Micromixing efficiency is an important parameter for evaluating the multiphase mass transfer performance and reaction efficiency of microreactors.In this work,the novel curved capillary reactor with different shapes w...Micromixing efficiency is an important parameter for evaluating the multiphase mass transfer performance and reaction efficiency of microreactors.In this work,the novel curved capillary reactor with different shapes was designed to generate Dean flow,which was used to enhance the liquid-liquid micromixing performance.The Villermaux-Dushman probe reaction was employed to characterize the micromixing performance in different curved capillary microreactors.The effects of experiment parameters such as liquid flow rate,inner diameter,tube length,and curve diameter on micromixing performance were systematically investigated.Under the optimal conditions,the minimum value of the segmentation factor XS was 0.008.It was worth noting that at the low Reynolds number(Re<30),the change of curved shape on the capillary microreactor can significantly improve the micromixing performance with XS reduced by 37.5%.Further,the correlations of segment index XS with dimensionless factor such as Reynolds number or Dean number were developed,which can be used to predict the liquid-liquid micromixing performance in capillary microreactors.展开更多
Surface/interface engineering of a multimetallic nanostructure with diverse electrocatalytic properties for direct liquid fuel cells is desirable yet challenging.Herein,using visible light,a class of quaternary Pt_(1)...Surface/interface engineering of a multimetallic nanostructure with diverse electrocatalytic properties for direct liquid fuel cells is desirable yet challenging.Herein,using visible light,a class of quaternary Pt_(1)Ag_(0.1)Bi_(0.16)Te_(0.29)ultrathin nanosheets is fabricated and used as high-performance anode electrocatalysts for formic acid-/alcohol-air fuel cells.The modified electronic structure of Pt,enhanced hydroxyl adsorption,and abundant exterior defects afford Pt_(1)Ag_(0.1)Bi_(0.16)Te_(0.29)/C high intrinsic anodic electrocatalytic activity to boost the power densities of direct formic acid-/methanol-/ethanol-/ethylene glycol-/glycerol-air fuel cells,and the corresponding peak power density of Pt_(1)Ag_(0.1)Bi_(0.16)Te_(0.29)/C is respectively 129.7,142.3,105.4,124.3,and 128.0 mW cm^(-2),considerably outperforming Pt/C.Operando in situ Fourier transform infrared reflection spectroscopy reveals that formic acid oxidation on Pt_(1)Ag_(0.1)Bi_(0.16)Te_(0.29)/C occurs via a CO_(2)-free direct pathway.Density functional theory calculations show that the presence of Ag,Bi,and Te in Pt_(1)Ag_(0.1)Bi_(0.16)Te_(0.29)suppresses CO^(*)formation while optimizing dehydrogenation steps and synergistic effect and modified Pt effectively enhance H_(2)O dissociation to improve electrocatalytic performance.This synthesis strategy can be extended to 43 other types of ultrathin multimetallic nanosheets(from ternary to octonary nanosheets),and efficiently capture precious metals(i.e.,Pd,Pt,Rh,Ru,Au,and Ag)from different water sources.展开更多
Selective conversion of fructose to 1,2-propanediol(1,2-PDO)is considered as a sustainable and cost-effective alternative to petroleum-based processes,however,this approach still faces challenges associated with low e...Selective conversion of fructose to 1,2-propanediol(1,2-PDO)is considered as a sustainable and cost-effective alternative to petroleum-based processes,however,this approach still faces challenges associated with low efficiency and harsh reaction conditions.Here,we have successfully synthesized a novel bifunctional Ru-WO_(x)-MgO_(y) catalyst through a facile'one-pot'solvothermal method.Remarkably,this catalyst exhibits exceptional catalytic performances in the conversion of fructose to 1,2-PDO under mild reaction conditions.The yield of 1,2-PDO is up to 56.2%at 140°C for 4 h under an ultra-low hydrogen pressure of only 0.2 MPa,surpassing the reported results in recent literature(below 51%).Comprehensive characterizations and density functional theory(DFT)calculations reveal that the presence of oxygen vacancies in the Ru-WO_(x)-MgO_(y) catalyst,serving as active acidic sites,facilitates the chemoselective cleavage of C-C bonds in fructose,which leads to the generation of active intermediates and ultimately resulted in the high yield of 1,2-PDO.展开更多
Interfacial water molecules are the most important participants in the hydrogen evolution reaction(HER).Hence,understanding the behavior and role that interfacial water plays will ultimately reveal the HER mechanism.U...Interfacial water molecules are the most important participants in the hydrogen evolution reaction(HER).Hence,understanding the behavior and role that interfacial water plays will ultimately reveal the HER mechanism.Unfortunately,investigating interfacial water is extremely challenging owing to the interference caused by bulk water molecules and complexity of the interfacial environment.Here,the behaviors of interfacial water in different cationic electrolytes on Pd surfaces were investigated by the electrochemistry,in situ core-shell nanostructure enhanced Raman spectroscopy and theoretical simulation techniques.Direct spectral evidence reveals a red shift in the frequency and a decrease in the intensity of interfacial water as the potential is shifted in the positively direction.When comparing the different cation electrolyte systems at a given potential,the frequency of the interfacial water peak increases in the specified order:Li+<Na^(+)<K^(+)<Ca^(2+)<Sr^(2+).The structure of interfacial water was optimized by adjusting the radius,valence,and concentration of cation to form the two-H down structure.This unique interfacial water structure will improve the charge transfer efficiency between the water and electrode further enhancing the HER performance.Therefore,local cation tuning strategies can be used to improve the HER performance by optimizing the interfacial water structure.展开更多
Hydrochemistry of underground brines along south coast of Laizhou Bay, Shandong, China has been analyzed. Brine samples were collected from 43 wells in this area. It was considered that the brines were originated from...Hydrochemistry of underground brines along south coast of Laizhou Bay, Shandong, China has been analyzed. Brine samples were collected from 43 wells in this area. It was considered that the brines were originated from seawater. However, whether they were formed by seawater evaporation or seawater freezing was not fully sure. We created a simple method by plotting Na/Cl vs. seawater concen-tration factor (SCF) and Ca/Mg vs. SCF to determine the brine formation geochemically. Comparison of our results to previous seawater freezing and evaporation experiments indicated that the brines were formed by seawater evaporation. The ratios of HCO3/Cl of some low salinity brines in the study area were relatively higher, indicating that the brines may have mixed with other waters after the generation. The Br/Cl ratios of the brines decreased annually in the past 20 to 30 years of exploitation, indicating down-ward permeation of the brine from which bromine was extracted.展开更多
Nanocrystalline cobalt powders have been prepared from aqueous solution by reducing their corresponding metal salts under suitable conditions. The experimental conditions have been studied in detail. X-ray powder diff...Nanocrystalline cobalt powders have been prepared from aqueous solution by reducing their corresponding metal salts under suitable conditions. The experimental conditions have been studied in detail. X-ray powder diffraction patterns show that the cobalt powder is hexagonal crystallite. The average particle size of the ultrafine cobalt powder is 55 nm.展开更多
In recent years,with the high rate of juvenile delinquency,people pay more attention to the moral education of students in secondary vocational colleges.Based on the framework of social learning theory,this paper expl...In recent years,with the high rate of juvenile delinquency,people pay more attention to the moral education of students in secondary vocational colleges.Based on the framework of social learning theory,this paper explores the systematic and comprehensive application of social learning theory in the moral education course.From the cognition of the behavior to the selection and internalization of the representation of the model behavior,and finally the selective extemalization of the representation symbol to generate the behavior,the influencing factors and their utility in each stage of the production of moral behavior are analyzed step by step,assisting students to establish correct outlook on life and values,and cultivating their"key abilities."When students face a complex and diverse social environment,they can make judgments in line with the general moral standards of the society,and then seek to improve the effectiveness of the moral standards of secondary vocational students,and strive to maximize the effectiveness of moral education.展开更多
The rational synergy of chemical composition and spatial nanostructures of electrode materials play important roles in high-performance energy storage devices.Here,we designed pea-like MoS_(2)@NiS_(1.03)-carbon hollow...The rational synergy of chemical composition and spatial nanostructures of electrode materials play important roles in high-performance energy storage devices.Here,we designed pea-like MoS_(2)@NiS_(1.03)-carbon hollow nanofibers using a simple electrospinning and thermal treatment method.The hierarchical hollow nanofiber is composed of a nitrogen-doped carbon-coated NiS_(1.03) tube wall,in which pea-like uniformly discrete MoS_(2) nanoparticles are enclosed.As a sodium-ion battery electrode material,the MoS_(2)@NiS_(1.03)-carbon hollow nanofibers have abundant diphasic heterointerfaces,a conductive network,and appropriate volume variation-buffering spaces,which can facilitate ion diffusion kinetics,shorten the diffusion path of electrons/ion,and buffer volume expansion during Na^(+)insertion/extraction.It shows outstanding rate capacity and long-cycle performance in a sodium-ion battery.This heterogeneous hollow nanoarchitectures designing enlightens an efficacious strategy to boost the capacity and long-life stability of sodium storage performance of electrode materials.展开更多
The depolymerization and upgrading of lignin from raw biomass,while keeping cellulose intact is important in biorefinery and various metal-based catalysts have been used in reductive catalytic fractionation,a key meth...The depolymerization and upgrading of lignin from raw biomass,while keeping cellulose intact is important in biorefinery and various metal-based catalysts have been used in reductive catalytic fractionation,a key method in"lignin-first"strategy,Recently,we found that a core-shell structured Co@CoO catalyst with CoO shell as the real active site had excellent performance in the hydrogenolysis of 5-hydromethylfurfural to 2,5-dimethylfuran due to its unique ability to dissociate H_(2)and yield active H^(δ-)species(Xiang et al.,2022).In this work,we report a one-pot depolymerization and upgrading of lignocellulose to alkylcyclohexanols,a flavour precursor,with intact cellulose over this unique core-shell structured catalyst,Co@CoO.Lignin model compounds(β-O-4,4-O-5,α-O-4)were first used to clarify the activity of Co@CoO catalyst.Then,the one-pot conversion of various organosolv lignin(birch,pine and poplar)to alkylcyclohexanols was realized with the mass yield of alkylcyclohexanols up to25.8 wt%from birch lignin under the reaction condition of 210℃,1 MPa H_(2),16 h.Finally,the corresponding woody sawdusts were used as feedstocks and found that the Co@CoO catalyst indeed preferentially depolymerized and upgraded the lignin part and obtained the same alkylcyclohexanols products with the retention of cellulose-rich pulp.The collected alkylcyclohexanols were further esterified to obtain valueadded esters,which can be used as flavors.This work will inspire the design of new efficient metal oxide catalysts in lignin fractionation and depolymerization to high-value-added chemicals with intact cellulose.展开更多
Hollow core-shell structure nanomaterials have been broadly used in energy storage, catalysis, reactor,and other fields due to their unique characteristics, including the synergy between different materials,a large sp...Hollow core-shell structure nanomaterials have been broadly used in energy storage, catalysis, reactor,and other fields due to their unique characteristics, including the synergy between different materials,a large specific surface area, small density, large charge carrying capacity and so on. However, their synthesis processes were mostly complicated, and few researches reported one-step encapsulation of different valence states of precious metals in carbon-based materials. Hence, a novel hollow core-shell nanostructure electrode material, RuO_(2)@Ru/HCs, with a lower mass of ruthenium to reduce costs was constructed by one-step hydrothermal method with hard template and co-assembled strategy, consisting of RuO_(2) core and ruthenium nanoparticles(Ru NPs) in carbon shell. The Ru NPs were uniformly assembled in the carbon layer, which not only improved the electronic conductivity but also provided more active centers to enhance the pseudocapacitance. The RuO_(2) core further enhanced the material’s energy storage capacity. Excellent capacitance storage(318.5 F·g^(-1)at 0.5 A·g^(-1)), rate performance(64.4%) from 0.5 A·g^(-1)to 20 A·g^(-1), and cycling stability(92.3% retention after 5000 cycles) were obtained by adjusting Ru loading to 0.92%(mass). It could be attributed to the wider pore size distribution in the micropores which increased the transfer of electrons and protons. The symmetrical supercapacitor device based on RuO_(2)@Ru/HCs could successfully light up the LED lamp. Therefore, our work verified that interfacial modification of RuO_(2) and carbon could bring attractive insights into energy density for nextgeneration supercapacitors.展开更多
This study presents an unexpected finding that the cis isomer of β-thio-Asp exhibits higher ligation ac-tivity than the trans isomer.This discovery sheds light on the intricate nature of native chemical ligation and ...This study presents an unexpected finding that the cis isomer of β-thio-Asp exhibits higher ligation ac-tivity than the trans isomer.This discovery sheds light on the intricate nature of native chemical ligation and highlights the importance of factors beyond the steric effects of the side chain in modulating ligation activity.展开更多
Four new complexes RE(ABMF)2AA(RE=Sm, Eu, Tb, Dy) were synthesized by the reaction of RECl3·6H2O with acrylic acid(HAA) and 1-(2-furyl)-3-phenyl-1,3-propanedione(ABMF).The copolymerization of the rare e...Four new complexes RE(ABMF)2AA(RE=Sm, Eu, Tb, Dy) were synthesized by the reaction of RECl3·6H2O with acrylic acid(HAA) and 1-(2-furyl)-3-phenyl-1,3-propanedione(ABMF).The copolymerization of the rare earth complexes with methyl methacrylate was studied by using 2,2-azobis-isobutyronitrile as an initiator.The composition and structure of the four complexes were characterized by elemental analysis, UV-vis and FTIR.The glass transition temperature and molecular weight of the copolymers were determined.Photolu-minescent measurement showed that ligand ABMF could efficiently transfer the energy to Sm^3+ and Eu^3+ ions in the complexes and sensitize the luminescence of the rare earth ions, but could not sensitize Tb^3+ and Dy^3+ ions.As a result, both Sm^3+ and Eu^3+ complexes emitted the characteristic fluorescence of Sm^3+ and Eu3+ ions due to the f-f transitions.The four copolymers could emit strong fluorescence of the rare earth ions.展开更多
Tungstophosphoric acid (HPW) catalyst supported on the neural alumina was studied. It was prepared by means of an equilibrium and incipient wetness impregnation technique. Solution of HPW in 50% V/V ethanol-water wa...Tungstophosphoric acid (HPW) catalyst supported on the neural alumina was studied. It was prepared by means of an equilibrium and incipient wetness impregnation technique. Solution of HPW in 50% V/V ethanol-water was used to impregnate Al2O3 at 25℃. It was found that the catalyst containing 30% PW by calcination at 500℃ showed a higher catalytic activity in the synthesis of acetals and/or ketals. In the following condition, that is, the molar ratio of aldehyde/ketone to glycol being 1:1.5, the mass fraction of the catalyst used was 0.5%, and the reaction time was 1.0 h; the yields of ketals and acetals could reach up to 60.5%-86.7%. Moreover, it could be easily recovered and reused.展开更多
Magnesium ion-exchanged a-zirconium phosphates(Mg-α-ZrP) with particle sizes of 600 and 80 nm were prepared through the sealed ion-exchange and one-step hydrothermal synthesis methods, respectively. It was found that...Magnesium ion-exchanged a-zirconium phosphates(Mg-α-ZrP) with particle sizes of 600 and 80 nm were prepared through the sealed ion-exchange and one-step hydrothermal synthesis methods, respectively. It was found that larger particles of Mg-α-ZrP had a higher load-carrying capacity than that of smaller particles, whereas smaller Mg-α-ZrP particles had better anti-wear properties than that of larger Mg-α-ZrP particles under mild loads. The correlation between the particle size of the sample and the surface roughness of the friction pair thus seems to be a key factor influencing the performance.展开更多
A new Cd(Ⅱ) coordination polymer, namely, [Cd(1,3-bip)(3,5-pdc)]n (1,3-bip = 1,3-bis(imidazol)propane and 3,5-pdc = pyridine-3,5-dicarboxylic acid) has been synthesized under hydrothermal conditions. Compou...A new Cd(Ⅱ) coordination polymer, namely, [Cd(1,3-bip)(3,5-pdc)]n (1,3-bip = 1,3-bis(imidazol)propane and 3,5-pdc = pyridine-3,5-dicarboxylic acid) has been synthesized under hydrothermal conditions. Compound 1 was characterized by infrared spectrum, elemental analysis, powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction analysis. It crystallizes in monoclinic, space group P21/c with a = 1.40178(7), b = 1.72502(12), c = 1.41635(6) ran, β = 92.653(4)°, V = 3.4212(3) nm3, Z = 4, C16HIsCdNsO4, Mr = 453.73, Dc = 1.762 g/cm3, F(000) = 1808,μ = 1.310 mm1, R = 0.0899 and wR = 0.1945. In compound 1, each 3,5-pdc ligand links three Cd(lI) ions and each Cd(Ⅱ) attaches to bip ligands to form a complicated 2D double-layer structure. In addition, the thermal stability and luminescent property of 1 have been studied in the solid state at room temperature.展开更多
A new coordination polymer,{[Ag2(bpp)2(H2O)2]·bpdc·3H2O}n,derived from the ligand biphenyl-4,4'-dicarboxylic acid(H2bpdc),has been obtained through a hydrothermal technique(bpp = l,3-bis(4-pyridyl)...A new coordination polymer,{[Ag2(bpp)2(H2O)2]·bpdc·3H2O}n,derived from the ligand biphenyl-4,4'-dicarboxylic acid(H2bpdc),has been obtained through a hydrothermal technique(bpp = l,3-bis(4-pyridyl)propane).Its single-crystal structure has been characterized by single-crystal X-ray diffraction,powder XRD,FT-IR,TGA and elemental analysis techniques.The single-crystal X-ray diffraction reveals that complex 1 consists of 1D infinite[Ag(bpp)(H2O)]n^(n+)cationic chains,2D anionic layer constructed by bpdc anions and free water which provide charge compensation in the crystal structure.The 1D infinite[Ag(bpp)(H2O)]n^(n+) cationic chains and 2D anionic layer are further stacked in-ABAB- fashion through intermolecular H-bonding to form a 3D sandwich-like framework.In addition,the luminescent property of complex 1 in the solid state at room temperature was investigated.展开更多
The conversion coating was formed by dipping AA6061 in a fluorotitanate/zirconate acid and amino trimethylene phosphonic acid (ATMP) solution at room temperature. The formation process and the anti-corrosion perform...The conversion coating was formed by dipping AA6061 in a fluorotitanate/zirconate acid and amino trimethylene phosphonic acid (ATMP) solution at room temperature. The formation process and the anti-corrosion performance of the conversion coating were investigated using electrochemical test and salt spray test (SST), respectively. The electrochemical test shows that the Zr/Ti and ATMP coating improves the corrosion resistance of AA6061 as good as the chromate (VI) coating. But the results of SST show that the corrosion resistance of Zr/Ti and ATMP coating is not as good as the chromate (VI) coating. The corrosion area is less than 2% after 72 h.展开更多
The corrosion behavior of hot dip galvanized steel pretrvated with bis-[triethoxysilylpropyl] tetrasulfide (BTESPT) modified with alumina particles was studied. The corrosion resistance of the passiving films was ev...The corrosion behavior of hot dip galvanized steel pretrvated with bis-[triethoxysilylpropyl] tetrasulfide (BTESPT) modified with alumina particles was studied. The corrosion resistance of the passiving films was evaluated by Tafel polarization curve and electrochemical impedance spectroscopy. The films formed on the galvanized steel substrate were characterized by Fourier transform infrared spectroscopy and energy dispersive X-ray spectrometry. The surface morphology of the treated hot dip galvanized steel samples was observed by Field Emission Scanning Electron Microscope. The results show that the pretrvatments on the basis of silane films modified with nanoalumina particles have reduced both anodic and cathodic current densities, and increased total impedance in the measured frequency, consequently, improving corrosion protection for hot dip galvanized steel during immersion in NaCl solutions compared to chromate films and silane films.展开更多
This study analyzed the concentrations and chemical forms of Zn,Cu,Pb,Sb,Cd and Mn in airborne particles,road dusts and soils collected along three expressways in Jiangxi Province,China,with different traffic densitie...This study analyzed the concentrations and chemical forms of Zn,Cu,Pb,Sb,Cd and Mn in airborne particles,road dusts and soils collected along three expressways in Jiangxi Province,China,with different traffic densities,and identified the levels and sources of heavy metal contamination.The concentrations of Zn,Cu,Pb,Sb,and Cd except Mn in airborne particles,road dusts and soils were all in direct proportion to traffic volume.Cd concentrations were low compared with other metals.For instance,the concentrations of Zn,Cu,Pb,Sb,Mn and Cd were 6.6,0.7,2.2,0.1,0.1 and 0.1μg·m-3in PM10along the Changjiu Expressway,792.8,241.4,248.3,9.6,340.5and 8.0 mg·kg-1in road dusts,and 201.1,143.2,59.5,9.5,338.9 and 2.3 mg·kg-1in soils,respectively,but in the case of the ratio of concentration to the environmental background value,most serious contamination was caused by Cd.The sources of the heavy metals were judged by comparisons of the chemical forms of the heavy metals in different environmental media.Pb and Mn in airborne particles were both derived from traffic;Pb in road dusts and soils resulted mainly from the use of leaded gasoline in the past;and Mn in road dusts and soils was derived from parent rocks.Zn,Cu,Sb and Cd in airborne particles,road dusts and soils were derived primarily from traffic,and differences in chemical forms of the heavy metals in different media were due to the interaction between heavy metals in airborne particles and organic matter and other surfaces in road dusts and soils.We also discussed the change of chemical forms of heavy metals in particles of different sizes and under different weather conditions.Bioavailability of heavy metals in airborne particles was much higher than that in road dusts and soils,especially Pb(0.676 in airborne particles,0.159 in road dusts and 0.095 in soils).展开更多
Vapor-liquid phase equilibrium data including composition,densities,molar volume and equilibrium constant of isobutanol in supercritical carbon dioxide from 313.2K to 353.2K were measured in a variable-volume visual c...Vapor-liquid phase equilibrium data including composition,densities,molar volume and equilibrium constant of isobutanol in supercritical carbon dioxide from 313.2K to 353.2K were measured in a variable-volume visual cell.The properties of critical point were obtained by extrapolation.The results showed that critical temperature,critical pressure and critical compressibility factor of CO2-isobutanol system decreased with the increase of critical CO2 content.The phase equilibrium model was established by Peng-Robinson equation of state and van der Waals-2 mixing regulation,and model parameters were determined by optimization calculation of nonlinear least square method.The correlation between calculated values and the experimental data showed good agreement.展开更多
基金supports of National Natural Science Foundation of China(22308057)Outstanding Talent Introduction Funds from Fuzhou University(0040-511175)Fuzhou University Testing Fund of precious apparatus(2023T003).
文摘Micromixing efficiency is an important parameter for evaluating the multiphase mass transfer performance and reaction efficiency of microreactors.In this work,the novel curved capillary reactor with different shapes was designed to generate Dean flow,which was used to enhance the liquid-liquid micromixing performance.The Villermaux-Dushman probe reaction was employed to characterize the micromixing performance in different curved capillary microreactors.The effects of experiment parameters such as liquid flow rate,inner diameter,tube length,and curve diameter on micromixing performance were systematically investigated.Under the optimal conditions,the minimum value of the segmentation factor XS was 0.008.It was worth noting that at the low Reynolds number(Re<30),the change of curved shape on the capillary microreactor can significantly improve the micromixing performance with XS reduced by 37.5%.Further,the correlations of segment index XS with dimensionless factor such as Reynolds number or Dean number were developed,which can be used to predict the liquid-liquid micromixing performance in capillary microreactors.
基金supported by the National Natural Science Foundation of China(21571038,22035004)the Education Department of Guizhou Province(2021312)+2 种基金the Foundation of Guizhou Province(2019-5666)the National Key R&D Program of China(2017YFA0700101)the State Key Laboratory of Physical Chemistry of Solid Surfaces(Xiamen University,202009)。
文摘Surface/interface engineering of a multimetallic nanostructure with diverse electrocatalytic properties for direct liquid fuel cells is desirable yet challenging.Herein,using visible light,a class of quaternary Pt_(1)Ag_(0.1)Bi_(0.16)Te_(0.29)ultrathin nanosheets is fabricated and used as high-performance anode electrocatalysts for formic acid-/alcohol-air fuel cells.The modified electronic structure of Pt,enhanced hydroxyl adsorption,and abundant exterior defects afford Pt_(1)Ag_(0.1)Bi_(0.16)Te_(0.29)/C high intrinsic anodic electrocatalytic activity to boost the power densities of direct formic acid-/methanol-/ethanol-/ethylene glycol-/glycerol-air fuel cells,and the corresponding peak power density of Pt_(1)Ag_(0.1)Bi_(0.16)Te_(0.29)/C is respectively 129.7,142.3,105.4,124.3,and 128.0 mW cm^(-2),considerably outperforming Pt/C.Operando in situ Fourier transform infrared reflection spectroscopy reveals that formic acid oxidation on Pt_(1)Ag_(0.1)Bi_(0.16)Te_(0.29)/C occurs via a CO_(2)-free direct pathway.Density functional theory calculations show that the presence of Ag,Bi,and Te in Pt_(1)Ag_(0.1)Bi_(0.16)Te_(0.29)suppresses CO^(*)formation while optimizing dehydrogenation steps and synergistic effect and modified Pt effectively enhance H_(2)O dissociation to improve electrocatalytic performance.This synthesis strategy can be extended to 43 other types of ultrathin multimetallic nanosheets(from ternary to octonary nanosheets),and efficiently capture precious metals(i.e.,Pd,Pt,Rh,Ru,Au,and Ag)from different water sources.
基金the financial support from the Natural Science Foundation of Chongqing(CSTB2022NSCQ-MSX0458)the State Key Laboratory of Coal Mine Disaster Dynamics and Control(2011DA105287-MS202203)+4 种基金the Joint Fund for Innovation and Development of Chongqing(CSTB2022NSCQ-LZX0030)the financial support from the National Natural Science Foundation of China(22168027 and 22308169)the financial support from the Natural Science Foundation of Chongqing(cstc2021jcyj-msxmX0741)the financial support from the National Natural Science Foundation of China(22105028)the Natural Science Foundation of Chongqing(cstc2021jcyj-msxmX0572)。
文摘Selective conversion of fructose to 1,2-propanediol(1,2-PDO)is considered as a sustainable and cost-effective alternative to petroleum-based processes,however,this approach still faces challenges associated with low efficiency and harsh reaction conditions.Here,we have successfully synthesized a novel bifunctional Ru-WO_(x)-MgO_(y) catalyst through a facile'one-pot'solvothermal method.Remarkably,this catalyst exhibits exceptional catalytic performances in the conversion of fructose to 1,2-PDO under mild reaction conditions.The yield of 1,2-PDO is up to 56.2%at 140°C for 4 h under an ultra-low hydrogen pressure of only 0.2 MPa,surpassing the reported results in recent literature(below 51%).Comprehensive characterizations and density functional theory(DFT)calculations reveal that the presence of oxygen vacancies in the Ru-WO_(x)-MgO_(y) catalyst,serving as active acidic sites,facilitates the chemoselective cleavage of C-C bonds in fructose,which leads to the generation of active intermediates and ultimately resulted in the high yield of 1,2-PDO.
基金the National Key Research and Development Program of China(2019YFA0705400)the National Natural Science Foundation of China(T2293692,21925404,22021001,21991151,and 22002036)+1 种基金the Natural Science Foundation of Fujian Province of China(2021J06001)the National Natural Science Foundation of Henan province(232300421081).
文摘Interfacial water molecules are the most important participants in the hydrogen evolution reaction(HER).Hence,understanding the behavior and role that interfacial water plays will ultimately reveal the HER mechanism.Unfortunately,investigating interfacial water is extremely challenging owing to the interference caused by bulk water molecules and complexity of the interfacial environment.Here,the behaviors of interfacial water in different cationic electrolytes on Pd surfaces were investigated by the electrochemistry,in situ core-shell nanostructure enhanced Raman spectroscopy and theoretical simulation techniques.Direct spectral evidence reveals a red shift in the frequency and a decrease in the intensity of interfacial water as the potential is shifted in the positively direction.When comparing the different cation electrolyte systems at a given potential,the frequency of the interfacial water peak increases in the specified order:Li+<Na^(+)<K^(+)<Ca^(2+)<Sr^(2+).The structure of interfacial water was optimized by adjusting the radius,valence,and concentration of cation to form the two-H down structure.This unique interfacial water structure will improve the charge transfer efficiency between the water and electrode further enhancing the HER performance.Therefore,local cation tuning strategies can be used to improve the HER performance by optimizing the interfacial water structure.
基金Supported by NSFC (No. 40276026), and the Key Science and Tech-nology Plan of The Ministry of Education of China ([2000]156-00079)
文摘Hydrochemistry of underground brines along south coast of Laizhou Bay, Shandong, China has been analyzed. Brine samples were collected from 43 wells in this area. It was considered that the brines were originated from seawater. However, whether they were formed by seawater evaporation or seawater freezing was not fully sure. We created a simple method by plotting Na/Cl vs. seawater concen-tration factor (SCF) and Ca/Mg vs. SCF to determine the brine formation geochemically. Comparison of our results to previous seawater freezing and evaporation experiments indicated that the brines were formed by seawater evaporation. The ratios of HCO3/Cl of some low salinity brines in the study area were relatively higher, indicating that the brines may have mixed with other waters after the generation. The Br/Cl ratios of the brines decreased annually in the past 20 to 30 years of exploitation, indicating down-ward permeation of the brine from which bromine was extracted.
基金Blazing A New Trail through Science and Technology Foundation" of Northwest Normal University and Educational Committee Founda
文摘Nanocrystalline cobalt powders have been prepared from aqueous solution by reducing their corresponding metal salts under suitable conditions. The experimental conditions have been studied in detail. X-ray powder diffraction patterns show that the cobalt powder is hexagonal crystallite. The average particle size of the ultrafine cobalt powder is 55 nm.
文摘In recent years,with the high rate of juvenile delinquency,people pay more attention to the moral education of students in secondary vocational colleges.Based on the framework of social learning theory,this paper explores the systematic and comprehensive application of social learning theory in the moral education course.From the cognition of the behavior to the selection and internalization of the representation of the model behavior,and finally the selective extemalization of the representation symbol to generate the behavior,the influencing factors and their utility in each stage of the production of moral behavior are analyzed step by step,assisting students to establish correct outlook on life and values,and cultivating their"key abilities."When students face a complex and diverse social environment,they can make judgments in line with the general moral standards of the society,and then seek to improve the effectiveness of the moral standards of secondary vocational students,and strive to maximize the effectiveness of moral education.
基金financially supported by the National Natural Science Foundation of China(NSFC)(Grant Nos.22175007,21975007,52172080,and 22005012)the National Natural Science Foundation for Outstanding Youth Foundation,the Fundamental Research Funds for the Central Universities,the National Program for Support of Top-notch Young Professionalsthe 111 project(Grant No.B14009).
文摘The rational synergy of chemical composition and spatial nanostructures of electrode materials play important roles in high-performance energy storage devices.Here,we designed pea-like MoS_(2)@NiS_(1.03)-carbon hollow nanofibers using a simple electrospinning and thermal treatment method.The hierarchical hollow nanofiber is composed of a nitrogen-doped carbon-coated NiS_(1.03) tube wall,in which pea-like uniformly discrete MoS_(2) nanoparticles are enclosed.As a sodium-ion battery electrode material,the MoS_(2)@NiS_(1.03)-carbon hollow nanofibers have abundant diphasic heterointerfaces,a conductive network,and appropriate volume variation-buffering spaces,which can facilitate ion diffusion kinetics,shorten the diffusion path of electrons/ion,and buffer volume expansion during Na^(+)insertion/extraction.It shows outstanding rate capacity and long-cycle performance in a sodium-ion battery.This heterogeneous hollow nanoarchitectures designing enlightens an efficacious strategy to boost the capacity and long-life stability of sodium storage performance of electrode materials.
基金supported financially by the National Natural Science Foundation of China(Nos.21832002,21808063,22002043,21872050)。
文摘The depolymerization and upgrading of lignin from raw biomass,while keeping cellulose intact is important in biorefinery and various metal-based catalysts have been used in reductive catalytic fractionation,a key method in"lignin-first"strategy,Recently,we found that a core-shell structured Co@CoO catalyst with CoO shell as the real active site had excellent performance in the hydrogenolysis of 5-hydromethylfurfural to 2,5-dimethylfuran due to its unique ability to dissociate H_(2)and yield active H^(δ-)species(Xiang et al.,2022).In this work,we report a one-pot depolymerization and upgrading of lignocellulose to alkylcyclohexanols,a flavour precursor,with intact cellulose over this unique core-shell structured catalyst,Co@CoO.Lignin model compounds(β-O-4,4-O-5,α-O-4)were first used to clarify the activity of Co@CoO catalyst.Then,the one-pot conversion of various organosolv lignin(birch,pine and poplar)to alkylcyclohexanols was realized with the mass yield of alkylcyclohexanols up to25.8 wt%from birch lignin under the reaction condition of 210℃,1 MPa H_(2),16 h.Finally,the corresponding woody sawdusts were used as feedstocks and found that the Co@CoO catalyst indeed preferentially depolymerized and upgraded the lignin part and obtained the same alkylcyclohexanols products with the retention of cellulose-rich pulp.The collected alkylcyclohexanols were further esterified to obtain valueadded esters,which can be used as flavors.This work will inspire the design of new efficient metal oxide catalysts in lignin fractionation and depolymerization to high-value-added chemicals with intact cellulose.
基金supported by Jinan Mingzhu Co., Ltd (HX20200364)。
文摘Hollow core-shell structure nanomaterials have been broadly used in energy storage, catalysis, reactor,and other fields due to their unique characteristics, including the synergy between different materials,a large specific surface area, small density, large charge carrying capacity and so on. However, their synthesis processes were mostly complicated, and few researches reported one-step encapsulation of different valence states of precious metals in carbon-based materials. Hence, a novel hollow core-shell nanostructure electrode material, RuO_(2)@Ru/HCs, with a lower mass of ruthenium to reduce costs was constructed by one-step hydrothermal method with hard template and co-assembled strategy, consisting of RuO_(2) core and ruthenium nanoparticles(Ru NPs) in carbon shell. The Ru NPs were uniformly assembled in the carbon layer, which not only improved the electronic conductivity but also provided more active centers to enhance the pseudocapacitance. The RuO_(2) core further enhanced the material’s energy storage capacity. Excellent capacitance storage(318.5 F·g^(-1)at 0.5 A·g^(-1)), rate performance(64.4%) from 0.5 A·g^(-1)to 20 A·g^(-1), and cycling stability(92.3% retention after 5000 cycles) were obtained by adjusting Ru loading to 0.92%(mass). It could be attributed to the wider pore size distribution in the micropores which increased the transfer of electrons and protons. The symmetrical supercapacitor device based on RuO_(2)@Ru/HCs could successfully light up the LED lamp. Therefore, our work verified that interfacial modification of RuO_(2) and carbon could bring attractive insights into energy density for nextgeneration supercapacitors.
基金the CAMS Innovation Fund for Medical Sciences (CIFMS,No.2021-I2M-1-026)the National Key R & D Program of China (No.2018YFE0111400)+5 种基金the NIH Research Project Grant Program (No.R01 EB025892)the National Natural Science Foundation of China (the Training Program of the Major Research Plan,No.91853120)the National Major Scientific and Technological Special Project of China (Nos.2018ZX09711001-005 and 2018ZX09711001-013)the State Key Laboratory of Bioactive Substance and Function of Natural Medicines,Institute of Materia Medicathe Biomedical High Performance Computing Platform,Chinese Academy of Medical Sciences,the Chinese Academy of Medical SciencesPeking Union Medical College for funding and support
文摘This study presents an unexpected finding that the cis isomer of β-thio-Asp exhibits higher ligation ac-tivity than the trans isomer.This discovery sheds light on the intricate nature of native chemical ligation and highlights the importance of factors beyond the steric effects of the side chain in modulating ligation activity.
基金supported by the Leaders Project of Inner Mongolia in their chosen field of learning (20041001)Chun-Hui Cooperated Project for the Chinese Ministry of Education (Z2005-2-01001)
文摘Four new complexes RE(ABMF)2AA(RE=Sm, Eu, Tb, Dy) were synthesized by the reaction of RECl3·6H2O with acrylic acid(HAA) and 1-(2-furyl)-3-phenyl-1,3-propanedione(ABMF).The copolymerization of the rare earth complexes with methyl methacrylate was studied by using 2,2-azobis-isobutyronitrile as an initiator.The composition and structure of the four complexes were characterized by elemental analysis, UV-vis and FTIR.The glass transition temperature and molecular weight of the copolymers were determined.Photolu-minescent measurement showed that ligand ABMF could efficiently transfer the energy to Sm^3+ and Eu^3+ ions in the complexes and sensitize the luminescence of the rare earth ions, but could not sensitize Tb^3+ and Dy^3+ ions.As a result, both Sm^3+ and Eu^3+ complexes emitted the characteristic fluorescence of Sm^3+ and Eu3+ ions due to the f-f transitions.The four copolymers could emit strong fluorescence of the rare earth ions.
基金This work was supported in part by the Combined Project between the Educational Commission and the Economic Com-mission of Gansu Province (No. 99CX-04)the Natural Science Foundation of Gansu Province (No. 3ZS041-A25-028),the Invention Project of Science & Technology, China (No. KJCXGC-01, NWNU).
文摘Tungstophosphoric acid (HPW) catalyst supported on the neural alumina was studied. It was prepared by means of an equilibrium and incipient wetness impregnation technique. Solution of HPW in 50% V/V ethanol-water was used to impregnate Al2O3 at 25℃. It was found that the catalyst containing 30% PW by calcination at 500℃ showed a higher catalytic activity in the synthesis of acetals and/or ketals. In the following condition, that is, the molar ratio of aldehyde/ketone to glycol being 1:1.5, the mass fraction of the catalyst used was 0.5%, and the reaction time was 1.0 h; the yields of ketals and acetals could reach up to 60.5%-86.7%. Moreover, it could be easily recovered and reused.
基金Funded by the Key Program of National Natural Science Foundation of China(No.21436008)the General Program of National Natural Science Foundation of China(No.51372162)+1 种基金Young Scientists Fund of the National Natural Science Foundation of China(No.21506145)the Natural Science Foundation for Young Scientists of Shanxi Province,China(No.2015021032)
文摘Magnesium ion-exchanged a-zirconium phosphates(Mg-α-ZrP) with particle sizes of 600 and 80 nm were prepared through the sealed ion-exchange and one-step hydrothermal synthesis methods, respectively. It was found that larger particles of Mg-α-ZrP had a higher load-carrying capacity than that of smaller particles, whereas smaller Mg-α-ZrP particles had better anti-wear properties than that of larger Mg-α-ZrP particles under mild loads. The correlation between the particle size of the sample and the surface roughness of the friction pair thus seems to be a key factor influencing the performance.
基金Supported by the National Natural Science Foundation of China(No.21373132)the Science Foundation of Education Department of Shaanxi Provincial Government(No.12JK0637)
文摘A new Cd(Ⅱ) coordination polymer, namely, [Cd(1,3-bip)(3,5-pdc)]n (1,3-bip = 1,3-bis(imidazol)propane and 3,5-pdc = pyridine-3,5-dicarboxylic acid) has been synthesized under hydrothermal conditions. Compound 1 was characterized by infrared spectrum, elemental analysis, powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction analysis. It crystallizes in monoclinic, space group P21/c with a = 1.40178(7), b = 1.72502(12), c = 1.41635(6) ran, β = 92.653(4)°, V = 3.4212(3) nm3, Z = 4, C16HIsCdNsO4, Mr = 453.73, Dc = 1.762 g/cm3, F(000) = 1808,μ = 1.310 mm1, R = 0.0899 and wR = 0.1945. In compound 1, each 3,5-pdc ligand links three Cd(lI) ions and each Cd(Ⅱ) attaches to bip ligands to form a complicated 2D double-layer structure. In addition, the thermal stability and luminescent property of 1 have been studied in the solid state at room temperature.
基金supported by the National Natural Science Foundation of China(No.21373132)the Foundation of Shaanxi university of technology(No.SLGKY15-36)
文摘A new coordination polymer,{[Ag2(bpp)2(H2O)2]·bpdc·3H2O}n,derived from the ligand biphenyl-4,4'-dicarboxylic acid(H2bpdc),has been obtained through a hydrothermal technique(bpp = l,3-bis(4-pyridyl)propane).Its single-crystal structure has been characterized by single-crystal X-ray diffraction,powder XRD,FT-IR,TGA and elemental analysis techniques.The single-crystal X-ray diffraction reveals that complex 1 consists of 1D infinite[Ag(bpp)(H2O)]n^(n+)cationic chains,2D anionic layer constructed by bpdc anions and free water which provide charge compensation in the crystal structure.The 1D infinite[Ag(bpp)(H2O)]n^(n+) cationic chains and 2D anionic layer are further stacked in-ABAB- fashion through intermolecular H-bonding to form a 3D sandwich-like framework.In addition,the luminescent property of complex 1 in the solid state at room temperature was investigated.
基金supported by the Science and Technology Plan Project of Liaoning Province,China(No.2006221011).
文摘The conversion coating was formed by dipping AA6061 in a fluorotitanate/zirconate acid and amino trimethylene phosphonic acid (ATMP) solution at room temperature. The formation process and the anti-corrosion performance of the conversion coating were investigated using electrochemical test and salt spray test (SST), respectively. The electrochemical test shows that the Zr/Ti and ATMP coating improves the corrosion resistance of AA6061 as good as the chromate (VI) coating. But the results of SST show that the corrosion resistance of Zr/Ti and ATMP coating is not as good as the chromate (VI) coating. The corrosion area is less than 2% after 72 h.
基金the National Natural Science Foundation of China(No.50674022).
文摘The corrosion behavior of hot dip galvanized steel pretrvated with bis-[triethoxysilylpropyl] tetrasulfide (BTESPT) modified with alumina particles was studied. The corrosion resistance of the passiving films was evaluated by Tafel polarization curve and electrochemical impedance spectroscopy. The films formed on the galvanized steel substrate were characterized by Fourier transform infrared spectroscopy and energy dispersive X-ray spectrometry. The surface morphology of the treated hot dip galvanized steel samples was observed by Field Emission Scanning Electron Microscope. The results show that the pretrvatments on the basis of silane films modified with nanoalumina particles have reduced both anodic and cathodic current densities, and increased total impedance in the measured frequency, consequently, improving corrosion protection for hot dip galvanized steel during immersion in NaCl solutions compared to chromate films and silane films.
文摘This study analyzed the concentrations and chemical forms of Zn,Cu,Pb,Sb,Cd and Mn in airborne particles,road dusts and soils collected along three expressways in Jiangxi Province,China,with different traffic densities,and identified the levels and sources of heavy metal contamination.The concentrations of Zn,Cu,Pb,Sb,and Cd except Mn in airborne particles,road dusts and soils were all in direct proportion to traffic volume.Cd concentrations were low compared with other metals.For instance,the concentrations of Zn,Cu,Pb,Sb,Mn and Cd were 6.6,0.7,2.2,0.1,0.1 and 0.1μg·m-3in PM10along the Changjiu Expressway,792.8,241.4,248.3,9.6,340.5and 8.0 mg·kg-1in road dusts,and 201.1,143.2,59.5,9.5,338.9 and 2.3 mg·kg-1in soils,respectively,but in the case of the ratio of concentration to the environmental background value,most serious contamination was caused by Cd.The sources of the heavy metals were judged by comparisons of the chemical forms of the heavy metals in different environmental media.Pb and Mn in airborne particles were both derived from traffic;Pb in road dusts and soils resulted mainly from the use of leaded gasoline in the past;and Mn in road dusts and soils was derived from parent rocks.Zn,Cu,Sb and Cd in airborne particles,road dusts and soils were derived primarily from traffic,and differences in chemical forms of the heavy metals in different media were due to the interaction between heavy metals in airborne particles and organic matter and other surfaces in road dusts and soils.We also discussed the change of chemical forms of heavy metals in particles of different sizes and under different weather conditions.Bioavailability of heavy metals in airborne particles was much higher than that in road dusts and soils,especially Pb(0.676 in airborne particles,0.159 in road dusts and 0.095 in soils).
文摘Vapor-liquid phase equilibrium data including composition,densities,molar volume and equilibrium constant of isobutanol in supercritical carbon dioxide from 313.2K to 353.2K were measured in a variable-volume visual cell.The properties of critical point were obtained by extrapolation.The results showed that critical temperature,critical pressure and critical compressibility factor of CO2-isobutanol system decreased with the increase of critical CO2 content.The phase equilibrium model was established by Peng-Robinson equation of state and van der Waals-2 mixing regulation,and model parameters were determined by optimization calculation of nonlinear least square method.The correlation between calculated values and the experimental data showed good agreement.