Cobalt-free cathode materials are attractive for their high capacity and low cost,yet they still encounter issues with structural and surface instability.AlPO_(4),in particular,has garnered attention as an effective s...Cobalt-free cathode materials are attractive for their high capacity and low cost,yet they still encounter issues with structural and surface instability.AlPO_(4),in particular,has garnered attention as an effective stabilizer for bulk and surface.However,the impact of interfacial reactions and elemental interdiffusion between AlPO_(4) and LiNi_(0.95)Mn_(0.05)O_(2) upon sintering on the bulk and surface remains elusive.In this study,we demonstrate that during the heat treatment process,AlPO_(4) decomposes,resulting in Al doping into the bulk of the cathode through elemental interdiffusion.Simultaneously,PO_(4)^(3-)reacts with the surface Li of material to form a Li_3PO_(4) coating,inducing lithium deficiency,thereby increasing Li/Ni mixing.The suitable Li/Ni mixing,previously overlooked in AlPO_(4) modification,plays a pivotal role in stabilizing the bulk and surface,exceeding the synergy of Al doping and Li_3PO_(4) coating.The presence of Ni^(2+)ions in the lithium layers contributes to the stabilization of the delithiated structure via a structural pillar effect.Moreover,suitable Li/Ni mixing can stabilize the lattice oxygen and electrode-electrolyte interface by increasing oxygen removal energy and reducing the overlap between the Ni^(3+/4+)e_g and O^(2-)2p orbitals.These findings offer new perspectives for the design of stable cobalt-free cathode materials.展开更多
Electrocatalytic hydrogen production from seawater holds enormous promise for clean energy generation.Nevertheless,the direct electrolysis of seawater encounters significant challenges due to poor anodic stability cau...Electrocatalytic hydrogen production from seawater holds enormous promise for clean energy generation.Nevertheless,the direct electrolysis of seawater encounters significant challenges due to poor anodic stability caused by detrimental chlorine chemistry.Herein,we present our recent discovery that the incorporation of Ce into Ni Fe layered double hydroxide nanosheet array on Ni foam(Ce-Ni Fe LDH/NF)emerges as a robust electrocatalyst for seawater oxidation.During the seawater oxidation process,CeO_(2)is generated,effectively repelling Cl^(-)and inhibiting the formation of Cl O-,resulting in a notable enhancement in the oxidation activity and stability of alkaline seawater.The prepared Ce-Ni Fe LDH/NF requires only overpotential of 390 m V to achieve the current density of 1 A cm^(-2),while maintaining long-term stability for 500 h,outperforming the performance of Ni Fe LDH/NF(430 m V,150 h)by a significant margin.This study highlights the effectiveness of a Ce-doping strategy in augmenting the activity and stability of materials based on Ni Fe LDH in seawater electrolysis for oxygen evolution.展开更多
以硝酸镍为镍源、酸/碱性硅溶胶为硅源,采用共沉淀法制备了2种Ni/SiO_(2)催化剂。采用固定床反应器,评价Ni/SiO_(2)催化剂对于2-甲基呋喃(2-MF)气相加氢合成2-甲基四氢呋喃(2-MTHF)的反应性能。通过XRD、N_(2)等温吸附-脱附、H_(2)-TPR...以硝酸镍为镍源、酸/碱性硅溶胶为硅源,采用共沉淀法制备了2种Ni/SiO_(2)催化剂。采用固定床反应器,评价Ni/SiO_(2)催化剂对于2-甲基呋喃(2-MF)气相加氢合成2-甲基四氢呋喃(2-MTHF)的反应性能。通过XRD、N_(2)等温吸附-脱附、H_(2)-TPR、NH3-TPD、XPS、FTIR和TEM对催化剂进行了表征。考察了硅溶胶的酸碱性对Ni/SiO_(2)催化剂结构及性能的影响。结果表明,以酸性硅溶胶为硅源制备的Ni/SiO_(2)催化剂以弱酸中心酸量为主且存在中强酸中心,比表面积、平均孔径大,因而该催化剂加氢活性和2-MTHF的选择性较高。Ni/SiO_(2)催化剂稳定性良好,在最优反应条件〔温度90℃、H_(2)压力2 MPa、质量空速4.4 g 2-MF/(g催化剂·h)、H_(2)与2-MF物质的量之比为4∶1〕下进行催化剂稳定性测试(200 h),2-MF的转化率达到99.8%,2-MTHF的选择性均保持在97.5%左右。展开更多
The conventional Ni cermet anode suffers from severe carbon deposition and sulfur poisoning when fossil fuels are used. Alternative anode materials are desired for high performance hydrocarbon fuel solid oxide fuel ce...The conventional Ni cermet anode suffers from severe carbon deposition and sulfur poisoning when fossil fuels are used. Alternative anode materials are desired for high performance hydrocarbon fuel solid oxide fuel cells （SOFCs）. We report the rational design of a very active Ni doped La0.6Sr0.4FeO3‐δ（LSFN） electrode for hydrocarbon fuel SOFCs. Homogeneously dispersed Ni‐Fe alloy nanoparticles were in situ extruded onto the surface of the LSFN particles during the operation of the cell. Sym‐metric SOFC single cells were prepared by impregnating a LSFN precursor solution onto a YSZ （yt‐tria stabilized zirconia） monolithic cell with a subsequent heat treatment. The open circuit voltage of the LSFN symmetric cell reached 1.18 and 1.0 V in humidified C3H8 and CH4 at 750？？, respective‐ly. The peak power densities of the cells were 400 and 230 mW/cm2 in humidified C3H8 and CH4, respectively. The electrode showed good stability in long term testing, which revealed LSFN has good catalytic activity for hydrocarbon fuel oxidation.展开更多
A series of Gd-doped Li-Ni ferrites with the formula of LiNi0.5GdxFe2-xO4 where x = 0.00 - 0.08 in steps of 0.02, were prepared by thermolysis of oxalate precursors obtained by rheological phase reaction. The structur...A series of Gd-doped Li-Ni ferrites with the formula of LiNi0.5GdxFe2-xO4 where x = 0.00 - 0.08 in steps of 0.02, were prepared by thermolysis of oxalate precursors obtained by rheological phase reaction. The structure, morphology, and the magnetic properties of the samples were characterized by powder X-ray diffraction （XRD）, atomic force microscopy （AFM） and a vibrating sample magnetometer （VSM）. A single spinel phase was obtained in the range of x = 0.00 - 0.04. The lattice parameters of the Gd-doped samples were larger than that of pure Li-Ni ferrite, and increased in the range of 0.00 ≤ x ≤ 0.04, then decreased up to x = 0.08, because of the formation of the secondary phase （Gd- FeO3）. All samples were spheric particles with an average size of about 100 nm, but agglomerated to some extent. The hysteresis loops indicated that the saturation magnetization decreased gradually with increasing Gd content, while the variation of coercivity was related to the microstructure of the Gd-doped samples.展开更多
Magnetic properties of diluted magnetic semiconductors (DMSs), Ni-doped ZnO materials, prepared by sol-gel method were investigated by measuring magnetization as functions of magnetic field. The Ni content affects the...Magnetic properties of diluted magnetic semiconductors (DMSs), Ni-doped ZnO materials, prepared by sol-gel method were investigated by measuring magnetization as functions of magnetic field. The Ni content affects the magnetic properties at low sintered temperature but it has few effects on the magnetic properties at high sintered temperature. The sintered temperature has great effects on the magnetic properties of Ni/ZnO at high original mole ratio of Ni/Zn while it has slight effects on the magnetic properties of Ni/ZnO at low original mole ratio of Ni/Zn whatever low or high sintered temperature.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
The relation among electronic structure, chemical bond and thermoelectric property of Ca3 Co2 O6 and Ni-doped was studied by density function theory and discrete variation method（DFT-DVM）. The results indicate that ...The relation among electronic structure, chemical bond and thermoelectric property of Ca3 Co2 O6 and Ni-doped was studied by density function theory and discrete variation method（DFT-DVM）. The results indicate that the highest valence band（ HVB ）attd the lowest conduction band（ LCB ） are mainly attribuled to Co3d, Ni3d and O2p atomic orbitals. The property of a semiconductor is shown from the gap between HVB and LCB. The gap of Ni-doped one is less than that of Ca3 Co2 O6. The non-metal bond or ceramic characteristic of Ni-doped one is weaker than that of Ca3 Co2 O6, but the metal characteristics of Ni-doped one are stronger than those of Ca3 Co2 O6. The thermoelectric property should be improved by adding Ni element into the system of Ca3 Co2 O6 .展开更多
Doping of foreign atoms and construction of unique structures are considered as effective approaches to design high-activity and strongdurability electrocatalysts.Herein,we report Fe-doped nickel hydroxide carbonate h...Doping of foreign atoms and construction of unique structures are considered as effective approaches to design high-activity and strongdurability electrocatalysts.Herein,we report Fe-doped nickel hydroxide carbonate hierarchical microtubes with Ag nanoparticles(denoted Ag/NiFeHC HMTs)through hydrolysis precipitation process.Experimental tests and density functional theory calculations reveal that Fe doping can tune the electron configuration to enhance the conductivity,markedly improve the electrochemical surface area to expose more active sites,and act as reactive centers to lower the free energy of the rate determination step.In addition,the unique hierarchical structure can also offer active sites and excellent cycling stability.Benefitting from these advantages,the as-obtained Ag/NiFeHC HMTs show excellent oxygen evolution reaction activity,with an overpotential of 208 mV at 10 mA cm^(−2)in 1.0M KOH.Also,it could achieve long-term stability at a current density of 20 mA cm^(−2)for 24 h.展开更多
Undoped and Ni–S co-doped mesoporous TiO2 nano materials were synthesized by using sol–gel method.The characteristic features of as prepared catalyst samples were investigated using various advanced spectroscopic an...Undoped and Ni–S co-doped mesoporous TiO2 nano materials were synthesized by using sol–gel method.The characteristic features of as prepared catalyst samples were investigated using various advanced spectroscopic and analytical techniques.The characterization results of the samples revealed that all the samples exhibited anatase phase(XRD),decreasing band gap(2.68 eV)(UV–Vis-DRS),small particle size(9.2 nm)(TEM),high surface area(142.156 m^2·g^-1)(BET),particles with spherical shape and smooth morphology(SEM);there is a frequency shift observed for co-doped sample(FT-IR)and the elemental composition electronic states and position of the doped elements(Ni and S)in the TiO2 lattice analyzed by XPS and EDX.These results supported the photocatalytic degradation of Bismarck Brown Red(BBR)achieved with in 110 min and also exhibited the antibacterial activity on Staphylococcus aureus(MTCC-3160),Pseudomonas fluorescence(MTCC-1688)under visible light irradiation.展开更多
Ni-doped ZnO nanopowder （Zn0.98Ni0.2O） was synthesized by improved coprecipitation method. The average particle size of the powder was estimated to be 50 nm. The powder was then processed by thermal treatment. Sampl...Ni-doped ZnO nanopowder （Zn0.98Ni0.2O） was synthesized by improved coprecipitation method. The average particle size of the powder was estimated to be 50 nm. The powder was then processed by thermal treatment. Samples were annealed at 1 073, 1 273, and 1 473 K, respectively. The solubility of NiO in ZnO and the lattice parameters of ZnO both increased with the temperature. The magnetic property of the doped samples was examined, and hysteresis loops were got. The results showed all the samples were ferromagnetic, while powder processed at 1 273 K for 4 h got a highest saturation magnetization （Ms） of 0.0457 emu/g. Also, magnetic properties were related to the grain size of the powder.展开更多
基金financial support from the Natural Science Foundation of Shandong Province (ZR2022QB140)the PhD Initiation Program of Liaocheng University (318052138)the Natural Science Foundation of Shandong Province (ZR2023MB002 and ZR2021MB114)。
文摘Cobalt-free cathode materials are attractive for their high capacity and low cost,yet they still encounter issues with structural and surface instability.AlPO_(4),in particular,has garnered attention as an effective stabilizer for bulk and surface.However,the impact of interfacial reactions and elemental interdiffusion between AlPO_(4) and LiNi_(0.95)Mn_(0.05)O_(2) upon sintering on the bulk and surface remains elusive.In this study,we demonstrate that during the heat treatment process,AlPO_(4) decomposes,resulting in Al doping into the bulk of the cathode through elemental interdiffusion.Simultaneously,PO_(4)^(3-)reacts with the surface Li of material to form a Li_3PO_(4) coating,inducing lithium deficiency,thereby increasing Li/Ni mixing.The suitable Li/Ni mixing,previously overlooked in AlPO_(4) modification,plays a pivotal role in stabilizing the bulk and surface,exceeding the synergy of Al doping and Li_3PO_(4) coating.The presence of Ni^(2+)ions in the lithium layers contributes to the stabilization of the delithiated structure via a structural pillar effect.Moreover,suitable Li/Ni mixing can stabilize the lattice oxygen and electrode-electrolyte interface by increasing oxygen removal energy and reducing the overlap between the Ni^(3+/4+)e_g and O^(2-)2p orbitals.These findings offer new perspectives for the design of stable cobalt-free cathode materials.
基金support from the Free Exploration Project of Frontier Technology for Laoshan Laboratory(No.16-02)the National Natural Science Foundation of China(Nos.22072015 and 21927811)。
文摘Electrocatalytic hydrogen production from seawater holds enormous promise for clean energy generation.Nevertheless,the direct electrolysis of seawater encounters significant challenges due to poor anodic stability caused by detrimental chlorine chemistry.Herein,we present our recent discovery that the incorporation of Ce into Ni Fe layered double hydroxide nanosheet array on Ni foam(Ce-Ni Fe LDH/NF)emerges as a robust electrocatalyst for seawater oxidation.During the seawater oxidation process,CeO_(2)is generated,effectively repelling Cl^(-)and inhibiting the formation of Cl O-,resulting in a notable enhancement in the oxidation activity and stability of alkaline seawater.The prepared Ce-Ni Fe LDH/NF requires only overpotential of 390 m V to achieve the current density of 1 A cm^(-2),while maintaining long-term stability for 500 h,outperforming the performance of Ni Fe LDH/NF(430 m V,150 h)by a significant margin.This study highlights the effectiveness of a Ce-doping strategy in augmenting the activity and stability of materials based on Ni Fe LDH in seawater electrolysis for oxygen evolution.
文摘以硝酸镍为镍源、酸/碱性硅溶胶为硅源,采用共沉淀法制备了2种Ni/SiO_(2)催化剂。采用固定床反应器,评价Ni/SiO_(2)催化剂对于2-甲基呋喃(2-MF)气相加氢合成2-甲基四氢呋喃(2-MTHF)的反应性能。通过XRD、N_(2)等温吸附-脱附、H_(2)-TPR、NH3-TPD、XPS、FTIR和TEM对催化剂进行了表征。考察了硅溶胶的酸碱性对Ni/SiO_(2)催化剂结构及性能的影响。结果表明,以酸性硅溶胶为硅源制备的Ni/SiO_(2)催化剂以弱酸中心酸量为主且存在中强酸中心,比表面积、平均孔径大,因而该催化剂加氢活性和2-MTHF的选择性较高。Ni/SiO_(2)催化剂稳定性良好,在最优反应条件〔温度90℃、H_(2)压力2 MPa、质量空速4.4 g 2-MF/(g催化剂·h)、H_(2)与2-MF物质的量之比为4∶1〕下进行催化剂稳定性测试(200 h),2-MF的转化率达到99.8%,2-MTHF的选择性均保持在97.5%左右。
基金supported by the National Natural Science Foundation of China (51372271,51172275)the National Basic Research Program of China (973 Program,2012CB215402)~~
文摘The conventional Ni cermet anode suffers from severe carbon deposition and sulfur poisoning when fossil fuels are used. Alternative anode materials are desired for high performance hydrocarbon fuel solid oxide fuel cells （SOFCs）. We report the rational design of a very active Ni doped La0.6Sr0.4FeO3‐δ（LSFN） electrode for hydrocarbon fuel SOFCs. Homogeneously dispersed Ni‐Fe alloy nanoparticles were in situ extruded onto the surface of the LSFN particles during the operation of the cell. Sym‐metric SOFC single cells were prepared by impregnating a LSFN precursor solution onto a YSZ （yt‐tria stabilized zirconia） monolithic cell with a subsequent heat treatment. The open circuit voltage of the LSFN symmetric cell reached 1.18 and 1.0 V in humidified C3H8 and CH4 at 750？？, respective‐ly. The peak power densities of the cells were 400 and 230 mW/cm2 in humidified C3H8 and CH4, respectively. The electrode showed good stability in long term testing, which revealed LSFN has good catalytic activity for hydrocarbon fuel oxidation.
基金Project supported by the Natural Science Foundation of China (Y405038) Science and Technology Key Project of ZhejiangProvince (2006C21080)
文摘A series of Gd-doped Li-Ni ferrites with the formula of LiNi0.5GdxFe2-xO4 where x = 0.00 - 0.08 in steps of 0.02, were prepared by thermolysis of oxalate precursors obtained by rheological phase reaction. The structure, morphology, and the magnetic properties of the samples were characterized by powder X-ray diffraction （XRD）, atomic force microscopy （AFM） and a vibrating sample magnetometer （VSM）. A single spinel phase was obtained in the range of x = 0.00 - 0.04. The lattice parameters of the Gd-doped samples were larger than that of pure Li-Ni ferrite, and increased in the range of 0.00 ≤ x ≤ 0.04, then decreased up to x = 0.08, because of the formation of the secondary phase （Gd- FeO3）. All samples were spheric particles with an average size of about 100 nm, but agglomerated to some extent. The hysteresis loops indicated that the saturation magnetization decreased gradually with increasing Gd content, while the variation of coercivity was related to the microstructure of the Gd-doped samples.
基金This work was financially supported by Korea Research Foundation of the Korea Government(MOEHRD)(KRF-2005-210-C00024).
文摘Magnetic properties of diluted magnetic semiconductors (DMSs), Ni-doped ZnO materials, prepared by sol-gel method were investigated by measuring magnetization as functions of magnetic field. The Ni content affects the magnetic properties at low sintered temperature but it has few effects on the magnetic properties at high sintered temperature. The sintered temperature has great effects on the magnetic properties of Ni/ZnO at high original mole ratio of Ni/Zn while it has slight effects on the magnetic properties of Ni/ZnO at low original mole ratio of Ni/Zn whatever low or high sintered temperature.
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The relation among electronic structure, chemical bond and thermoelectric property of Ca3 Co2 O6 and Ni-doped was studied by density function theory and discrete variation method（DFT-DVM）. The results indicate that the highest valence band（ HVB ）attd the lowest conduction band（ LCB ） are mainly attribuled to Co3d, Ni3d and O2p atomic orbitals. The property of a semiconductor is shown from the gap between HVB and LCB. The gap of Ni-doped one is less than that of Ca3 Co2 O6. The non-metal bond or ceramic characteristic of Ni-doped one is weaker than that of Ca3 Co2 O6, but the metal characteristics of Ni-doped one are stronger than those of Ca3 Co2 O6. The thermoelectric property should be improved by adding Ni element into the system of Ca3 Co2 O6 .
基金Zhejiang Provincial Natural Science Foundation of China,Grant/Award Number:LQ20B010002。
文摘Doping of foreign atoms and construction of unique structures are considered as effective approaches to design high-activity and strongdurability electrocatalysts.Herein,we report Fe-doped nickel hydroxide carbonate hierarchical microtubes with Ag nanoparticles(denoted Ag/NiFeHC HMTs)through hydrolysis precipitation process.Experimental tests and density functional theory calculations reveal that Fe doping can tune the electron configuration to enhance the conductivity,markedly improve the electrochemical surface area to expose more active sites,and act as reactive centers to lower the free energy of the rate determination step.In addition,the unique hierarchical structure can also offer active sites and excellent cycling stability.Benefitting from these advantages,the as-obtained Ag/NiFeHC HMTs show excellent oxygen evolution reaction activity,with an overpotential of 208 mV at 10 mA cm^(−2)in 1.0M KOH.Also,it could achieve long-term stability at a current density of 20 mA cm^(−2)for 24 h.
基金the University Grants Commission (UGC) for providing BSR fellowship
文摘Undoped and Ni–S co-doped mesoporous TiO2 nano materials were synthesized by using sol–gel method.The characteristic features of as prepared catalyst samples were investigated using various advanced spectroscopic and analytical techniques.The characterization results of the samples revealed that all the samples exhibited anatase phase(XRD),decreasing band gap(2.68 eV)(UV–Vis-DRS),small particle size(9.2 nm)(TEM),high surface area(142.156 m^2·g^-1)(BET),particles with spherical shape and smooth morphology(SEM);there is a frequency shift observed for co-doped sample(FT-IR)and the elemental composition electronic states and position of the doped elements(Ni and S)in the TiO2 lattice analyzed by XPS and EDX.These results supported the photocatalytic degradation of Bismarck Brown Red(BBR)achieved with in 110 min and also exhibited the antibacterial activity on Staphylococcus aureus(MTCC-3160),Pseudomonas fluorescence(MTCC-1688)under visible light irradiation.
文摘Ni-doped ZnO nanopowder （Zn0.98Ni0.2O） was synthesized by improved coprecipitation method. The average particle size of the powder was estimated to be 50 nm. The powder was then processed by thermal treatment. Samples were annealed at 1 073, 1 273, and 1 473 K, respectively. The solubility of NiO in ZnO and the lattice parameters of ZnO both increased with the temperature. The magnetic property of the doped samples was examined, and hysteresis loops were got. The results showed all the samples were ferromagnetic, while powder processed at 1 273 K for 4 h got a highest saturation magnetization （Ms） of 0.0457 emu/g. Also, magnetic properties were related to the grain size of the powder.
