The efficient, green, facile, mild and straightforward conversion procedure for the oxidation of cyclic ketones to lactones at room temperature utilizing potassium peroxydisulfate （K2S2O8） in acidic media is satisfa...The efficient, green, facile, mild and straightforward conversion procedure for the oxidation of cyclic ketones to lactones at room temperature utilizing potassium peroxydisulfate （K2S2O8） in acidic media is satisfactory to high yields without using traditional chlorinated solvents is reported. This oxidative reagent is cheap and friendly environmental procedure for industrial purposes than use of organic peracids.展开更多
The green and effective Baeyer-Villiger oxidation reaction of cyclohexanone for preparing e-caprolactone is of particular importance in the synthesis of new polymer materials. We have discussed here several mechanism ...The green and effective Baeyer-Villiger oxidation reaction of cyclohexanone for preparing e-caprolactone is of particular importance in the synthesis of new polymer materials. We have discussed here several mechanism types of Baeyer-Villiger oxidation of cyclohexanone with H2O2 in different reaction systems. Five main types have been addressed, i. e.： （1） the non-catalyzed reaction type, where the C=O of ketones is activated by H＋, which is electrolytically dissociated from H202 and H20, to improve the capability of C=O group for accepting the electron pairs; （2） the thermally activated radical reaction type, where the Criegee intermediate is produced via two steps of radical reaction with -OH attack, with much more hydroxyl radicals being excited in the presence of TS-1 zeolite; （3） the Bronsted acid catalysis reaction type, where both O-O moiety and C=O group could be activated by BriSnsted acid; （4） the solid Lewis acid catalyzed C=O of the substrate activation reaction type through enhancing the donor-acceptor interaction between the antibonding π＊c-o orbital of cyclohexanone and HOMO of Sn-containing zeolites; and （5） the solid Lewis acid catalyzed H202 to form Me-OOH oxidative species by converting the highest occupied molecular orbital （HOMO） of Ti-OOH into a singly occupied molecular orbital （SOMO）, making the O--O group highly electrophilic to attack the C--O of cyclohexanone during the Baeyer-Villiger oxidation process. In the end, we have also compared the different mechanisms and put forward our opinions on the development direction of catalytic materials aiming at eco-friendly Baeyer-Villiger oxidation of cyclohexanone in the years to come.展开更多
Sn-aniline complex was prepared by a simple procedure. Cyclic and acyclic ketones were oxidized into lactones or esters with very high selectivity and yield with 30% hydrogen peroxide in the presence of Sn-aniline com...Sn-aniline complex was prepared by a simple procedure. Cyclic and acyclic ketones were oxidized into lactones or esters with very high selectivity and yield with 30% hydrogen peroxide in the presence of Sn-aniline complex.展开更多
A high thrust-to-weight ratio poses challenges to the high-temperature performance of Ni-based superalloys. The oxidation behavior of GH4738 at extreme temperatures has been investigated by isothermal and non-isotherm...A high thrust-to-weight ratio poses challenges to the high-temperature performance of Ni-based superalloys. The oxidation behavior of GH4738 at extreme temperatures has been investigated by isothermal and non-isothermal experiments. As a result of the competitive diffusion of alloying elements, the oxide scale included an outermost porous oxide layer (OOL), an inner relatively dense oxide layer (IOL), and an internal oxide zone (IOZ), depending on the temperature and time. A high temperature led to the formation of large voids at the IOL/IOZ interface. At 1200℃, the continuity of the Cr-rich oxide layer in the IOL was destroyed, and thus, spallation occurred. Extension of oxidation time contributed to the size of Al-rich oxide particles with the increase in the IOZ. Based on this finding,the oxidation kinetics of GH4738 was discussed, and the corresponding oxidation behavior at 900-1100℃ was predicted.展开更多
With graphite currently leading as the most viable anode for potassium-ion batteries(KIBs),other materials have been left relatively underexamined.Transition metal oxides are among these,with many positive attributes ...With graphite currently leading as the most viable anode for potassium-ion batteries(KIBs),other materials have been left relatively underexamined.Transition metal oxides are among these,with many positive attributes such as synthetic maturity,longterm cycling stability and fast redox kinetics.Therefore,to address this research deficiency we report herein a layered potassium titanium niobate KTiNbO5(KTNO)and its rGO nanocomposite(KTNO/rGO)synthesised via solvothermal methods as a high-performance anode for KIBs.Through effective distribution across the electrically conductive rGO,the electrochemical performance of the KTNO nanoparticles was enhanced.The potassium storage performance of the KTNO/rGO was demonstrated by its first charge capacity of 128.1 mAh g^(−1) and reversible capacity of 97.5 mAh g^(−1) after 500 cycles at 20 mA g^(−1),retaining 76.1%of the initial capacity,with an exceptional rate performance of 54.2 mAh g^(−1)at 1 A g^(−1).Furthermore,to investigate the attributes of KTNO in-situ XRD was performed,indicating a low-strain material.Ex-situ X-ray photoelectron spectra further investigated the mechanism of charge storage,with the titanium showing greater redox reversibility than the niobium.This work suggests this lowstrain nature is a highly advantageous property and well worth regarding KTNO as a promising anode for future high-performance KIBs.展开更多
In order to better understand the specific substituent effects on the electrochemical oxidation process of β-O-4 bond, a series of methoxyphenyl type β-O-4 dimer model compounds with different localized methoxyl gro...In order to better understand the specific substituent effects on the electrochemical oxidation process of β-O-4 bond, a series of methoxyphenyl type β-O-4 dimer model compounds with different localized methoxyl groups, including 2-(2-methoxyphenoxy)-1-phenylethanone, 2-(2-methoxyphenoxy)-1-phenylethanol, 2-(2-methoxyphenoxy)-1-(4-methoxyphenyl)ethanone, 2-(2-methoxyphenoxy)-1-(4-methoxyphenyl)ethanol, 2-(2,6-dimethoxyphenoxy)-1-(4-methoxyphenyl)ethanone, 2-(2,6-dimethoxyphenoxy)-1-(4-methoxyphenyl)ethanol have been selected and their electrochemical properties have been studied experimentally by cyclic voltammetry, and FT-IR spectroelectrochemistry. Combining with electrolysis products distribution analysis and density functional theory calculations, oxidation mechanisms of all six model dimers have been explored. In particular, a total effect from substituents of both para-methoxy(on the aryl ring closing to Cα) and Cα-OH on the oxidation mechanisms has been clearly observed, showing a significant selectivity on the Cα-Cβbond cleavage induced by electrochemical oxidations.展开更多
The scarcity,high cost and susceptibility to CO of Platinum severely restrict its application in alkaline hydrogen oxidation reaction(HOR).Hybridizing Pt with other transition metals provides an effective strategy to ...The scarcity,high cost and susceptibility to CO of Platinum severely restrict its application in alkaline hydrogen oxidation reaction(HOR).Hybridizing Pt with other transition metals provides an effective strategy to modulate its catalytic HOR performance,but at the cost of mass activity due to the coverage of modifiers on Pt surface.Herein,we constructed dual junctions'Pt/nitrogen-doped carbon(Pt/NC)andδ-MoC/NC to modify electronic structure of Pt via interfacial electron transfer to acquire Pt-MoC@NC catalyst with electron-deficient Pt nanoparticles,simultaneously endowing it with high mass activity and durability of alkaline HOR.Moreover,the unique structure of Pt-MoC@NC endows Pt with a high COtolerance at 1,000 ppm CO/H_(2),a quality that commercial Pt-C catalyst lacks.The theoretical calculations not only confirm the diffusion of electrons from Pt/NC to Mo C/NC could occur,but also demonstrate the negative shift of Pt d-band center for the optimized binding energies of*H,*OH and CO.展开更多
The microbial production of either ester/lactones or enantio-enriched alcohols through Baeyer-Villiger oxidation or stereoselective reduction of ketones,respectively,is possible by using whole cells of A.subglaciale F...The microbial production of either ester/lactones or enantio-enriched alcohols through Baeyer-Villiger oxidation or stereoselective reduction of ketones,respectively,is possible by using whole cells of A.subglaciale F134 as a bifunctional biocatalyst.The chemoselective pattern of acetophenone biotransformation catalyzed by these cells can be regulated through reaction temperature,directing the reaction either towards oxidation or reduction products.The Baeyer–Villiger oxidation activity of A.subglaciale F134 whole cells is particularly dependent on reaction temperature.Acetophenone was transformed efficiently to phenol via the primary Baeyer–Villiger product phenyl acetate at 20℃ after 48 h with 100% conversion.In contrast,at 35℃,enantio-enriched(S)-1-phenylethanol was obtained as the sole product with 64% conversion and 89% ee.In addition,A.subglaciale F134 cells also catalyze the selective reduction of various structurally different aldehydes and ketones to alcohols with 40% to 100% yield,indicating broad substrate spectrum and good enantioselectivity in relevant cases.Our study provides a bifunctional biocatalyst systemthat can be used in Baeyer–Villiger oxidation aswell as in asymmetric carbonyl reduction,setting the stage for future work concerning the identification and isolation of the respective enzymes.展开更多
Exploitation of oxygen evolution reaction(OER)and urea oxidation reaction(UOR)catalysts with high activity and stability at large current density is a major challenge for energy-saving H_(2) production in water electr...Exploitation of oxygen evolution reaction(OER)and urea oxidation reaction(UOR)catalysts with high activity and stability at large current density is a major challenge for energy-saving H_(2) production in water electrolysis.Herein,we use the pyridinic-N doping carbon layers coupled with tensile strain of FeNi alloy activated by NiFe_(2)O_(4)(FeNi/NiFe_(2)O_(4)@NC)for efficiently increasing the performance of water and urea oxidation.Due to the tensile strain effect on FeNi/NiFe_(2)O_(4)@NC,it provides a favorable modulation on the electronic properties of the active center,thus enabling amazing OER(η_(100)=196 mV)and UOR(E_(10)=1.32 V)intrinsic activity.Besides,the carbon-coated layers can be used as armor to prevent FeNi alloy from being corroded by the electrolyte for enhancing the OER/UOR stability at large current density,showing high industrial practicability.This work thus provides a simple way to prepare high-efficiency catalyst for activating water and urea oxidation.展开更多
Solid oxide electrolysis cells(SOECs)represent a crucial stride toward sustainable hydrogen generation,and this review explores their current scientific challenges,significant advancements,and potential for large-scal...Solid oxide electrolysis cells(SOECs)represent a crucial stride toward sustainable hydrogen generation,and this review explores their current scientific challenges,significant advancements,and potential for large-scale hydrogen production.In SOEC technology,the application of innovative fabrication tech-niques,doping strategies,and advanced materials has enhanced the performance and durability of these systems,although degradation challenges persist,implicating the prime focus for future advancements.Here we provide in-depth analysis of the recent developments in SOEC technology,including Oxygen-SOECs,Proton-SOECs,and Hybrid-SOECs.Specifically,Hybrid-SOECs,with their mixed ionic conducting electrolytes,demonstrate superior efficiency and the concurrent production of hydrogen and oxygen.Coupled with the capacity to harness waste heat,these advancements in SOEC technology present signif-icant promise for pilot-scale applications in industries.The review also highlights remarkable achieve-ments and potential reductions in capital expenditure for future SOEC systems,while elaborating on the micro and macro aspects of sOECs with an emphasis on ongoing research for optimization and scal-ability.It concludes with the potential of SOEC technology to meet various industrial energy needs and its significant contribution considering the key research priorities to tackle the global energy demands,ful-fillment,and decarbonization efforts.展开更多
The Mn-based oxide cathode with enriched crystal phase structure and component diversity can provide the excellent chemistry structure for Na-ion batteries.Nevertheless,the broad application prospect is obstructed by ...The Mn-based oxide cathode with enriched crystal phase structure and component diversity can provide the excellent chemistry structure for Na-ion batteries.Nevertheless,the broad application prospect is obstructed by the sluggish Na^(+)kinetics and the phase transitions upon cycling.Herein,we establish the thermodynamically stable phase diagram of various Mn-based oxide composites precisely controlled by sodium content tailoring strategy coupling with co-doping and solid-state reaction.The chemical environment of the P2/P'3 and P2/P3 biphasic composites indicate that the charge compensation mechanism stems from the cooperative contribution of anions and cations.Benefiting from the no phase transition to scavenge the structure strain,P2/P'3 electrode can deliver long cycling stability(capacity retention of 73.8%after 1000 cycles at 10 C)and outstanding rate properties(the discharge capacity of 84.08 mA h g^(-1)at 20 C)than P2/P3 electrode.Furthermore,the DFT calculation demonstrates that the introducing novel P'3 phase can significantly regulate the Na^(+)reaction dynamics and modify the local electron configuration of Mn.The effective phase engineering can provide a reference for designing other high-performance electrode materials for Na-ion batteries.展开更多
The global energy-related CO_(2) emissions have rapidly increased as the world economy heavily relied on fossil fuels.This paper explores the pressing challenge of CO_(2) emissions and highlights the role of porous me...The global energy-related CO_(2) emissions have rapidly increased as the world economy heavily relied on fossil fuels.This paper explores the pressing challenge of CO_(2) emissions and highlights the role of porous metal oxide materials in the electrocatalytic reduction of CO_(2)(CO_(2)RR).The focus is on the development of robust and selective catalysts,particularly metal and metal-oxide-based materials.Porous metal oxides offer high surface area,enhancing the accessibility to active sites and improving reaction kinetics.The tunability of these materials allows for tailored catalytic behavior,targeting optimized reaction mechanisms for CO_(2)RR.The work also discusses the various synthesis strategies and identifies key structural and compositional features,addressing challenges like high overpotential,poor selectivity,and low stability.Based on these insights,we suggest avenues for future research on porous metal oxide materials for electrochemical CO_(2) reduction.展开更多
Co-Ni-based superalloys are known for their capability to function at elevated temperatures and superior hot corrosion and thermal fatigue resistance.Therefore,these alloys show potential as crucial high-temperature s...Co-Ni-based superalloys are known for their capability to function at elevated temperatures and superior hot corrosion and thermal fatigue resistance.Therefore,these alloys show potential as crucial high-temperature structural materials for aeroengine and gas turbine hot-end components.Our previous work elucidated the influence of Ti and Ta on the high-temperature mechanical properties of alloys.However,the intricate interaction among elements considerably affects the oxidation resistance of alloys.In this paper,Co-35Ni-10Al-2W-5Cr-2Mo-1Nb-xTi-(5−x)Ta alloys(x=1,2,3,4)with varying Ti and Ta contents were designed and compounded,and their oxidation resistance was investigated at the temperature range from 800 to 1000℃.After oxidation at three test conditions,namely,800℃for 200 h,900℃for 200 h,and 1000℃for 50 h,the main structure of the oxide layer of the alloy consisted of spinel,Cr_(2)O_(3),and Al_(2)O_(3)from outside to inside.Oxides consisting of Ta,W,and Mo formed below the Cr_(2)O_(3)layer.The interaction of Ti and Ta imparted the highest oxidation resistance to 3Ti2Ta alloy.Conversely,an excessive amount of Ti or Ta resulted in an adverse effect on the oxidation resistance of the alloys.This study reports the volatilization of W and Mo oxides during the oxidation process of Co-Ni-based cast superalloys with a high Al content for the first time and explains the formation mechanism of holes in the oxide layer.The results provide a basis for gaining insights into the effects of the interaction of alloying elements on the oxidation resistance of the alloys they form.展开更多
Electrocatalytic hydrogen production from seawater holds enormous promise for clean energy generation.Nevertheless,the direct electrolysis of seawater encounters significant challenges due to poor anodic stability cau...Electrocatalytic hydrogen production from seawater holds enormous promise for clean energy generation.Nevertheless,the direct electrolysis of seawater encounters significant challenges due to poor anodic stability caused by detrimental chlorine chemistry.Herein,we present our recent discovery that the incorporation of Ce into Ni Fe layered double hydroxide nanosheet array on Ni foam(Ce-Ni Fe LDH/NF)emerges as a robust electrocatalyst for seawater oxidation.During the seawater oxidation process,CeO_(2)is generated,effectively repelling Cl^(-)and inhibiting the formation of Cl O-,resulting in a notable enhancement in the oxidation activity and stability of alkaline seawater.The prepared Ce-Ni Fe LDH/NF requires only overpotential of 390 m V to achieve the current density of 1 A cm^(-2),while maintaining long-term stability for 500 h,outperforming the performance of Ni Fe LDH/NF(430 m V,150 h)by a significant margin.This study highlights the effectiveness of a Ce-doping strategy in augmenting the activity and stability of materials based on Ni Fe LDH in seawater electrolysis for oxygen evolution.展开更多
Developing efficient and stable cathodes for low-temperature solid oxide fuel cells(LT-SOFCs) is of great importance for the practical commercialization.Herein,we propose a series of Sm-modified Bi_(0.7-x)Sm_xSr_(0.3)...Developing efficient and stable cathodes for low-temperature solid oxide fuel cells(LT-SOFCs) is of great importance for the practical commercialization.Herein,we propose a series of Sm-modified Bi_(0.7-x)Sm_xSr_(0.3)FeO_(3-δ) perovskites as highly-active catalysts for LT-SOFCs.Sm doping can significantly enhance the electrocata lytic activity and chemical stability of cathode.At 600℃,Bi_(0.675)Sm_(0.025)Sr_(0.3)FeO_(3-δ)(BSSF25) cathode has been found to be the optimum composition with a polarization resistance of 0.098 Ω cm^2,which is only around 22.8% of Bi_(0.7)Sr_(0.3)FeO_(3-δ)(BSF).A full cell utilizing BSSF25 displays an exceptional output density of 790 mW cm^(-2),which can operate continuously over100 h without obvious degradation.The remarkable electrochemical performance observed can be attributed to the improved O_(2) transport kinetics,superior surface oxygen adsorption capacity,as well as O_(2)p band centers in close proximity to the Fermi level.Moreover,larger average bonding energy(ABE) and the presence of highly acidic Bi,Sm,and Fe ions restrict the adsorption of CO_(2) on the cathode surface,resulting in excellent CO_(2) resistivity.This work provides valuable guidance for systematic design of efficient and durable catalysts for LT-SOFCs.展开更多
Previous studies have shown that Biochanin A,a flavonoid compound with estrogenic effects,can serve as a neuroprotective agent in the context of cerebral ischemia/reperfusion injury;howeve r,its effect on spinal cord ...Previous studies have shown that Biochanin A,a flavonoid compound with estrogenic effects,can serve as a neuroprotective agent in the context of cerebral ischemia/reperfusion injury;howeve r,its effect on spinal cord injury is still unclea r. In this study,a rat model of spinal cord injury was established using the heavy o bject impact method,and the rats were then treated with Biochanin A(40 mg/kg) via intrape ritoneal injection for 14 consecutive days.The res ults showed that Biochanin A effectively alleviated spinal cord neuronal injury and spinal co rd tissue injury,reduced inflammation and oxidative stress in spinal cord neuro ns,and reduced apoptosis and pyroptosis.In addition,Biochanin A inhibited the expression of inflammasome-related proteins(ASC,NLRP3,and GSDMD)and the Toll-like receptor 4/nuclear factor-κB pathway,activated the Nrf2/heme oxygenase 1 signaling pathway,and increased the expression of the autophagy markers LC3 Ⅱ,Beclin-1,and P62.Moreove r,the therapeutic effects of Biochanin A on early post-s pinal cord injury were similar to those of methylprednisolone.These findings suggest that Biochanin A protected neurons in the injured spinal cord through the Toll-like receptor 4/nuclear factor κB and Nrf2/heme oxygenase 1 signaling pathways.These findings suggest that Biochanin A can alleviate post-spinal cord injury at an early stage.展开更多
Accumulating evidence suggests that oxidative stress and the Wnt/β-catenin pathway participate in stroke-induced disruption of the blood-brain barrier.However,the potential links between them following ischemic strok...Accumulating evidence suggests that oxidative stress and the Wnt/β-catenin pathway participate in stroke-induced disruption of the blood-brain barrier.However,the potential links between them following ischemic stroke remain largely unknown.The present study found that cerebral ischemia leads to oxidative stress and repression of the Wnt/β-catenin pathway.Meanwhile,Wnt/β-catenin pathway activation by the pharmacological inhibito r,TWS119,relieved oxidative stress,increased the levels of cytochrome P4501B1(CYP1B1)and tight junction-associated proteins(zonula occludens-1[ZO-1],occludin and claudin-5),as well as brain microvascular density in cerebral ischemia rats.Moreove r,rat brain microvascular endothelial cells that underwent oxygen glucose deprivation/reoxygenation displayed intense oxidative stress,suppression of the Wnt/β-catenin pathway,aggravated cell apoptosis,downregulated CYP1B1and tight junction protein levels,and inhibited cell prolife ration and migration.Overexpression ofβ-catenin or knockdown ofβ-catenin and CYP1B1 genes in rat brain mic rovascular endothelial cells at least partly ameliorated or exacerbated these effects,respectively.In addition,small interfering RNA-mediatedβ-catenin silencing decreased CYP1B1 expression,whereas CYP1B1 knoc kdown did not change the levels of glycogen synthase kinase 3β,Wnt-3a,andβ-catenin proteins in rat brain microvascular endothelial cells after oxygen glucose deprivatio n/reoxygenation.Thus,the data suggest that CYP1B1 can be regulated by Wnt/β-catenin signaling,and activation of the Wnt/β-catenin/CYP1B1 pathway contributes to alleviation of oxidative stress,increased tight junction levels,and protection of the blood-brain barrier against ischemia/hypoxia-induced injury.展开更多
基金support and purchase of Hewlett-Packard 6890 GC-Hewlett-Packard 5973N MSD instrument.
文摘The efficient, green, facile, mild and straightforward conversion procedure for the oxidation of cyclic ketones to lactones at room temperature utilizing potassium peroxydisulfate （K2S2O8） in acidic media is satisfactory to high yields without using traditional chlorinated solvents is reported. This oxidative reagent is cheap and friendly environmental procedure for industrial purposes than use of organic peracids.
文摘The green and effective Baeyer-Villiger oxidation reaction of cyclohexanone for preparing e-caprolactone is of particular importance in the synthesis of new polymer materials. We have discussed here several mechanism types of Baeyer-Villiger oxidation of cyclohexanone with H2O2 in different reaction systems. Five main types have been addressed, i. e.： （1） the non-catalyzed reaction type, where the C=O of ketones is activated by H＋, which is electrolytically dissociated from H202 and H20, to improve the capability of C=O group for accepting the electron pairs; （2） the thermally activated radical reaction type, where the Criegee intermediate is produced via two steps of radical reaction with -OH attack, with much more hydroxyl radicals being excited in the presence of TS-1 zeolite; （3） the Bronsted acid catalysis reaction type, where both O-O moiety and C=O group could be activated by BriSnsted acid; （4） the solid Lewis acid catalyzed C=O of the substrate activation reaction type through enhancing the donor-acceptor interaction between the antibonding π＊c-o orbital of cyclohexanone and HOMO of Sn-containing zeolites; and （5） the solid Lewis acid catalyzed H202 to form Me-OOH oxidative species by converting the highest occupied molecular orbital （HOMO） of Ti-OOH into a singly occupied molecular orbital （SOMO）, making the O--O group highly electrophilic to attack the C--O of cyclohexanone during the Baeyer-Villiger oxidation process. In the end, we have also compared the different mechanisms and put forward our opinions on the development direction of catalytic materials aiming at eco-friendly Baeyer-Villiger oxidation of cyclohexanone in the years to come.
文摘Sn-aniline complex was prepared by a simple procedure. Cyclic and acyclic ketones were oxidized into lactones or esters with very high selectivity and yield with 30% hydrogen peroxide in the presence of Sn-aniline complex.
基金financially supported by the National Key R&D Program of China (No.2021YFB3700400)the National Natural Science Foundation of China (Nos.52074030,51904021,and 52174294)。
文摘A high thrust-to-weight ratio poses challenges to the high-temperature performance of Ni-based superalloys. The oxidation behavior of GH4738 at extreme temperatures has been investigated by isothermal and non-isothermal experiments. As a result of the competitive diffusion of alloying elements, the oxide scale included an outermost porous oxide layer (OOL), an inner relatively dense oxide layer (IOL), and an internal oxide zone (IOZ), depending on the temperature and time. A high temperature led to the formation of large voids at the IOL/IOZ interface. At 1200℃, the continuity of the Cr-rich oxide layer in the IOL was destroyed, and thus, spallation occurred. Extension of oxidation time contributed to the size of Al-rich oxide particles with the increase in the IOZ. Based on this finding,the oxidation kinetics of GH4738 was discussed, and the corresponding oxidation behavior at 900-1100℃ was predicted.
基金Y.X.acknowledges the financial support of the Engineering and Physical Sciences Research Council(EP/X000087/1,EP/V000152/1)Leverhulme Trust(RPG-2021-138)Royal Society(IEC\NSFC\223016).
文摘With graphite currently leading as the most viable anode for potassium-ion batteries(KIBs),other materials have been left relatively underexamined.Transition metal oxides are among these,with many positive attributes such as synthetic maturity,longterm cycling stability and fast redox kinetics.Therefore,to address this research deficiency we report herein a layered potassium titanium niobate KTiNbO5(KTNO)and its rGO nanocomposite(KTNO/rGO)synthesised via solvothermal methods as a high-performance anode for KIBs.Through effective distribution across the electrically conductive rGO,the electrochemical performance of the KTNO nanoparticles was enhanced.The potassium storage performance of the KTNO/rGO was demonstrated by its first charge capacity of 128.1 mAh g^(−1) and reversible capacity of 97.5 mAh g^(−1) after 500 cycles at 20 mA g^(−1),retaining 76.1%of the initial capacity,with an exceptional rate performance of 54.2 mAh g^(−1)at 1 A g^(−1).Furthermore,to investigate the attributes of KTNO in-situ XRD was performed,indicating a low-strain material.Ex-situ X-ray photoelectron spectra further investigated the mechanism of charge storage,with the titanium showing greater redox reversibility than the niobium.This work suggests this lowstrain nature is a highly advantageous property and well worth regarding KTNO as a promising anode for future high-performance KIBs.
基金The authors gratefully acknowledge the financial support of the Natural Science Foundation of China,China(Grant No.21975082 and 21736003)the Guangdong Basic and Applied Basic Research Foundation(Grant Number:2019A1515011472 and 2022A1515011341)the Science and Technology Program of Guangzhou(Grant Number:202102080479).
文摘In order to better understand the specific substituent effects on the electrochemical oxidation process of β-O-4 bond, a series of methoxyphenyl type β-O-4 dimer model compounds with different localized methoxyl groups, including 2-(2-methoxyphenoxy)-1-phenylethanone, 2-(2-methoxyphenoxy)-1-phenylethanol, 2-(2-methoxyphenoxy)-1-(4-methoxyphenyl)ethanone, 2-(2-methoxyphenoxy)-1-(4-methoxyphenyl)ethanol, 2-(2,6-dimethoxyphenoxy)-1-(4-methoxyphenyl)ethanone, 2-(2,6-dimethoxyphenoxy)-1-(4-methoxyphenyl)ethanol have been selected and their electrochemical properties have been studied experimentally by cyclic voltammetry, and FT-IR spectroelectrochemistry. Combining with electrolysis products distribution analysis and density functional theory calculations, oxidation mechanisms of all six model dimers have been explored. In particular, a total effect from substituents of both para-methoxy(on the aryl ring closing to Cα) and Cα-OH on the oxidation mechanisms has been clearly observed, showing a significant selectivity on the Cα-Cβbond cleavage induced by electrochemical oxidations.
基金supported by the National Natural Science Foundation of China (Grant Nos.52072272,52171145 and 22109120)the Zhejiang Provincial Natural Science Foundation of China (LQ21B030002)+1 种基金the Zhejiang Provincial Special Support Program for High-level Talents (2019R52042)the Key programs for Science and Technology Innovation of Wenzhou (ZG2022037)。
文摘The scarcity,high cost and susceptibility to CO of Platinum severely restrict its application in alkaline hydrogen oxidation reaction(HOR).Hybridizing Pt with other transition metals provides an effective strategy to modulate its catalytic HOR performance,but at the cost of mass activity due to the coverage of modifiers on Pt surface.Herein,we constructed dual junctions'Pt/nitrogen-doped carbon(Pt/NC)andδ-MoC/NC to modify electronic structure of Pt via interfacial electron transfer to acquire Pt-MoC@NC catalyst with electron-deficient Pt nanoparticles,simultaneously endowing it with high mass activity and durability of alkaline HOR.Moreover,the unique structure of Pt-MoC@NC endows Pt with a high COtolerance at 1,000 ppm CO/H_(2),a quality that commercial Pt-C catalyst lacks.The theoretical calculations not only confirm the diffusion of electrons from Pt/NC to Mo C/NC could occur,but also demonstrate the negative shift of Pt d-band center for the optimized binding energies of*H,*OH and CO.
基金financially supported by the National Natural Science Foundation of China(No.21646014 and 21776134)the program of Jiangsu Synergetic Innovation Center for Advanced Bio-Manufacture(XTE1851).
文摘The microbial production of either ester/lactones or enantio-enriched alcohols through Baeyer-Villiger oxidation or stereoselective reduction of ketones,respectively,is possible by using whole cells of A.subglaciale F134 as a bifunctional biocatalyst.The chemoselective pattern of acetophenone biotransformation catalyzed by these cells can be regulated through reaction temperature,directing the reaction either towards oxidation or reduction products.The Baeyer–Villiger oxidation activity of A.subglaciale F134 whole cells is particularly dependent on reaction temperature.Acetophenone was transformed efficiently to phenol via the primary Baeyer–Villiger product phenyl acetate at 20℃ after 48 h with 100% conversion.In contrast,at 35℃,enantio-enriched(S)-1-phenylethanol was obtained as the sole product with 64% conversion and 89% ee.In addition,A.subglaciale F134 cells also catalyze the selective reduction of various structurally different aldehydes and ketones to alcohols with 40% to 100% yield,indicating broad substrate spectrum and good enantioselectivity in relevant cases.Our study provides a bifunctional biocatalyst systemthat can be used in Baeyer–Villiger oxidation aswell as in asymmetric carbonyl reduction,setting the stage for future work concerning the identification and isolation of the respective enzymes.
基金supported by the National Natural Science Foundation of China(21872040,22162004)the Excellent Scholars and Innovation Team of Guangxi Universities,the Innovation Project of Guangxi Graduate Education(YCBZ2022038)the High-performance Computing Platform of Guangxi University.
文摘Exploitation of oxygen evolution reaction(OER)and urea oxidation reaction(UOR)catalysts with high activity and stability at large current density is a major challenge for energy-saving H_(2) production in water electrolysis.Herein,we use the pyridinic-N doping carbon layers coupled with tensile strain of FeNi alloy activated by NiFe_(2)O_(4)(FeNi/NiFe_(2)O_(4)@NC)for efficiently increasing the performance of water and urea oxidation.Due to the tensile strain effect on FeNi/NiFe_(2)O_(4)@NC,it provides a favorable modulation on the electronic properties of the active center,thus enabling amazing OER(η_(100)=196 mV)and UOR(E_(10)=1.32 V)intrinsic activity.Besides,the carbon-coated layers can be used as armor to prevent FeNi alloy from being corroded by the electrolyte for enhancing the OER/UOR stability at large current density,showing high industrial practicability.This work thus provides a simple way to prepare high-efficiency catalyst for activating water and urea oxidation.
基金the support of the Natural Sciences and Engineering Research Council of Canada(NSERC)Tier 1 Canada Research Chair in Green Hydrogen Production,the Québec Ministere de I'Economie,de I'lnnovation et de I'Energie(MEIE)[Développement de catalyseurs et d'electrodes innovants,a faibles couts,performants et durables pour la production d'hydrogene vert,funding reference number 00393501]。
文摘Solid oxide electrolysis cells(SOECs)represent a crucial stride toward sustainable hydrogen generation,and this review explores their current scientific challenges,significant advancements,and potential for large-scale hydrogen production.In SOEC technology,the application of innovative fabrication tech-niques,doping strategies,and advanced materials has enhanced the performance and durability of these systems,although degradation challenges persist,implicating the prime focus for future advancements.Here we provide in-depth analysis of the recent developments in SOEC technology,including Oxygen-SOECs,Proton-SOECs,and Hybrid-SOECs.Specifically,Hybrid-SOECs,with their mixed ionic conducting electrolytes,demonstrate superior efficiency and the concurrent production of hydrogen and oxygen.Coupled with the capacity to harness waste heat,these advancements in SOEC technology present signif-icant promise for pilot-scale applications in industries.The review also highlights remarkable achieve-ments and potential reductions in capital expenditure for future SOEC systems,while elaborating on the micro and macro aspects of sOECs with an emphasis on ongoing research for optimization and scal-ability.It concludes with the potential of SOEC technology to meet various industrial energy needs and its significant contribution considering the key research priorities to tackle the global energy demands,ful-fillment,and decarbonization efforts.
基金supported by the National Natural Science Foundation of China (52173273)Fundamental Research Funds for the Central Universities (2022CX11013)+2 种基金Shanxi Province Science Foundation for Youths (No.202203021212391)the Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi (No.2022L253)Institute Foundation Project of China Academy of Railway Sciences Corporation Limited Metals and Chemistry Research Institute (No.2023SJ02)。
文摘The Mn-based oxide cathode with enriched crystal phase structure and component diversity can provide the excellent chemistry structure for Na-ion batteries.Nevertheless,the broad application prospect is obstructed by the sluggish Na^(+)kinetics and the phase transitions upon cycling.Herein,we establish the thermodynamically stable phase diagram of various Mn-based oxide composites precisely controlled by sodium content tailoring strategy coupling with co-doping and solid-state reaction.The chemical environment of the P2/P'3 and P2/P3 biphasic composites indicate that the charge compensation mechanism stems from the cooperative contribution of anions and cations.Benefiting from the no phase transition to scavenge the structure strain,P2/P'3 electrode can deliver long cycling stability(capacity retention of 73.8%after 1000 cycles at 10 C)and outstanding rate properties(the discharge capacity of 84.08 mA h g^(-1)at 20 C)than P2/P3 electrode.Furthermore,the DFT calculation demonstrates that the introducing novel P'3 phase can significantly regulate the Na^(+)reaction dynamics and modify the local electron configuration of Mn.The effective phase engineering can provide a reference for designing other high-performance electrode materials for Na-ion batteries.
基金funded by the National Natural Science Foundation of China,China (Nos.52272303 and 52073212)the General Program of Municipal Natural Science Foundation of Tianjin,China (Nos.17JCYBJC22700 and 17JCYBJC17000)the State Scholarship Fund of China Scholarship Council,China (Nos.201709345012 and 201706255009)。
文摘The global energy-related CO_(2) emissions have rapidly increased as the world economy heavily relied on fossil fuels.This paper explores the pressing challenge of CO_(2) emissions and highlights the role of porous metal oxide materials in the electrocatalytic reduction of CO_(2)(CO_(2)RR).The focus is on the development of robust and selective catalysts,particularly metal and metal-oxide-based materials.Porous metal oxides offer high surface area,enhancing the accessibility to active sites and improving reaction kinetics.The tunability of these materials allows for tailored catalytic behavior,targeting optimized reaction mechanisms for CO_(2)RR.The work also discusses the various synthesis strategies and identifies key structural and compositional features,addressing challenges like high overpotential,poor selectivity,and low stability.Based on these insights,we suggest avenues for future research on porous metal oxide materials for electrochemical CO_(2) reduction.
基金the National Major Science and Technology Projects of China(Nos.J2019-VII-0010-0150 and J2019-VI-0009-0123)National Natural Science Foundation of China(Nos.52022011 and 52090041)+3 种基金Beijing Nova Program(No.Z211100002121170)Science Center for Gas Turbine Project(No.P2021-A-IV-001-002)Science and Technology on Advanced High Temperature Structural Materials Laboratory(No.6142903210306)Xiaomi Young Scholars Program.
文摘Co-Ni-based superalloys are known for their capability to function at elevated temperatures and superior hot corrosion and thermal fatigue resistance.Therefore,these alloys show potential as crucial high-temperature structural materials for aeroengine and gas turbine hot-end components.Our previous work elucidated the influence of Ti and Ta on the high-temperature mechanical properties of alloys.However,the intricate interaction among elements considerably affects the oxidation resistance of alloys.In this paper,Co-35Ni-10Al-2W-5Cr-2Mo-1Nb-xTi-(5−x)Ta alloys(x=1,2,3,4)with varying Ti and Ta contents were designed and compounded,and their oxidation resistance was investigated at the temperature range from 800 to 1000℃.After oxidation at three test conditions,namely,800℃for 200 h,900℃for 200 h,and 1000℃for 50 h,the main structure of the oxide layer of the alloy consisted of spinel,Cr_(2)O_(3),and Al_(2)O_(3)from outside to inside.Oxides consisting of Ta,W,and Mo formed below the Cr_(2)O_(3)layer.The interaction of Ti and Ta imparted the highest oxidation resistance to 3Ti2Ta alloy.Conversely,an excessive amount of Ti or Ta resulted in an adverse effect on the oxidation resistance of the alloys.This study reports the volatilization of W and Mo oxides during the oxidation process of Co-Ni-based cast superalloys with a high Al content for the first time and explains the formation mechanism of holes in the oxide layer.The results provide a basis for gaining insights into the effects of the interaction of alloying elements on the oxidation resistance of the alloys they form.
基金support from the Free Exploration Project of Frontier Technology for Laoshan Laboratory(No.16-02)the National Natural Science Foundation of China(Nos.22072015 and 21927811)。
文摘Electrocatalytic hydrogen production from seawater holds enormous promise for clean energy generation.Nevertheless,the direct electrolysis of seawater encounters significant challenges due to poor anodic stability caused by detrimental chlorine chemistry.Herein,we present our recent discovery that the incorporation of Ce into Ni Fe layered double hydroxide nanosheet array on Ni foam(Ce-Ni Fe LDH/NF)emerges as a robust electrocatalyst for seawater oxidation.During the seawater oxidation process,CeO_(2)is generated,effectively repelling Cl^(-)and inhibiting the formation of Cl O-,resulting in a notable enhancement in the oxidation activity and stability of alkaline seawater.The prepared Ce-Ni Fe LDH/NF requires only overpotential of 390 m V to achieve the current density of 1 A cm^(-2),while maintaining long-term stability for 500 h,outperforming the performance of Ni Fe LDH/NF(430 m V,150 h)by a significant margin.This study highlights the effectiveness of a Ce-doping strategy in augmenting the activity and stability of materials based on Ni Fe LDH in seawater electrolysis for oxygen evolution.
基金supported by the National Natural Science Foundation of China(22279025,21773048)the Natural Science Foundation of Heilongjiang Province(LH2021A013)+1 种基金the Sichuan Science and Technology Program(2021YFSY0022)the Fundamental Research Funds for the Central Universities(2023FRFK06005,HIT.NSRIF202204)。
文摘Developing efficient and stable cathodes for low-temperature solid oxide fuel cells(LT-SOFCs) is of great importance for the practical commercialization.Herein,we propose a series of Sm-modified Bi_(0.7-x)Sm_xSr_(0.3)FeO_(3-δ) perovskites as highly-active catalysts for LT-SOFCs.Sm doping can significantly enhance the electrocata lytic activity and chemical stability of cathode.At 600℃,Bi_(0.675)Sm_(0.025)Sr_(0.3)FeO_(3-δ)(BSSF25) cathode has been found to be the optimum composition with a polarization resistance of 0.098 Ω cm^2,which is only around 22.8% of Bi_(0.7)Sr_(0.3)FeO_(3-δ)(BSF).A full cell utilizing BSSF25 displays an exceptional output density of 790 mW cm^(-2),which can operate continuously over100 h without obvious degradation.The remarkable electrochemical performance observed can be attributed to the improved O_(2) transport kinetics,superior surface oxygen adsorption capacity,as well as O_(2)p band centers in close proximity to the Fermi level.Moreover,larger average bonding energy(ABE) and the presence of highly acidic Bi,Sm,and Fe ions restrict the adsorption of CO_(2) on the cathode surface,resulting in excellent CO_(2) resistivity.This work provides valuable guidance for systematic design of efficient and durable catalysts for LT-SOFCs.
基金supported by the National Natural Science Foundation of China,Nos.LY20H090018(to XL)and LY20H060008(to HS).
文摘Previous studies have shown that Biochanin A,a flavonoid compound with estrogenic effects,can serve as a neuroprotective agent in the context of cerebral ischemia/reperfusion injury;howeve r,its effect on spinal cord injury is still unclea r. In this study,a rat model of spinal cord injury was established using the heavy o bject impact method,and the rats were then treated with Biochanin A(40 mg/kg) via intrape ritoneal injection for 14 consecutive days.The res ults showed that Biochanin A effectively alleviated spinal cord neuronal injury and spinal co rd tissue injury,reduced inflammation and oxidative stress in spinal cord neuro ns,and reduced apoptosis and pyroptosis.In addition,Biochanin A inhibited the expression of inflammasome-related proteins(ASC,NLRP3,and GSDMD)and the Toll-like receptor 4/nuclear factor-κB pathway,activated the Nrf2/heme oxygenase 1 signaling pathway,and increased the expression of the autophagy markers LC3 Ⅱ,Beclin-1,and P62.Moreove r,the therapeutic effects of Biochanin A on early post-s pinal cord injury were similar to those of methylprednisolone.These findings suggest that Biochanin A protected neurons in the injured spinal cord through the Toll-like receptor 4/nuclear factor κB and Nrf2/heme oxygenase 1 signaling pathways.These findings suggest that Biochanin A can alleviate post-spinal cord injury at an early stage.
基金supported by the National Natural Science Foundation of China,No.81771250(to XC)the Natural Science Foundation of Fujian Province,Nos.2020J011059(to XC),2020R1011004(to YW),2021J01374(to XZ)+1 种基金Medical Innovation Project of Fujian Province,No.2021 CXB002(to XC)Fujian Research and Training Grants for Young and Middle-aged Leaders in Healthcare(to XC)。
文摘Accumulating evidence suggests that oxidative stress and the Wnt/β-catenin pathway participate in stroke-induced disruption of the blood-brain barrier.However,the potential links between them following ischemic stroke remain largely unknown.The present study found that cerebral ischemia leads to oxidative stress and repression of the Wnt/β-catenin pathway.Meanwhile,Wnt/β-catenin pathway activation by the pharmacological inhibito r,TWS119,relieved oxidative stress,increased the levels of cytochrome P4501B1(CYP1B1)and tight junction-associated proteins(zonula occludens-1[ZO-1],occludin and claudin-5),as well as brain microvascular density in cerebral ischemia rats.Moreove r,rat brain microvascular endothelial cells that underwent oxygen glucose deprivation/reoxygenation displayed intense oxidative stress,suppression of the Wnt/β-catenin pathway,aggravated cell apoptosis,downregulated CYP1B1and tight junction protein levels,and inhibited cell prolife ration and migration.Overexpression ofβ-catenin or knockdown ofβ-catenin and CYP1B1 genes in rat brain mic rovascular endothelial cells at least partly ameliorated or exacerbated these effects,respectively.In addition,small interfering RNA-mediatedβ-catenin silencing decreased CYP1B1 expression,whereas CYP1B1 knoc kdown did not change the levels of glycogen synthase kinase 3β,Wnt-3a,andβ-catenin proteins in rat brain microvascular endothelial cells after oxygen glucose deprivatio n/reoxygenation.Thus,the data suggest that CYP1B1 can be regulated by Wnt/β-catenin signaling,and activation of the Wnt/β-catenin/CYP1B1 pathway contributes to alleviation of oxidative stress,increased tight junction levels,and protection of the blood-brain barrier against ischemia/hypoxia-induced injury.
