Fe doped Beta zeolite with different Fe contents were prepared by ion exchange by changing the volume or the concentration of a Fe salt solution. For a particular mass of Fe salt precursor, the concentration of the me...Fe doped Beta zeolite with different Fe contents were prepared by ion exchange by changing the volume or the concentration of a Fe salt solution. For a particular mass of Fe salt precursor, the concentration of the metal salt solution during ion exchange influenced the ion exchange capacity of Fe, and resulted in different activities of the Fe-Beta catalyst. Fe-Beta catalysts with the Fe contents of （2.6, 6.3 and 9） wt% were synthesized using different amounts of 0.02 mol/L Fe salt solution. These catalysts were studied by various characterization techniques and their NH3-SCR activities were evaluated. The Fe-Beta catalyst with the Fe content of 6.3 wt% exhibited the highest activity, with a temperature range of 202-616℃ where the NOx conversion was 〉 80%. The Fe content in Beta zeolite did not influence the structure of Beta zeolite and valence state of Fe. Compared with the Fe-Beta catalysts with low Fe content （2.6 wt%）, Fe-Beta catalysts with 6.3 wt% Fe content possessed more isolated Fe3. active sites which led to its higher NH3-SCR activity. A high capacity for NH3 and NO adsorption, and a high activity for NO oxidation also contributed to the high NH3-SCR activity of the Fe-Beta catalyst with 6.3 wt%. However, when the Fe content was further increased to 9.0 wt%, the amount of FexOy nanoparticles increased while the amount of isolated Fe3＋ active sites was unchanged, which promoted NH3 oxidation and decreased the NH3-SCR activity at high temperature.展开更多
The design and development of low-cost,efficient,and stable bifunctional electrocatalysts for the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)are desirable for rechargeable metal-air batteries.In t...The design and development of low-cost,efficient,and stable bifunctional electrocatalysts for the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)are desirable for rechargeable metal-air batteries.In this work,N-doped porous hollow carbon spheres encapsulated with ultrafine Fe/Fe3O4 nanoparticles(FeOx@N-PHCS)were fabricated by impregnation and subsequent pyrolysis,using melamine-formaldehyde resin spheres as self-sacrifice templates and polydopamine as N and C sources.The sufficient adsorption of Fe3+on the polydopamine endowed the formation of Fe-Nx species upon high-temperature carbonization.The prepared FeOx@N-PHCS has advanced features of large specific surface area,porous hollow structure,high content of N dopants,sufficient Fe-Nx species and ultrafine FeOx nanoparticles.These features endow FeOx@N-PHCS with enhanced mass transfer and considerable active sites,leading to high activity and stability in catalyzing ORR and OER in alkaline electrolyte.Furthermore,the rechargeable Zn-air battery with FeOx@N-PHCS as air cathode catalyst exhibits a large peak power density,narrow charge-discharge potential gap and robust cycling stability,demonstrating the potential of the fabricated FeOx@N-PHCS as a promising electrode material for metal-air batteries.This new finding may open an avenue for rational design of bifunctional catalysts by integrating different active components within all-in-one catalyst for different electrochemical reactions.展开更多
Efficient photocatalytic reduction of CO_(2) to high-calorific-value CH4,an ideal target product,is a blueprint for C_(1)industry relevance and carbon neutrality,but it also faces great challenges.Herein,we demonstrat...Efficient photocatalytic reduction of CO_(2) to high-calorific-value CH4,an ideal target product,is a blueprint for C_(1)industry relevance and carbon neutrality,but it also faces great challenges.Herein,we demonstrate unprecedented hybrid SiC photocatalysts modified by Fe-based cocatalyst,which are prepared via a facile impregnation-reduction method,featuring an optimized local electronic structure.It exhibits a superior photocatalytic carbon-based products yield of 30.0μmol g^(−1) h^(−1) and achieves a record CH_(4) selectivity of up to 94.3%,which highlights the effectiveness of electron-rich Fe cocatalyst for boosting photocatalytic performance and selectivity.Specifically,the synergistic effects of directional migration of photogenerated electrons and strongπ-back bonding on low-valence Fe effectively strengthen the adsorption and activation of reactants and intermediates in the CO_(2)→CH_(4) pathway.This study inspires an effective strategy for enhancing the multielectron reduction capacity of semiconductor photocatalysts with low-cost Fe instead of noble metals as cocatalysts.展开更多
Fe-based biodegradable materials have attracted significant attention due to their exceptional mechanical properties and favorable biocompatibility.Currently,research on Fe-based materials mainly focuses on regulating...Fe-based biodegradable materials have attracted significant attention due to their exceptional mechanical properties and favorable biocompatibility.Currently,research on Fe-based materials mainly focuses on regulating the degradation rate.However,excessive release of Fe ions during material degrada-tion will induce the generation of reactive oxygen species(ROS),leading to oxidative stress and ferroptosis.Therefore,the con-trol of RoS release and the improvement of biocompatibility for Fe-based materials are very important.In this study,new Fe-Zn alloys were prepared by electrodeposition with the intention of using Zn as an antioxidant to reduce oxidative damage during alloy degradation.Initially,the impact of three potential degra-dation ions(Fe^(2+),Fe^(3+),Zn^(2+))from the Fe-Zn alloy on human endothelial cell(EC)activity and migration ability was investigated.Subsequently,cell adhesion,cell activity,ROs production and DNA damage were assessed at various locations surrounding the alloy.Finally,the influence of different concentrations of Zn^(2+) in the medium on cell viability and ROS production was evaluated.High levels of ROS exhibited evident toxic effects on ECs and promoted DNA damage.As an antioxidant,Zn?+effectively reduced ROS production around Fe and improved the cell viability on its surface at a concentration of 0.04 mmol/l.These findings demonstrate that Fe-Zn alloy can attenuate the ROS generated from Fe degradation therebyenhancingcytocompatibility.展开更多
CaC12 can be sprayed onto sinter surface, which can improve the low temperature reduction degradation index （RDI＋3.15） of sinter. This has been recognized; however, there are various opinions on the inhibition mech...CaC12 can be sprayed onto sinter surface, which can improve the low temperature reduction degradation index （RDI＋3.15） of sinter. This has been recognized; however, there are various opinions on the inhibition mechanism of it. At the same time, the corrosion of C1 element on equipment is very serious. First-principle calculations based on density functional theory were performed to investigate the binding mechanisms of calcium species on a a-Fe2 03 （0 0 1） surface. This is crucial in demonstrating the role of the CaC12 on improving the low temperature reduction degrada tion index. It has been determined that C1 could greatly increase the adsorption of the vacuum layer for the Ca/Fe2 03 system and the relaxation produced by adsorption made bond length decrease, bond energies increase and structure compact. Those are the main reasons that inhibiting the reduction disintegration of sinter.展开更多
Photoelectrochemical（PEC） water splitting is a promising approach to producing H2 and O2. Hematite（α-Fe2O3） is considered one of the most promising photoelectrodes for PEC water splitting, due to its good photoch...Photoelectrochemical（PEC） water splitting is a promising approach to producing H2 and O2. Hematite（α-Fe2O3） is considered one of the most promising photoelectrodes for PEC water splitting, due to its good photochemical stability, non-toxicity, abundance in earth, and suitable bandgap（Eg2.1 eV）. However, the PEC water splitting efficiency of hematite is severely hampered by its short hole diffusion length（2–4 nm）, poor conductivity, and ultrafast recombination of photogenerated carriers（about 10 ps）. Here,we show a novel and effective method for significantly improving the PEC water splitting performance of hematite by Au ion implantation and the following high-temperature annealing process. Based on a series of characterizations and analyses, we have found Fe2＋ species and tightly attached Au particles were produced at Au-implanted hematite. As a result,the charge separation and charge injection efficiency of Auimplanted Fe2O3 are markedly increased. The photocurrent density of optimized Au-implanted Fe2O3 could reach1.16 m A cm-2 at 1.5 V vs. RHE which was nearly 300 times higher than that of the pristine Fe2O3（4 μA cm-2）. Furthermore, the Au-implanted Fe2O3 photoelectrode exhibited great stability for the 8-hour PEC water splitting test without photocurrent decay.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
Fe species were loaded by two different loading ways （absorption method and addition method） to investigate their effect on thermal properties of coke. The particulate coke reactivity of coke samples indicated that ...Fe species were loaded by two different loading ways （absorption method and addition method） to investigate their effect on thermal properties of coke. The particulate coke reactivity of coke samples indicated that the added sample showed higher catalytic activity than the adsorbed sample at first, owing to the decreased structure and properties of coke and more catalytic active sites caused by the strong interaction between Fe species and coke. The presence of Fe species in the added sample weakened the microstructure of coke, and the Fe species were easier to be reduced than those in the absorbed sample due to its different existence form in coke. With further increased loading of Fe species, the different existence positions of Fe species caused more decrease in surface active sites in the added sample than in the adsorbed sample, leading to lower catalytic activity of added sample when the total iron content exceeded 1%. The catalytic mechanism implied that there may be a catalytic dominant factor change in the reaction between the catalytic effect of iron species and carbon surface active sites in coke; the catalytic effect of iron species is dominant in the reaction at first, but the catalytic effect of carbon surface active sites is dominant in the reaction with the further increased loading amount of Fe species.展开更多
基金supported by the National Key Basic Research Program of China (973 Program, 2013CB933201)the National Natural Science Foun-dation of China (21577034, 21333003, 91545103)+1 种基金Science and Technology Commission of Shanghai Municipality (16ZR1407900)Fundamental Research Funds for the Central Universities (WJ1514020)~~
文摘Fe doped Beta zeolite with different Fe contents were prepared by ion exchange by changing the volume or the concentration of a Fe salt solution. For a particular mass of Fe salt precursor, the concentration of the metal salt solution during ion exchange influenced the ion exchange capacity of Fe, and resulted in different activities of the Fe-Beta catalyst. Fe-Beta catalysts with the Fe contents of （2.6, 6.3 and 9） wt% were synthesized using different amounts of 0.02 mol/L Fe salt solution. These catalysts were studied by various characterization techniques and their NH3-SCR activities were evaluated. The Fe-Beta catalyst with the Fe content of 6.3 wt% exhibited the highest activity, with a temperature range of 202-616℃ where the NOx conversion was 〉 80%. The Fe content in Beta zeolite did not influence the structure of Beta zeolite and valence state of Fe. Compared with the Fe-Beta catalysts with low Fe content （2.6 wt%）, Fe-Beta catalysts with 6.3 wt% Fe content possessed more isolated Fe3. active sites which led to its higher NH3-SCR activity. A high capacity for NH3 and NO adsorption, and a high activity for NO oxidation also contributed to the high NH3-SCR activity of the Fe-Beta catalyst with 6.3 wt%. However, when the Fe content was further increased to 9.0 wt%, the amount of FexOy nanoparticles increased while the amount of isolated Fe3＋ active sites was unchanged, which promoted NH3 oxidation and decreased the NH3-SCR activity at high temperature.
基金supported by the National Natural Science Foundation of China(21421001,21573115,21875118)Tianjin Science and Technology Commission(18JCTPJC55900)+1 种基金the Natural Science Foundation of Tianjin(17JCYBJC17100,19JCZDJC37700)the 111 Project(B12015).
文摘The design and development of low-cost,efficient,and stable bifunctional electrocatalysts for the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)are desirable for rechargeable metal-air batteries.In this work,N-doped porous hollow carbon spheres encapsulated with ultrafine Fe/Fe3O4 nanoparticles(FeOx@N-PHCS)were fabricated by impregnation and subsequent pyrolysis,using melamine-formaldehyde resin spheres as self-sacrifice templates and polydopamine as N and C sources.The sufficient adsorption of Fe3+on the polydopamine endowed the formation of Fe-Nx species upon high-temperature carbonization.The prepared FeOx@N-PHCS has advanced features of large specific surface area,porous hollow structure,high content of N dopants,sufficient Fe-Nx species and ultrafine FeOx nanoparticles.These features endow FeOx@N-PHCS with enhanced mass transfer and considerable active sites,leading to high activity and stability in catalyzing ORR and OER in alkaline electrolyte.Furthermore,the rechargeable Zn-air battery with FeOx@N-PHCS as air cathode catalyst exhibits a large peak power density,narrow charge-discharge potential gap and robust cycling stability,demonstrating the potential of the fabricated FeOx@N-PHCS as a promising electrode material for metal-air batteries.This new finding may open an avenue for rational design of bifunctional catalysts by integrating different active components within all-in-one catalyst for different electrochemical reactions.
基金supported by the National Natural Science Foundation of China(Grant No.22072022)the Natural Science Foundation of Fujian Province(2021L3003)the Science Foundation of Shandong Province(ZR2019BB065).
文摘Efficient photocatalytic reduction of CO_(2) to high-calorific-value CH4,an ideal target product,is a blueprint for C_(1)industry relevance and carbon neutrality,but it also faces great challenges.Herein,we demonstrate unprecedented hybrid SiC photocatalysts modified by Fe-based cocatalyst,which are prepared via a facile impregnation-reduction method,featuring an optimized local electronic structure.It exhibits a superior photocatalytic carbon-based products yield of 30.0μmol g^(−1) h^(−1) and achieves a record CH_(4) selectivity of up to 94.3%,which highlights the effectiveness of electron-rich Fe cocatalyst for boosting photocatalytic performance and selectivity.Specifically,the synergistic effects of directional migration of photogenerated electrons and strongπ-back bonding on low-valence Fe effectively strengthen the adsorption and activation of reactants and intermediates in the CO_(2)→CH_(4) pathway.This study inspires an effective strategy for enhancing the multielectron reduction capacity of semiconductor photocatalysts with low-cost Fe instead of noble metals as cocatalysts.
文摘适用p H范围窄是限制亚铁/过一硫酸盐(Fe(Ⅱ)/PMS)体系进一步推广应用的关键因素之一,亟需开发拓宽Fe(Ⅱ)/PMS体系适用p H范围的策略。该文旨在探究含氮络合剂1,10-邻菲罗啉(phen)和2,2'-联吡啶(bipy)对Fe(Ⅱ)/PMS体系降解有机污染物效能和机制的影响。结果表明,引入phen和bipy可显著促进Fe(Ⅱ)/PMS体系对富含供电子基团的有机污染物苯酚和双氯芬酸的降解。当phen/Fe(Ⅱ)和bipy/Fe(Ⅱ)的摩尔比分别为3.0和4.5时,phen/Fe(Ⅱ)/PMS和bipy/Fe(Ⅱ)/PMS体系对苯酚的去除效果最佳。phen/Fe(Ⅱ)/PMS和bipy/Fe(Ⅱ)/PMS体系在p H 3.0~9.0条件下均能有效降解苯酚。化学探针、电子顺磁共振和淬灭剂实验结果表明,phen/Fe(Ⅱ)/PMS和bipy/Fe(Ⅱ)/PMS体系产生的活性氧化剂包括^(1)O_(2)和Fe(Ⅳ),且^(1)O_(2)对这2个体系中苯酚的降解起主要作用。
基金supported by“the Fundamental Research Funds for the Central Universities”of China(DUT23YG229,DUT22YG118)SEM and EPMA data were obtained using equipment(IT800-SHL,JXA-8530F PLUS)maintained by the School of Materials Science and Engineering,Dalian University of Technology.
文摘Fe-based biodegradable materials have attracted significant attention due to their exceptional mechanical properties and favorable biocompatibility.Currently,research on Fe-based materials mainly focuses on regulating the degradation rate.However,excessive release of Fe ions during material degrada-tion will induce the generation of reactive oxygen species(ROS),leading to oxidative stress and ferroptosis.Therefore,the con-trol of RoS release and the improvement of biocompatibility for Fe-based materials are very important.In this study,new Fe-Zn alloys were prepared by electrodeposition with the intention of using Zn as an antioxidant to reduce oxidative damage during alloy degradation.Initially,the impact of three potential degra-dation ions(Fe^(2+),Fe^(3+),Zn^(2+))from the Fe-Zn alloy on human endothelial cell(EC)activity and migration ability was investigated.Subsequently,cell adhesion,cell activity,ROs production and DNA damage were assessed at various locations surrounding the alloy.Finally,the influence of different concentrations of Zn^(2+) in the medium on cell viability and ROS production was evaluated.High levels of ROS exhibited evident toxic effects on ECs and promoted DNA damage.As an antioxidant,Zn?+effectively reduced ROS production around Fe and improved the cell viability on its surface at a concentration of 0.04 mmol/l.These findings demonstrate that Fe-Zn alloy can attenuate the ROS generated from Fe degradation therebyenhancingcytocompatibility.
基金Item Sponsored by National Natural Science Foundation of China(51174074)Open Fund Project of National Key Laboratory in University of Science and Technology Beijing of China(KF13-02)
文摘CaC12 can be sprayed onto sinter surface, which can improve the low temperature reduction degradation index （RDI＋3.15） of sinter. This has been recognized; however, there are various opinions on the inhibition mechanism of it. At the same time, the corrosion of C1 element on equipment is very serious. First-principle calculations based on density functional theory were performed to investigate the binding mechanisms of calcium species on a a-Fe2 03 （0 0 1） surface. This is crucial in demonstrating the role of the CaC12 on improving the low temperature reduction degrada tion index. It has been determined that C1 could greatly increase the adsorption of the vacuum layer for the Ca/Fe2 03 system and the relaxation produced by adsorption made bond length decrease, bond energies increase and structure compact. Those are the main reasons that inhibiting the reduction disintegration of sinter.
基金supported by the National Natural Science Foundation of China (51371131, 11375134, 51571153 and 11722543)the Fundamental Research Funds for the Central Universities (2042017kf0168)
文摘Photoelectrochemical（PEC） water splitting is a promising approach to producing H2 and O2. Hematite（α-Fe2O3） is considered one of the most promising photoelectrodes for PEC water splitting, due to its good photochemical stability, non-toxicity, abundance in earth, and suitable bandgap（Eg2.1 eV）. However, the PEC water splitting efficiency of hematite is severely hampered by its short hole diffusion length（2–4 nm）, poor conductivity, and ultrafast recombination of photogenerated carriers（about 10 ps）. Here,we show a novel and effective method for significantly improving the PEC water splitting performance of hematite by Au ion implantation and the following high-temperature annealing process. Based on a series of characterizations and analyses, we have found Fe2＋ species and tightly attached Au particles were produced at Au-implanted hematite. As a result,the charge separation and charge injection efficiency of Auimplanted Fe2O3 are markedly increased. The photocurrent density of optimized Au-implanted Fe2O3 could reach1.16 m A cm-2 at 1.5 V vs. RHE which was nearly 300 times higher than that of the pristine Fe2O3（4 μA cm-2）. Furthermore, the Au-implanted Fe2O3 photoelectrode exhibited great stability for the 8-hour PEC water splitting test without photocurrent decay.
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.
文摘Fe species were loaded by two different loading ways （absorption method and addition method） to investigate their effect on thermal properties of coke. The particulate coke reactivity of coke samples indicated that the added sample showed higher catalytic activity than the adsorbed sample at first, owing to the decreased structure and properties of coke and more catalytic active sites caused by the strong interaction between Fe species and coke. The presence of Fe species in the added sample weakened the microstructure of coke, and the Fe species were easier to be reduced than those in the absorbed sample due to its different existence form in coke. With further increased loading of Fe species, the different existence positions of Fe species caused more decrease in surface active sites in the added sample than in the adsorbed sample, leading to lower catalytic activity of added sample when the total iron content exceeded 1%. The catalytic mechanism implied that there may be a catalytic dominant factor change in the reaction between the catalytic effect of iron species and carbon surface active sites in coke; the catalytic effect of iron species is dominant in the reaction at first, but the catalytic effect of carbon surface active sites is dominant in the reaction with the further increased loading amount of Fe species.
