MgH_(2) is a promising high-capacity solid-state hydrogen storage material,while its application is greatly hindered by the high desorption temperature and sluggish kinetics.Herein,intertwined 2D oxygen vacancy-rich V...MgH_(2) is a promising high-capacity solid-state hydrogen storage material,while its application is greatly hindered by the high desorption temperature and sluggish kinetics.Herein,intertwined 2D oxygen vacancy-rich V_(2)O_(5) nanosheets(H-V_(2)O_(5))are specifically designed and used as catalysts to improve the hydrogen storage properties of MgH_(2).The as-prepared MgH_(2)-H-V_(2)O_(5) composites exhibit low desorption temperatures(Tonset=185℃)with a hydrogen capacity of 6.54 wt%,fast kinetics(Ea=84.55±1.37 kJ mol^(-1) H_(2) for desorption),and long cycling stability.Impressively,hydrogen absorption can be achieved at a temperature as low as 30℃ with a capacity of 2.38 wt%within 60 min.Moreover,the composites maintain a capacity retention rate of~99%after 100 cycles at 275℃.Experimental studies and theoretical calculations demonstrate that the in-situ formed VH_(2)/V catalysts,unique 2D structure of H-V_(2)O_(5) nanosheets,and abundant oxygen vacancies positively contribute to the improved hydrogen sorption properties.Notably,the existence of oxygen vacancies plays a double role,which could not only directly accelerate the hydrogen ab/de-sorption rate of MgH_(2),but also indirectly affect the activity of the catalytic phase VH_(2)/V,thereby further boosting the hydrogen storage performance of MgH_(2).This work highlights an oxygen vacancy excited“hydrogen pump”effect of VH_(2)/V on the hydrogen sorption of Mg/MgH_(2).The strategy developed here may pave a new way toward the development of oxygen vacancy-rich transition metal oxides catalyzed hydride systems.展开更多
Rational design of oxygen evolution reaction(OER)catalysts at low cost would greatly benefit the economy.Taking advantage of earth-abundant elements Si,Co and Ni,we produce a unique-structure where cobalt-nickel silic...Rational design of oxygen evolution reaction(OER)catalysts at low cost would greatly benefit the economy.Taking advantage of earth-abundant elements Si,Co and Ni,we produce a unique-structure where cobalt-nickel silicate hydroxide[Co_(2.5)Ni_(0.5)Si_(2)O_(5)(OH)_(4)]is vertically grown on a reduced graphene oxide(rGO)support(CNS@rGO).This is developed as a low-cost and prospective OER catalyst.Compared to cobalt or nickel silicate hydroxide@rGO(CS@rGO and NS@rGO,respectively)nanoarrays,the bimetal CNS@rGO nanoarray exhibits impressive OER performance with an overpotential of 307 mV@10 mA cm^(-2).This value is higher than that of CS@rGO and NS@rGO.The CNS@rGO nanoarray has an overpotential of 446 mV@100 mA cm^(-2),about 1.4 times that of the commercial RuO_(2)electrocatalyst.The achieved OER activity is superior to the state-of-the-art metal oxides/hydroxides and their derivatives.The vertically grown nanostructure and optimized metal-support electronic interactions play an indispensable role for OER performance improvement,including a fast electron transfer pathway,short proton/electron diffusion distance,more active metal centers,as well as optimized dualatomic electron density.Taking advantage of interlay chemical regulation and the in-situ growth method,the advanced-structural CNS@rGO nanoarrays provide a new horizon to the rational and flexible design of efficient and promising OER electrocatalysts.展开更多
Obejective:To explore the establishment of an oxygen glucose deprivation/reperfusion model of senescent SH-SY5Y cells.Methods:SH-SY5Y cells were randomly divided into control(D-galactose 0 mmol/L group),D-galactose(25...Obejective:To explore the establishment of an oxygen glucose deprivation/reperfusion model of senescent SH-SY5Y cells.Methods:SH-SY5Y cells were randomly divided into control(D-galactose 0 mmol/L group),D-galactose(25 mmol/L,50 mmol/L,100 mmol/L,200 mmol/L,400 mmol/L)groups,and treated with corresponding concentrations of D-galactose for 48 h.The changes of cell morphology,β-galactosidase,the cell morphology,β-galactosidase activity by microscopic observation,cell proliferation rate by EdU kit and cell survival rate by CCK-8 assay were used to determine the decaying concentration of D-galactose and to establish the senescence model.The senescent SH-SY5Y cells were randomly divided into control group(oxygen glucose deprivation without treatment group),oxygen glucose deprivation treatment(0.5 h,1 h,1.5 h,2 h)group,followed by re-glucose reoxygenation for 24 h,and CCK-8 assay for the survival rate of senescent SH-SY5Y cells.Results:There were no significant changes in cell morphology and β-gal activity in the 25 mmol/L and 50 mmol/L groups compared with the control group(P>0.05),cytosolic hypertrophy was seen in the cells of the 100 mmol/L group,chromatin fixation in the cells of the 200 mmol/L group,and massive vacuolization in the cells of the 400 mmol/L group;the positive rate ofβ-galactosidase staining in the cells of the(100-400 mmol/L)group was significantly higher compared with the control group(P<0.05),with little difference between the 100 mmol/L and 200 mmol/L groups(P>0.05);the cell proliferation ability of the(100-400 mmol/L)group was significantly decreased in a concentration-dependent manner(P<0.05);the cell survival rate was decreased in a concentration-dependent manner(P<0.05),with IC_(50) between 100 mmol/L and 200 mmol/L.The survival of senescent SH-SY5Y cells showed a time-dependent decrease in oxygen-glucose deprivation(P<0.05),with an IC_(50) close to 1 h.Conclusion:D-gal concentration of 100 mmoL/L and 48 h of cell action could establish a survival rate of about 50%of senescent SH-SY5Y cells,and oxygen glucose deprivation of senescent SH-SY5Y cells for 1 h and reperfusion for 24 h could establish an oxygen glucose deprivation/reperfusion model of senescent SH-SY5Y cells with a survival rate close to 50%.展开更多
Vanadium oxide cathode materials with stable crystal structure and fast Zn^(2+)storage capabilities are extremely important to achieving outstanding electrochemical performance in aqueous zinc‐ion batteries.In this w...Vanadium oxide cathode materials with stable crystal structure and fast Zn^(2+)storage capabilities are extremely important to achieving outstanding electrochemical performance in aqueous zinc‐ion batteries.In this work,a one‐step hydrothermal method was used to manipulate the bimetallic ion intercalation into the interlayer of vanadium oxide.The pre‐intercalated Cu ions act as pillars to pin the vanadium oxide(V‐O)layers,establishing stabilized two‐dimensional channels for fast Zn^(2+)diffusion.The occupation of Mn ions between V‐O interlayer further expands the layer spacing and increases the concentration of oxygen defects(Od),which boosts the Zn^(2+)diffusion kinetics.As a result,as‐prepared Cu_(0.17)Mn_(0.03)V_(2)O_(5−□)·2.16H_(2)O cathode shows outstanding Zn‐storage capabilities under room‐and lowtemperature environments(e.g.,440.3 mAh g^(−1)at room temperature and 294.3 mAh g^(−1)at−60°C).Importantly,it shows a long cycling life and high capacity retention of 93.4%over 2500 cycles at 2 A g^(−1)at−60°C.Furthermore,the reversible intercalation chemistry mechanisms during discharging/charging processes were revealed via operando X‐ray powder diffraction and ex situ Raman characterizations.The strategy of a couple of 3d transition metal doping provides a solution for the development of superior room‐/lowtemperature vanadium‐based cathode materials.展开更多
Silicoaluminophosphate（SAPO） molecular sieves doped with cobalt（Co-SAPO-5） were synthesized hydrothermally with different concentrations of Co.Each sample was characterized by X-ray diffraction,N2 adsorption-desor...Silicoaluminophosphate（SAPO） molecular sieves doped with cobalt（Co-SAPO-5） were synthesized hydrothermally with different concentrations of Co.Each sample was characterized by X-ray diffraction,N2 adsorption-desorption,scanning electron microscopy,ultraviolet-visible spectroscopy,temperature-programmed desorption of NH3（NH3-TPD）,and infrared spectrascopy of adsorbed pyridine（Py-IR）.The results showed that Co was highly dispersed in the Co-SAPO-5 samples.In addition,a part of the Co content had been incorporated into the SAPO-5 framework,while the remainder existed on the surface as extra-framework Co.The surface areas of the Co-SAOP-5 samples were similar to the SAPO-5 sample.However,the pore volumes of the Co-SAOP-5 samples were lower than that of the SAOP-5 sample.As the concentration of Co increased,the pore volume gradually decreased because extra-framework cobalt oxide was present on the catalyst surface.NH3-TPD and Py-IR results revealed that the amount of Br（？）nsted acid and the total amount of acid for the Co-SAPO-5 samples were higher than that for the SAPO-5 sample.These values were also higher for samples with higher Co content.The catalytic activity of the Co-SAPO-5 samples was evaluated for the oxidation of cyclohexane with molecular oxygen.When Co was added to the SAPO-5 catalyst,the catalytic activity of the Co-SAPO-5 catalysts improved.In addition,the conversion of cyclohexane increased as the Co content in the Co-SAPO-5 catalysts increased.However,with a high conversion of cyclohexane（6.30%）,the total selectivity of cyclohexanone（K） and cyclohexanol（A） decreased sharply.The K/A ratio ranged from 1.15 to 2.47.The effects of reaction conditions（i.e.,reaction temperature,reaction time,initial oxygen pressure,and the catalyst amount） on the performance of the Co-SAPO-5 catalysts have also been measured.Furthermore,the stability of the Co-SAPO-5 catalyst was explored and found to be good for the selective oxidation of cyclohexane by molecular oxygen.展开更多
The effect of steam-treatment to HZSM-5 zeolite and Mo/HZSM-5 with a steaming time range of 0.5-1 h on the catalytic performance of methane dehydro-aromatization （MDA） over Mo/HZSM-5 catalyst prepared with impregnat...The effect of steam-treatment to HZSM-5 zeolite and Mo/HZSM-5 with a steaming time range of 0.5-1 h on the catalytic performance of methane dehydro-aromatization （MDA） over Mo/HZSM-5 catalyst prepared with impregnation has been studied in detail in combination with the characterization of 1H MAS NMR technique. Both the deactivation rate constant （kd） and the Brtnsted acid sites per unit cell were calculated to quantitatively evaluate the stability of Mo/HZSM-5 catalysts treated with steam at 813 K before and after impregnation of molybdenum species, and the corresponding variation of their Brtnsted acid sites. The results reveal that a V-shape relationship between kd and the number of B 1 acid sites per unit cell is presented on Mo/HZSM-5 catalyst under the tested steam-treatment and reaction conditions.展开更多
5-Aminolevulinic acid （ALA） is a common precursor for tetrapyrrole compounds in all kinds of organ isms and has wide applications in agriculture and medicines. In this study, a new strategy, i.e. short-term dissolve...5-Aminolevulinic acid （ALA） is a common precursor for tetrapyrrole compounds in all kinds of organ isms and has wide applications in agriculture and medicines. In this study, a new strategy, i.e. short-term dissolved oxygen （DO） shock during aerobic fermentation, was introduced to produce 5-aminolevulinic acid with a recombi-nant E. coli. Effects of duration time of DO shock operation on plasmid concentration, intracellular ALA synthase （ALAS） activity and ALA production were investigated in Erlenmeyer shake flasks. The results indicated that both ALAS activity and ALA yield were enhanced in an anaerobic operation of 45 rain in the early exponential phase during fermentation, while they decreased when the anaerobic operation time was further increased to 60 rain. The DO shock protocol was confirmed with the fed-batch fermentation in a 15 L fermenter and the ALA production achieved 9.4 g.L-1 （72 mmol.L-1）, which is the highest yield in the fermentation broth reported up to now.展开更多
The fabrication of efficient catalysts to reduce nitrogen(N_(2))to ammonia(NH3)is a significant challenge for artificial N_(2) fixation under mild conditions.In this work,we demonstrated that the simultaneous introduc...The fabrication of efficient catalysts to reduce nitrogen(N_(2))to ammonia(NH3)is a significant challenge for artificial N_(2) fixation under mild conditions.In this work,we demonstrated that the simultaneous introduction of oxygen vacancies(OVs)and Mo dopants into Bi_(5)O_(7)Br nanosheets can significantly increase the activity for photocatalytic N_(2) fixation.The 1 mol% Mo-doped Bi_(5)O_(7)Br nanosheets exhibited an optimal NH_(3) generation rate of 122.9μmol g^(-1) h^(-1) and durable stability,which is attributed to their optimized conduction band position,suitable absorption edge,large number of light-switchable OVs,and improved charge carrier separation.This work provides a promising approach to design photocatalysts with light-switchable OVs for N_(2) reduction to NH_(3) under mild conditions,highlighting the wide application scope of nanostructured BiOBr-based photocatalysts as effective N_(2) fixation systems.展开更多
The climatologies of dissolved oxygen concentration in the ocean simulated by nine Earth system models(ESMs) from the historical emission driven experiment of CMIP5(Phase 5 of the Climate Model Intercomparison Project...The climatologies of dissolved oxygen concentration in the ocean simulated by nine Earth system models(ESMs) from the historical emission driven experiment of CMIP5(Phase 5 of the Climate Model Intercomparison Project) are quantitatively evaluated by comparing the simulated oxygen to the WOA09 observation based on common statistical metrics. At the sea surface, distribution of dissolved oxygen is well simulated by all nine ESMs due to well-simulated sea surface temperature(SST), with both globally-averaged error and root mean square error(RMSE) close to zero, and both correlation coefficients and normalized standard deviation close to 1. However, the model performance differs from each other at the intermediate depth and deep ocean where important water masses exist. At the depth of 500 to 1 000 m where the oxygen minimum zones(OMZs) exist, all ESMs show a maximum of globally-averaged error and RMSE, and a minimum of the spatial correlation coefficient. In the ocean interior, the reason for model biases is complicated, and both the meridional overturning circulation(MOC) and the particulate organic carbon flux contribute to the biases of dissolved oxygen distribution. Analysis results show the physical bias contributes more. Simulation bias of important water masses such as North Atlantic Deep Water(NADW), Antarctic Bottom Water(AABW) and North Pacific Intermediate Water(NPIW) indicated by distributions of MOCs greatly affects the distributions of oxygen in north Atlantic, Southern Ocean and north Pacific, respectively.Although the model simulations of oxygen differ greatly from each other in the ocean interior, the multi-model mean shows a better agreement with the observation.展开更多
Kinetics of oxygen adsorption on single crystal Mn<sub>5</sub>Si<sub>3</sub> （111） surface and initial surface oxidation were investigated. Oxygen chemisorbs dissociatively at room temperatur...Kinetics of oxygen adsorption on single crystal Mn<sub>5</sub>Si<sub>3</sub> （111） surface and initial surface oxidation were investigated. Oxygen chemisorbs dissociatively at room temperature on Mn and Si atoms. A fast oxidation of Si atoms occurs followed by oxidation of Mn atoms at RT. The MnO<sub>2</sub> was reduced by Si atoms and the SiO was oxidized further to SiO<sub>2</sub> during the sample heating.展开更多
Despite wide applications of noble metal-based catalysts in 5-hydroxymethylfurfural(HMF)oxidation,promoting the catalytic performance at low loading amounts still remains a significant challenge.Herein,a series of met...Despite wide applications of noble metal-based catalysts in 5-hydroxymethylfurfural(HMF)oxidation,promoting the catalytic performance at low loading amounts still remains a significant challenge.Herein,a series of metal oxide modified MO_(x)-Au/TiO_(2)(M=Fe,Co,Ni)catalysts with low Au loading amount of 0.5 wt%were synthesized.Addition of transition metal oxides promotes electron transfer and generation of the Au^(δ-)-O_(v)-Ti^(3+)interface.A combination study reveals that the dual-active site(Au^(δ-)-O_(v)-Ti^(3+))governs the catalytic performance of the ratedetermining step,namely hydroxyl group oxidation.Au^(δ-) site facilitates chemisorption and activation of O_(2) molecules.At the same time,O_(v)-Ti^(3+) site acts as the role of“killing two birds with one stone”:enhancing adsorption of both reactants,accelerating the activation and dissociation of H_(2)O,and facilitating activation of the adsorbed O_(2).Besides,superoxide radicals instead of base is the active oxygen species during the rate-determining step.On this basis,a FDCA yield of 71.2% was achieved under base-free conditions,complying with the“green chemistry”principle.This work provides a new strategy for the transition metal oxides modification of Au-based catalysts,which would be constructive for the rational design of other heterogeneous catalysts.展开更多
Designing single-atom catalysts for oxygen reduction reaction(ORR)are fashionable but challenging to boost the zinc-air battery performance.Significantly enhanced ORR activity by manganese(Mn)singleatom catalysts can ...Designing single-atom catalysts for oxygen reduction reaction(ORR)are fashionable but challenging to boost the zinc-air battery performance.Significantly enhanced ORR activity by manganese(Mn)singleatom catalysts can be achieved by accurately regulating the coordination number of isolated Mn atoms.Theoretical calculations indicate that the single Mn-N5sites possess lower free energy barrier and higher oxygen adsorption performance than single Mn-N4sites to accelerate the ORR kinetics.Target to it,here we synthesize an atomically dispersed Mn-N5catalyst by precisely axial coordination of pyridinic-N doped into two-dimensional(2D)porous nanocarbon sheets(~3.56 nm thickness),which reveals outstanding catalytic activity and ultrahigh stability for the ORR in zinc-air battery owing to the inhomogeneous charge distribution of Mn-N5sites compared to the conventional single-site Mn-N4catalyst and Pt/C.This work gives a new strategy for in situ regulating the electronic structure of metal single-atoms and further promoting the overall ORR performance in energy systems.展开更多
基金the support from the National Key Research&Development Program(2022YFB3803700)of ChinaNational Natural Science Foundation(No.52171186)the financial support from the Center of Hydrogen Science,Shanghai Jiao Tong University。
文摘MgH_(2) is a promising high-capacity solid-state hydrogen storage material,while its application is greatly hindered by the high desorption temperature and sluggish kinetics.Herein,intertwined 2D oxygen vacancy-rich V_(2)O_(5) nanosheets(H-V_(2)O_(5))are specifically designed and used as catalysts to improve the hydrogen storage properties of MgH_(2).The as-prepared MgH_(2)-H-V_(2)O_(5) composites exhibit low desorption temperatures(Tonset=185℃)with a hydrogen capacity of 6.54 wt%,fast kinetics(Ea=84.55±1.37 kJ mol^(-1) H_(2) for desorption),and long cycling stability.Impressively,hydrogen absorption can be achieved at a temperature as low as 30℃ with a capacity of 2.38 wt%within 60 min.Moreover,the composites maintain a capacity retention rate of~99%after 100 cycles at 275℃.Experimental studies and theoretical calculations demonstrate that the in-situ formed VH_(2)/V catalysts,unique 2D structure of H-V_(2)O_(5) nanosheets,and abundant oxygen vacancies positively contribute to the improved hydrogen sorption properties.Notably,the existence of oxygen vacancies plays a double role,which could not only directly accelerate the hydrogen ab/de-sorption rate of MgH_(2),but also indirectly affect the activity of the catalytic phase VH_(2)/V,thereby further boosting the hydrogen storage performance of MgH_(2).This work highlights an oxygen vacancy excited“hydrogen pump”effect of VH_(2)/V on the hydrogen sorption of Mg/MgH_(2).The strategy developed here may pave a new way toward the development of oxygen vacancy-rich transition metal oxides catalyzed hydride systems.
基金supported by the Fundamental Research Funds for the Central Universities(DUT21LK34)Natural Science Foundation of Liaoning Province(2020-MS-113).
文摘Rational design of oxygen evolution reaction(OER)catalysts at low cost would greatly benefit the economy.Taking advantage of earth-abundant elements Si,Co and Ni,we produce a unique-structure where cobalt-nickel silicate hydroxide[Co_(2.5)Ni_(0.5)Si_(2)O_(5)(OH)_(4)]is vertically grown on a reduced graphene oxide(rGO)support(CNS@rGO).This is developed as a low-cost and prospective OER catalyst.Compared to cobalt or nickel silicate hydroxide@rGO(CS@rGO and NS@rGO,respectively)nanoarrays,the bimetal CNS@rGO nanoarray exhibits impressive OER performance with an overpotential of 307 mV@10 mA cm^(-2).This value is higher than that of CS@rGO and NS@rGO.The CNS@rGO nanoarray has an overpotential of 446 mV@100 mA cm^(-2),about 1.4 times that of the commercial RuO_(2)electrocatalyst.The achieved OER activity is superior to the state-of-the-art metal oxides/hydroxides and their derivatives.The vertically grown nanostructure and optimized metal-support electronic interactions play an indispensable role for OER performance improvement,including a fast electron transfer pathway,short proton/electron diffusion distance,more active metal centers,as well as optimized dualatomic electron density.Taking advantage of interlay chemical regulation and the in-situ growth method,the advanced-structural CNS@rGO nanoarrays provide a new horizon to the rational and flexible design of efficient and promising OER electrocatalysts.
基金This is supported by the Youth Science Foundation of Guangxi Medical University(GXMUYSF202127)。
文摘Obejective:To explore the establishment of an oxygen glucose deprivation/reperfusion model of senescent SH-SY5Y cells.Methods:SH-SY5Y cells were randomly divided into control(D-galactose 0 mmol/L group),D-galactose(25 mmol/L,50 mmol/L,100 mmol/L,200 mmol/L,400 mmol/L)groups,and treated with corresponding concentrations of D-galactose for 48 h.The changes of cell morphology,β-galactosidase,the cell morphology,β-galactosidase activity by microscopic observation,cell proliferation rate by EdU kit and cell survival rate by CCK-8 assay were used to determine the decaying concentration of D-galactose and to establish the senescence model.The senescent SH-SY5Y cells were randomly divided into control group(oxygen glucose deprivation without treatment group),oxygen glucose deprivation treatment(0.5 h,1 h,1.5 h,2 h)group,followed by re-glucose reoxygenation for 24 h,and CCK-8 assay for the survival rate of senescent SH-SY5Y cells.Results:There were no significant changes in cell morphology and β-gal activity in the 25 mmol/L and 50 mmol/L groups compared with the control group(P>0.05),cytosolic hypertrophy was seen in the cells of the 100 mmol/L group,chromatin fixation in the cells of the 200 mmol/L group,and massive vacuolization in the cells of the 400 mmol/L group;the positive rate ofβ-galactosidase staining in the cells of the(100-400 mmol/L)group was significantly higher compared with the control group(P<0.05),with little difference between the 100 mmol/L and 200 mmol/L groups(P>0.05);the cell proliferation ability of the(100-400 mmol/L)group was significantly decreased in a concentration-dependent manner(P<0.05);the cell survival rate was decreased in a concentration-dependent manner(P<0.05),with IC_(50) between 100 mmol/L and 200 mmol/L.The survival of senescent SH-SY5Y cells showed a time-dependent decrease in oxygen-glucose deprivation(P<0.05),with an IC_(50) close to 1 h.Conclusion:D-gal concentration of 100 mmoL/L and 48 h of cell action could establish a survival rate of about 50%of senescent SH-SY5Y cells,and oxygen glucose deprivation of senescent SH-SY5Y cells for 1 h and reperfusion for 24 h could establish an oxygen glucose deprivation/reperfusion model of senescent SH-SY5Y cells with a survival rate close to 50%.
基金National Natural Science Foundation of China,Grant/Award Numbers:52372188,51902090,51922008,520721142023 Introduction of studying abroad talent program,the China Postdoctoral Science Foundation,Grant/Award Number:2019 M652546+3 种基金Xinxiang Major Science and Technology Projects,Grant/Award Number:21ZD001Henan Province Postdoctoral Start‐Up Foundation,Grant/Award Number:1901017Henan Center for Outstanding Overseas Scientists,Grant/Award Number:GZS2018003Overseas Expertise Introduction Project for Discipline Innovation,Grant/Award Number:D17007。
文摘Vanadium oxide cathode materials with stable crystal structure and fast Zn^(2+)storage capabilities are extremely important to achieving outstanding electrochemical performance in aqueous zinc‐ion batteries.In this work,a one‐step hydrothermal method was used to manipulate the bimetallic ion intercalation into the interlayer of vanadium oxide.The pre‐intercalated Cu ions act as pillars to pin the vanadium oxide(V‐O)layers,establishing stabilized two‐dimensional channels for fast Zn^(2+)diffusion.The occupation of Mn ions between V‐O interlayer further expands the layer spacing and increases the concentration of oxygen defects(Od),which boosts the Zn^(2+)diffusion kinetics.As a result,as‐prepared Cu_(0.17)Mn_(0.03)V_(2)O_(5−□)·2.16H_(2)O cathode shows outstanding Zn‐storage capabilities under room‐and lowtemperature environments(e.g.,440.3 mAh g^(−1)at room temperature and 294.3 mAh g^(−1)at−60°C).Importantly,it shows a long cycling life and high capacity retention of 93.4%over 2500 cycles at 2 A g^(−1)at−60°C.Furthermore,the reversible intercalation chemistry mechanisms during discharging/charging processes were revealed via operando X‐ray powder diffraction and ex situ Raman characterizations.The strategy of a couple of 3d transition metal doping provides a solution for the development of superior room‐/lowtemperature vanadium‐based cathode materials.
基金supported by the National Basic Research Program of China(2010CB732300)the National Natural Science Foundation of China(21103048)~~
文摘Silicoaluminophosphate（SAPO） molecular sieves doped with cobalt（Co-SAPO-5） were synthesized hydrothermally with different concentrations of Co.Each sample was characterized by X-ray diffraction,N2 adsorption-desorption,scanning electron microscopy,ultraviolet-visible spectroscopy,temperature-programmed desorption of NH3（NH3-TPD）,and infrared spectrascopy of adsorbed pyridine（Py-IR）.The results showed that Co was highly dispersed in the Co-SAPO-5 samples.In addition,a part of the Co content had been incorporated into the SAPO-5 framework,while the remainder existed on the surface as extra-framework Co.The surface areas of the Co-SAOP-5 samples were similar to the SAPO-5 sample.However,the pore volumes of the Co-SAOP-5 samples were lower than that of the SAOP-5 sample.As the concentration of Co increased,the pore volume gradually decreased because extra-framework cobalt oxide was present on the catalyst surface.NH3-TPD and Py-IR results revealed that the amount of Br（？）nsted acid and the total amount of acid for the Co-SAPO-5 samples were higher than that for the SAPO-5 sample.These values were also higher for samples with higher Co content.The catalytic activity of the Co-SAPO-5 samples was evaluated for the oxidation of cyclohexane with molecular oxygen.When Co was added to the SAPO-5 catalyst,the catalytic activity of the Co-SAPO-5 catalysts improved.In addition,the conversion of cyclohexane increased as the Co content in the Co-SAPO-5 catalysts increased.However,with a high conversion of cyclohexane（6.30%）,the total selectivity of cyclohexanone（K） and cyclohexanol（A） decreased sharply.The K/A ratio ranged from 1.15 to 2.47.The effects of reaction conditions（i.e.,reaction temperature,reaction time,initial oxygen pressure,and the catalyst amount） on the performance of the Co-SAPO-5 catalysts have also been measured.Furthermore,the stability of the Co-SAPO-5 catalyst was explored and found to be good for the selective oxidation of cyclohexane by molecular oxygen.
基金supported by Foundation for University Key Teacher by the Education of Heilongjiang Province(No.1152G018)
文摘The effect of steam-treatment to HZSM-5 zeolite and Mo/HZSM-5 with a steaming time range of 0.5-1 h on the catalytic performance of methane dehydro-aromatization （MDA） over Mo/HZSM-5 catalyst prepared with impregnation has been studied in detail in combination with the characterization of 1H MAS NMR technique. Both the deactivation rate constant （kd） and the Brtnsted acid sites per unit cell were calculated to quantitatively evaluate the stability of Mo/HZSM-5 catalysts treated with steam at 813 K before and after impregnation of molybdenum species, and the corresponding variation of their Brtnsted acid sites. The results reveal that a V-shape relationship between kd and the number of B 1 acid sites per unit cell is presented on Mo/HZSM-5 catalyst under the tested steam-treatment and reaction conditions.
基金Supported by the National Natural Science Foundation of China （20306026 and 20876141） and the National Basic Research program of China （2007CB707805）.
文摘5-Aminolevulinic acid （ALA） is a common precursor for tetrapyrrole compounds in all kinds of organ isms and has wide applications in agriculture and medicines. In this study, a new strategy, i.e. short-term dissolved oxygen （DO） shock during aerobic fermentation, was introduced to produce 5-aminolevulinic acid with a recombi-nant E. coli. Effects of duration time of DO shock operation on plasmid concentration, intracellular ALA synthase （ALAS） activity and ALA production were investigated in Erlenmeyer shake flasks. The results indicated that both ALAS activity and ALA yield were enhanced in an anaerobic operation of 45 rain in the early exponential phase during fermentation, while they decreased when the anaerobic operation time was further increased to 60 rain. The DO shock protocol was confirmed with the fed-batch fermentation in a 15 L fermenter and the ALA production achieved 9.4 g.L-1 （72 mmol.L-1）, which is the highest yield in the fermentation broth reported up to now.
文摘The fabrication of efficient catalysts to reduce nitrogen(N_(2))to ammonia(NH3)is a significant challenge for artificial N_(2) fixation under mild conditions.In this work,we demonstrated that the simultaneous introduction of oxygen vacancies(OVs)and Mo dopants into Bi_(5)O_(7)Br nanosheets can significantly increase the activity for photocatalytic N_(2) fixation.The 1 mol% Mo-doped Bi_(5)O_(7)Br nanosheets exhibited an optimal NH_(3) generation rate of 122.9μmol g^(-1) h^(-1) and durable stability,which is attributed to their optimized conduction band position,suitable absorption edge,large number of light-switchable OVs,and improved charge carrier separation.This work provides a promising approach to design photocatalysts with light-switchable OVs for N_(2) reduction to NH_(3) under mild conditions,highlighting the wide application scope of nanostructured BiOBr-based photocatalysts as effective N_(2) fixation systems.
基金The National Natural Science Foundation of China under contract No.41306029the Basic Scientific Fund for National Public Research Institutes of China under contract Nos 2013T01 and 2014G25
文摘The climatologies of dissolved oxygen concentration in the ocean simulated by nine Earth system models(ESMs) from the historical emission driven experiment of CMIP5(Phase 5 of the Climate Model Intercomparison Project) are quantitatively evaluated by comparing the simulated oxygen to the WOA09 observation based on common statistical metrics. At the sea surface, distribution of dissolved oxygen is well simulated by all nine ESMs due to well-simulated sea surface temperature(SST), with both globally-averaged error and root mean square error(RMSE) close to zero, and both correlation coefficients and normalized standard deviation close to 1. However, the model performance differs from each other at the intermediate depth and deep ocean where important water masses exist. At the depth of 500 to 1 000 m where the oxygen minimum zones(OMZs) exist, all ESMs show a maximum of globally-averaged error and RMSE, and a minimum of the spatial correlation coefficient. In the ocean interior, the reason for model biases is complicated, and both the meridional overturning circulation(MOC) and the particulate organic carbon flux contribute to the biases of dissolved oxygen distribution. Analysis results show the physical bias contributes more. Simulation bias of important water masses such as North Atlantic Deep Water(NADW), Antarctic Bottom Water(AABW) and North Pacific Intermediate Water(NPIW) indicated by distributions of MOCs greatly affects the distributions of oxygen in north Atlantic, Southern Ocean and north Pacific, respectively.Although the model simulations of oxygen differ greatly from each other in the ocean interior, the multi-model mean shows a better agreement with the observation.
文摘Kinetics of oxygen adsorption on single crystal Mn<sub>5</sub>Si<sub>3</sub> （111） surface and initial surface oxidation were investigated. Oxygen chemisorbs dissociatively at room temperature on Mn and Si atoms. A fast oxidation of Si atoms occurs followed by oxidation of Mn atoms at RT. The MnO<sub>2</sub> was reduced by Si atoms and the SiO was oxidized further to SiO<sub>2</sub> during the sample heating.
基金support of State Key Laboratory of Chemical Engineering (No.SKL-ChE-20A02)the support of International Clean Energy Talent Program by China Scholarship Council.
文摘Despite wide applications of noble metal-based catalysts in 5-hydroxymethylfurfural(HMF)oxidation,promoting the catalytic performance at low loading amounts still remains a significant challenge.Herein,a series of metal oxide modified MO_(x)-Au/TiO_(2)(M=Fe,Co,Ni)catalysts with low Au loading amount of 0.5 wt%were synthesized.Addition of transition metal oxides promotes electron transfer and generation of the Au^(δ-)-O_(v)-Ti^(3+)interface.A combination study reveals that the dual-active site(Au^(δ-)-O_(v)-Ti^(3+))governs the catalytic performance of the ratedetermining step,namely hydroxyl group oxidation.Au^(δ-) site facilitates chemisorption and activation of O_(2) molecules.At the same time,O_(v)-Ti^(3+) site acts as the role of“killing two birds with one stone”:enhancing adsorption of both reactants,accelerating the activation and dissociation of H_(2)O,and facilitating activation of the adsorbed O_(2).Besides,superoxide radicals instead of base is the active oxygen species during the rate-determining step.On this basis,a FDCA yield of 71.2% was achieved under base-free conditions,complying with the“green chemistry”principle.This work provides a new strategy for the transition metal oxides modification of Au-based catalysts,which would be constructive for the rational design of other heterogeneous catalysts.
基金supported by the National Natural Science Foundation of China(22275026 and 21805024)the Natural Science Foundation of Chongqing,China(cstc2021jcyj-msxm X0783,cstc2019jscx-msxm X0393 and cstc2018jcyj AX0461)+1 种基金the Scientific and Technological Research Program of Chongqing Municipal Education Commission(KJZD-K202101303,KJQN201901335 and KJQN202001322)the Scientific Research Program of Chongqing Urban Administration(CGKZ2020-26)。
文摘Designing single-atom catalysts for oxygen reduction reaction(ORR)are fashionable but challenging to boost the zinc-air battery performance.Significantly enhanced ORR activity by manganese(Mn)singleatom catalysts can be achieved by accurately regulating the coordination number of isolated Mn atoms.Theoretical calculations indicate that the single Mn-N5sites possess lower free energy barrier and higher oxygen adsorption performance than single Mn-N4sites to accelerate the ORR kinetics.Target to it,here we synthesize an atomically dispersed Mn-N5catalyst by precisely axial coordination of pyridinic-N doped into two-dimensional(2D)porous nanocarbon sheets(~3.56 nm thickness),which reveals outstanding catalytic activity and ultrahigh stability for the ORR in zinc-air battery owing to the inhomogeneous charge distribution of Mn-N5sites compared to the conventional single-site Mn-N4catalyst and Pt/C.This work gives a new strategy for in situ regulating the electronic structure of metal single-atoms and further promoting the overall ORR performance in energy systems.
