Lithium-sulfur(Li-S)batteries are regarded as the most formidable competitor to lithium-ion batteries due to their superior theoretical capacity.However,the negative impact of soluble lithium polysulfide(LiPSs)and slo...Lithium-sulfur(Li-S)batteries are regarded as the most formidable competitor to lithium-ion batteries due to their superior theoretical capacity.However,the negative impact of soluble lithium polysulfide(LiPSs)and slow redox reaction kinetics seriously hamper the commercialization of Li-S batteries.In this study,a defect-rich single-atom catalyst with an oversaturated asymmetric Fe-N_(5)coordination structure anchored in defective g-C_(3)N_(4)(C_(3)N_(4)-Fe@rGO)is designed via an absorption-pyrolysis strategy.The two-dimensional(2D)conducting C_(3)N_(4)@graphene structure with abundant defect sites accelerates the trans-fer and transportation of lithium ions and electrons.The oversaturated asymmetric Fe-N_(5)coordination structure effectively improves the adsorbility of LiPSs and accelerates the redox kinetics of sulfur species.Hence,the Li-S cell with a C_(3)N_(4)-Fe@rGO modified separator reveals a high initial capacity(1197.1 mAh g^(-1) at 0.2 C)and a low capacity decay rate(0.037%per cycle after 900 cycles at 1 C).Even at high sulfur loading and extreme temperatures of 0℃,it also shows good cycling performance.This work creates ideas for synthesizing oversaturated single-atom coordination environments and an efficient route to the practical realization of the Li-S batteries.展开更多
Oxygen reduction reaction(ORR)in neutral electrolyte is urgently needed in various areas,such as metalair batteries.However,the N-coordinated transition-metal single-atom electrocatalysts confront sluggish catalytic k...Oxygen reduction reaction(ORR)in neutral electrolyte is urgently needed in various areas,such as metalair batteries.However,the N-coordinated transition-metal single-atom electrocatalysts confront sluggish catalytic kinetics due to the inappropriate electronic structure and the as-resulted unreasonable adsorption strength towards oxygen-containing intermediates.In this work,we develop a strategy to tune the Fe d-orbital spin state by introducing inert Si atom into the first coordination sphere of Fe-N_(4)moieties.The experimental and theoretical results suggest that Si atom generates the coordination field distortion of Fe and induces the Fe d-orbital spin state transforming from low to medium spin state.The optimized spin-electron filled state(t2g^(4)eg^(1))of Fe sites weakens the adsorption strength to intermediates and reduces the energy barrier of^(∗)OH desorption.Consequently,Fe-Si/NC catalyst exhibits superior ORR performance compared with that of Fe-NC and commercial Pt/C,showing a more positive half-wave potential of 0.753 V(vs.RHE)in 0.1 mol/L phosphate buffered saline.In addition,Fe-Si/NC-based neutral zinc-air batteries show a maximum power density of 108.9 mW cm^(−2)and long-term stability for 200 h.This work represents the possibility of constructing distorted coordination configurations of single-atom catalysts to modulate electronic structure and enhance ORR activity in neutral electrolyte.展开更多
With the rapid development of economy,the consumption of fossil fuels and excessive emissions of carbon dioxide(CO_(2))have led to many environmental issues.The thermocatalytic conversion of CO_(2) to high value‐adde...With the rapid development of economy,the consumption of fossil fuels and excessive emissions of carbon dioxide(CO_(2))have led to many environmental issues.The thermocatalytic conversion of CO_(2) to high value‐added chemicals is an effective strategy to meet the need of carbon neutralization.Among them,CO_(2) hydrogenation to light olefins has been well researched so that the selectivity of desired products can exceed the Anderson–Schulz–Flory(ASF)distribution to acquire an extremely high yield.However,although huge progress has been made in CO_(2) hydrogenation to produce long‐chain α‐olefins based on Fe catalysts as well,designing efficient catalysts with promoted C‐O dissociation and C‐C coupling remains challenging.In addition,ASF distribution restrains the selectivity of desired long‐chain products,whereas the approaches to breaking it still face issues.In this review,we focus on the design of Fe‐based catalysts for the synthesis of long‐chainα‐olefins through CO_(2) hydrogenation.We have summarized and analyzed the reaction mechanism,design of catalysts,structure–activity relationship,interaction between Fe and promoters,and strategies to break the ASF distribution.At the same time,the issues faced by CO_(2) hydrogenation to long‐chain α‐olefins are proposed and the possible future solutions are prospected.This review aims to provide a recent development on the design of Fe‐based catalysts for CO_(2) hydrogenation to long‐chain α‐olefins while considering the ASF distribution.展开更多
A variety of spherical and structured activated charcoal supported Pt/Fe3O4 composites with an average particle size of ~100 nm have been synthesized by a self-assembly method using the difference of reduction potenti...A variety of spherical and structured activated charcoal supported Pt/Fe3O4 composites with an average particle size of ~100 nm have been synthesized by a self-assembly method using the difference of reduction potential between Pt （Ⅳ） and Fe （Ⅱ） precursors as driving force. The formed Fe3O4 nanoparticles （NPs） effectively prevent the aggregation of Pt nanocrystallites and promote the dispersion of Pt NPs on the surface of catalyst, which will be favorable for the exposure of Pt active sites for high-efficient adsorption and contact of substrate and hydrogen donor. The electron-enrichment state of Pt NPs donated by Fe304 nanocrystallites is corroborated by XPS measurement, which is responsible for promoting and activating the terminal C=O bond of adsorbed substrate via a vertical configuration. The experimental results show that the activated charcoal supported Pt/Fe3O4 catalyst exhibits 94.8% selectivity towards cinnamyl alcohol by the transfer hydrogenation of einnamaldehyde with Pt loading of 2.46% under the optimum conditions of 120 ℃ for 6 h, and 2-propanol as a hydrogen donor. Additionally, the present study demonstrates that a high-efficient and recyclable catalyst can be rapidly separated from the mixture due to its natural magnetism upon the application of magnetic field.展开更多
separation is an attractive alternative to filtration or centrifugation for separating solid catalysts from a liquid phase, Here, core-shell Fe3O4@UiO-66-NH2 nanohybrids with well-defined structures were constructed b...separation is an attractive alternative to filtration or centrifugation for separating solid catalysts from a liquid phase, Here, core-shell Fe3O4@UiO-66-NH2 nanohybrids with well-defined structures were constructed by dispersing magnets in a dimethylformamide （DMF） solution con- taining two metal-organic framework （MOF） precursors, namely ZrCI4 and 2-aminobenzenetricar- boxylic acid. This method is simpler and more efficient than previously reported step-by-step method in which magnets were consecutively dispersed in DMF solutions each containing one MOF precursor, and the obtained Fe304@UiO-66-NH2 with three assembly cycles has a higher degree of crystallinity and porosiW. The core-shell Fe3O4@UiO-66-NH2 is highly active and selective in Knoevenagel condensations because of the bifunctionality of UiO-66-NH2 and better mass transfer in the nano-sized shells. It also has good recycling stability, and can be recovered magnetically and reused at least four times without significant loss of catalytic activity and framework integrity. The effects of substitution on the reactivity of benzaldehyde and of substrate size were also investigated.展开更多
Fe（HSO4）3 has been used as an efficient and recyclable catalyst for the one-pot synthesis of 14-aryl- or alkyl-14Hdibenzo[aj]xanthene derivatives by the reaction of 2-naphtol and aldehydes. Different types of aromat...Fe（HSO4）3 has been used as an efficient and recyclable catalyst for the one-pot synthesis of 14-aryl- or alkyl-14Hdibenzo[aj]xanthene derivatives by the reaction of 2-naphtol and aldehydes. Different types of aromatic and aliphatic aldehydes are used in the reaction and in all cases the products were obtained in good to excellent yields.展开更多
The partial oxidation of ethanol to hydrogen was investigated over Ni/Fe/La catalysts prepared by the co precipitation method. The effects of introduction of La promoter and the reaction temperature on the catalytic ...The partial oxidation of ethanol to hydrogen was investigated over Ni/Fe/La catalysts prepared by the co precipitation method. The effects of introduction of La promoter and the reaction temperature on the catalytic performance were studied. It was found that the introduction of La into Ni/Fe catalysts is helpful to increase the selectivity to hydrogen and the stability of the catalysts. The results of XRD and XPS characterization show that the structure of the catalyst was changed during the reaction. The existence of LaFeO 3 species is possibly the main reason of the increase of the catalyst stability.展开更多
A novel plasmonic photo‐Fenton catalyst of Ag/AgCl/Fe‐S was synthesized by ion exchange and photoreduction methods.The obtained catalyst was characterized by X‐ray diffraction,X‐ray photoelectron spectroscopy,scan...A novel plasmonic photo‐Fenton catalyst of Ag/AgCl/Fe‐S was synthesized by ion exchange and photoreduction methods.The obtained catalyst was characterized by X‐ray diffraction,X‐ray photoelectron spectroscopy,scanning electron microscope imaging,and Brunauer‐Emmett‐Teller measurements.Moreover,the photocatalytic activity of Ag/AgCl/Fe‐S was investigated for its degradation activity towards bisphenol A(BPA)as target pollutant under visible light irradiation.The effects of H2O2concentration,pH value,illumination intensity,and catalyst dosage on BPA degradation were examined.Our results indicated that the Ag/AgCl material was successfully loaded onto Fe‐sepiolite and showed a high photocatalytic activity under illumination by visible light.Furthermore,active species capture experiments were performed to explore the photocatalytic mechanism of the Ag/AgCl/Fe‐S in this heterogeneous photo‐Fenton process,where the major active species included hydroxyl radicals(?OH)and holes(h+).展开更多
Supported Ir catalysts were prepared using layered double hydrotalcite‐like materials,such as Mg_(3)Al_(1-x)Fe_(x),containing Fe and Al species in varying amounts as supports.These Ir catalysts were applied for the s...Supported Ir catalysts were prepared using layered double hydrotalcite‐like materials,such as Mg_(3)Al_(1-x)Fe_(x),containing Fe and Al species in varying amounts as supports.These Ir catalysts were applied for the selective hydrogenation of cinnamaldehyde(CAL).When x was changed from 0(Ir/Mg_(3)Al)to 1(Ir/Mg_(3)Fe),the rate of CAL hydrogenation reached a maximum at approximately x=0.25,while the selectivity to unsaturated alcohol,i.e.,cinnamyl alcohol,monotonously increased from 44.9%to 80.3%.Meanwhile,the size of the supported Ir particles did not change significantly with x,remaining at 1.7-0.2 nm,as determined by transmission electron microscopy.The chemical state of Ir and Fe species in the Ir/Mg3Al1-xFex catalysts was examined by temperature programmed reduction by H2 and X‐ray photoelectron spectroscopy.The surface of the supported Ir particles was also examined through the in‐situ diffuse reflectance infrared Fourier‐transform of a probe molecule of CO.On the basis of these characterization results,the effects of Fe doping to Mg_(3)Al on the structural and catalytic properties of Ir particles in selective CAL hydrogenation were discussed.The significant factors are the electron transfer from Fe2+in the Mg_(3)Al_(1–x)Fex support to the dispersed Ir particles and the surface geometry.展开更多
Fe（II）/γ-Al2O3 powders synthesized using the dipping method were produced from a mixed aqueous solution containing aluminium oxide （γ-Al2O3） and iron（II）-precursor （FeSO4）, and used for photoFenton degradati...Fe（II）/γ-Al2O3 powders synthesized using the dipping method were produced from a mixed aqueous solution containing aluminium oxide （γ-Al2O3） and iron（II）-precursor （FeSO4）, and used for photoFenton degradation of phthalocyanine dyes （PCs） under ultraviolet （UV） irradiation in an up-flow fluidized bed. The catalysts were characterized by XRD, ESCA, BET, EDS and SEM. The results showed that Fe2＋ ion was compounded on the γ-Al2O3 carder. The effects of different reaction parameters such as catalyst activity, dosage and solution pH on the decolorization of PCs were assessed. Results indicated that maximum decolorization （more than 95%） of PCs occurred with 20 wt% Fe（II）/γ-Al2O3 catalyst （dosage of 60 g/L） using a combination of UV irradiation and heterogeneous Fenton system. The degradation efficiency of PCs increases as pH decreases, exhibiting a maximum efficiency at pH 3.5. The recycled catalyst was capable of repeating three runs without a significant decrease in treatment efficiency, and this demonstrated the stability and reusability of catalyst.展开更多
基金supported by the National Natural Science Foundation of China(Nos.U21A2060 and 22178116)the Natural Science Foundation of Shanghai(No.22ZR1417400)the Fundamental Research Funds for the Central Universities(Nos.222201817001,50321041918013,JKA01221601,JKD01241701).
文摘Lithium-sulfur(Li-S)batteries are regarded as the most formidable competitor to lithium-ion batteries due to their superior theoretical capacity.However,the negative impact of soluble lithium polysulfide(LiPSs)and slow redox reaction kinetics seriously hamper the commercialization of Li-S batteries.In this study,a defect-rich single-atom catalyst with an oversaturated asymmetric Fe-N_(5)coordination structure anchored in defective g-C_(3)N_(4)(C_(3)N_(4)-Fe@rGO)is designed via an absorption-pyrolysis strategy.The two-dimensional(2D)conducting C_(3)N_(4)@graphene structure with abundant defect sites accelerates the trans-fer and transportation of lithium ions and electrons.The oversaturated asymmetric Fe-N_(5)coordination structure effectively improves the adsorbility of LiPSs and accelerates the redox kinetics of sulfur species.Hence,the Li-S cell with a C_(3)N_(4)-Fe@rGO modified separator reveals a high initial capacity(1197.1 mAh g^(-1) at 0.2 C)and a low capacity decay rate(0.037%per cycle after 900 cycles at 1 C).Even at high sulfur loading and extreme temperatures of 0℃,it also shows good cycling performance.This work creates ideas for synthesizing oversaturated single-atom coordination environments and an efficient route to the practical realization of the Li-S batteries.
基金financially supported by the National Natural Science Foundation of China(Nos.52422314,U23A20687,and 52231008)the International Science&Technology Cooperation Program of Hainan Province(No.GHYF2023007).
文摘Oxygen reduction reaction(ORR)in neutral electrolyte is urgently needed in various areas,such as metalair batteries.However,the N-coordinated transition-metal single-atom electrocatalysts confront sluggish catalytic kinetics due to the inappropriate electronic structure and the as-resulted unreasonable adsorption strength towards oxygen-containing intermediates.In this work,we develop a strategy to tune the Fe d-orbital spin state by introducing inert Si atom into the first coordination sphere of Fe-N_(4)moieties.The experimental and theoretical results suggest that Si atom generates the coordination field distortion of Fe and induces the Fe d-orbital spin state transforming from low to medium spin state.The optimized spin-electron filled state(t2g^(4)eg^(1))of Fe sites weakens the adsorption strength to intermediates and reduces the energy barrier of^(∗)OH desorption.Consequently,Fe-Si/NC catalyst exhibits superior ORR performance compared with that of Fe-NC and commercial Pt/C,showing a more positive half-wave potential of 0.753 V(vs.RHE)in 0.1 mol/L phosphate buffered saline.In addition,Fe-Si/NC-based neutral zinc-air batteries show a maximum power density of 108.9 mW cm^(−2)and long-term stability for 200 h.This work represents the possibility of constructing distorted coordination configurations of single-atom catalysts to modulate electronic structure and enhance ORR activity in neutral electrolyte.
基金supported by the CNPC Innovation Found(2021DQ02‐0702).
文摘With the rapid development of economy,the consumption of fossil fuels and excessive emissions of carbon dioxide(CO_(2))have led to many environmental issues.The thermocatalytic conversion of CO_(2) to high value‐added chemicals is an effective strategy to meet the need of carbon neutralization.Among them,CO_(2) hydrogenation to light olefins has been well researched so that the selectivity of desired products can exceed the Anderson–Schulz–Flory(ASF)distribution to acquire an extremely high yield.However,although huge progress has been made in CO_(2) hydrogenation to produce long‐chain α‐olefins based on Fe catalysts as well,designing efficient catalysts with promoted C‐O dissociation and C‐C coupling remains challenging.In addition,ASF distribution restrains the selectivity of desired long‐chain products,whereas the approaches to breaking it still face issues.In this review,we focus on the design of Fe‐based catalysts for the synthesis of long‐chainα‐olefins through CO_(2) hydrogenation.We have summarized and analyzed the reaction mechanism,design of catalysts,structure–activity relationship,interaction between Fe and promoters,and strategies to break the ASF distribution.At the same time,the issues faced by CO_(2) hydrogenation to long‐chain α‐olefins are proposed and the possible future solutions are prospected.This review aims to provide a recent development on the design of Fe‐based catalysts for CO_(2) hydrogenation to long‐chain α‐olefins while considering the ASF distribution.
基金This work is supported by the National Natural Science Foundation of China （No.51372248, No.51432009 and No.51502297）, Instrument Developing Project of the Chinese Academy of Sciences （No.yz201421）, the CAS/SAFEA International Partnership Program for Creative Research Teams of Chinese Academy of Sciences, China.
文摘A variety of spherical and structured activated charcoal supported Pt/Fe3O4 composites with an average particle size of ~100 nm have been synthesized by a self-assembly method using the difference of reduction potential between Pt （Ⅳ） and Fe （Ⅱ） precursors as driving force. The formed Fe3O4 nanoparticles （NPs） effectively prevent the aggregation of Pt nanocrystallites and promote the dispersion of Pt NPs on the surface of catalyst, which will be favorable for the exposure of Pt active sites for high-efficient adsorption and contact of substrate and hydrogen donor. The electron-enrichment state of Pt NPs donated by Fe304 nanocrystallites is corroborated by XPS measurement, which is responsible for promoting and activating the terminal C=O bond of adsorbed substrate via a vertical configuration. The experimental results show that the activated charcoal supported Pt/Fe3O4 catalyst exhibits 94.8% selectivity towards cinnamyl alcohol by the transfer hydrogenation of einnamaldehyde with Pt loading of 2.46% under the optimum conditions of 120 ℃ for 6 h, and 2-propanol as a hydrogen donor. Additionally, the present study demonstrates that a high-efficient and recyclable catalyst can be rapidly separated from the mixture due to its natural magnetism upon the application of magnetic field.
基金supported by the National Natural Science Foundation of China (21203017)Open Fund of State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences (N-11-3)+1 种基金Program for Liaoning Excellent Talents in University (LNET)the Funda-mental Research Funds for the Central Universities (DC201502020304)~~
文摘separation is an attractive alternative to filtration or centrifugation for separating solid catalysts from a liquid phase, Here, core-shell Fe3O4@UiO-66-NH2 nanohybrids with well-defined structures were constructed by dispersing magnets in a dimethylformamide （DMF） solution con- taining two metal-organic framework （MOF） precursors, namely ZrCI4 and 2-aminobenzenetricar- boxylic acid. This method is simpler and more efficient than previously reported step-by-step method in which magnets were consecutively dispersed in DMF solutions each containing one MOF precursor, and the obtained Fe304@UiO-66-NH2 with three assembly cycles has a higher degree of crystallinity and porosiW. The core-shell Fe3O4@UiO-66-NH2 is highly active and selective in Knoevenagel condensations because of the bifunctionality of UiO-66-NH2 and better mass transfer in the nano-sized shells. It also has good recycling stability, and can be recovered magnetically and reused at least four times without significant loss of catalytic activity and framework integrity. The effects of substitution on the reactivity of benzaldehyde and of substrate size were also investigated.
文摘Fe（HSO4）3 has been used as an efficient and recyclable catalyst for the one-pot synthesis of 14-aryl- or alkyl-14Hdibenzo[aj]xanthene derivatives by the reaction of 2-naphtol and aldehydes. Different types of aromatic and aliphatic aldehydes are used in the reaction and in all cases the products were obtained in good to excellent yields.
基金Supported by the 973project of China(G2 0 0 0 0 2 6 4 )
文摘The partial oxidation of ethanol to hydrogen was investigated over Ni/Fe/La catalysts prepared by the co precipitation method. The effects of introduction of La promoter and the reaction temperature on the catalytic performance were studied. It was found that the introduction of La into Ni/Fe catalysts is helpful to increase the selectivity to hydrogen and the stability of the catalysts. The results of XRD and XPS characterization show that the structure of the catalyst was changed during the reaction. The existence of LaFeO 3 species is possibly the main reason of the increase of the catalyst stability.
基金supported by the National Natural Science Foundation of China(41573118)Research Foundation of Education Bureau of Hunan Province,China(14B177)Special Project of Xiangtan University~~
文摘A novel plasmonic photo‐Fenton catalyst of Ag/AgCl/Fe‐S was synthesized by ion exchange and photoreduction methods.The obtained catalyst was characterized by X‐ray diffraction,X‐ray photoelectron spectroscopy,scanning electron microscope imaging,and Brunauer‐Emmett‐Teller measurements.Moreover,the photocatalytic activity of Ag/AgCl/Fe‐S was investigated for its degradation activity towards bisphenol A(BPA)as target pollutant under visible light irradiation.The effects of H2O2concentration,pH value,illumination intensity,and catalyst dosage on BPA degradation were examined.Our results indicated that the Ag/AgCl material was successfully loaded onto Fe‐sepiolite and showed a high photocatalytic activity under illumination by visible light.Furthermore,active species capture experiments were performed to explore the photocatalytic mechanism of the Ag/AgCl/Fe‐S in this heterogeneous photo‐Fenton process,where the major active species included hydroxyl radicals(?OH)and holes(h+).
文摘Supported Ir catalysts were prepared using layered double hydrotalcite‐like materials,such as Mg_(3)Al_(1-x)Fe_(x),containing Fe and Al species in varying amounts as supports.These Ir catalysts were applied for the selective hydrogenation of cinnamaldehyde(CAL).When x was changed from 0(Ir/Mg_(3)Al)to 1(Ir/Mg_(3)Fe),the rate of CAL hydrogenation reached a maximum at approximately x=0.25,while the selectivity to unsaturated alcohol,i.e.,cinnamyl alcohol,monotonously increased from 44.9%to 80.3%.Meanwhile,the size of the supported Ir particles did not change significantly with x,remaining at 1.7-0.2 nm,as determined by transmission electron microscopy.The chemical state of Ir and Fe species in the Ir/Mg3Al1-xFex catalysts was examined by temperature programmed reduction by H2 and X‐ray photoelectron spectroscopy.The surface of the supported Ir particles was also examined through the in‐situ diffuse reflectance infrared Fourier‐transform of a probe molecule of CO.On the basis of these characterization results,the effects of Fe doping to Mg_(3)Al on the structural and catalytic properties of Ir particles in selective CAL hydrogenation were discussed.The significant factors are the electron transfer from Fe2+in the Mg_(3)Al_(1–x)Fex support to the dispersed Ir particles and the surface geometry.
文摘Fe（II）/γ-Al2O3 powders synthesized using the dipping method were produced from a mixed aqueous solution containing aluminium oxide （γ-Al2O3） and iron（II）-precursor （FeSO4）, and used for photoFenton degradation of phthalocyanine dyes （PCs） under ultraviolet （UV） irradiation in an up-flow fluidized bed. The catalysts were characterized by XRD, ESCA, BET, EDS and SEM. The results showed that Fe2＋ ion was compounded on the γ-Al2O3 carder. The effects of different reaction parameters such as catalyst activity, dosage and solution pH on the decolorization of PCs were assessed. Results indicated that maximum decolorization （more than 95%） of PCs occurred with 20 wt% Fe（II）/γ-Al2O3 catalyst （dosage of 60 g/L） using a combination of UV irradiation and heterogeneous Fenton system. The degradation efficiency of PCs increases as pH decreases, exhibiting a maximum efficiency at pH 3.5. The recycled catalyst was capable of repeating three runs without a significant decrease in treatment efficiency, and this demonstrated the stability and reusability of catalyst.
