The adsorption of DNA bases on a magnetic probe composed of Fe atoms and graphene is studied by using first- principles calculations. The stability of geometry, the electronic structure and magnetic property are inves...The adsorption of DNA bases on a magnetic probe composed of Fe atoms and graphene is studied by using first- principles calculations. The stability of geometry, the electronic structure and magnetic property are investigated. The results indicate that four DNA bases, i.e., adenine, thymine, cytosine and guanine, can all be adsorbed on the probe solidly. However, the magnetic moments of the composite structure can be observed only when adenine adsorbs on the probe. In the cases of the adsorption of the other three bases, the magnetic moments of the composite structure are zero. Based on the significant change of magnetic moment of the composite structure, adenine can be distinguished conveniently from thymine, cytosine and guanine. This work may provide a new way to detect DNA bases.展开更多
Adsorption behavior of Fe atoms on a metal-free naphthalocyanine（H2Nc） monolayer on Ag（111） surface at room temperature has been investigated using scanning tunneling microscopy combined with density functional th...Adsorption behavior of Fe atoms on a metal-free naphthalocyanine（H2Nc） monolayer on Ag（111） surface at room temperature has been investigated using scanning tunneling microscopy combined with density functional theory（DFT）based calculations. We found that the Fe atoms were adsorbed on the centers of H2Nc molecules and formed Fe–H2Nc complexes at low coverage. DFT calculations show that Fe sited in the center of the molecule is the most stable configuration, in good agreement with the experimental observations. After an Fe–H2Nc complex monolayer was formed, the extra Fe atoms self-assembled to Fe clusters of uniform size and adsorbed dispersively at the interstitial positions of Fe–H2Nc complex monolayer. Therefore, the H2Nc monolayer grown on Ag（111） could be a good template to grow dispersed magnetic metal atoms and clusters at room temperature for further investigation of their magnetism-related properties.展开更多
In this study,we aim to contribute an understanding of the pathway of formation of Fe species during top-down synthesis of dispersed Fe on N-functionalized few layer graphene,widely used in electrocatalysis.We use X-r...In this study,we aim to contribute an understanding of the pathway of formation of Fe species during top-down synthesis of dispersed Fe on N-functionalized few layer graphene,widely used in electrocatalysis.We use X-ray absorption spectroscopy to determine the electronic structure and coordination geometry of the Fe species and in situ high angle annular dark field scanning transmission electron microscopy combined with atomic resolved electron energy loss spectroscopy to localize these,identify their chemical configuration and monitor their dynamics during thermal annealing.We show the high mobility of peripheral Fe atoms,first diffusing rapidly at the trims of the graphene layers and at temperatures as high as 573 K,diffusing from the edge planes towards in-plane locations of the graphene layers forming three-,four-coordinated metal sites and more complexes polynuclear Fe species.This process occurs via bond C-C breaking which partially reduces the extension of the graphene domains.However,the vast majority of Fe is segregated as a metal phase.This dynamic interconversion depends on the structural details of the surrounding graphitic environment in which these are formed as well as the Fe loading.N species appear stabilizing isolated and polynuclear Fe species even at temperatures as high as 873 K.The significance of our results lies on the fact that single Fe atoms in graphene are highly mobile and therefore a structural description of the electroactive sites as such is insufficient and more complex species might be more relevant,especially in the case of multielectron transfer reactions.Here we provide the experimental evidence of the formation of these polynuclear Fe-N sites and their structural characteristics.展开更多
Herein,an oxygen-doped porous g-C_(3)N_(4)photocatalyst modified with atomically dispersed Fe(Fe_(1)/OPCN)issuccessfully prepared and exhibits significant superiority in removing refractory sulfonic azo contaminants f...Herein,an oxygen-doped porous g-C_(3)N_(4)photocatalyst modified with atomically dispersed Fe(Fe_(1)/OPCN)issuccessfully prepared and exhibits significant superiority in removing refractory sulfonic azo contaminants fromwater via catalyst-contaminant interaction.The elimination performance of Fe_(1)/OPCN towards acid red 9,acidred 13 and amaranth containing similar azonaphthalene structure and increasing sulfonic acid groups increasesgradually.The amaranth degradation rate of Fe_(1)/OPCN is 17.7 and 6.1 times as that of homogeneous Fenton andOPCN,respectively.In addition,Fe_(1)/OPCN also has more outstanding removal activities towards other con-taminantswith sulfonic acid and azo groups alone.The considerable enhancement for removing sulfonic azocontaminants of Fe_(1)/OPCN is mainly ascribed to the following aspects:(1)The modified Fe could enhance theadsorption towards sulfonic azo compounds to accelerate the mass transfer,act as e^(-)acceptor to promoteinterfacial charge separation,and trigger the self-Fenton reaction to convert in-situ generated H_(2)O_(2)into·OH.(2)Fe(Ⅲ)could coordinate with-N=N-to form d-πconjugation,which could attract e^(-)transfer to attack-N=N-bond.Meanwhile,the inhibited charge recombination could release more free h^(þ)to oxidize sulfonicacid groups into SO4^(-)·.(3)Under the cooperation of abundant multiple active species(·O_(2)^(-),h^(þ),e^(-),·OH,SO4^(-)·)formed during the degradation reaction,sulfonic azo compounds could be completely mineralized into harmlesssmall molecules(CO_(2),H_(2)O,etc.)by means of-N=N-cleavage,hydroxyl substitution,and aromatic ringopening.This work offers a novel approach for effectively eliminating refractory sulfonic azo compounds fromwastewater.展开更多
Energy crises and environmental pollution have become urgent problems with human civilization development.Photocatalysis technology is a green method to deal with these challenges.The key to improve photocatalytic eff...Energy crises and environmental pollution have become urgent problems with human civilization development.Photocatalysis technology is a green method to deal with these challenges.The key to improve photocatalytic efficiency lies in the effective separation of photogenerated electron-hole pairs.In this work,we designed the Fe atom embedded N-doped graphene oxide(Fe-NGO)supporting on tantalum nitride(Ta_(3)N_(5))catalyst,which was employed to improve the photocatalytic oxygen production activity.The oxygen production of 5 wt%Fe atom embedded N-doped graphene oxide supporting on tantalum nitride(Fe-NGO/Ta_(3)N_(5))was 184.7μmol·g^(-1),about 3.5 times higher than that of the pure Ta_(3)N_(5).The introduction of the cocatalyst Fe-NGO acting as an electron conductor in the Fe-NGO/Ta_(3)N_(5) accelerates the carrier migration of Ta_(3)N_(5) and further enhances the photocatalytic oxygen production activity.N-doping increases the conductivity of graphene oxide(GO),and Fe atoms are used as the reactive sites to promote the combination of electron and sacrificial agent in the system.This work may provide insights into the research of new carbon.展开更多
Phase manipulation of MoS_(2) from thermodynamically stable 2H phase to the unstable but more reactive 1T phase represents a crucial strategy for improving the reactivity in many reactions.The widely adopted wet chemi...Phase manipulation of MoS_(2) from thermodynamically stable 2H phase to the unstable but more reactive 1T phase represents a crucial strategy for improving the reactivity in many reactions.The widely adopted wet chemistry approach uses intercalating entities especially alkali metal ions to achieve the phase transition;however,these entities are normally inert for the target reaction.Here,we describe the first use of iron atoms for the intercalation of 2H-MoS_(2) layers,driving the partial transition from 2H to 1T phase.Interestingly,in the peroxymonosulfate(PMS)-based Fenton-like reactions,the interlayered confinement of Fe atoms not only activates the inert basal plane,but also adds more reactive Fe sites for the formation of metal-PMS complex as primary reactive species for pollutant removal.In the degradation of a model pollutant carbamazepine(CBZ),the Fe-intercalated MoS_(2) exhibits a first order rate constant 13.3 times higher than 2H-MoS_(2).This strategy is a new direction for manipulating the phase composition and boosting the catalytic reactivity of MoS_(2)-based catalysts in various scenarios,including environmental remediation and energy applications.展开更多
Air cathodes with high electrocatalytic activity are vital for developing H2/O_(2) proton exchange membrane fuel cells(PEMFC)and Zn-air batteries.However,the state-of-the-art air cathodes suffer from either limited ca...Air cathodes with high electrocatalytic activity are vital for developing H2/O_(2) proton exchange membrane fuel cells(PEMFC)and Zn-air batteries.However,the state-of-the-art air cathodes suffer from either limited catalytic activity or high cost,which thus hinder their applications.Herein,we designed ZIF-8 derived nitrogen and atomic iron dual-doped porous carbon nanocubes as high-quality catalysts for ORR,through a novel gas-doping approach.The porous carbon nanocubic architecture and abundant Fe-Nxactive species endow ZIF-8 derived single atomic iron catalyst(PCN-A@Fe SA)with superior catalytic activity,and surpass Pt/C and a majority of the reported catalysts.Both XAS and DFT calculations suggest that Fe2+N4 moieties are the main active centers that are favorable for oxygen affinity and OH*intermediate desorption,which can result in promising catalytic performance.Most importantly,PCNA@Fe SA can achieve power density of 514 m W cm^(-2) as cathodic catalyst in a PEMFC and discharge peak power density of 185 m W cm^(-2) in an alkaline Zn-air battery.The outstanding performance is derived from both the high specific surface area and high-density of iron single atom in nitrogen doped nanocubic carbon matrix.展开更多
Fe-N-C endowed with inexpensiveness,high activity,and excellent anti-poisoning power have emerged as promising candidate catalysts for oxygen reduction reaction(ORR).Single-atom Fe-N-C electrocatalysts derived from Fe...Fe-N-C endowed with inexpensiveness,high activity,and excellent anti-poisoning power have emerged as promising candidate catalysts for oxygen reduction reaction(ORR).Single-atom Fe-N-C electrocatalysts derived from Fe-doped ZIF-8 represent the top-level ORR performance.However,the current fabrication of Fe-doped ZIF-8 relies on heavy consumption of time,energy,cost and organic solvents.Herein,we develop a rapid and solvent-free method to produce Fe-doped ZIF-8 under microwave irradiation,which can be easily amplified in combination with ball-milling.After rational pyrolysis,Fe-N-C catalysts with atomic FeN4 sites well dispersed on the hierarchically porous carbon matrix are obtained,which exhibit exceptional ORR performance with a half-wave potential of 0.782 V(vs.reversible hydrogen electrode(RHE))and brilliant methanol tolerance.The assembled direct methanol fuel cells(DMFCs)endow a peak power density of 61 mW cm^(-2) and extraordinary stability,highlighting the application perspective of this strategy.展开更多
Exploring platinum group metal-free electrocatalysts with superior catalytic performance and favorable durability for oxygen reduction reaction is a remaining bottleneck in process of developing sustainable techniques...Exploring platinum group metal-free electrocatalysts with superior catalytic performance and favorable durability for oxygen reduction reaction is a remaining bottleneck in process of developing sustainable techniques in energy storage and conversion. Herein, a hierarchical porous single atomic Fe electrocatalyst(Fe/Z8-E-C) is rationally designed and synthesized via acid etching, calcination, adsorption of Fe precursor and recalcination processes. This unique electrocatalyst Fe/Z8-E-C shows excellent oxygen reduction performance with a half-wave potential of 0.89 V in 0.1 mol/L KOH, 30 m V superior to that of commercial Pt/C(0.86 V), which is also significantly higher than that of typical Fe-doped ZIF-8 derived carbon nanoparticles(Fe/Z8-C) with a half-wave potential of 0.84 V. Furthermore, Fe/Z8-E-C-based Zn-air battery exhibits greatly enhanced peak power density and specific capacity than those of original Fe/Z8-C,verifying the remarkable performance and practicability of this specially designed hierarchical structure due to its efficient utilization of the active sites and rapid mass transfer. This present work proposes a new method to rationally synthesize single atom electrocatalysts loaded on hierarchical porous frame materials for catalysis and energy conversion.展开更多
Rechargeable aluminum-sulfur(Al-S)batteries have been considered as a highly potential energy storage system owing to the high theoretical capacity,good safety,abundant natural reserves,and low cost of Al and S.Howeve...Rechargeable aluminum-sulfur(Al-S)batteries have been considered as a highly potential energy storage system owing to the high theoretical capacity,good safety,abundant natural reserves,and low cost of Al and S.However,the research progress of Al-S batteries is limited by the slow kinetics and shuttle effect of soluble polysulfides intermediates.Herein,an interconnected free-standing interlayer of iron sin-gle atoms supported on porous nitrogen-doped carbon nanofibers(FeSAs-NCF)on the separator is developed and used as both catalyst and chemical barrier for Al-S batteries.The atomically dispersed iron active sites(Fe-N_(4))are clearly identified by aberration-corrected high-angle annular dark-field scanning transmission electron microscopy and X-ray absorption near-edge structure.The Al-S battery with the FeSAs-NCF shows an improved specific capacity of 780 mAh g^(−1)and enhanced cycle stability.As evidenced by experimental and theoretical results,the atomically dispersed iron active centers on the separator can chemically adsorb the polysulfides and accelerate reaction kinetics to inhibit the shuttle effect and promote the reversible conversion between aluminum polysulfides,thus improving the electrochemical performance of the Al-S battery.This work provides a new way that can not only promote the conversion of aluminum sulfides but also suppress the shuttle effect in Al-S batteries.展开更多
The diffusible hydrogen contents in precharged (Co,Fe) 3V alloy were measured. It is found that atomic ordering can not promote hydrogen penetration in the (Co,Fe) 3V alloy. The ultimate tensile strength (UTS) and duc...The diffusible hydrogen contents in precharged (Co,Fe) 3V alloy were measured. It is found that atomic ordering can not promote hydrogen penetration in the (Co,Fe) 3V alloy. The ultimate tensile strength (UTS) and ductilities in various condition were also investigated. The results show that the UTS and elongation of disordered alloy are higher than that of ordered one with fixed diffusible hydrogen content and (Co,Fe) 3V alloy with ordered structure is highly susceptible to the embrittlement in hydrogen gas. The factor which may affect the susceptibility to the embrittlement of (Co,Fe) 3V alloy in hydrogen gas is mainly due to that the atomic ordering may accelerate the kinetics of the catalytic reaction for the dissociation of molecular hydrogen into atomic hydrogen. However, it can not be roled out that atomic ordering intensifies planar slip and restricts cross slip at the grain boundaries and enhances the susceptibility of the alloy to hydrogen embrittlement.展开更多
The microstructural evolution of the gas atomized Fe-25Cr-3.2C powders was investigated by using optical microscope, scanning electron microscope, and X-ray diffraction. The experimental results showed that the atomiz...The microstructural evolution of the gas atomized Fe-25Cr-3.2C powders was investigated by using optical microscope, scanning electron microscope, and X-ray diffraction. The experimental results showed that the atomized Fe-25Cr-3.2C powders were mainly composed of austenite and （Fe,Cr）7 C3 carbide. Eutectic microstructure was developed in the larger particles, whereas dendritic microstrueture was obtained in the particles with diameter less than 38 μm. The reason for microstructure change should be the difference of nucleation undercooling for particles.展开更多
Developing cost-effective,robust and stable non-precious metal catalysts for oxygen reduction reaction(ORR) is of paramount importance for electrochemical energy conversion devices such as fuel cells and metal-air bat...Developing cost-effective,robust and stable non-precious metal catalysts for oxygen reduction reaction(ORR) is of paramount importance for electrochemical energy conversion devices such as fuel cells and metal-air batteries.Although Fe-N-C single atom catalysts(SACs) have been hailed as the most promising candidate due to the optimal binding strength of ORR intermediates on the Fe-N_(4) sites,they suffer from serious mass transport limitations as microporous templates/substrates,i.e.,zeolitic imidazolate frameworks(ZIFs),are usually employed to host the active sites.Motivated by this challenge,we herein develop a hydrogen-bonded organic framework(HOF)-assisted pyrolysis strategy to construct hierarchical micro/mesoporous carbon nanoplates for the deposition of atomically dispersed Fe-N_(4) sites.Such a design is accomplished by employing HOF nanoplates assembled from 2-aminoterephthalic acid(NH_(2)-BDC) and p-phenylenediamine(PDA) as both soft templates and C,N precursors.Benefitting from the structural merits inherited from HOF templates,the optimized catalyst(denoted as Fe-N-C SAC-950) displays outstanding ORR activity with a high half-wave potential of 0.895 V(vs.reversible hydrogen electrode(RHE)) and a small overpotential of 356 mV at 10 mA cm^(-2) for the oxygen evolution reaction(OER).More excitingly,its application potential is further verified by delivering superb rechargeability and cycling stability with a nearly unfading charge-discharge gap of 0.72 V after 160 h.Molecular dynamics(MD) simulations reveal that micro/mesoporous structure is conducive to the rapid mass transfer of O_(2),thus enhancing the ORR performance.In situ Raman results further indicate that the conversion of O_(2) to~*O_(2)-the rate-determining step(RDS) for Fe-N-C SAC-950.This work will provide a versatile strategy to construct single atom catalysts with desirable catalytic properties.展开更多
The structure stability, elastic property and electronic structure of a-Fe supercell with La atom were inves- tigated by first-principles, in which, generalized gradient approximation （GGA） with the Perdew Burke Ern...The structure stability, elastic property and electronic structure of a-Fe supercell with La atom were inves- tigated by first-principles, in which, generalized gradient approximation （GGA） with the Perdew Burke Ernzerhof （PBE） was used as exchange-correlation functional, a-Fe supercells with La atom include a-Fe supercell with La atom in octahedral interstitial solid solute （La-OISS）, that with La atom in tetrahedral interstitial solid solute （La-TISS） and that with La atom in substitutional solid solute （La-SSS）. The results show that the La-SSS a-Fe supercell is more stable than La-OISS one. The resistance to volume change, reversible deformation and stiffness of La-OISS a-Fe supercell are stronger than those of La-SSS one. Moreover, the degrees of anisotropy and ionization in La-SSS a-Fe supercell are both stronger than those in La-OISS one. The bonding strength between La atom and Fe atom in La-SSS a-Fe supercell is larger than that in La-OISS one.展开更多
[目的]为进一步拓展单原子催化剂在亚硝酸盐还原制氨领域的应用,提出了一种铁-氮-碳(Fe-N-C)单原子催化剂电催化亚硝酸盐还原制氨的新体系.[方法]以二氧化硅为硬模板,2,6-二氨基吡啶为碳氮前驱体,硝酸铁为金属盐,通过“热解-刻蚀”策略...[目的]为进一步拓展单原子催化剂在亚硝酸盐还原制氨领域的应用,提出了一种铁-氮-碳(Fe-N-C)单原子催化剂电催化亚硝酸盐还原制氨的新体系.[方法]以二氧化硅为硬模板,2,6-二氨基吡啶为碳氮前驱体,硝酸铁为金属盐,通过“热解-刻蚀”策略制备了Fe-N-C单原子催化剂,并将其应用于亚硝酸盐制氨反应.[结果]多种结构表征结果显示,Fe-N-C催化剂表面的Fe物种呈现高度分散特征并以单原子形式存在.此外,Fe物种的化学环境主要是+2和+3价混合态,且通过与4个吡啶氮配位而稳定存在,即Fe-N-C催化剂的金属中心微观配位环境为Fe-N4结构.与纯氮碳(N-C)载体相比,本研究制备的Fe-N-C催化剂具有优异的亚硝酸盐还原性能,不仅表现出更高的起始还原电位(0 V vs可逆氢电极),具有接近100%的产氨法拉第效率和高的氨产率[8.4 mg/(h·cm^(2))],并且在连续20次催化循环测试中显示出优异的催化稳定性.[结论]本研究制备的Fe-N-C单原子催化剂对亚硝酸盐还原制氨具有优异的电催化活性,其高活性可能来源于对NO_(2)^(-)的显著吸附,并进一步促进活性氢参与脱氧加氢过程.该Fe-N-C单原子催化亚硝酸盐还原体系可为后续合成氨的活性中心设计提供指导方向.展开更多
Zn-CO_(2)batteries(ZCBs)are promising for CO_(2)conversion and electric energy release.However,the ZCBs couple the electrochemical CO_(2)reduction(ECO_(2)R)with the oxygen evolution reaction and competitive hydrogen e...Zn-CO_(2)batteries(ZCBs)are promising for CO_(2)conversion and electric energy release.However,the ZCBs couple the electrochemical CO_(2)reduction(ECO_(2)R)with the oxygen evolution reaction and competitive hydrogen evolution reaction,which normally causes ultrahigh charge voltage and CO_(2)conversion efficiency attenuation,thereby resulting in~90%total power consumption.Herein,isolated FeN_(3)sites encapsulated in hierarchical porous carbon nanoboxes(Fe-HPCN,derived from the thermal activation process of ferrocene and polydopamine-coated cubic ZIF-8)were proposed for hydrazine-assisted rechargeable ZCBs based on ECO_(2)R(discharging process:CO_(2)+2H+→CO+H_(2)O)and hydrazine oxidation reaction(HzOR,charging process:N_(2)H_(4)+4OH−→N_(2)+4H_(2)O+4e^(−)).The isolated FeN_(3)endows the HzOR with a lower overpotential and boosts the ECO_(2)R with a 96%CO Faraday efficiency(FECO).Benefitting from the bifunctional ECO_(2)R and HzOR catalytic activities,the homemade hydrazine-assisted rechargeable ZCBs assembled with the Fe-HPCN air cathode exhibited an ultralow charge voltage(decreasing by~1.84 V),excellent CO selectivity(FECO close to 100%),and high 89%energy efficiency.In situ infrared spectroscopy confirmed that Fe-HPCN can generate rate-determining*N_(2)and*CO intermediates during HzOR and ECO_(2)R.This paper proposes FeN_(3)centers for bifunctional ECO_(2)R/HzOR performance and further presents the pioneering achievements of ECO_(2)R and HzOR for hydrazine-assisted rechargeable ZCBs.展开更多
Raoultian activity coefficients γ0c of C in infinitely dilute Fe-C binary melts at temperatures of 1833, 1873, 1923, and 1973 K have been determined from the converted mass action concentrations Nc of C in Fe-C binar...Raoultian activity coefficients γ0c of C in infinitely dilute Fe-C binary melts at temperatures of 1833, 1873, 1923, and 1973 K have been determined from the converted mass action concentrations Nc of C in Fe-C binary melts by the developed AMCT-Ni model based on the atom-molecule coexistence theory （AMCT）. The obtained expression of γ0c by the developed AMCT-Ni model has been evaluated to be accurate based on the reported ones from the literature. Meanwhile, three activity coefficients γc,f%,c, andfH,c of C coupled with activity aR,C or a%,c or aH,c have been obtained by the developed AMCT-Ni model and assessed through comparing with the predicted ones by other models from the literature. The first-order activity interaction coefficients ec, ec, and hcc related to γc f%,c, and fH,c are also determined and assessed in comparison with the reported ones from the literature. Furthermore, the integral molar mixing thermodynamic functions such as AmixHm,Fe-C, △mix-Sm,Fe-C, and △mixGm,Fe-C of Fe-C binary melts over a temperature range from 1833 to 1973 K have been determined and evaluated to be valid based on the determined ones from the literature.展开更多
基金Supported by the National Natural Science Foundation of China under Grant Nos 51301119 and 11204201the Natural Science Foundation for Young Scientists of Shanxi Province under Grant No 2013021010-1
文摘The adsorption of DNA bases on a magnetic probe composed of Fe atoms and graphene is studied by using first- principles calculations. The stability of geometry, the electronic structure and magnetic property are investigated. The results indicate that four DNA bases, i.e., adenine, thymine, cytosine and guanine, can all be adsorbed on the probe solidly. However, the magnetic moments of the composite structure can be observed only when adenine adsorbs on the probe. In the cases of the adsorption of the other three bases, the magnetic moments of the composite structure are zero. Based on the significant change of magnetic moment of the composite structure, adenine can be distinguished conveniently from thymine, cytosine and guanine. This work may provide a new way to detect DNA bases.
基金supported by the National Natural Science Foundation of China(Grant Nos.61390501,51325204,and 11204361)the National Basic Research Program of China(Grant Nos.2011CB808401 and 2011CB921702)+1 种基金the National Key Scientific Instrument and Equipment Development Project of China(Grant No.2013YQ1203451)the National Supercomputing Center in Tianjin,China,and the Chinese Academy of Sciences
文摘Adsorption behavior of Fe atoms on a metal-free naphthalocyanine（H2Nc） monolayer on Ag（111） surface at room temperature has been investigated using scanning tunneling microscopy combined with density functional theory（DFT）based calculations. We found that the Fe atoms were adsorbed on the centers of H2Nc molecules and formed Fe–H2Nc complexes at low coverage. DFT calculations show that Fe sited in the center of the molecule is the most stable configuration, in good agreement with the experimental observations. After an Fe–H2Nc complex monolayer was formed, the extra Fe atoms self-assembled to Fe clusters of uniform size and adsorbed dispersively at the interstitial positions of Fe–H2Nc complex monolayer. Therefore, the H2Nc monolayer grown on Ag（111） could be a good template to grow dispersed magnetic metal atoms and clusters at room temperature for further investigation of their magnetism-related properties.
基金The UK Catalysis Hub for support provided via the membership of the UK Catalysis Hub Consortium and funded by EPSRC (portfolio grants EP/K014706/1, EP/K014668/1, EP/K014854/1, EP/K014714/1 and EP/I019693/1).
文摘In this study,we aim to contribute an understanding of the pathway of formation of Fe species during top-down synthesis of dispersed Fe on N-functionalized few layer graphene,widely used in electrocatalysis.We use X-ray absorption spectroscopy to determine the electronic structure and coordination geometry of the Fe species and in situ high angle annular dark field scanning transmission electron microscopy combined with atomic resolved electron energy loss spectroscopy to localize these,identify their chemical configuration and monitor their dynamics during thermal annealing.We show the high mobility of peripheral Fe atoms,first diffusing rapidly at the trims of the graphene layers and at temperatures as high as 573 K,diffusing from the edge planes towards in-plane locations of the graphene layers forming three-,four-coordinated metal sites and more complexes polynuclear Fe species.This process occurs via bond C-C breaking which partially reduces the extension of the graphene domains.However,the vast majority of Fe is segregated as a metal phase.This dynamic interconversion depends on the structural details of the surrounding graphitic environment in which these are formed as well as the Fe loading.N species appear stabilizing isolated and polynuclear Fe species even at temperatures as high as 873 K.The significance of our results lies on the fact that single Fe atoms in graphene are highly mobile and therefore a structural description of the electroactive sites as such is insufficient and more complex species might be more relevant,especially in the case of multielectron transfer reactions.Here we provide the experimental evidence of the formation of these polynuclear Fe-N sites and their structural characteristics.
基金supported by the Natural Science Foundation of Jiangsu Province(BK20221541)National Natural Science Foundation of China(21707052)Jiangsu Agriculture Science and Technology Innovation Fund(CX(20)3108).
文摘Herein,an oxygen-doped porous g-C_(3)N_(4)photocatalyst modified with atomically dispersed Fe(Fe_(1)/OPCN)issuccessfully prepared and exhibits significant superiority in removing refractory sulfonic azo contaminants fromwater via catalyst-contaminant interaction.The elimination performance of Fe_(1)/OPCN towards acid red 9,acidred 13 and amaranth containing similar azonaphthalene structure and increasing sulfonic acid groups increasesgradually.The amaranth degradation rate of Fe_(1)/OPCN is 17.7 and 6.1 times as that of homogeneous Fenton andOPCN,respectively.In addition,Fe_(1)/OPCN also has more outstanding removal activities towards other con-taminantswith sulfonic acid and azo groups alone.The considerable enhancement for removing sulfonic azocontaminants of Fe_(1)/OPCN is mainly ascribed to the following aspects:(1)The modified Fe could enhance theadsorption towards sulfonic azo compounds to accelerate the mass transfer,act as e^(-)acceptor to promoteinterfacial charge separation,and trigger the self-Fenton reaction to convert in-situ generated H_(2)O_(2)into·OH.(2)Fe(Ⅲ)could coordinate with-N=N-to form d-πconjugation,which could attract e^(-)transfer to attack-N=N-bond.Meanwhile,the inhibited charge recombination could release more free h^(þ)to oxidize sulfonicacid groups into SO4^(-)·.(3)Under the cooperation of abundant multiple active species(·O_(2)^(-),h^(þ),e^(-),·OH,SO4^(-)·)formed during the degradation reaction,sulfonic azo compounds could be completely mineralized into harmlesssmall molecules(CO_(2),H_(2)O,etc.)by means of-N=N-cleavage,hydroxyl substitution,and aromatic ringopening.This work offers a novel approach for effectively eliminating refractory sulfonic azo compounds fromwastewater.
基金support from the National Natural Science Foundation of China (Nos.22106053,22008095)the China Postdoctoral Science Foundation (Nos.2021M691305,2020TQ0127)the Jiangsu Province Postdoctoral Science Foundation (Nos.2021K079A,2021K396C,2021K382C).
文摘Energy crises and environmental pollution have become urgent problems with human civilization development.Photocatalysis technology is a green method to deal with these challenges.The key to improve photocatalytic efficiency lies in the effective separation of photogenerated electron-hole pairs.In this work,we designed the Fe atom embedded N-doped graphene oxide(Fe-NGO)supporting on tantalum nitride(Ta_(3)N_(5))catalyst,which was employed to improve the photocatalytic oxygen production activity.The oxygen production of 5 wt%Fe atom embedded N-doped graphene oxide supporting on tantalum nitride(Fe-NGO/Ta_(3)N_(5))was 184.7μmol·g^(-1),about 3.5 times higher than that of the pure Ta_(3)N_(5).The introduction of the cocatalyst Fe-NGO acting as an electron conductor in the Fe-NGO/Ta_(3)N_(5) accelerates the carrier migration of Ta_(3)N_(5) and further enhances the photocatalytic oxygen production activity.N-doping increases the conductivity of graphene oxide(GO),and Fe atoms are used as the reactive sites to promote the combination of electron and sacrificial agent in the system.This work may provide insights into the research of new carbon.
基金support from the National Natural Science Foundation of China(Nos.22276095,22106071,and 81801029)the Natural Science Foundation of Jiangsu Province(Nos.BK20211522 and BK20200504)the Project of Jiangsu Provincial Commission of Health(No.M2022060).We gratefully acknowledge HZWTECH for providing computation facilities.
文摘Phase manipulation of MoS_(2) from thermodynamically stable 2H phase to the unstable but more reactive 1T phase represents a crucial strategy for improving the reactivity in many reactions.The widely adopted wet chemistry approach uses intercalating entities especially alkali metal ions to achieve the phase transition;however,these entities are normally inert for the target reaction.Here,we describe the first use of iron atoms for the intercalation of 2H-MoS_(2) layers,driving the partial transition from 2H to 1T phase.Interestingly,in the peroxymonosulfate(PMS)-based Fenton-like reactions,the interlayered confinement of Fe atoms not only activates the inert basal plane,but also adds more reactive Fe sites for the formation of metal-PMS complex as primary reactive species for pollutant removal.In the degradation of a model pollutant carbamazepine(CBZ),the Fe-intercalated MoS_(2) exhibits a first order rate constant 13.3 times higher than 2H-MoS_(2).This strategy is a new direction for manipulating the phase composition and boosting the catalytic reactivity of MoS_(2)-based catalysts in various scenarios,including environmental remediation and energy applications.
基金supported by the National Natural Science Foundation of China(NSFC Project Nos.21776104,21476088)the National Key Research and Development Program of China(Project Nos.2016YFB0101201,2017YFB0102900)+1 种基金the Guangdong Provincial Department of Science and Technology(Project No.2015B010106012)the Guangzhou Science,Technology and Innovation Committee(Project Nos.201504281614372,2016GJ006)。
文摘Air cathodes with high electrocatalytic activity are vital for developing H2/O_(2) proton exchange membrane fuel cells(PEMFC)and Zn-air batteries.However,the state-of-the-art air cathodes suffer from either limited catalytic activity or high cost,which thus hinder their applications.Herein,we designed ZIF-8 derived nitrogen and atomic iron dual-doped porous carbon nanocubes as high-quality catalysts for ORR,through a novel gas-doping approach.The porous carbon nanocubic architecture and abundant Fe-Nxactive species endow ZIF-8 derived single atomic iron catalyst(PCN-A@Fe SA)with superior catalytic activity,and surpass Pt/C and a majority of the reported catalysts.Both XAS and DFT calculations suggest that Fe2+N4 moieties are the main active centers that are favorable for oxygen affinity and OH*intermediate desorption,which can result in promising catalytic performance.Most importantly,PCNA@Fe SA can achieve power density of 514 m W cm^(-2) as cathodic catalyst in a PEMFC and discharge peak power density of 185 m W cm^(-2) in an alkaline Zn-air battery.The outstanding performance is derived from both the high specific surface area and high-density of iron single atom in nitrogen doped nanocubic carbon matrix.
基金financially supported by the Key Program of the Chinese Academy of Sciences(KFZD-SW-419),Chinathe Major Research Plan of the National Natural Science Foundation of China(91834301),China。
文摘Fe-N-C endowed with inexpensiveness,high activity,and excellent anti-poisoning power have emerged as promising candidate catalysts for oxygen reduction reaction(ORR).Single-atom Fe-N-C electrocatalysts derived from Fe-doped ZIF-8 represent the top-level ORR performance.However,the current fabrication of Fe-doped ZIF-8 relies on heavy consumption of time,energy,cost and organic solvents.Herein,we develop a rapid and solvent-free method to produce Fe-doped ZIF-8 under microwave irradiation,which can be easily amplified in combination with ball-milling.After rational pyrolysis,Fe-N-C catalysts with atomic FeN4 sites well dispersed on the hierarchically porous carbon matrix are obtained,which exhibit exceptional ORR performance with a half-wave potential of 0.782 V(vs.reversible hydrogen electrode(RHE))and brilliant methanol tolerance.The assembled direct methanol fuel cells(DMFCs)endow a peak power density of 61 mW cm^(-2) and extraordinary stability,highlighting the application perspective of this strategy.
基金supported by National Key R&D Program of China (No.2018YFA0108300)the Overseas High-level Talents Plan of China and Guangdong Province+3 种基金the Fundamental Research Funds for the Central Universitiesthe 100 Talents Plan Foundation of Sun Yat-sen Universitythe Program for Guangdong Introducing Innovative and Entrepreneurial Teams (No.2017ZT07C069)the Natinoal Natural Science Foundation of China (Nos.22075321,21821003,21890380 and 21905315)。
文摘Exploring platinum group metal-free electrocatalysts with superior catalytic performance and favorable durability for oxygen reduction reaction is a remaining bottleneck in process of developing sustainable techniques in energy storage and conversion. Herein, a hierarchical porous single atomic Fe electrocatalyst(Fe/Z8-E-C) is rationally designed and synthesized via acid etching, calcination, adsorption of Fe precursor and recalcination processes. This unique electrocatalyst Fe/Z8-E-C shows excellent oxygen reduction performance with a half-wave potential of 0.89 V in 0.1 mol/L KOH, 30 m V superior to that of commercial Pt/C(0.86 V), which is also significantly higher than that of typical Fe-doped ZIF-8 derived carbon nanoparticles(Fe/Z8-C) with a half-wave potential of 0.84 V. Furthermore, Fe/Z8-E-C-based Zn-air battery exhibits greatly enhanced peak power density and specific capacity than those of original Fe/Z8-C,verifying the remarkable performance and practicability of this specially designed hierarchical structure due to its efficient utilization of the active sites and rapid mass transfer. This present work proposes a new method to rationally synthesize single atom electrocatalysts loaded on hierarchical porous frame materials for catalysis and energy conversion.
基金financially supported by the National Natural Science Foundation of China (No.51874197)Natural Science Foundation of Shanghai (Nos.21ZR1429400,22ZR1429700)
文摘Rechargeable aluminum-sulfur(Al-S)batteries have been considered as a highly potential energy storage system owing to the high theoretical capacity,good safety,abundant natural reserves,and low cost of Al and S.However,the research progress of Al-S batteries is limited by the slow kinetics and shuttle effect of soluble polysulfides intermediates.Herein,an interconnected free-standing interlayer of iron sin-gle atoms supported on porous nitrogen-doped carbon nanofibers(FeSAs-NCF)on the separator is developed and used as both catalyst and chemical barrier for Al-S batteries.The atomically dispersed iron active sites(Fe-N_(4))are clearly identified by aberration-corrected high-angle annular dark-field scanning transmission electron microscopy and X-ray absorption near-edge structure.The Al-S battery with the FeSAs-NCF shows an improved specific capacity of 780 mAh g^(−1)and enhanced cycle stability.As evidenced by experimental and theoretical results,the atomically dispersed iron active centers on the separator can chemically adsorb the polysulfides and accelerate reaction kinetics to inhibit the shuttle effect and promote the reversible conversion between aluminum polysulfides,thus improving the electrochemical performance of the Al-S battery.This work provides a new way that can not only promote the conversion of aluminum sulfides but also suppress the shuttle effect in Al-S batteries.
文摘The diffusible hydrogen contents in precharged (Co,Fe) 3V alloy were measured. It is found that atomic ordering can not promote hydrogen penetration in the (Co,Fe) 3V alloy. The ultimate tensile strength (UTS) and ductilities in various condition were also investigated. The results show that the UTS and elongation of disordered alloy are higher than that of ordered one with fixed diffusible hydrogen content and (Co,Fe) 3V alloy with ordered structure is highly susceptible to the embrittlement in hydrogen gas. The factor which may affect the susceptibility to the embrittlement of (Co,Fe) 3V alloy in hydrogen gas is mainly due to that the atomic ordering may accelerate the kinetics of the catalytic reaction for the dissociation of molecular hydrogen into atomic hydrogen. However, it can not be roled out that atomic ordering intensifies planar slip and restricts cross slip at the grain boundaries and enhances the susceptibility of the alloy to hydrogen embrittlement.
基金Item Sponsored by National Natural Science Foundation of China (50701030)National Basic Research Program of China(2010CB630802)
文摘The microstructural evolution of the gas atomized Fe-25Cr-3.2C powders was investigated by using optical microscope, scanning electron microscope, and X-ray diffraction. The experimental results showed that the atomized Fe-25Cr-3.2C powders were mainly composed of austenite and （Fe,Cr）7 C3 carbide. Eutectic microstructure was developed in the larger particles, whereas dendritic microstrueture was obtained in the particles with diameter less than 38 μm. The reason for microstructure change should be the difference of nucleation undercooling for particles.
基金financially supported by the National Key R&D Program of China(2022YFB4004100)the National Natural Science Foundation of China(22272161)+6 种基金the Jilin Province Science and Technology Development Program(20230101367JC)financially supported by the National Natural Science Foundation of China(22073094)the Science and Technology Development Program of Jilin Province(20210402059GH)the Science and Technology Plan Projects of Yunnan Province(202101BC070001–007)the Major Science and Technology Projects for Independent Innovation of China FAW Group Co.,Ltd(20220301018GX)the essential support of the Network and Computing Center,CIAC,CASthe Computing Center of Jilin Province。
文摘Developing cost-effective,robust and stable non-precious metal catalysts for oxygen reduction reaction(ORR) is of paramount importance for electrochemical energy conversion devices such as fuel cells and metal-air batteries.Although Fe-N-C single atom catalysts(SACs) have been hailed as the most promising candidate due to the optimal binding strength of ORR intermediates on the Fe-N_(4) sites,they suffer from serious mass transport limitations as microporous templates/substrates,i.e.,zeolitic imidazolate frameworks(ZIFs),are usually employed to host the active sites.Motivated by this challenge,we herein develop a hydrogen-bonded organic framework(HOF)-assisted pyrolysis strategy to construct hierarchical micro/mesoporous carbon nanoplates for the deposition of atomically dispersed Fe-N_(4) sites.Such a design is accomplished by employing HOF nanoplates assembled from 2-aminoterephthalic acid(NH_(2)-BDC) and p-phenylenediamine(PDA) as both soft templates and C,N precursors.Benefitting from the structural merits inherited from HOF templates,the optimized catalyst(denoted as Fe-N-C SAC-950) displays outstanding ORR activity with a high half-wave potential of 0.895 V(vs.reversible hydrogen electrode(RHE)) and a small overpotential of 356 mV at 10 mA cm^(-2) for the oxygen evolution reaction(OER).More excitingly,its application potential is further verified by delivering superb rechargeability and cycling stability with a nearly unfading charge-discharge gap of 0.72 V after 160 h.Molecular dynamics(MD) simulations reveal that micro/mesoporous structure is conducive to the rapid mass transfer of O_(2),thus enhancing the ORR performance.In situ Raman results further indicate that the conversion of O_(2) to~*O_(2)-the rate-determining step(RDS) for Fe-N-C SAC-950.This work will provide a versatile strategy to construct single atom catalysts with desirable catalytic properties.
基金Item Sponsored by National Natural Science Foundation of China(51271163,51471148)
文摘The structure stability, elastic property and electronic structure of a-Fe supercell with La atom were inves- tigated by first-principles, in which, generalized gradient approximation （GGA） with the Perdew Burke Ernzerhof （PBE） was used as exchange-correlation functional, a-Fe supercells with La atom include a-Fe supercell with La atom in octahedral interstitial solid solute （La-OISS）, that with La atom in tetrahedral interstitial solid solute （La-TISS） and that with La atom in substitutional solid solute （La-SSS）. The results show that the La-SSS a-Fe supercell is more stable than La-OISS one. The resistance to volume change, reversible deformation and stiffness of La-OISS a-Fe supercell are stronger than those of La-SSS one. Moreover, the degrees of anisotropy and ionization in La-SSS a-Fe supercell are both stronger than those in La-OISS one. The bonding strength between La atom and Fe atom in La-SSS a-Fe supercell is larger than that in La-OISS one.
文摘[目的]为进一步拓展单原子催化剂在亚硝酸盐还原制氨领域的应用,提出了一种铁-氮-碳(Fe-N-C)单原子催化剂电催化亚硝酸盐还原制氨的新体系.[方法]以二氧化硅为硬模板,2,6-二氨基吡啶为碳氮前驱体,硝酸铁为金属盐,通过“热解-刻蚀”策略制备了Fe-N-C单原子催化剂,并将其应用于亚硝酸盐制氨反应.[结果]多种结构表征结果显示,Fe-N-C催化剂表面的Fe物种呈现高度分散特征并以单原子形式存在.此外,Fe物种的化学环境主要是+2和+3价混合态,且通过与4个吡啶氮配位而稳定存在,即Fe-N-C催化剂的金属中心微观配位环境为Fe-N4结构.与纯氮碳(N-C)载体相比,本研究制备的Fe-N-C催化剂具有优异的亚硝酸盐还原性能,不仅表现出更高的起始还原电位(0 V vs可逆氢电极),具有接近100%的产氨法拉第效率和高的氨产率[8.4 mg/(h·cm^(2))],并且在连续20次催化循环测试中显示出优异的催化稳定性.[结论]本研究制备的Fe-N-C单原子催化剂对亚硝酸盐还原制氨具有优异的电催化活性,其高活性可能来源于对NO_(2)^(-)的显著吸附,并进一步促进活性氢参与脱氧加氢过程.该Fe-N-C单原子催化亚硝酸盐还原体系可为后续合成氨的活性中心设计提供指导方向.
基金National Natural Science Foundation of China,Grant/Award Number:12274118Double First Class University Plan,Grant/Award Number:C176220100042+2 种基金National Natural Science Foundation of China-Yunnan Joint Fund,Grant/Award Number:U2002213Open Foundation of Guangxi Key Laboratory of Processing for Non-Ferrous Metals and Featured Materials,Grant/Award Number:2022GXYSOF10Henan Center for Outstanding Overseas Scientists,Grant/Award Number:GZS2023007.
文摘Zn-CO_(2)batteries(ZCBs)are promising for CO_(2)conversion and electric energy release.However,the ZCBs couple the electrochemical CO_(2)reduction(ECO_(2)R)with the oxygen evolution reaction and competitive hydrogen evolution reaction,which normally causes ultrahigh charge voltage and CO_(2)conversion efficiency attenuation,thereby resulting in~90%total power consumption.Herein,isolated FeN_(3)sites encapsulated in hierarchical porous carbon nanoboxes(Fe-HPCN,derived from the thermal activation process of ferrocene and polydopamine-coated cubic ZIF-8)were proposed for hydrazine-assisted rechargeable ZCBs based on ECO_(2)R(discharging process:CO_(2)+2H+→CO+H_(2)O)and hydrazine oxidation reaction(HzOR,charging process:N_(2)H_(4)+4OH−→N_(2)+4H_(2)O+4e^(−)).The isolated FeN_(3)endows the HzOR with a lower overpotential and boosts the ECO_(2)R with a 96%CO Faraday efficiency(FECO).Benefitting from the bifunctional ECO_(2)R and HzOR catalytic activities,the homemade hydrazine-assisted rechargeable ZCBs assembled with the Fe-HPCN air cathode exhibited an ultralow charge voltage(decreasing by~1.84 V),excellent CO selectivity(FECO close to 100%),and high 89%energy efficiency.In situ infrared spectroscopy confirmed that Fe-HPCN can generate rate-determining*N_(2)and*CO intermediates during HzOR and ECO_(2)R.This paper proposes FeN_(3)centers for bifunctional ECO_(2)R/HzOR performance and further presents the pioneering achievements of ECO_(2)R and HzOR for hydrazine-assisted rechargeable ZCBs.
文摘Raoultian activity coefficients γ0c of C in infinitely dilute Fe-C binary melts at temperatures of 1833, 1873, 1923, and 1973 K have been determined from the converted mass action concentrations Nc of C in Fe-C binary melts by the developed AMCT-Ni model based on the atom-molecule coexistence theory （AMCT）. The obtained expression of γ0c by the developed AMCT-Ni model has been evaluated to be accurate based on the reported ones from the literature. Meanwhile, three activity coefficients γc,f%,c, andfH,c of C coupled with activity aR,C or a%,c or aH,c have been obtained by the developed AMCT-Ni model and assessed through comparing with the predicted ones by other models from the literature. The first-order activity interaction coefficients ec, ec, and hcc related to γc f%,c, and fH,c are also determined and assessed in comparison with the reported ones from the literature. Furthermore, the integral molar mixing thermodynamic functions such as AmixHm,Fe-C, △mix-Sm,Fe-C, and △mixGm,Fe-C of Fe-C binary melts over a temperature range from 1833 to 1973 K have been determined and evaluated to be valid based on the determined ones from the literature.
