Developing robust and efficient non-noble electrocatalysts for the hydrogen evolution reaction(HER)is paramount for sustainably producing hydrogen fuel from electrochemical water splitting.Engineering morphology and c...Developing robust and efficient non-noble electrocatalysts for the hydrogen evolution reaction(HER)is paramount for sustainably producing hydrogen fuel from electrochemical water splitting.Engineering morphology and chemical composition are significant for fabricating electrocatalysts with superior activity and durability.Herein,novel Ni-doped CoSe_(2)composites are prepared by a facile one-step hydrothermal method.The optimized 1T-phase Co_(0.75)Ni_(0.25)Se_(2)shows excellent HER performance,exhibiting overpotential of as low as 172 mV at 10 mA·cm^(–2) and a small Tafel slope of 32.4 mV·dec^(–1) in 0.5 mol·L^(-1) H_(2)SO_(4)solution,approaching that of com-mercial Pt/C electrocatalyst(30.7 mV·dec^(–1)).Furthermore,the electrocatalyst possesses superior long-term stability under acidic condition.Physicochemical measurements indicate that the homogeneous nanoparticles morphology,the unique electronic structure,and the 1T-phase are responsible for its superior HER performance.This work comes up with a promising strategy in synthesizing other earth-abundant and low-cost catalysts for industrial applications.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
Regulating the selectivity of CO2 photoreduction is particularly challenging. Herein, we propose ideal models of atomic layers with/without element doping to investigate the effect of doping engineering to tune the se...Regulating the selectivity of CO2 photoreduction is particularly challenging. Herein, we propose ideal models of atomic layers with/without element doping to investigate the effect of doping engineering to tune the selectivity of CO2 photoreduction. Prototypical ZnCo2O4 atomic layers with/without Ni-doping were first synthesized. Density functional theory calculations reveal that introducing Ni atoms creates several new energy levels and increases the density-of-states at the conduction band minimum. Synchrotron radiation photoemission spectroscopy demonstrates that the band structures are suitable for CO2 photoreduction, while the surface photovoltage spectra demonstrate that Ni doping increases the carrier separation efficiency. In situ diffuse reflectance Fourier transform infrared spectra disclose that the CO2^- radical is the main intermediate, while temperature-programed desorption curves reveal that the ZnCo2O4 atomic layers with/without Ni doping favor the respective CO and CH4 desorption. The Ni-doped ZnCo2O4 atomic layers exhibit a 3.5-time higher CO selectivity than the ZnCo2O4 atomic layers. This work establishes a clear correlation between elemental doping and selectivity regulation for CO2 photoreduction, opening new possibilities for tailoring solar-driven photocatalytic behaviors.展开更多
Over the last two decades,extensive study has been done on two-dimensional Molybdenum Sulphide(MoS_(2))due to its outstanding features in energy storage applications.Although MoS_(2)has a lot of active sulphur edges,t...Over the last two decades,extensive study has been done on two-dimensional Molybdenum Sulphide(MoS_(2))due to its outstanding features in energy storage applications.Although MoS_(2)has a lot of active sulphur edges,the presence of inactive surfaces leads to limit conductivity and efficiency.Hence,in this article,we aimed to promote the additional active sites by doping various weight percentages(2%,4%,6%,8%and 10%)of Nickel(Ni)into the MoS_(2)matrix by simple hydrothermal technique,and their doping effects were investigated with the help of Physio-chemical analyses.X-ray diffraction(XRD)pattern,Raman,and chemical composition(XPS)analyses were used to confirm the Ni incorporation in MoS_(2)nanosheets.Microscopic investigations demonstrated that Ni-doped MoS_(2)nanosheets were vertically aligned with enhanced interlayer spacing.Cyclic voltammetry,Galvanostatic charge-discharge,and electrochemical impedance spectroscopy investigations were used to characterize the electrochemical characteristics.The 6%Ni-doped MoS_(2)electrode material showed better CSPof 528.7 F/g@1 A/g and excellent electrochemical stability(85%of capacitance retention after 10,000 cycles at 5 A/g)compared to other electrode materials.Furthermore,the solid-state asymmetric supercapacitor was assembled using Nidoped MoS_(2)and graphite as anode and cathode materials and analysed the electrochemical properties in the two-electrode system.To determine the impact of the Ni-atom on the MoS_(2)surface,firstprinciples computations were performed.Further,it was examined for electronic band structure,the projected density of states(PDOS)and Bader charge transfer analyses.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
Ni-doped BiFeO_(3) powders with the composition BiFe_(1-x)Ni_(x)O_(3)(x=0.05,0.1 and 0.15)were prepared by a self-propagating high-temperature synthesis(SHS),using metal nitrates as oxidizers and glycine as fuel.The X...Ni-doped BiFeO_(3) powders with the composition BiFe_(1-x)Ni_(x)O_(3)(x=0.05,0.1 and 0.15)were prepared by a self-propagating high-temperature synthesis(SHS),using metal nitrates as oxidizers and glycine as fuel.The X-ray diffraction(XRD)patterns depict that Ni-doped BiFeO_(3) ceramics crystallize in a rhombhohedral phase.The scanning electron micrographs of Ni-doped BiFeO_(3) ceramics show a dense morphology with interconnected structure.It is found that,the room-temperature magnetization measurements in Ni-incorporated BiFeO_(3) ceramics give rise to nonzero magnetization.The magnetization of Ni-doped BiFeO_(3) ceramics is significantly enhanced when Ni doping concentration reaches to x=0.1 at 5 K.The variations of dielectric constant with temperature in BiFe_(0.95)Ni_(0.05)O_(3),BiFe_(0.9)Ni_(0.1)O_(3) and BiFe_(0.85)Ni_(0.15)O_(3) samples exhibit clear dielectric anomalies approximately around 450℃,425℃and 410℃respectively,which correspond to antiferromagnetic to paramagnetic phase transition of the parent compound BiFeO_(3).展开更多
Nickel-CeO_(2)-based materials are commonly used for the thermal catalytic hydrogenation of CO_(2).However,high Ni loadings and low CO selectivity restrict their use in the reverse water–gas shift(RWGS)reaction.Herei...Nickel-CeO_(2)-based materials are commonly used for the thermal catalytic hydrogenation of CO_(2).However,high Ni loadings and low CO selectivity restrict their use in the reverse water–gas shift(RWGS)reaction.Herein,we demonstrate a highly active,robust,and low-Ni-doped(1.1 wt.%)CeO_(2) catalyst(1.0-Ni-CeO_(2)).The Ni-based-mass-specific CO formation rate reaches up to 1,542 mmol·gNi^(−1)·h^(−1) with 100%CO selectivity at 300°C for 100 h,among the best values reported in the literature.Density functional theory(DFT)and diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS)results reveal that the enhanced catalytic activity is attributed to the abundant Ce–H species,while the high selectivity results from low CO affinity.More importantly,a new reaction mechanism is proposed,which involves the reduction of bicarbonate to generate formate intermediate and CO by the H−released from Ce–H species.The new findings in this work will benefit the design of economic,efficient,and robust catalysts for low-temperature RWGS reactions.展开更多
基金financially supported by the National Natural Science Foundation of China (Nos. 52002254 and 51773049)the National Program for Support of Top-notch Young Professionals, China Aerospace Science and Technology Corporation-Harbin Institute of Technology Joint Center for Technology Innovation Fund (No. HIT15-1A01)+4 种基金Shanghai Academy of Spaceflight Technology Fund (No. SAST2017-126)the Scientific and Technological Cooperation and Development Fund (No. 2017KJHZ002)Sichuan Science and Technology Program (No. 2020YJ0262)Chunhui Plan of Ministry of Education of China, Fundamental Research Funds for the Central Universities, China (No. YJ201893)State Key Laboratory of Advanced Metals and Materials, China (No. 2019-Z03)。
文摘Developing robust and efficient non-noble electrocatalysts for the hydrogen evolution reaction(HER)is paramount for sustainably producing hydrogen fuel from electrochemical water splitting.Engineering morphology and chemical composition are significant for fabricating electrocatalysts with superior activity and durability.Herein,novel Ni-doped CoSe_(2)composites are prepared by a facile one-step hydrothermal method.The optimized 1T-phase Co_(0.75)Ni_(0.25)Se_(2)shows excellent HER performance,exhibiting overpotential of as low as 172 mV at 10 mA·cm^(–2) and a small Tafel slope of 32.4 mV·dec^(–1) in 0.5 mol·L^(-1) H_(2)SO_(4)solution,approaching that of com-mercial Pt/C electrocatalyst(30.7 mV·dec^(–1)).Furthermore,the electrocatalyst possesses superior long-term stability under acidic condition.Physicochemical measurements indicate that the homogeneous nanoparticles morphology,the unique electronic structure,and the 1T-phase are responsible for its superior HER performance.This work comes up with a promising strategy in synthesizing other earth-abundant and low-cost catalysts for industrial applications.
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.
文摘Regulating the selectivity of CO2 photoreduction is particularly challenging. Herein, we propose ideal models of atomic layers with/without element doping to investigate the effect of doping engineering to tune the selectivity of CO2 photoreduction. Prototypical ZnCo2O4 atomic layers with/without Ni-doping were first synthesized. Density functional theory calculations reveal that introducing Ni atoms creates several new energy levels and increases the density-of-states at the conduction band minimum. Synchrotron radiation photoemission spectroscopy demonstrates that the band structures are suitable for CO2 photoreduction, while the surface photovoltage spectra demonstrate that Ni doping increases the carrier separation efficiency. In situ diffuse reflectance Fourier transform infrared spectra disclose that the CO2^- radical is the main intermediate, while temperature-programed desorption curves reveal that the ZnCo2O4 atomic layers with/without Ni doping favor the respective CO and CH4 desorption. The Ni-doped ZnCo2O4 atomic layers exhibit a 3.5-time higher CO selectivity than the ZnCo2O4 atomic layers. This work establishes a clear correlation between elemental doping and selectivity regulation for CO2 photoreduction, opening new possibilities for tailoring solar-driven photocatalytic behaviors.
文摘Over the last two decades,extensive study has been done on two-dimensional Molybdenum Sulphide(MoS_(2))due to its outstanding features in energy storage applications.Although MoS_(2)has a lot of active sulphur edges,the presence of inactive surfaces leads to limit conductivity and efficiency.Hence,in this article,we aimed to promote the additional active sites by doping various weight percentages(2%,4%,6%,8%and 10%)of Nickel(Ni)into the MoS_(2)matrix by simple hydrothermal technique,and their doping effects were investigated with the help of Physio-chemical analyses.X-ray diffraction(XRD)pattern,Raman,and chemical composition(XPS)analyses were used to confirm the Ni incorporation in MoS_(2)nanosheets.Microscopic investigations demonstrated that Ni-doped MoS_(2)nanosheets were vertically aligned with enhanced interlayer spacing.Cyclic voltammetry,Galvanostatic charge-discharge,and electrochemical impedance spectroscopy investigations were used to characterize the electrochemical characteristics.The 6%Ni-doped MoS_(2)electrode material showed better CSPof 528.7 F/g@1 A/g and excellent electrochemical stability(85%of capacitance retention after 10,000 cycles at 5 A/g)compared to other electrode materials.Furthermore,the solid-state asymmetric supercapacitor was assembled using Nidoped MoS_(2)and graphite as anode and cathode materials and analysed the electrochemical properties in the two-electrode system.To determine the impact of the Ni-atom on the MoS_(2)surface,firstprinciples computations were performed.Further,it was examined for electronic band structure,the projected density of states(PDOS)and Bader charge transfer analyses.
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This study was supported by UGC-SAP,DRS Phase II of Indiathe author Y.A.Chaudhari is very much thankful for the funding agency.
文摘Ni-doped BiFeO_(3) powders with the composition BiFe_(1-x)Ni_(x)O_(3)(x=0.05,0.1 and 0.15)were prepared by a self-propagating high-temperature synthesis(SHS),using metal nitrates as oxidizers and glycine as fuel.The X-ray diffraction(XRD)patterns depict that Ni-doped BiFeO_(3) ceramics crystallize in a rhombhohedral phase.The scanning electron micrographs of Ni-doped BiFeO_(3) ceramics show a dense morphology with interconnected structure.It is found that,the room-temperature magnetization measurements in Ni-incorporated BiFeO_(3) ceramics give rise to nonzero magnetization.The magnetization of Ni-doped BiFeO_(3) ceramics is significantly enhanced when Ni doping concentration reaches to x=0.1 at 5 K.The variations of dielectric constant with temperature in BiFe_(0.95)Ni_(0.05)O_(3),BiFe_(0.9)Ni_(0.1)O_(3) and BiFe_(0.85)Ni_(0.15)O_(3) samples exhibit clear dielectric anomalies approximately around 450℃,425℃and 410℃respectively,which correspond to antiferromagnetic to paramagnetic phase transition of the parent compound BiFeO_(3).
基金the Science and Technology Project of Shenzhen(No.JCYJ20190806155814624)the National Natural Science Foundation of China(No.22002120)the Fundamental Research Funds for the Central Universities(No.3102017jc01001).
文摘Nickel-CeO_(2)-based materials are commonly used for the thermal catalytic hydrogenation of CO_(2).However,high Ni loadings and low CO selectivity restrict their use in the reverse water–gas shift(RWGS)reaction.Herein,we demonstrate a highly active,robust,and low-Ni-doped(1.1 wt.%)CeO_(2) catalyst(1.0-Ni-CeO_(2)).The Ni-based-mass-specific CO formation rate reaches up to 1,542 mmol·gNi^(−1)·h^(−1) with 100%CO selectivity at 300°C for 100 h,among the best values reported in the literature.Density functional theory(DFT)and diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS)results reveal that the enhanced catalytic activity is attributed to the abundant Ce–H species,while the high selectivity results from low CO affinity.More importantly,a new reaction mechanism is proposed,which involves the reduction of bicarbonate to generate formate intermediate and CO by the H−released from Ce–H species.The new findings in this work will benefit the design of economic,efficient,and robust catalysts for low-temperature RWGS reactions.
