a facile solvothermal route for Ni-doped BiOBr/Bi^(0) with ZnO 3D hierarchical heterojunction(denoted as Z@B/BiNi).The optimal photocatalysts of Z@B/Bi-Ni sample presented a remarkable catalytic performance of high concentrations of tetracycline solution(40 mg/L)than those of the Z@B/Bi,Z@B,BOB and ZnO photocatalysts toward the visible-light-driven degradation.The enhanced photocatalytic mechanism can be proposed as follows:(ⅰ)3D hierarchical heterojunction provided more active sites and accelerated the separation of charge carriers for photocatalytic TC;(ⅱ)formation of oxygen vacancies on the surface over Z@B/Bi-Ni by in-situ reduction of Bi^(0) and Ni doping could serve as the active sites for oxygen activation to adsorb free O_(2) and generate more superoxide radicals;(ⅲ)SPR effect of Bi metal were beneficial to carrier separation and also act as the active site to trap O_(2) molecules.This work clarified the role of unique morphologies,surface plasmonic resonance(SPR)effect of metal Bi,and Ni doping in Z@B/Bi-Ni,and its photocatalytic reaction mechanism was proposed by a series of experiments,characterization and DFT calculations,arousing a new perspective to design hierarchical heterojunction photocatalysts.
基金the National Natural Science Foundation of China(Nos.21776302 and 21776308)the Science Foundation of China University of Petroleum,Beijing(No.2462020YXZZ033)。
文摘A novel Ni doped carbon quantum dots(Ni-CQDs)fluorescence probe was synthesized by facile electrolysis of monoatomic Ni dispersed porous carbon(Ni–N–C).The obtained Ni-CQDs showed a high quantum yield of 6.3%with the strongest excitation and emission peaks of 360 nm and 460 nm,and maintained over 90%of the maximum fluorescence intensity in a wide p H range of 3–12.The metal ions detectability of Ni-CQDs was enhanced by Ni doping and functional groups modification,and the rapid and selective detection of Fe^(3+)and Cu^(2+)ions was achieved with Ni-CQDs through dynamic and static quenching mechanism,respectively.On one hand,the energy band gap of Ni-CQDs was regulated by Ni doping,so that excited electrons in Ni-CQDs were able to transfer to Fe^(3+)easily.On the other hand,the abundant functional groups promoted the generation of static quenching complexation between Cu^(2+)and Ni-CQDs.In metal ions detection,the linear quantitation range of Fe^(3+)and Cu^(2+)were 100–1000μM(R^(2)=0.9955)and 300–900μM(R^(2)=0.9978),respectively.The limits of detection(LOD)were calculated as 10.17 and 7.88μM,respectively.Moreover,the fluorescence quenched by Cu^(2+)could be recovered by EDTA2-due to the destruction of the static quenching complexation.In this way,NiCQDs showed the ability to identify the two metal ions to a certain degree under the condition of Fe^(3+)and Cu^(2+)coexistent.This work paves the way of facile multiple metal ion detection with high sensitivity.
基金This work was supported by the 12th Graduate Innovative Fund of Wuhan Institute of Technology(Grant No.CX2020269)。
文摘In this work,pure SnO_(2) and Ni-doped SnO_(2) nanorods were synthesized through a one-step template-free hydrothermal method and then used to detect isopropanol.Sensors fabricated with the Ni-doped SnO_(2) nanocomposites showed the best gas sensing performance when the Ni doping amount was 1.5 mol.%.The response reached 250 at 225℃,which was approximately 8.3 times higher than that of the pure SnO_(2) nanorods.The limit of detection for isopropanol was as low as 10 ppb at the optimum working temperature.In addition,it also displayed good selectivity and excellent reproducibility.It is believed that the enhanced isopropanol sensing behavior benefit from the increased oxygen defects and larger specific surface area by Ni doping.
基金This work was financially supported by the National Natural Science Foundation of China(Grant Nos.51862024,51772140,and 51962023)Key Research and Development Program of Jiangxi Province(Grant No.20203BBE53066).
文摘Developing highly efficient and stable non-precious metal catalysts for water splitting is urgently required.In this work,we report a facile one-step molten salt method for the preparation of self-supporting Ni-doped Mo_(2)C on carbon fiber paper(Ni–Mo_(2)CCB/CFP)for hydrogen evolution reaction(HER).The effects of nickel nitrate concentration on the phase composition,morphology,and electrocatalytic HER performance of Ni-doped Mo_(2)C@CFP electrocatalysts was investigated.With the continuous increase of Ni(NO_(3))_(2)concentration,the morphology of Mo_(2)C gradually changes from granular to flower-like,providing larger specific surface area and more active sites.Doping nickel(Ni)into the crystal lattice of Mo_(2)C largely reduces the impedance of the electrocatalysts and enhances their electrocatalytic activity.The as-developed Mo_(2)C–3 M Ni(NO_(3))_(2)/CFP electrocatalyst exhibits high catalytic activity with a small overpotential of 56 mV at a current density of 10 mA·cm^(-2).This catalyst has a fast HER kinetics,as demonstrated by a very small Tafel slope of 27.4 mV·dec^(-1),and persistent long-term stability.A further higher Ni concentration had an adverse effect on the electrocatalytic performance.Density functional theory(DFT)calculations further verified the experimental results.Ni doping could reduce the binding energy of Mo–H,facilitating the desorption of the adsorbed hydrogen(Hads)on the surface,thereby improving the intrinsic catalytic activity of Ni-doped Mo_(2)C-based catalysts.Nevertheless,excessive Ni doping would inhibit the catalytic activity of the electrocatalysts.This work not only provides a simple strategy for the facile preparation of non-precious metal electrocatalysts with high catalytic activity,but also unveils the influence mechanism of the Ni doping concentration on the HER performance of the electrocatalysts from the theoretical perspective.
基金the China Academy of Launch Vehicle Technology(Nos.5120200522 and 5120210234)the National Natural Science Foundation of China(No.21875190)+1 种基金Foundation of Aeronautics Science Fund(No.2020Z056053002)Fundamental Research Funds for the Central Universities(construction and low-frequency microwave absorption properties of metamaterials).
文摘Hierarchical hollow-structured magnetic–dielectric materials are considered to be promising and competitive functional absorbers for microwave absorption(MA).Herein,a hierarchical hollow hydrangea multicomponent metal oxides/metal-carbon was designed and successfully produced via a facile self-assembly method and calcination process.Adequate magnetic NiO and Ni nanoparticles were suspended within the hollow hydrangea-like nitrogen-doped carbon matrix(HH N-NiO/Ni/C),constructing a unique hierarchical hollow structured multicomponent magnetic–dielectric MA composite.The annealing temperature and oxidation time were carefully regulated to investigate the complex permittivity and permeability.HH N-NiO/Ni/C delivers exceptional MA properties with maximum reflection loss of–45.8 dB at 1.7 mm thickness and displays a wide effective absorption frequency range of 5.6 GHz.The superior MA performance can be attributed to the following aspects:(1)The hierarchical hollow multicomponent structure offers plentiful of heterojunction interfaces triggering interfacial polarization;(2)nitrogen doped-carbon(N-C)facilitates the conductive loss by the unique electron migration path in the graphitized C and NiO/Ni;(3)magnetic NiO/Ni nanoparticles homogeneously dispersed within N-C form extensive C skeleton and strengthen the magnetic response ability;(4)hierarchical hollow wrinkled structures possess a large interspace and heterogeneous interface improving polarization loss and enhancing multireflection process and the unique structure satisfies magnetic and dielectric loss simultaneously resulting from synergistic effects of different components within the composites.
基金supported by the National Natural Science Foundation of China(Grant Nos.51872006,and 22273081)and Anhui Province Natural Science Foundation for Excellent Youth Scholars(Grant No.2208085Y17).
文摘The enhancements in thermoelectric(TE)performances of p-type skutterudites are usually limited due to the relatively low Seebeck coefficients owing to the higher carrier concentration and more impurity phases induced by inherent structural instability of a Fe-based skutterudite.As shown in this study,alloying engineering of Ni doping at Fe sites in a p-type CeFe_(3.8)Co_(0.2)Sb_(12)skutterudite can not only reduce the impurity phases with high thermal conductivity but also regulate the carrier concentration,and thus significantly increase the Seebeck coefficient.The thermal conductivity was largely suppressed due to the enhanced point defect phonon scattering and decreased hole concentration.As a result,a TE figure of merit ZT of the CeFe_(3.5)Ni_(0.3)Co_(0.2)Sb_(12)sample reached 0.8,which is approximately 50%higher than that of a Ni-free sample.Appropriate Ni doping can maintain a high ZT at a high temperature by controlling the reduction in a band gap.Therefore,a high average ZT close to 0.8 at 650–800 K for CeFe_(3.5)Ni_(0.3)Co_(0.2)Sb_(12)was obtained,which was comparable to or even higher than those of the reported Ce-filled Fe-based skutterudites due to the synergistic optimization of electrical and thermal performances.This study provides a strategy to synergistically optimize electrical–thermal performances of the p-type skutterudites by alloying engineering.
