Nanostructured iron oxyhydroxide（Fe OOH） thin films have been synthesized using an electrodeposition method on a nickel foam（NF） substrate and effect of air annealing temperature on the catalytic performance is st...Nanostructured iron oxyhydroxide（Fe OOH） thin films have been synthesized using an electrodeposition method on a nickel foam（NF） substrate and effect of air annealing temperature on the catalytic performance is studied. The as-deposited and annealed thin films were characterized by X-ray diffraction（XRD）,X-ray photoelectron spectroscopy（XPS）, field emission scanning electron microscopy（FE-SEM） and linear sweep voltammetry（LSV） to determine their structural, morphological, compositional and electrochemical properties, respectively. The as-deposited nanostructured amorphous Fe OOH thin film is converted into a polycrystalline Fe;O;with hematite crystal structure at a high temperature. The Fe OOH thin film acts as an efficient electrocatalyst for the oxygen evolution reaction（OER） in an alkaline 1 M KOH electrolyte. The film annealed at 200 °C shows high catalytic activity with an onset overpotential of 240 m V with a smaller Tafel slope of 48 m V/dec. Additionally, it needs an overpotential of 290 mV to the drive the current density of 10 m A/cm;and shows good stability in the 1 M KOH electrolyte solution.展开更多
Polypyrrole(PPy)@cellulose fiber-based composites have been widely investigated as electrode materials for use in flexible supercapacitors.However,they cannot readily provide high specific capacitance and cyclic stabi...Polypyrrole(PPy)@cellulose fiber-based composites have been widely investigated as electrode materials for use in flexible supercapacitors.However,they cannot readily provide high specific capacitance and cyclic stability owing to their inherent drawbacks,such as high resistance,Weber impedance,and volume expansion or collapse during charging/discharging.In this study,iron oxyhydroxide(FeOOH)is incorporated in the abovementioned composite to decrease the equivalent series resistance,charge transfer resistance,and Weber impedance,thereby enhancing electron transfer and ion diffusion,which results in superior electrochemical performance.The PPy-wrapped FeOOH@cellulose fiber-based composite electrode with the molar ratio of FeSO_(4) to NaBH4 of 1∶1 exhibits a high specific capacitance of 513.8 F/g at a current density of 0.2 A/g,as well as an excellent capacitance retention of 89.4% after 1000 cycles.展开更多
Synthesized iron oxyhydroxide was applied for the adsorptive removal of As(V)and As(III)from the aquas media.Additionally,this investigation highlighted the synergistic effect of calcium carbonate in conjunction with ...Synthesized iron oxyhydroxide was applied for the adsorptive removal of As(V)and As(III)from the aquas media.Additionally,this investigation highlighted the synergistic effect of calcium carbonate in conjunction with iron oxyhydroxide,resulting in enhanced removal efficiency.The experiment was conducted under various conditions:concentration,dosage,pH,agitation,and temperature.Material characterizations such as Brunauer Emmett Teller,X-ray diffraction,scanning electron microscopy,and Fourier transform infrared spectroscopy were implied to understand adsorption mechanisms.The Langmuir model revealed optimal concentrations for As(V)=500μg/L at pH-5 and As(III)=200μg/L at pH-7,resulting in 95%and 93%adsorption efficiencies,respectively.Maximum adsorption capacities“qm”were found to be 1266.943μg/g for As(V)and 1080.241μg/g for As(III).Freundlich model demonstrated favorable adsorption by indicating“n>1”such as As(V)=2.542 and As(III)=2.707;similarly,the speciation factor“RL<1”for both species as As(V)=0.1 and As(III)=0.5,respectively.The kinetic study presented a pseudo-second-order model as best fitted,indicating throughout chemisorption processes for removing As(V)and As(III).Furthermore,incorporating calcium carbonate presented a significant leap in the removal efficiency,indicating As(V)from 95%to 98%and As(III)from 93%to 96%,respectively.Our findings offer profound motivation for developing effective and sustainable solutions to tackle arsenic contamination,underscoring the exceptional promise of iron oxyhydroxide in conjunction with calcium carbonate to achieve maximum removal efficiency.展开更多
An efficient and economical oxygen evolution reaction(OER)catalyst is critical to the widespread application of solar energy to fuel conversion.Among many potential OER catalysts,the metal oxyhydroxides,especially FeO...An efficient and economical oxygen evolution reaction(OER)catalyst is critical to the widespread application of solar energy to fuel conversion.Among many potential OER catalysts,the metal oxyhydroxides,especially FeOOH,show promising OER reactivity.In the present work,we performed a DFT+U study of the OER mechanism on theγ‐FeOOH(010)surface.In particular,we established the chemical potential of the OH?and hole pair and included the OH?anion in the reaction pathway,accounting to the alkaline conditions of anodic OER process.We then analyzed the OER pathways on the surface with OH‐,O‐and Fe‐terminations.On the surface with OH‐and O‐terminations,the O2molecule could form from either OH reacting with the surface oxygen species(-OH*and-O*)or the combination of two surface oxygen species.On the Fe‐terminated surface,O2can only form by adsorbing OH on the Fe sites first.The potential‐limiting step of the oxygen evolution with different surface terminations was determined by following the free‐energy change of the elementary steps along each pathway.Our results show that oxygen formation requires recreating the surface Fe sites,and consequently,the condition that favors the partially exposed Fe sites will promote oxygen formation.展开更多
The iron rust phases formed on low alloy steels containing different quantities of Cr element have been characterized using EPMA, Raman spectroscopy, TEM, optical microscopy etc. The ion selective properties of synthe...The iron rust phases formed on low alloy steels containing different quantities of Cr element have been characterized using EPMA, Raman spectroscopy, TEM, optical microscopy etc. The ion selective properties of synthesized rust films with the same phase constituent as the atmospheric corrosion products were investigated using self-made apparatus. The results showed that corrosion loss of steels exposed in marine atmosphere decreased rapidly as the Cr content of the steel was increased. Cr-containing steels were covered by a uniform compacted rust layer composed of fine particles with an average diameter of several nanometers. Inner rust layer of Cr-containing steel (2 mass fraction) was composed of a-CrxFe1-xOOH, with Cr content of about 5 mass fraction. Such rust layer showed cation selective property, and could depress the penetration of Cl- to contact substrate steel directly.展开更多
The low-cost and high-capacity metal oxides/oxyhydroxides possess great merits as anodes for lithium-ion batteries(LIBs)with high energy density.However,their commercialization is greatly hindered by insufficient rate...The low-cost and high-capacity metal oxides/oxyhydroxides possess great merits as anodes for lithium-ion batteries(LIBs)with high energy density.However,their commercialization is greatly hindered by insufficient rate capability and cyclability.Rational regulations of metal oxides/oxyhydroxides with hollow geometry and disordered atomic frameworks represent efficient ways to improve their electrochemical properties.Herein,we propose a fast alkalietching method to realize the in-situ fabrication of iron oxyhydroxide with one-dimensional(1D)hierarchical hollow nanostructure and amorphous atomic structure from the iron vanadate nanowires.Benefiting from the improved electron/ion kinetics and efficient buffer ability for the volumetric change during the electro-cycles both in nanoscale and atomic level,the graphene-modified amorphous hierarchical FeOOH nanotubes(FeOOH-NTs)display high rate capability(~650 mA h g^−1 at 2000 mA g^−1)and superior long-term cycling stability(463 mA h g^−1 after 1800 cycles),which represents the best cycling performance among the reported FeOOH-based materials.More importantly,the selective dissolutionregrowth mechanism is demonstrated based on the time tracking of the whole transition process,in which the dissolution of FeVO4 and the in-situ selective re-nucleation of FeOOH during the formation of FeOOH-NTs play the key roles.The present strategy is also a general method to prepare various metal(such as Fe,Mn,Co,and Cu)oxides/oxyhydroxides with 1D hierarchical nanostructures.展开更多
Designing efficient and stable electrocatalysts to improve the oxygen evolution reaction(OER)with slow reaction kinetics is essential to improve hydrogen production from electrochemical water splitting.This research h...Designing efficient and stable electrocatalysts to improve the oxygen evolution reaction(OER)with slow reaction kinetics is essential to improve hydrogen production from electrochemical water splitting.This research has prepared a series of FeOOH/Ni(HCO_(3))_(2)heterostructured materials(denoted as FeOOH_(x)/Ni(HCO_(3))_(2))by a one-pot solvothermal method.The OER performance of the catalysts was maximized by finely tuning the content of different components,heterogeneous interfaces,and electronic structures.Specifically,the obtained FeOOH0.60/Ni(HCO_(3))_(2)heterostructured nanosheets had the lowest overpotential of 216 mV at a current density of 10 mA·cm^(−2)and were stable at a high current density of 100 mA·cm^(−2)for more than 96 h.The excellent OER activity and stability were still maintained in alkaline natural seawater(1 M KOH+seawater).When FeOOH0.60/Ni(HCO_(3))_(2)was used as the anode for water splitting,the electrolyzer provided a current density of 10 mA·cm^(−2)at a very low cell voltage of 1.51 V(1.56 V at 1 M KOH+seawater)and exhibited superior stability.The outstanding OER performance is ascribed to the synergistic effect of FeOOH and Ni(HCO_(3))_(2)upon heterostructure formation,as well as the altered electronic structure between the heterogeneous interfaces and the suitable hierarchical nanosheet morphology facilitating many active sites.This work provides a promising direction for improving the electrocatalytic activity of nickel-based catalysts in seawater splitting,which has important implications for both hydrogen economy and environmental remediation.展开更多
对高效催化剂进行多尺度调控可优化中间体的吸附能量(原子层面),并实现快速传质(三维宏观层面),这对于提升整体水分解性能至关重要.在本工作中,我们首先在镍铁氢氧化物中引入氧空位,然后通过磷化反应将其转化为具有纳米阵列形态的NiFe-V...对高效催化剂进行多尺度调控可优化中间体的吸附能量(原子层面),并实现快速传质(三维宏观层面),这对于提升整体水分解性能至关重要.在本工作中,我们首先在镍铁氢氧化物中引入氧空位,然后通过磷化反应将其转化为具有纳米阵列形态的NiFe-Vo-P催化剂.在析氧反应催化过程中,NiFe-Vo-P表面会原位形成磷酸盐阴离子及具有催化活性的Ni(Fe)OOH,能显著优化反应中间体的吸附强度.结果表明,NiFeVo-P在过电位为289 mV时电流密度可达1.5 A cm^(-2).同时,其超亲水/超疏气纳米阵列形貌可有效促进传质,在25和70℃的条件下,可在~2.0V的电池电压下分别获得580 mA cm^(-2)和1.0 A cm^(-2)的电流密度,是未进行超疏气形貌工程催化剂的电流密度的2倍以上.展开更多
Efficient and robust noble-metal-free bifunctional electrocatalysts for overall water splitting(OWS)is of great importance to realize the large-scale hydrogen production.Herein,we report the growth of undoped and Cr-d...Efficient and robust noble-metal-free bifunctional electrocatalysts for overall water splitting(OWS)is of great importance to realize the large-scale hydrogen production.Herein,we report the growth of undoped and Cr-doped NiCo2O4(Cr-NiCo2O4)nanoneedles(NNs)on nickel foam(NF)as bifunctional electrocatalysts for both hydrogen evolution reaction(HER)and oxygen evolution reaction(OER).We demonstrate that Cr-doping significantly improves activity for HER and OER by increasing the conductivity of NNs and allowing more active sites on NNs electrochemically accessible.When amorphous FeOOH is electrodeposited on the surface of Cr-NiCo2O4 NNs,the resulting FeOOH/Cr-NiCo2O4/NF exhibits itself as an excellent bifunctional catalyst for OWS.In the two-electrode cell where FeOOH/Cr-NiCo2O4/NF is used both as cathode and anode for OWS,a cell voltage of only 1.65 V is required to achieve an electrolysis current density of 100 mA·cm^−2.In addition,the catalyst shows a very high stability for OWS,the two-electrode cell can operate at a consist current density of 20 mA·cm^−2 for 10 h OWS with the cell voltage being stable at ca.1.60 V.These results demonstrate that FeOOH/Cr-NiCo2O4/NF possesses an OWS performance superior to most of transition-metal based bifunctional electrocatalysts working in alkaline medium.The excellent bifunctional activity and stability of FeOOH/Cr-NiCo2O4/NF are attributed to the following reasons:(i)The NN structure provides a large specific surface area;(ii)the high conductivity of Cr-NiCo2O4 enables more active centers on the far-end part of NNs to be electrochemically reached;(iii)the deposition of FeOOH supplies additional active sites for OWS.展开更多
Electrochemical nitrogen reduction reaction(NRR)under ambient conditions is highly desirable to achieve sustainable ammonia(NH3)production via an alternative carbon free strategy.Single-atom catalysts(SACs)with super ...Electrochemical nitrogen reduction reaction(NRR)under ambient conditions is highly desirable to achieve sustainable ammonia(NH3)production via an alternative carbon free strategy.Single-atom catalysts(SACs)with super high atomic utilization and catalytic efficiency exhibit great potential for NRR.Herein,a high-performance NRR SAC is facilely prepared via a simple deposition method to anchor Au single atoms onto porousβ-FeOOH nanotubes.The resulting Au-SA/FeOOH can efficiently drive NRR under ambient conditions,and the NH3 yield reaches as high as 2,860μg·h^(-1)·mg_(Au)^(-1)at-0.4 V vs.reversible hydrogen electrode(RHE)with 14.2%faradaic efficiency,much superior to those of all the reported Au-based electrocatalysts.Systematic investigations demonstrate that the synergy of much enhanced N_(2)adsorption,directional electron export,and mass transfer ability in Au-SA/FeOOH greatly contributes to the superior NRR activity.This work highlights a new insight into the design of high efficient NRR electrocatalysts by combination of porous metal oxide matrix and highly active single-atom sites.展开更多
基金supported by the Human Resources Development program(no.20124010203180) of the Korea Institute of Energy Technology Evaluation and Planning(KETEP)Grant funded by the Korea government Ministry of Trade,Industry and Energysupported by Basic Science Research Program through the National Research Foundation of Korea(NRF) funded by the Ministry of Science,ICT and Future Planning(NRF-2015R1A2A2A01006856)
文摘Nanostructured iron oxyhydroxide（Fe OOH） thin films have been synthesized using an electrodeposition method on a nickel foam（NF） substrate and effect of air annealing temperature on the catalytic performance is studied. The as-deposited and annealed thin films were characterized by X-ray diffraction（XRD）,X-ray photoelectron spectroscopy（XPS）, field emission scanning electron microscopy（FE-SEM） and linear sweep voltammetry（LSV） to determine their structural, morphological, compositional and electrochemical properties, respectively. The as-deposited nanostructured amorphous Fe OOH thin film is converted into a polycrystalline Fe;O;with hematite crystal structure at a high temperature. The Fe OOH thin film acts as an efficient electrocatalyst for the oxygen evolution reaction（OER） in an alkaline 1 M KOH electrolyte. The film annealed at 200 °C shows high catalytic activity with an onset overpotential of 240 m V with a smaller Tafel slope of 48 m V/dec. Additionally, it needs an overpotential of 290 mV to the drive the current density of 10 m A/cm;and shows good stability in the 1 M KOH electrolyte solution.
基金This study was supported by the National Natural Science Foundation of China(grant no.31770620).
文摘Polypyrrole(PPy)@cellulose fiber-based composites have been widely investigated as electrode materials for use in flexible supercapacitors.However,they cannot readily provide high specific capacitance and cyclic stability owing to their inherent drawbacks,such as high resistance,Weber impedance,and volume expansion or collapse during charging/discharging.In this study,iron oxyhydroxide(FeOOH)is incorporated in the abovementioned composite to decrease the equivalent series resistance,charge transfer resistance,and Weber impedance,thereby enhancing electron transfer and ion diffusion,which results in superior electrochemical performance.The PPy-wrapped FeOOH@cellulose fiber-based composite electrode with the molar ratio of FeSO_(4) to NaBH4 of 1∶1 exhibits a high specific capacitance of 513.8 F/g at a current density of 0.2 A/g,as well as an excellent capacitance retention of 89.4% after 1000 cycles.
基金funded by the National Natural Science Foundation of China(Nos.42177078 and 42020104005).
文摘Synthesized iron oxyhydroxide was applied for the adsorptive removal of As(V)and As(III)from the aquas media.Additionally,this investigation highlighted the synergistic effect of calcium carbonate in conjunction with iron oxyhydroxide,resulting in enhanced removal efficiency.The experiment was conducted under various conditions:concentration,dosage,pH,agitation,and temperature.Material characterizations such as Brunauer Emmett Teller,X-ray diffraction,scanning electron microscopy,and Fourier transform infrared spectroscopy were implied to understand adsorption mechanisms.The Langmuir model revealed optimal concentrations for As(V)=500μg/L at pH-5 and As(III)=200μg/L at pH-7,resulting in 95%and 93%adsorption efficiencies,respectively.Maximum adsorption capacities“qm”were found to be 1266.943μg/g for As(V)and 1080.241μg/g for As(III).Freundlich model demonstrated favorable adsorption by indicating“n>1”such as As(V)=2.542 and As(III)=2.707;similarly,the speciation factor“RL<1”for both species as As(V)=0.1 and As(III)=0.5,respectively.The kinetic study presented a pseudo-second-order model as best fitted,indicating throughout chemisorption processes for removing As(V)and As(III).Furthermore,incorporating calcium carbonate presented a significant leap in the removal efficiency,indicating As(V)from 95%to 98%and As(III)from 93%to 96%,respectively.Our findings offer profound motivation for developing effective and sustainable solutions to tackle arsenic contamination,underscoring the exceptional promise of iron oxyhydroxide in conjunction with calcium carbonate to achieve maximum removal efficiency.
基金supported by the Chemical,Biological,Environmental,and Transport Systems(CBET)program of US National Science Foundation(CBET-1438440)~~
文摘An efficient and economical oxygen evolution reaction(OER)catalyst is critical to the widespread application of solar energy to fuel conversion.Among many potential OER catalysts,the metal oxyhydroxides,especially FeOOH,show promising OER reactivity.In the present work,we performed a DFT+U study of the OER mechanism on theγ‐FeOOH(010)surface.In particular,we established the chemical potential of the OH?and hole pair and included the OH?anion in the reaction pathway,accounting to the alkaline conditions of anodic OER process.We then analyzed the OER pathways on the surface with OH‐,O‐and Fe‐terminations.On the surface with OH‐and O‐terminations,the O2molecule could form from either OH reacting with the surface oxygen species(-OH*and-O*)or the combination of two surface oxygen species.On the Fe‐terminated surface,O2can only form by adsorbing OH on the Fe sites first.The potential‐limiting step of the oxygen evolution with different surface terminations was determined by following the free‐energy change of the elementary steps along each pathway.Our results show that oxygen formation requires recreating the surface Fe sites,and consequently,the condition that favors the partially exposed Fe sites will promote oxygen formation.
基金This research were supported by the Science and Technology Society of Shanghai, China Appreciation is expressed to Y.F.Zhu of the Instrumental Analysis Center of Shanghai JiaoTong University for the use of Raman Spectroscope.
文摘The iron rust phases formed on low alloy steels containing different quantities of Cr element have been characterized using EPMA, Raman spectroscopy, TEM, optical microscopy etc. The ion selective properties of synthesized rust films with the same phase constituent as the atmospheric corrosion products were investigated using self-made apparatus. The results showed that corrosion loss of steels exposed in marine atmosphere decreased rapidly as the Cr content of the steel was increased. Cr-containing steels were covered by a uniform compacted rust layer composed of fine particles with an average diameter of several nanometers. Inner rust layer of Cr-containing steel (2 mass fraction) was composed of a-CrxFe1-xOOH, with Cr content of about 5 mass fraction. Such rust layer showed cation selective property, and could depress the penetration of Cl- to contact substrate steel directly.
基金This work was supported by the National Key Research and Development Program of China(2017YFE0127600,2016YFA0202600)the Program of Introducing Talents of Discipline to Universities(B17034)+3 种基金the National Natural Science Foundation of China(51521001 and 51602239)the National Natural Science Fund for Distinguished Young Scholars(51425204)Hubei Provincial Natural Science Foundation(2016CFB267)the Fundamental Research Funds for the Central Universities(WUT:2017-YB-001).
文摘The low-cost and high-capacity metal oxides/oxyhydroxides possess great merits as anodes for lithium-ion batteries(LIBs)with high energy density.However,their commercialization is greatly hindered by insufficient rate capability and cyclability.Rational regulations of metal oxides/oxyhydroxides with hollow geometry and disordered atomic frameworks represent efficient ways to improve their electrochemical properties.Herein,we propose a fast alkalietching method to realize the in-situ fabrication of iron oxyhydroxide with one-dimensional(1D)hierarchical hollow nanostructure and amorphous atomic structure from the iron vanadate nanowires.Benefiting from the improved electron/ion kinetics and efficient buffer ability for the volumetric change during the electro-cycles both in nanoscale and atomic level,the graphene-modified amorphous hierarchical FeOOH nanotubes(FeOOH-NTs)display high rate capability(~650 mA h g^−1 at 2000 mA g^−1)and superior long-term cycling stability(463 mA h g^−1 after 1800 cycles),which represents the best cycling performance among the reported FeOOH-based materials.More importantly,the selective dissolutionregrowth mechanism is demonstrated based on the time tracking of the whole transition process,in which the dissolution of FeVO4 and the in-situ selective re-nucleation of FeOOH during the formation of FeOOH-NTs play the key roles.The present strategy is also a general method to prepare various metal(such as Fe,Mn,Co,and Cu)oxides/oxyhydroxides with 1D hierarchical nanostructures.
基金supported by the Tianjin Science and Technology Support Key Projects(No.20JCYBJC01420).
文摘Designing efficient and stable electrocatalysts to improve the oxygen evolution reaction(OER)with slow reaction kinetics is essential to improve hydrogen production from electrochemical water splitting.This research has prepared a series of FeOOH/Ni(HCO_(3))_(2)heterostructured materials(denoted as FeOOH_(x)/Ni(HCO_(3))_(2))by a one-pot solvothermal method.The OER performance of the catalysts was maximized by finely tuning the content of different components,heterogeneous interfaces,and electronic structures.Specifically,the obtained FeOOH0.60/Ni(HCO_(3))_(2)heterostructured nanosheets had the lowest overpotential of 216 mV at a current density of 10 mA·cm^(−2)and were stable at a high current density of 100 mA·cm^(−2)for more than 96 h.The excellent OER activity and stability were still maintained in alkaline natural seawater(1 M KOH+seawater).When FeOOH0.60/Ni(HCO_(3))_(2)was used as the anode for water splitting,the electrolyzer provided a current density of 10 mA·cm^(−2)at a very low cell voltage of 1.51 V(1.56 V at 1 M KOH+seawater)and exhibited superior stability.The outstanding OER performance is ascribed to the synergistic effect of FeOOH and Ni(HCO_(3))_(2)upon heterostructure formation,as well as the altered electronic structure between the heterogeneous interfaces and the suitable hierarchical nanosheet morphology facilitating many active sites.This work provides a promising direction for improving the electrocatalytic activity of nickel-based catalysts in seawater splitting,which has important implications for both hydrogen economy and environmental remediation.
基金supported by the National Key R&D Program of China(2021YFB3801301)the National Natural Science Foundation of China(22075076 and 22005098)the Central Government Funds for Guiding Local Science and Technology Development(2021Szvup040)。
文摘对高效催化剂进行多尺度调控可优化中间体的吸附能量(原子层面),并实现快速传质(三维宏观层面),这对于提升整体水分解性能至关重要.在本工作中,我们首先在镍铁氢氧化物中引入氧空位,然后通过磷化反应将其转化为具有纳米阵列形态的NiFe-Vo-P催化剂.在析氧反应催化过程中,NiFe-Vo-P表面会原位形成磷酸盐阴离子及具有催化活性的Ni(Fe)OOH,能显著优化反应中间体的吸附强度.结果表明,NiFeVo-P在过电位为289 mV时电流密度可达1.5 A cm^(-2).同时,其超亲水/超疏气纳米阵列形貌可有效促进传质,在25和70℃的条件下,可在~2.0V的电池电压下分别获得580 mA cm^(-2)和1.0 A cm^(-2)的电流密度,是未进行超疏气形貌工程催化剂的电流密度的2倍以上.
基金We gratefully acknowledge the financial support of this work by the National Natural Science Foundation of China(Nos.51872015 and 51672017).
文摘Efficient and robust noble-metal-free bifunctional electrocatalysts for overall water splitting(OWS)is of great importance to realize the large-scale hydrogen production.Herein,we report the growth of undoped and Cr-doped NiCo2O4(Cr-NiCo2O4)nanoneedles(NNs)on nickel foam(NF)as bifunctional electrocatalysts for both hydrogen evolution reaction(HER)and oxygen evolution reaction(OER).We demonstrate that Cr-doping significantly improves activity for HER and OER by increasing the conductivity of NNs and allowing more active sites on NNs electrochemically accessible.When amorphous FeOOH is electrodeposited on the surface of Cr-NiCo2O4 NNs,the resulting FeOOH/Cr-NiCo2O4/NF exhibits itself as an excellent bifunctional catalyst for OWS.In the two-electrode cell where FeOOH/Cr-NiCo2O4/NF is used both as cathode and anode for OWS,a cell voltage of only 1.65 V is required to achieve an electrolysis current density of 100 mA·cm^−2.In addition,the catalyst shows a very high stability for OWS,the two-electrode cell can operate at a consist current density of 20 mA·cm^−2 for 10 h OWS with the cell voltage being stable at ca.1.60 V.These results demonstrate that FeOOH/Cr-NiCo2O4/NF possesses an OWS performance superior to most of transition-metal based bifunctional electrocatalysts working in alkaline medium.The excellent bifunctional activity and stability of FeOOH/Cr-NiCo2O4/NF are attributed to the following reasons:(i)The NN structure provides a large specific surface area;(ii)the high conductivity of Cr-NiCo2O4 enables more active centers on the far-end part of NNs to be electrochemically reached;(iii)the deposition of FeOOH supplies additional active sites for OWS.
基金This work was supported by the Natural Science Foundation of Tianjin City of China(No.18JCJQJC47700)the Key Laboratory of Resource Chemistry of Chinese Ministry of Education(No.KLRC_ME1902)+2 种基金the Opening Project of Key Laboratory of Polyoxometalate and Reticular Material Chemistry of Chinese Ministry of Education,the National Natural Science Foundation of China(No.21701168)Dalian high level talent innovation project(No.2019RQ063)the Open Project Foundation of State Key Laboratory of Structural Chemistry,and Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences(No.20200021).
文摘Electrochemical nitrogen reduction reaction(NRR)under ambient conditions is highly desirable to achieve sustainable ammonia(NH3)production via an alternative carbon free strategy.Single-atom catalysts(SACs)with super high atomic utilization and catalytic efficiency exhibit great potential for NRR.Herein,a high-performance NRR SAC is facilely prepared via a simple deposition method to anchor Au single atoms onto porousβ-FeOOH nanotubes.The resulting Au-SA/FeOOH can efficiently drive NRR under ambient conditions,and the NH3 yield reaches as high as 2,860μg·h^(-1)·mg_(Au)^(-1)at-0.4 V vs.reversible hydrogen electrode(RHE)with 14.2%faradaic efficiency,much superior to those of all the reported Au-based electrocatalysts.Systematic investigations demonstrate that the synergy of much enhanced N_(2)adsorption,directional electron export,and mass transfer ability in Au-SA/FeOOH greatly contributes to the superior NRR activity.This work highlights a new insight into the design of high efficient NRR electrocatalysts by combination of porous metal oxide matrix and highly active single-atom sites.
