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
In order to remove gas-phase mercury and NOx from flue gas, experimental studies on flue gas mercury oxidation removal and denitration of Guizhou anthracite combustion with NH4Br addition were carried out. The influen...In order to remove gas-phase mercury and NOx from flue gas, experimental studies on flue gas mercury oxidation removal and denitration of Guizhou anthracite combustion with NH4Br addition were carried out. The influence of NH4Br addition on the ignition temperature and combustion characteristics was studied using a thermogravimetric analyzer. The effects of the NHaBr addition amount on gas-phase mercury oxidation and removal were investigated in a bench scale of 6 kW fluidized bed combustor (FBC). Mercury concentrations in flue gas were determined by the Ontario hydro method (OHM) and the mercury mass balance was obtained. Results show that the NH4Br addition has little influence on the ignition temperature of Guizhou anthracite. With the mercury mass balance of 95.47%, the proportion of particulate mercury Hg^p, gaseous mercury Hg^0 and Hg^2+ are 75.28%, 11.60% and 13. 12%, respectively, as raw coal combustion. The high particulate mercury Hg^p in flue gas is caused by the high unburned carbon content in fly ash. When the NH4Br addition amount increases from 0 to 0. 3%, the concentration of gaseous Hg^0 and Hg^2+ in flue gas decreases continuously, leading to the Hg^p increase accordingly. The oxidation rate of Hg^0 is positively correlated to the Br addition amount. It demonstrates that coal combustion with NH4Br addition can promote Hg^0 oxidation and removal. NOx concentration in flue gas exhibits a descending trend with the NHaBr addition and the removal rate reaches 17.31% with the addition amount of 0.3%. Adding NH4Br to coal also plays a synergistic role in denitration.展开更多
It is urgent to develop catalysts with application potential for oxidative coupling of methane(OCM)at relatively lower temperature.Herein,three-dimensional ordered macro porous(3 DOM)La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)(...It is urgent to develop catalysts with application potential for oxidative coupling of methane(OCM)at relatively lower temperature.Herein,three-dimensional ordered macro porous(3 DOM)La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)(A_(2)B_(2)O_(7)-type)catalysts with disordered defective cubic fluorite phased structure were successfully prepared by a colloidal crystal template method.3DOM structure promotes the accessibility of the gaseous reactants(O2and CH4)to the active sites.The co-doping of Ca and Sr ions in La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)catalysts improved the formation of oxygen vacancies,thereby leading to increased density of surface-active oxygen species(O_(2)^(-))for the activation of CH4and the formation of C2products(C2H6and C2H4).3DOM La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)catalysts exhibit high catalytic activity for OCM at low temperature.3DOM La1.7Sr0.3Ce1.7Ca0.3O7-δcatalyst with the highest density of O_(2)^(-)species exhibited the highest catalytic activity for low-temperature OCM,i.e.,its CH4conversion,selectivity and yield of C2products at 650℃are 32.2%,66.1%and 21.3%,respectively.The mechanism was proposed that the increase in surface oxygen vacancies induced by the co-doping of Ca and Sr ions boosts the key step of C-H bond breaking and C-C bond coupling in catalyzing low-temperature OCM.It is meaningful for the development of the low-temperature and high-efficient catalysts for OCM reaction in practical application.展开更多
Platinum/cerium-zirconium-sulfate(Pt/Ce-Zr-SO_4^(2-)) catalysts were prepared by wetness impregnation.Catalytic activities were evaluated from the combustion of propene and CO.Sulfate(SO_4^(2-))addition improv...Platinum/cerium-zirconium-sulfate(Pt/Ce-Zr-SO_4^(2-)) catalysts were prepared by wetness impregnation.Catalytic activities were evaluated from the combustion of propene and CO.Sulfate(SO_4^(2-))addition improved the catalytic activity significantly.When using Pt/Ce-Zr-SO_4^(2-) with 10 wt%SO_4^(2-),the temperature for 90%conversion of propene and CO decreased by 75℃ compared with Pt/Ce-Zr.The conversion exceeded 95%at 240℃ even after 0.02%sulfur dioxide poisoning for 20 h.Temperature-programmed desorption of CO and X-ray photoelectron spectroscopy analyses revealed an improvement in Pt dispersion onto the Ce-Zr-SO_4^(2-) support,and the increased number of Pt particles built up more Pt^(-)-(SO_4^(2-))^(-) couples,which resulted in excellent activity.The increased total acidity and new Bronsted acid sites on the surface provided the Pt/Ce-Zr-SO_4^(2-) with good sulfur resistance.展开更多
Recent studies have shown that chlorogenic acid(CGA),which is present in coffee,has protective effects on the nervous system.However,its role in neonatal hypoxic-ischemic brain injury remains unclear.In this study,we ...Recent studies have shown that chlorogenic acid(CGA),which is present in coffee,has protective effects on the nervous system.However,its role in neonatal hypoxic-ischemic brain injury remains unclear.In this study,we established a newborn mouse model of hypoxic-ischemic brain injury using a modified Rice-Vannucci method and performed intraperitoneal injection of CGA.We found that CGA intervention effectively reduced the volume of cerebral infarct,alleviated cerebral edema,restored brain tissue structure after injury,and promoted axon growth in injured brain tissue.Moreover,CGA pretreatment alleviated oxygen-glucose deprivation damage of primary neurons and promoted neuron survival.In addition,changes in ferroptosis-related proteins caused by hypoxic-ischemic brain injury were partially reversed by CGA.Furthermore,CGA intervention upregulated the expression of the key ferroptosis factor glutathione peroxidase 4 and its upstream glutamate/cystine antiporter related factors SLC7A11 and SLC3A2.In summary,our findings reveal that CGA alleviates hypoxic-ischemic brain injury in neonatal mice by reducing ferroptosis,providing new ideas for the treatment of neonatal hypoxic-ischemic brain injury.展开更多
In this paper, the partial oxidation of methane to synthesis gas using lattice oxygen of La1- SrxMO3-λ (M=Fe, x ...In this paper, the partial oxidation of methane to synthesis gas using lattice oxygen of La1- SrxMO3-λ (M=Fe, x Mn) perovskite oxides instead of molecular oxygen was investigated. The redox circulation between 11% O2/Ar flow and 11% CH4/He flow at 900℃ shows that methane can be oxidized to CO and H2 with a selectivity of over 90.7% using the lattice oxygen of La1- SrxFeO3-λ (x≤0.2) perovskite oxides in an appropriate reaction condition, while the lost lattice x oxygen can be supplemented by air re-oxidation. It is viable for the lattice oxygen of La1- SrxFeO3-λ (x≤0.2) perovskite x oxides instead of molecular oxygen to react with methane to synthesis gas in the redox mode.展开更多
Bi12O17Br2and Bi4O5Br2visible‐light driven photocatalysts,were respectively fabricated by hydrothermal and room‐temperature deposition methods with the use of BiBr3and NaOH as precursors.Both Bi12O17Br2and Bi4O5Br2w...Bi12O17Br2and Bi4O5Br2visible‐light driven photocatalysts,were respectively fabricated by hydrothermal and room‐temperature deposition methods with the use of BiBr3and NaOH as precursors.Both Bi12O17Br2and Bi4O5Br2were composed of irregular nanosheets.The Bi4O5Br2nanosheets exhibited high and stable visible‐light photocatalytic efficiency for ppb‐level NO removal.The performance of Bi4O5Br2was markedly higher than that of the Bi12O17Br2nanosheets.The hydroxyl radical(?OH)was determined to be the main reactive oxygen species for the photo‐degradation processes of both Bi12O17Br2and Bi4O5Br2.However,in situ diffuse reflectance infrared Fourier transform spectroscopy analysis revealed that Bi12O17Br2and Bi4O5Br2featured different conversion pathways for visible light driven photocatalytic NO oxidation.The excellent photocatalytic activity of Bi4O5Br2resulted from a high surface area and large pore volumes,which facilitated the transport of reactants and intermediate products,and provided more active sites for photochemical reaction.Furthermore,the Bi4O5Br2nanosheets produced more?OH and presented stronger valence band holeoxidation.In addition,the oxygen atoms of NO could insert into oxygen‐vacancies of Bi4O5Br2,whichprovided more active sites for the reaction.This work gives insight into the photocatalytic pollutant‐degradation mechanism of bismuth oxyhalide.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
In order to develop the catalysts with low corrosiveness for the oxidative carbonylation of methanol to dimethyl carbonate(DMC), Cu Br2 was selected as the metal source to prepare Cu coordination compounds, Cu(phen)Br...In order to develop the catalysts with low corrosiveness for the oxidative carbonylation of methanol to dimethyl carbonate(DMC), Cu Br2 was selected as the metal source to prepare Cu coordination compounds, Cu(phen)Br2,[Cu(phen)2Br]Br and [Cu(phen)3]Br2(phen = 1,10-phenanthroline). These complexes were characterized by thermogravimetric analysis and temperature-programmed reduction. Their catalytic performances were investigated. It was found that the metal coordination environments and thermal stability of the complexes played an important role in their catalytic activities. Cu(phen)Br2exhibited the highest activity due to the lowest steric hindrance, the most positions occupied by the bromide ions and the highest thermal stability. The turnover number was up to 47.6 DMC mol·(Cu mol)-1with selectivity of 92.8% under conditions of 120 °C, ratio of partial pressure of CO to O2 of 19:1(below the explosion limit of CO) and catalyst concentration of 0.011 mol·L-1.Furthermore, a plausible reaction mechanism was suggested on the basis of the experimental data.展开更多
Non-isothermal oxidation of brown coal with 5 wt% of Cu(NO3)2, 5 wt% of Ce(NO3)3 and {2.5 wt% Cu(NO3)2 + 2.5 wt% Ce(NO3)3} additives was studied. The introduction of additives was carried out by an incipient wet impre...Non-isothermal oxidation of brown coal with 5 wt% of Cu(NO3)2, 5 wt% of Ce(NO3)3 and {2.5 wt% Cu(NO3)2 + 2.5 wt% Ce(NO3)3} additives was studied. The introduction of additives was carried out by an incipient wet impregnation method to ensure uniform distribution of cerium and copper nitrates within the structure of coal powdery samples (according to SEM and EDX mapping). The samples reactivity was studied in an isothermal oxidation regime at 200 °C (1 h) and by DSC/TGA at 2.5 °C/min heating rate. The additives implementation was found to reduce significantly the oxidation onset temperature (△Ti = 20-55 °C), the samples oxidation delay time (△ti= 2-22 min) and overall duration of the oxidation process (△tc = 8-16 min). The additives efficiency could be graded in accordance with the activation on the coal oxidation in the following row: Cu(NO3)2 >{Cu(NO3)2 + Ce(NO3)3}> Ce(NO3)3. According to the mass spectroscopy, the obtained row of activation correlates well with the initial temperature of the studied nitrate's decomposition (from 190 to 223 °C). A presence of nitrates was found to change significantly the trend of heat release taking place during the oxidation of coal samples (according to DSC/TGA data). The influence of coal morphology and volatiles concern in initial sample on the parameters of the oxidation process was studied as well. Activation energy (Ea) of the coal oxidation was calculated using Coats-Redfern method. Maximum decrease in Ea from 69 to 58 kJ/mol was observed for the samples with Cu(NO3)2. Graphical abstract.展开更多
In this paper, poly(amide-6-β-ethylene oxide) (PEBA1657) copolymer was used to prepare multilayer polyetherimide (PEI)/polydimethylsiloxane (PDMS)/PEBA1657/PDMS composite membranes by dip-coating method. Permeation b...In this paper, poly(amide-6-β-ethylene oxide) (PEBA1657) copolymer was used to prepare multilayer polyetherimide (PEI)/polydimethylsiloxane (PDMS)/PEBA1657/PDMS composite membranes by dip-coating method. Permeation behaviors of ethylene, ethane, propylene, propane, n-butane, methane and nitrogen through the multilayer composite membranes were investigated over a range of operating temperature and pressure. The permeances of light hydrocarbons through PEI/PDMS/PEBA1657/PDMS composite membranes increase with their increasing condensability, and the olefins are more permeable than their corresponding paraffins. For light hydrocarbons, the gas permeances increase significantly as temperature increasing. When the transmembrane pressure difference increases, the gas permeance increases moderately due to plasticization effect, while their apparent activation energies for permeation decrease.展开更多
[Objectives]To study the inhibitory activity of two flavonoid glycosides isolated from Chlorophytum comosum Laxum R.Br on human nasopharyngeal carcinoma(NPC)cell line 5-8F in vitro and its mechanism.[Methods]The flavo...[Objectives]To study the inhibitory activity of two flavonoid glycosides isolated from Chlorophytum comosum Laxum R.Br on human nasopharyngeal carcinoma(NPC)cell line 5-8F in vitro and its mechanism.[Methods]The flavonoid glycosides were isolated and purified from the ethanol alcoholic extract of the roots of Liliaceae plant Chlorophytum comosum by silica gel column chromatography,macroporous resin column chromatography,Sephadex LH-20,and reverse column chromatography(ODS).The inhibitory activity of flavonoid glycosides on human nasopharyngeal carcinoma cells was analyzed by CCK-8 method,and the potential mechanism was preliminarily analyzed by molecular docking.[Results]Two flavonoid glycosides were identified as isovitexin 2″-0-rhamnoside and 7-2″-di-O-β-glucopyranosylisovitexin.Two flavonoid glycosides showed promising inhibitory effect on human nasopharyngeal carcinoma cell line 5-8F,with IC_(50) values of 24.8 and 27.5μmol/L,respectively.Molecular docking results showed that the potential targets of two flavonoid glycosides include CyclinD1,Bcl-2β-Catenin,ILK,TGF-β,in addition,two glycosides showed higher predicted binding affinity towards CyclinD1,which verifies the cytotoxicity of the two compounds on human nasopharyngeal carcinoma cell line 5-8F in vitro.[Conclusions]Two flavonoid glycosides are the active molecules in Chlorophytum comosum that can inhibit the proliferation of human nasopharyngeal carcinoma cells,and have the potential to be used in the research and development of anti nasopharyngeal carcinoma drugs.展开更多
Al-containing low carbon MgO - C refractories were prepared using 70% (in mass, the same hereinafter) fused magnesia ( ≤3 mm), 24% fused magnesia powder ( 〈0. 074 mm) , 3% flake graphite, 3% Al powder and 4% p...Al-containing low carbon MgO - C refractories were prepared using 70% (in mass, the same hereinafter) fused magnesia ( ≤3 mm), 24% fused magnesia powder ( 〈0. 074 mm) , 3% flake graphite, 3% Al powder and 4% phenolic resin (extra-added) as the basic formulation. Influence of ZnO addhion on oxidation resistance of the materials was investigated by adding 1% ZnO to substitute fused magnesia powder. The relationship between in-situ formed spinel and ZnO in the matrix was discussed by comparing apparent porosity, cold crushing strength, and phase evolution of the materials matrix. The oxidation resistances of the two materials were compared by observing the formed dense MgO layer between the decarburized layer and the original layer. The result shows that adding ZnO in MgO - C refractories accelerates the in-situ formation of ZnAl204 spinel and the formation of dense MgO layer, thus improves the oxidation resistance of the low carbon MgO - C refractories.展开更多
The thermodynamic instability of zinc anodes in aqueous electrolytes leads to issues such as corrosion,hydrogen evolution reactions(HER), and dendrite growth, severely hindering the practical application of zinc-based...The thermodynamic instability of zinc anodes in aqueous electrolytes leads to issues such as corrosion,hydrogen evolution reactions(HER), and dendrite growth, severely hindering the practical application of zinc-based aqueous energy storage devices. To address these challenges, this work proposes a dualfunction zinc anode protective layer, composed of Zn-Al-In layered double oxides(ILDO) by rationally designing Zn-Al layered double hydroxides(Zn-Al LDHs) for the first time. Differing from previous works on the LDHs coatings, firstly, the ILDO layer accelerates zinc-ion desolvation and also captures and anchors SO_(4)^(2-). Secondly, the in-situ formation of the Zn-In alloy phase effectively lowers the nucleation energy barrier, thereby regulating zinc nucleation. Consequently, the zinc anode with the ILDO protective layer demonstrates long-term stability exceeding 1900 h and low voltage hysteresis of 7.5 m V at 0.5 m A cm^(-2) and 0.5 m A h cm^(-2). Additionally, it significantly enhances the rate capability and cycling performance of Zn@ILDO//MnO_(2) full batteries and Zn@ILDO//activated carbon zinc-ion hybrid capacitors.This simple and effective dual-function protective layer strategy offers a promising approach for achieving high-performance zinc-ion batteries.展开更多
Synthesis of pyridine bases by way of relatively simple transformations with use of cheaper and available raw, is an actual problem. In this aspect the method in which the reactions of hydro-carbons oxidation are indu...Synthesis of pyridine bases by way of relatively simple transformations with use of cheaper and available raw, is an actual problem. In this aspect the method in which the reactions of hydro-carbons oxidation are induced by nitrous oxide, is of scientific and practical interest. In the present work, the authors report the results of the experiments coherent-synchronized oxidation of pyridine with nitrous oxide to 2,2- and 2,3-dipyridyle.展开更多
A series of M-substituted hexaaluminates LaMAl11O19-δ (M=Fe, Co, Ni, Mn, and Cu) were prepared and characterized by XRD, XPS, TPR and TGA techniques, respectively. They exhibited different reducibility and catalyti...A series of M-substituted hexaaluminates LaMAl11O19-δ (M=Fe, Co, Ni, Mn, and Cu) were prepared and characterized by XRD, XPS, TPR and TGA techniques, respectively. They exhibited different reducibility and catalytic activity for partial oxidation of methane (POM) to synthesis gas. Among the LaMAl11019-δ samples, LaNiAl11O19-δ showed the best catalytic activity for the topic reaction and selectivity for synthesis gas at 780 ℃ for 2 h. The conversion of CH4 was over 99.2%, and the product selectivity for both CO and H2 was above 90.3%.展开更多
The oxidation behavior of Al2O3-30%TiCN-0.2%Y2O3 composite and its effect on high temperature bending strength was studied. The result indicates that the mass gain during static oxidation of the material under normal ...The oxidation behavior of Al2O3-30%TiCN-0.2%Y2O3 composite and its effect on high temperature bending strength was studied. The result indicates that the mass gain during static oxidation of the material under normal atmosphere follows the parabolic law. Oxide increases with increasing temperature and prolonging time. It has good oxidation resistance. The product of oxidation of the material is TiO2. Therefore, the volume of the material expands. The oxide film is destroyed because residual stress inside the oxide film is released. Proper oxidation is beneficial to the improvement of bending strength of Al2O3-30%TiCN-0.2%Y2O3 composite. The strength increase is up to 4.5%.展开更多
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The National Natural Science Foundation of China(No.51376046,51076030)the National Key Technology R&D Program of China during the 12th Five-Year Plan Period(No.2012BAA02B01)+2 种基金the United Creative Foundation of Jiangsu Province(No.BY2013073-10)the Fundamental Research Funds for the Central Universitiesthe Scientific Innovation Research of College Graduates in Jiangsu Province(CXZZ13_0093,KYLX_0115,KYLX_0184)
文摘In order to remove gas-phase mercury and NOx from flue gas, experimental studies on flue gas mercury oxidation removal and denitration of Guizhou anthracite combustion with NH4Br addition were carried out. The influence of NH4Br addition on the ignition temperature and combustion characteristics was studied using a thermogravimetric analyzer. The effects of the NHaBr addition amount on gas-phase mercury oxidation and removal were investigated in a bench scale of 6 kW fluidized bed combustor (FBC). Mercury concentrations in flue gas were determined by the Ontario hydro method (OHM) and the mercury mass balance was obtained. Results show that the NH4Br addition has little influence on the ignition temperature of Guizhou anthracite. With the mercury mass balance of 95.47%, the proportion of particulate mercury Hg^p, gaseous mercury Hg^0 and Hg^2+ are 75.28%, 11.60% and 13. 12%, respectively, as raw coal combustion. The high particulate mercury Hg^p in flue gas is caused by the high unburned carbon content in fly ash. When the NH4Br addition amount increases from 0 to 0. 3%, the concentration of gaseous Hg^0 and Hg^2+ in flue gas decreases continuously, leading to the Hg^p increase accordingly. The oxidation rate of Hg^0 is positively correlated to the Br addition amount. It demonstrates that coal combustion with NH4Br addition can promote Hg^0 oxidation and removal. NOx concentration in flue gas exhibits a descending trend with the NHaBr addition and the removal rate reaches 17.31% with the addition amount of 0.3%. Adding NH4Br to coal also plays a synergistic role in denitration.
基金supported by the National Key Research and Development Program of China(Nos.2022YFB3504100,2022YFB3506200)the National Natural Science Foundation of China(Nos.22208373,22376217)+1 种基金the Beijing Nova Program(No.20220484215)the Science Foundation of China University of Petroleum,Beijing(No.2462023YJRC030)。
文摘It is urgent to develop catalysts with application potential for oxidative coupling of methane(OCM)at relatively lower temperature.Herein,three-dimensional ordered macro porous(3 DOM)La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)(A_(2)B_(2)O_(7)-type)catalysts with disordered defective cubic fluorite phased structure were successfully prepared by a colloidal crystal template method.3DOM structure promotes the accessibility of the gaseous reactants(O2and CH4)to the active sites.The co-doping of Ca and Sr ions in La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)catalysts improved the formation of oxygen vacancies,thereby leading to increased density of surface-active oxygen species(O_(2)^(-))for the activation of CH4and the formation of C2products(C2H6and C2H4).3DOM La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)catalysts exhibit high catalytic activity for OCM at low temperature.3DOM La1.7Sr0.3Ce1.7Ca0.3O7-δcatalyst with the highest density of O_(2)^(-)species exhibited the highest catalytic activity for low-temperature OCM,i.e.,its CH4conversion,selectivity and yield of C2products at 650℃are 32.2%,66.1%and 21.3%,respectively.The mechanism was proposed that the increase in surface oxygen vacancies induced by the co-doping of Ca and Sr ions boosts the key step of C-H bond breaking and C-C bond coupling in catalyzing low-temperature OCM.It is meaningful for the development of the low-temperature and high-efficient catalysts for OCM reaction in practical application.
基金supported by the National Natural Science Foundation of China(21506194,21676255)the Provincial Natural Science Foundation of Zhejiang Province(LY16B070011)the Commission of Science and Technology of Zhejiang Province(2017C33106,2017C03007)~~
文摘Platinum/cerium-zirconium-sulfate(Pt/Ce-Zr-SO_4^(2-)) catalysts were prepared by wetness impregnation.Catalytic activities were evaluated from the combustion of propene and CO.Sulfate(SO_4^(2-))addition improved the catalytic activity significantly.When using Pt/Ce-Zr-SO_4^(2-) with 10 wt%SO_4^(2-),the temperature for 90%conversion of propene and CO decreased by 75℃ compared with Pt/Ce-Zr.The conversion exceeded 95%at 240℃ even after 0.02%sulfur dioxide poisoning for 20 h.Temperature-programmed desorption of CO and X-ray photoelectron spectroscopy analyses revealed an improvement in Pt dispersion onto the Ce-Zr-SO_4^(2-) support,and the increased number of Pt particles built up more Pt^(-)-(SO_4^(2-))^(-) couples,which resulted in excellent activity.The increased total acidity and new Bronsted acid sites on the surface provided the Pt/Ce-Zr-SO_4^(2-) with good sulfur resistance.
基金supported by the National Natural Science Foundation of China,No.81971425the Natural Science Foundation of Zhejiang Province,No.LY20H040002(both to XQF).
文摘Recent studies have shown that chlorogenic acid(CGA),which is present in coffee,has protective effects on the nervous system.However,its role in neonatal hypoxic-ischemic brain injury remains unclear.In this study,we established a newborn mouse model of hypoxic-ischemic brain injury using a modified Rice-Vannucci method and performed intraperitoneal injection of CGA.We found that CGA intervention effectively reduced the volume of cerebral infarct,alleviated cerebral edema,restored brain tissue structure after injury,and promoted axon growth in injured brain tissue.Moreover,CGA pretreatment alleviated oxygen-glucose deprivation damage of primary neurons and promoted neuron survival.In addition,changes in ferroptosis-related proteins caused by hypoxic-ischemic brain injury were partially reversed by CGA.Furthermore,CGA intervention upregulated the expression of the key ferroptosis factor glutathione peroxidase 4 and its upstream glutamate/cystine antiporter related factors SLC7A11 and SLC3A2.In summary,our findings reveal that CGA alleviates hypoxic-ischemic brain injury in neonatal mice by reducing ferroptosis,providing new ideas for the treatment of neonatal hypoxic-ischemic brain injury.
文摘In this paper, the partial oxidation of methane to synthesis gas using lattice oxygen of La1- SrxMO3-λ (M=Fe, x Mn) perovskite oxides instead of molecular oxygen was investigated. The redox circulation between 11% O2/Ar flow and 11% CH4/He flow at 900℃ shows that methane can be oxidized to CO and H2 with a selectivity of over 90.7% using the lattice oxygen of La1- SrxFeO3-λ (x≤0.2) perovskite oxides in an appropriate reaction condition, while the lost lattice x oxygen can be supplemented by air re-oxidation. It is viable for the lattice oxygen of La1- SrxFeO3-λ (x≤0.2) perovskite x oxides instead of molecular oxygen to react with methane to synthesis gas in the redox mode.
基金supported by the National Natural Science Foundation of China(51708078,21576034)Chongqing Postdoctoral Science Foundation funded project(Xm2016027)the Innovative Research Team of Chongqing(CXTDG201602014,CXTDX201601016)~~
文摘Bi12O17Br2and Bi4O5Br2visible‐light driven photocatalysts,were respectively fabricated by hydrothermal and room‐temperature deposition methods with the use of BiBr3and NaOH as precursors.Both Bi12O17Br2and Bi4O5Br2were composed of irregular nanosheets.The Bi4O5Br2nanosheets exhibited high and stable visible‐light photocatalytic efficiency for ppb‐level NO removal.The performance of Bi4O5Br2was markedly higher than that of the Bi12O17Br2nanosheets.The hydroxyl radical(?OH)was determined to be the main reactive oxygen species for the photo‐degradation processes of both Bi12O17Br2and Bi4O5Br2.However,in situ diffuse reflectance infrared Fourier transform spectroscopy analysis revealed that Bi12O17Br2and Bi4O5Br2featured different conversion pathways for visible light driven photocatalytic NO oxidation.The excellent photocatalytic activity of Bi4O5Br2resulted from a high surface area and large pore volumes,which facilitated the transport of reactants and intermediate products,and provided more active sites for photochemical reaction.Furthermore,the Bi4O5Br2nanosheets produced more?OH and presented stronger valence band holeoxidation.In addition,the oxygen atoms of NO could insert into oxygen‐vacancies of Bi4O5Br2,whichprovided more active sites for the reaction.This work gives insight into the photocatalytic pollutant‐degradation mechanism of bismuth oxyhalide.
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.
基金Supported by the National Natural Science Foundation of China(20936003,21276201)
文摘In order to develop the catalysts with low corrosiveness for the oxidative carbonylation of methanol to dimethyl carbonate(DMC), Cu Br2 was selected as the metal source to prepare Cu coordination compounds, Cu(phen)Br2,[Cu(phen)2Br]Br and [Cu(phen)3]Br2(phen = 1,10-phenanthroline). These complexes were characterized by thermogravimetric analysis and temperature-programmed reduction. Their catalytic performances were investigated. It was found that the metal coordination environments and thermal stability of the complexes played an important role in their catalytic activities. Cu(phen)Br2exhibited the highest activity due to the lowest steric hindrance, the most positions occupied by the bromide ions and the highest thermal stability. The turnover number was up to 47.6 DMC mol·(Cu mol)-1with selectivity of 92.8% under conditions of 120 °C, ratio of partial pressure of CO to O2 of 19:1(below the explosion limit of CO) and catalyst concentration of 0.011 mol·L-1.Furthermore, a plausible reaction mechanism was suggested on the basis of the experimental data.
文摘Non-isothermal oxidation of brown coal with 5 wt% of Cu(NO3)2, 5 wt% of Ce(NO3)3 and {2.5 wt% Cu(NO3)2 + 2.5 wt% Ce(NO3)3} additives was studied. The introduction of additives was carried out by an incipient wet impregnation method to ensure uniform distribution of cerium and copper nitrates within the structure of coal powdery samples (according to SEM and EDX mapping). The samples reactivity was studied in an isothermal oxidation regime at 200 °C (1 h) and by DSC/TGA at 2.5 °C/min heating rate. The additives implementation was found to reduce significantly the oxidation onset temperature (△Ti = 20-55 °C), the samples oxidation delay time (△ti= 2-22 min) and overall duration of the oxidation process (△tc = 8-16 min). The additives efficiency could be graded in accordance with the activation on the coal oxidation in the following row: Cu(NO3)2 >{Cu(NO3)2 + Ce(NO3)3}> Ce(NO3)3. According to the mass spectroscopy, the obtained row of activation correlates well with the initial temperature of the studied nitrate's decomposition (from 190 to 223 °C). A presence of nitrates was found to change significantly the trend of heat release taking place during the oxidation of coal samples (according to DSC/TGA data). The influence of coal morphology and volatiles concern in initial sample on the parameters of the oxidation process was studied as well. Activation energy (Ea) of the coal oxidation was calculated using Coats-Redfern method. Maximum decrease in Ea from 69 to 58 kJ/mol was observed for the samples with Cu(NO3)2. Graphical abstract.
基金Supported by Key Projects in the National Science & Technology Pillar Program (2011BAC08B00)
文摘In this paper, poly(amide-6-β-ethylene oxide) (PEBA1657) copolymer was used to prepare multilayer polyetherimide (PEI)/polydimethylsiloxane (PDMS)/PEBA1657/PDMS composite membranes by dip-coating method. Permeation behaviors of ethylene, ethane, propylene, propane, n-butane, methane and nitrogen through the multilayer composite membranes were investigated over a range of operating temperature and pressure. The permeances of light hydrocarbons through PEI/PDMS/PEBA1657/PDMS composite membranes increase with their increasing condensability, and the olefins are more permeable than their corresponding paraffins. For light hydrocarbons, the gas permeances increase significantly as temperature increasing. When the transmembrane pressure difference increases, the gas permeance increases moderately due to plasticization effect, while their apparent activation energies for permeation decrease.
基金Supported by Youth Fund Project of Zhaoqing University(QZ202235)Zhaoqing Science and Technology Plan Project(2022040311011).
文摘[Objectives]To study the inhibitory activity of two flavonoid glycosides isolated from Chlorophytum comosum Laxum R.Br on human nasopharyngeal carcinoma(NPC)cell line 5-8F in vitro and its mechanism.[Methods]The flavonoid glycosides were isolated and purified from the ethanol alcoholic extract of the roots of Liliaceae plant Chlorophytum comosum by silica gel column chromatography,macroporous resin column chromatography,Sephadex LH-20,and reverse column chromatography(ODS).The inhibitory activity of flavonoid glycosides on human nasopharyngeal carcinoma cells was analyzed by CCK-8 method,and the potential mechanism was preliminarily analyzed by molecular docking.[Results]Two flavonoid glycosides were identified as isovitexin 2″-0-rhamnoside and 7-2″-di-O-β-glucopyranosylisovitexin.Two flavonoid glycosides showed promising inhibitory effect on human nasopharyngeal carcinoma cell line 5-8F,with IC_(50) values of 24.8 and 27.5μmol/L,respectively.Molecular docking results showed that the potential targets of two flavonoid glycosides include CyclinD1,Bcl-2β-Catenin,ILK,TGF-β,in addition,two glycosides showed higher predicted binding affinity towards CyclinD1,which verifies the cytotoxicity of the two compounds on human nasopharyngeal carcinoma cell line 5-8F in vitro.[Conclusions]Two flavonoid glycosides are the active molecules in Chlorophytum comosum that can inhibit the proliferation of human nasopharyngeal carcinoma cells,and have the potential to be used in the research and development of anti nasopharyngeal carcinoma drugs.
文摘Al-containing low carbon MgO - C refractories were prepared using 70% (in mass, the same hereinafter) fused magnesia ( ≤3 mm), 24% fused magnesia powder ( 〈0. 074 mm) , 3% flake graphite, 3% Al powder and 4% phenolic resin (extra-added) as the basic formulation. Influence of ZnO addhion on oxidation resistance of the materials was investigated by adding 1% ZnO to substitute fused magnesia powder. The relationship between in-situ formed spinel and ZnO in the matrix was discussed by comparing apparent porosity, cold crushing strength, and phase evolution of the materials matrix. The oxidation resistances of the two materials were compared by observing the formed dense MgO layer between the decarburized layer and the original layer. The result shows that adding ZnO in MgO - C refractories accelerates the in-situ formation of ZnAl204 spinel and the formation of dense MgO layer, thus improves the oxidation resistance of the low carbon MgO - C refractories.
基金Natural Science Foundation of Hunan Province (No.2020JJ4734)High Performance Computing Center of Central South University。
文摘The thermodynamic instability of zinc anodes in aqueous electrolytes leads to issues such as corrosion,hydrogen evolution reactions(HER), and dendrite growth, severely hindering the practical application of zinc-based aqueous energy storage devices. To address these challenges, this work proposes a dualfunction zinc anode protective layer, composed of Zn-Al-In layered double oxides(ILDO) by rationally designing Zn-Al layered double hydroxides(Zn-Al LDHs) for the first time. Differing from previous works on the LDHs coatings, firstly, the ILDO layer accelerates zinc-ion desolvation and also captures and anchors SO_(4)^(2-). Secondly, the in-situ formation of the Zn-In alloy phase effectively lowers the nucleation energy barrier, thereby regulating zinc nucleation. Consequently, the zinc anode with the ILDO protective layer demonstrates long-term stability exceeding 1900 h and low voltage hysteresis of 7.5 m V at 0.5 m A cm^(-2) and 0.5 m A h cm^(-2). Additionally, it significantly enhances the rate capability and cycling performance of Zn@ILDO//MnO_(2) full batteries and Zn@ILDO//activated carbon zinc-ion hybrid capacitors.This simple and effective dual-function protective layer strategy offers a promising approach for achieving high-performance zinc-ion batteries.
文摘Synthesis of pyridine bases by way of relatively simple transformations with use of cheaper and available raw, is an actual problem. In this aspect the method in which the reactions of hydro-carbons oxidation are induced by nitrous oxide, is of scientific and practical interest. In the present work, the authors report the results of the experiments coherent-synchronized oxidation of pyridine with nitrous oxide to 2,2- and 2,3-dipyridyle.
基金This work was supported by the Education Department of Jilin Province and Science and Technology office of Siping Municipality.
文摘A series of M-substituted hexaaluminates LaMAl11O19-δ (M=Fe, Co, Ni, Mn, and Cu) were prepared and characterized by XRD, XPS, TPR and TGA techniques, respectively. They exhibited different reducibility and catalytic activity for partial oxidation of methane (POM) to synthesis gas. Among the LaMAl11019-δ samples, LaNiAl11O19-δ showed the best catalytic activity for the topic reaction and selectivity for synthesis gas at 780 ℃ for 2 h. The conversion of CH4 was over 99.2%, and the product selectivity for both CO and H2 was above 90.3%.
文摘The oxidation behavior of Al2O3-30%TiCN-0.2%Y2O3 composite and its effect on high temperature bending strength was studied. The result indicates that the mass gain during static oxidation of the material under normal atmosphere follows the parabolic law. Oxide increases with increasing temperature and prolonging time. It has good oxidation resistance. The product of oxidation of the material is TiO2. Therefore, the volume of the material expands. The oxide film is destroyed because residual stress inside the oxide film is released. Proper oxidation is beneficial to the improvement of bending strength of Al2O3-30%TiCN-0.2%Y2O3 composite. The strength increase is up to 4.5%.