This work adopts a multi⁃step etching⁃heat treatment strategy to prepare porous silicon microsphere com⁃posite with Sb⁃Sn surface modification and carbon coating(pSi/Sb⁃Sn@C),using industrial grade SiAl alloy micro⁃sp...This work adopts a multi⁃step etching⁃heat treatment strategy to prepare porous silicon microsphere com⁃posite with Sb⁃Sn surface modification and carbon coating(pSi/Sb⁃Sn@C),using industrial grade SiAl alloy micro⁃spheres as a precursor.pSi/Sb⁃Sn@C had a 3D structure with bimetallic(Sb⁃Sn)modified porous silicon micro⁃spheres(pSi/Sb⁃Sn)as the core and carbon coating as the shell.Carbon shells can improve the electronic conductivi⁃ty and mechanical stability of porous silicon microspheres,which is beneficial for obtaining a stable solid electrolyte interface(SEI)film.The 3D porous core promotes the diffusion of lithium ions,increases the intercalation/delithia⁃tion active sites,and buffers the volume expansion during the intercalation process.The introduction of active met⁃als(Sb⁃Sn)can improve the conductivity of the composite and contribute to a certain amount of lithium storage ca⁃pacity.Due to its unique composition and microstructure,pSi/Sb⁃Sn@C showed a reversible capacity of 1247.4 mAh·g^(-1) after 300 charge/discharge cycles at a current density of 1.0 A·g^(-1),demonstrating excellent rate lithium storage performance and enhanced electrochemical cycling stability.展开更多
An eco-friendly superhydrophobic protective film(DTMS/TEOS silane film)was fabricated on sintered NdFeB substrate through the utilization of electrochemically assisted deposition technology.The structure,properties,an...An eco-friendly superhydrophobic protective film(DTMS/TEOS silane film)was fabricated on sintered NdFeB substrate through the utilization of electrochemically assisted deposition technology.The structure,properties,and film-forming mechanism of dodecyltrime-thoxysilane(DTMS)/tetraethoxysilane(TEOS)silane films were comprehensively analyzed using Fourier transform infrared spectroscopy(FT-IR),scanning electron microscopy(SEM),X-ray photoelectron spectroscopy(XPS),potentiodynamic polarization curves and electrochemical impedance spectroscopy(EIS).Based on the test results,it can be determined that this film has a superhydrophobic property with a hydrophobicity angle of 152°.This special property can be attributed to the long alkyl chains in the DTMS molecule,the rough morphology,and the low surface energy of the DTMS/TEOS silane film.The surface of sintered NdFeB is coated with a layered three-dimensional network silane film that forms through the condensation of silanol substances.This film provides excellent corrosion resistance to the sintered NdFeB substrate,reducing its corrosion current density to 2.02×10~(-6)A/cm~2.Moreover,the impact of film on the magnetic characteristics of sintered NdFeB was assessed and found to be minimal.展开更多
In 1978, Professor Songshou Jin, a Chinese prestigious physical chemist, established Institute of Catalysis, Hangzhou University, the forerunner of Institute of Catalysis, Zhejiang University. In 1998, the current Ins...In 1978, Professor Songshou Jin, a Chinese prestigious physical chemist, established Institute of Catalysis, Hangzhou University, the forerunner of Institute of Catalysis, Zhejiang University. In 1998, the current Institute of Catalysis was re-established through the merger of Zhejiang University and Hangzhou University et al. During the past forty years, researchers in Institute of Catalysis had always paid much attention to the combination of fundamental researches and industrial applications under the lead of Songshou Jin, Xiaoming Zheng, Weimin Lu, Hui Lou, and Yong Wang. The major research interest includes:(1) basic application research and exploitation of catalysts and catalytic process regarding conversion of biomass, methane, syngas and carbon dioxide;(2) development of catalysts and reaction apparatus for industrial hazardous gas, indoor gas, vehicle emissions and oil smoke from hotels and restaurants;(3) synthesis, characterization of functional materials and their applications in the green synthesis in fields of medicine, pesticide and fine chemical;(4) heterogeneous and homogeneous catalytic reaction kinetics and surface chemistry;(5) catalytic researches regarding military project.展开更多
A series of CeO_(2)-TiO_(2)mixed oxides supports with various Ce/Ti molar ratio were synthesized by modified coprecipitation method. The corresponding Pt loaded(0.5 wt% Pt) catalysts were prepared by electronless depo...A series of CeO_(2)-TiO_(2)mixed oxides supports with various Ce/Ti molar ratio were synthesized by modified coprecipitation method. The corresponding Pt loaded(0.5 wt% Pt) catalysts were prepared by electronless deposition method and evaluated for the deep oxidation of n-hexane as a model VOCs. The results show that the CeO_(2)and TiOxnanoparticles can highly disperse into each other and form Ce_(2)Ti_(2)O_(7)solid solution with appropriate Ce/Ti molar ratio, which significantly improves their redox ability by enhancing the interaction between CeO_(2)and TiO_(x). The dispersibility of Pt species can also be adjusted by altering the Ce/Ti molar ratio, and Pt/CeTi-2/1 catalyst with Ce/Ti molar ratio of 2:1 exhibits the best Pt dispersibility that Pt species mainly exist as Pt single atoms. The high dispersion of Pt species in the Pt/CeO_(2)-TiO_(2)catalysts would promote the catalytic activity of VOCs oxidation with low T90% values(1000 ppm, GHSV = 15,000 h^(-1)), such as for n-hexane degradation with T90% of 139℃. The characterizations reveal that the superior activity is mainly related to possessing the more Pt2+species,adsorbed oxygen species and higher low-temperature reducibility owing to the strong interaction between highly dispersed Pt species and CeO_(2)-TiO_(2)as well as the promoted migration of lattice oxygen by the formation of more Ce_(2)Ti_(2)O_(7)species. Furthermore, the Pt/CeTi-2/1 catalyst also exhibits excellent stability for chlorinated and other non-chlorinated VOCs oxidation, making it very promising for real application under various operating conditions.展开更多
The solid electrolyte interphase(SEI)with strong mechanical strength and high ion conductivity is highly desired for Li metal batteries,especially for harsh anode-free batteries.Herein,we report a pragmatic approach t...The solid electrolyte interphase(SEI)with strong mechanical strength and high ion conductivity is highly desired for Li metal batteries,especially for harsh anode-free batteries.Herein,we report a pragmatic approach to the in-situ construction of high-quality SEI by applying synergistic additives of Li NO_(3)and ethylene sulfite(ES)in the electrolyte.The obtained SEI exhibits a high average Young’s modulus(9.02GPa)and exchanging current density(4.59 mA cm^(-2)),which are 3.0 and 1.2 times as large as those using the sole additive of LiNO_(3),respectively.With this improved SEI,Li-dendrite growth and side reactions are effectively suppressed,leading to an ultra-high Coulombic efficiency(CE)of 99.7%for Li plating and stripping.When applying this improved electrolyte in full cells,it achieves a high capacity retention of 89.7%for over 150 cycles in a LiFePO_(4)||Li battery(~12 mg cm^(-2)cathode,50μm Li)and of 44.5%over 100 cycles in a LiFePO_(4)||Cu anode-free battery.展开更多
The surface properties of catalysts determine the intrinsic activity and adaptability.Ruthenium is regarded as a potential candidate to substitute platinum for water electrolysis due to the low cost and analogous elec...The surface properties of catalysts determine the intrinsic activity and adaptability.Ruthenium is regarded as a potential candidate to substitute platinum for water electrolysis due to the low cost and analogous electronic structures while it suffers from severe dissolution and stability problems.Herein,the modification of Ru/C with atomically dispersed cobalt atoms is achieved via a simple thermal doping method.The newly formed amorphous shell with Ru-Co sites on the Ru/C catalyst improved the hydrogen evolution reaction activity and stability significantly.Impressively,the obtained Co1Ru@Ru/CN_(x)catalyst exhibited an overpotential as low as 30 mV at 10 mA cm^(-2)in an alkaline medium,which is among the best HER catalysts reported so far.The oxygen oxophile Co prevents the fast oxidation and dissolution of Ru species,ensuring outstanding long-term durability up to 70 h.Theoretical calculations reveal that the Ru-Co coordination acts as a more active site for water dissociation than the Ru-Ru.Meanwhile,the"Ru-Co shell/Ru core"structures show high adaptability for the reaction conditions.This simple doping strategy offers prospects for scalable preparation of highly active electrocatalysts.展开更多
Selective hydrogenation of phenol to cyclohexanone is intriguing in chemical industry.Though a few catalysts with promising performances have been developed in recent years,the basic principle for catalyst design is s...Selective hydrogenation of phenol to cyclohexanone is intriguing in chemical industry.Though a few catalysts with promising performances have been developed in recent years,the basic principle for catalyst design is still missing owing to the unclear catalytic mechanism.This work tries to unravel the mechanism of phenol hydro-genation and the reasons causing the selectivity discrepancy on noble metal catalysts under mild conditions.Results show that different reaction pathways always firstly converge to the formation of cyclohexanone under mild conditions.The selectivity discrepancy mainly depends on the activity for cyclohexanone sequential hy-drogenation,in which two factors are found to be responsible,i.e.the hydrogenation energy barrier and the competitive chemisorption between phenol and cyclohexanone,if the specific co-catalyzing effect of H 2 O on Ru is not considered.Based on the above results,a quantitative descriptor,E b(one/pl)/E a,in which E a can be further correlated to the d band center of the noble metal catalyst,is proposed by the first time to roughly evaluate and predict the selectivity to cyclohexanone for catalyst screening.展开更多
^(23)Na is a nuclear magnetic resonance(NMR)-active isotope with a nuclear spin quantum number of 3/2.^(23)Na relaxation phenomenon is at the core of ^(23)Na NMR measurement and analysis.Due to the dominance of quadru...^(23)Na is a nuclear magnetic resonance(NMR)-active isotope with a nuclear spin quantum number of 3/2.^(23)Na relaxation phenomenon is at the core of ^(23)Na NMR measurement and analysis.Due to the dominance of quadrupolar interaction,the relaxation behavior of ^(23)Na is physically and mathematically more complex than that of a typical spin-1/2 isotope.In this review,we overview the semi-classical Redfield theory for deriving the formulations of ^(23)Na relaxation.We show that the relaxation behaviors of ^(23)Na can be quantitatively described by constructing the spectral density functions based on the second-order perturbation theory.In addition,we summarize the applications of ^(23)Na relaxometry in different research fields,including biomedicine,sodium ion batteries,and quantum information processing.Because sodium is an essential element in our body,food and industrial materials,the research on sodium by ^(23)Na NMR emerges as important future directions.The theoretical and practical understandings on ^(23)Na relaxation are the step stones for mastering advanced ^(23)Na NMR techniques.展开更多
The corrosion behaviours of four kinds of rolled magnesium alloys of AZ31, AZ91, AM60 and ZK60 were studied in 1 mol/L sodium chloride solution. The results of EIS and potentiodynamic polarization show that the corros...The corrosion behaviours of four kinds of rolled magnesium alloys of AZ31, AZ91, AM60 and ZK60 were studied in 1 mol/L sodium chloride solution. The results of EIS and potentiodynamic polarization show that the corrosion resistance of the four materials is ranked as ZK60>AM60>AZ31>AZ91. The corrosion processes of the four magnesium alloys were also analyzed by SEM and energy dispersive spectroscopy(EDS). The results show that the corrosion patterns of the four alloys are localized corrosion and the galvanic couples formed by the second phase particles and the matrix are the main source of the localized corrosion of magnesium alloys. The corrosion resistance of the different magnesium alloys has direct relationship with the concentration of alloying elements and microstructure of magnesium alloys. The ratio of the β phase in AZ91 is higher than that in AZ31 and the β phase can form micro-galvanic cell with the alloy matrix, as a result, the corrosion resistance of AZ31 will be higher than AZ91. The manganese element in AM60 magnesium alloy can form the second phase particle of AlMnFe, which can reduce the Fe content in magnesium alloy matrix, purifying the microstructure of alloy, as a result, the corrosion resistance of AM60 is improved. However, due to the more noble galvanic couples of AlMnFe and matrix, the microscopic corrosion morphology of AM60 is more localized. The zirconium element in ZK60 magnesium alloy can refine grain, form stable compounds with Fe and Si, and purify the composition of alloy, which results in the good corrosion resistance of ZK60 magnesium alloy.展开更多
Catalytic transformation of glycerol to value-added products has attracted the attention of scientists all over the world. Among various transformations, selective oxidation of glycerol with molecular oxygen to dihydr...Catalytic transformation of glycerol to value-added products has attracted the attention of scientists all over the world. Among various transformations, selective oxidation of glycerol with molecular oxygen to dihydroxyacetone, glyceric acid, glyceraldehydes, and tartronic acid is challenging both from the viewpoint of academic research and industrial application. Herein, we review the recent progresses in the selective oxidation of glycerol under base-free conditions. Those catalysts widely reported for the selective oxidation of the terminal hydroxyl and secondary hydroxyl groups in glycerol, such as monometallic Au, Pt, and Pd NPs, and bimetallic Au-Pt, Au-Pd, Pt-Bi, Pt-Sb, and Pt-Cu, were compared and discussed in detail. The reaction mechanism over Pt-based catalysts, possible catalyst deactivation, and the corresponding improvements are presented. Further, the recent progresses in the continuous oxidation of glycerol in fixed bed reactors and its excellent selectivity in the formation of dihydroxyacetone are highlighted.展开更多
The effects of dietary supplementation with Clostridium butyricum on growth performance and humoral immune response in Miichthys miiuy were evaluated. One hundred and fifty Miichthys miiuy weighing approximately 200-2...The effects of dietary supplementation with Clostridium butyricum on growth performance and humoral immune response in Miichthys miiuy were evaluated. One hundred and fifty Miichthys miiuy weighing approximately 200-260 g were divided into five groups and reared in 15 tanks with closed circuiting culture system. The animals were fed 5 diets： basal diet only （control） or supplemented of the basal diet with C. butyricum at doses of 10^3 （CB1）, 10^5 （CB2）, 10^7 （CB3） or 10^9 （CB4） CFU/g. Compared with the control, the serum phenoloxidase activity was significantly increased by the supplementation （P〈0.05）, acid phosphatases activity was increased significantly （P〈0.05） at the doses of 10^9 CFU/g. Serum lysozyme activity peaked at dose of 10^7 CFU/g and in the skin mucus at dose of 10^9 CFU/g. Immunoglobulin M level in the serum and skin mucus was increased except at dose of 10^3 CFU/g （P〈0.05）. The growth at the dose of 10^9 CFU/g was higher than that of the control （P〈0.05）. It is concluded that supplementation of C. butyricum can mediate the humoral immune responses and improve the growth performance in Miichthys miiuy.展开更多
Plasma electrolytic oxidation of Mg-based AM60 alloys was investigated using 50 Hz AC anodizing technique in an alkaline borate solution,which contained a new kind of organic.The anodic film is relatively smooth with ...Plasma electrolytic oxidation of Mg-based AM60 alloys was investigated using 50 Hz AC anodizing technique in an alkaline borate solution,which contained a new kind of organic.The anodic film is relatively smooth with some micro pores and cracks,while the anodic film consists of MgO,MgAl2O4 and MgSiO3.The electrochemical behavior of anodic film was studied by electrochemical impedance spectroscopy and potentiodynamic polarization.Polarization results indicate the PEO treatment can decrease corrosion current by 3-4 magnitude compared with blank AM60 alloy.The anodic film presents a good level of corrosion protection for AM60 magnesium alloy,over 272 h of the salt spray test based on ASTM B117.The effect of micro-structure and composition on corrosion protection efficiency was also investigated.展开更多
Bentonite is a kind of natural clay with good exchanging ability. By exchanging its interlamellar cations with various soluble cations, such as quaternary ammonium cations and inorganic metal ions, the properties of n...Bentonite is a kind of natural clay with good exchanging ability. By exchanging its interlamellar cations with various soluble cations, such as quaternary ammonium cations and inorganic metal ions, the properties of natural bentonite can be greatly improved. In this study, hexadecyltrimethylammonium bromide (HDTMA), CaCl2, MgCl2, FeCl3, AlCl3 were used as organic and inorganic pillared materials respectively to produce several kinds of Ca-, Mg-, Fe-, Al-organo pillared bentonites. Sorption of reactive red X-3B on them was studied to determine their potential application as sorbents in wastewater treatment. The results showed that these pillared bentonites had much improved sorption properties, and that the dye solutions’ pH value had some effect on the performance of these inorgano-organo pillared bentonites. Isotherms of reactive X-3B on these pillared bentonites sug-gested a Langmuir-type sorption mechanism.展开更多
Abstract: The anodization of AZ91 magnesium alloy in an alkaline electrolyte of 100 g/L NaOH+20 g/L Na2B4O7·10H2O+50 g/L C6H5Na3O7·2H2O+60 g/L Na2SiO3·9H2O was studied. The corrosion resistance of the a...Abstract: The anodization of AZ91 magnesium alloy in an alkaline electrolyte of 100 g/L NaOH+20 g/L Na2B4O7·10H2O+50 g/L C6H5Na3O7·2H2O+60 g/L Na2SiO3·9H2O was studied. The corrosion resistance of the anodized films was studied by electrochemical impedance spectroscopy(EIS) and potentiodynamic polarization techniques. The microstructure of the films was examined with scanning electronic microscope(SEM) and X-ray diffractometer(XRD). The results show that, under the experimental conditions, the optimum anodizing time and the optimum anodizing current density are 40 min and 20 mA/cm2 respectively for obtaining the anodic film with high corrosion resistance. The XRD pattern shows that the components of the anodized film consist of MgO and Mg2(SiO4).展开更多
The corrosion process of AZ91D magnesium alloy in neutral 1%(mass fraction) sodium chloride aqueous solution was investigated by electrochemical noise(EN),SEM and EDX. Fractal theory was primarily used to depict the c...The corrosion process of AZ91D magnesium alloy in neutral 1%(mass fraction) sodium chloride aqueous solution was investigated by electrochemical noise(EN),SEM and EDX. Fractal theory was primarily used to depict the corrosion process of the alloy. The fast wavelet transform(FWT),as well as the fast Fourier transform(FFT),was employed to analyze the EN data. The results show that the overall corrosion process can be described by three stages. The first stage corresponds to the pit nucleation and growth; the second stage involves the growth of a passive oxide layer; and the third stage involves reactivation. With increasing immersion time,fractal dimension increases fast initially,fluctuates in the medium and increases again at last. Pitting corrosion and fractal dimension increase due to the initiation and formation of pits in the initial and the end of immersion,while depresses due to the passivation in the medium period. The results of SEM and EDX support the above conclusions.展开更多
The absorption, fluorescence and Raman spectra of Ce(NO3)(3)(phen)(2) complex were assigned and the crystal structure of the complex was studied. Meanwhile the interactions between Cc (NO3)(3) (phen)(2) and DNA were s...The absorption, fluorescence and Raman spectra of Ce(NO3)(3)(phen)(2) complex were assigned and the crystal structure of the complex was studied. Meanwhile the interactions between Cc (NO3)(3) (phen)(2) and DNA were studied by spectrum methods. As DNA was added, it is found that both the UV absorption bands of Ce(NO3)(3)(phen)(2) and the SERS bands of Ce(NO3)(3)(phen)(2) weaken evidently, while the fluorescence intensity of Ce(NO3)(3)(phen)(2) enhance dramatically. The complex compete against EB on the reaction with DNA. It is indicated by this spectrum methods that there are strong interactions between Ce(NO3)(3)(phen)(2) and DNA, and the bond mode is intercalation. The bond constant of the complex with DNA is determined to be 1.7 x 10(5).展开更多
The point of zero charge(PZC) of SiC nanoparticles was determined by means of standard potentiometric titration method, while the influences of the main technological parameters on the microstructure of electrodeposit...The point of zero charge(PZC) of SiC nanoparticles was determined by means of standard potentiometric titration method, while the influences of the main technological parameters on the microstructure of electrodeposited Ni-SiC composite film were studied and optimized. The results show that high bath pH value favors SiC nanoparticles negatively charged and high bath temperature promotes them positively charged. Under the experimental conditions, sodium dodecyl-glycol is proven to be an effective surface modification anionic surfactant for SiC nanoparticles. The results also show that the optimized Ni-SiC composite film is composed of the nanoparticles with the average grain size in the nanometer range (100 nm), and SiC nanoparticles disperse into the nickel matrix uniformly.展开更多
Visible light promoted difunctionalization of alkynes is reviewed. The difunctionalization reaction is achieved by different reagents. Radicals such as carbon(sp3), carbon(sp2), and other heteroatom(P, S, N, Se, O, an...Visible light promoted difunctionalization of alkynes is reviewed. The difunctionalization reaction is achieved by different reagents. Radicals such as carbon(sp3), carbon(sp2), and other heteroatom(P, S, N, Se, O, and halide) radicals initiated by visible light can undergo radical addition to a carbon-carbon triple bond. Upon further transformation, the desired difunctionalized products are obtained. Some organometallic complexes can be activated by visible light;the difunctionalization of alkynes is catalyzed by these species. Other reagents like 1,3-dipole precursors could also react with alkynes to give difunctionalization products;here, the 1,3-dipole derivatives are obtained by visible light photocatalysis. So far, the strategy has been succeeded in the formation of C–C bonds and C–X bonds. Several valuable chemical skeletons have been constructed under mild conditions. However, high regio-and stereoselectivities in some direct difunctionalization methodologies are yet to be achieved.展开更多
A cyclomaltoheptaose--cyclodextrin (-CD) crosslinked chitosan derivative via glyoxal or glutaraldehyde was prepared. The structures of -CD crosslined chitosan with glyoxal or glutaraldehyde were characterized by IR s...A cyclomaltoheptaose--cyclodextrin (-CD) crosslinked chitosan derivative via glyoxal or glutaraldehyde was prepared. The structures of -CD crosslined chitosan with glyoxal or glutaraldehyde were characterized by IR spectra. The surface morphology of the -CD crosslinked chitosan particles was examined using a scanning electron microscope. The immobilization capacity of ?CD on chitosan was affected on the weight ratio of -CD/chitosan, the utilization amount of crosslinking agent, the acidity of the reaction system and the temperature. The adsorption for nicotine indicated that the chitosan--CD was a good adsorbent.展开更多
pH-responsive-chitosan nanoparticles for the control release of protein drug were prepared by combining two-step crosslinking method, in which chitosan was subsequently crosslinked by sodium tripolyphosphate （TPP） a...pH-responsive-chitosan nanoparticles for the control release of protein drug were prepared by combining two-step crosslinking method, in which chitosan was subsequently crosslinked by sodium tripolyphosphate （TPP） and glycidoxypropyltrimethoxysilane （GPTMS）. Compared with TPP crosslinked chitosan particles, the two-step crosslinked nanoparticles were not only pH-responsive but also more stable in wide pH range. Fluorescein isothiocyanate （FITC） labeled anti-human-IgG antibody was used as a model protein drug for evaluating the control release profile of the nano-carrier. The amount of released antibody increased from 5.6% to 50% when the pH of solution shifted from 7.4 to 6.0. The results suggest the possible application of the nanoparticles as pH- responsive drug delivery materials.展开更多
文摘This work adopts a multi⁃step etching⁃heat treatment strategy to prepare porous silicon microsphere com⁃posite with Sb⁃Sn surface modification and carbon coating(pSi/Sb⁃Sn@C),using industrial grade SiAl alloy micro⁃spheres as a precursor.pSi/Sb⁃Sn@C had a 3D structure with bimetallic(Sb⁃Sn)modified porous silicon micro⁃spheres(pSi/Sb⁃Sn)as the core and carbon coating as the shell.Carbon shells can improve the electronic conductivi⁃ty and mechanical stability of porous silicon microspheres,which is beneficial for obtaining a stable solid electrolyte interface(SEI)film.The 3D porous core promotes the diffusion of lithium ions,increases the intercalation/delithia⁃tion active sites,and buffers the volume expansion during the intercalation process.The introduction of active met⁃als(Sb⁃Sn)can improve the conductivity of the composite and contribute to a certain amount of lithium storage ca⁃pacity.Due to its unique composition and microstructure,pSi/Sb⁃Sn@C showed a reversible capacity of 1247.4 mAh·g^(-1) after 300 charge/discharge cycles at a current density of 1.0 A·g^(-1),demonstrating excellent rate lithium storage performance and enhanced electrochemical cycling stability.
基金financial support from the Public Welfare Projects of Zhejiang Province,China(No.LGG22E010002)the National Natural Science Foundation of China(Nos.52001300,52171083)。
文摘An eco-friendly superhydrophobic protective film(DTMS/TEOS silane film)was fabricated on sintered NdFeB substrate through the utilization of electrochemically assisted deposition technology.The structure,properties,and film-forming mechanism of dodecyltrime-thoxysilane(DTMS)/tetraethoxysilane(TEOS)silane films were comprehensively analyzed using Fourier transform infrared spectroscopy(FT-IR),scanning electron microscopy(SEM),X-ray photoelectron spectroscopy(XPS),potentiodynamic polarization curves and electrochemical impedance spectroscopy(EIS).Based on the test results,it can be determined that this film has a superhydrophobic property with a hydrophobicity angle of 152°.This special property can be attributed to the long alkyl chains in the DTMS molecule,the rough morphology,and the low surface energy of the DTMS/TEOS silane film.The surface of sintered NdFeB is coated with a layered three-dimensional network silane film that forms through the condensation of silanol substances.This film provides excellent corrosion resistance to the sintered NdFeB substrate,reducing its corrosion current density to 2.02×10~(-6)A/cm~2.Moreover,the impact of film on the magnetic characteristics of sintered NdFeB was assessed and found to be minimal.
文摘In 1978, Professor Songshou Jin, a Chinese prestigious physical chemist, established Institute of Catalysis, Hangzhou University, the forerunner of Institute of Catalysis, Zhejiang University. In 1998, the current Institute of Catalysis was re-established through the merger of Zhejiang University and Hangzhou University et al. During the past forty years, researchers in Institute of Catalysis had always paid much attention to the combination of fundamental researches and industrial applications under the lead of Songshou Jin, Xiaoming Zheng, Weimin Lu, Hui Lou, and Yong Wang. The major research interest includes:(1) basic application research and exploitation of catalysts and catalytic process regarding conversion of biomass, methane, syngas and carbon dioxide;(2) development of catalysts and reaction apparatus for industrial hazardous gas, indoor gas, vehicle emissions and oil smoke from hotels and restaurants;(3) synthesis, characterization of functional materials and their applications in the green synthesis in fields of medicine, pesticide and fine chemical;(4) heterogeneous and homogeneous catalytic reaction kinetics and surface chemistry;(5) catalytic researches regarding military project.
基金supported by a grant from the National Key Research and Development Program of China (2016YFC0204300)the National Nature Science Foundation of China (21477109)。
文摘A series of CeO_(2)-TiO_(2)mixed oxides supports with various Ce/Ti molar ratio were synthesized by modified coprecipitation method. The corresponding Pt loaded(0.5 wt% Pt) catalysts were prepared by electronless deposition method and evaluated for the deep oxidation of n-hexane as a model VOCs. The results show that the CeO_(2)and TiOxnanoparticles can highly disperse into each other and form Ce_(2)Ti_(2)O_(7)solid solution with appropriate Ce/Ti molar ratio, which significantly improves their redox ability by enhancing the interaction between CeO_(2)and TiO_(x). The dispersibility of Pt species can also be adjusted by altering the Ce/Ti molar ratio, and Pt/CeTi-2/1 catalyst with Ce/Ti molar ratio of 2:1 exhibits the best Pt dispersibility that Pt species mainly exist as Pt single atoms. The high dispersion of Pt species in the Pt/CeO_(2)-TiO_(2)catalysts would promote the catalytic activity of VOCs oxidation with low T90% values(1000 ppm, GHSV = 15,000 h^(-1)), such as for n-hexane degradation with T90% of 139℃. The characterizations reveal that the superior activity is mainly related to possessing the more Pt2+species,adsorbed oxygen species and higher low-temperature reducibility owing to the strong interaction between highly dispersed Pt species and CeO_(2)-TiO_(2)as well as the promoted migration of lattice oxygen by the formation of more Ce_(2)Ti_(2)O_(7)species. Furthermore, the Pt/CeTi-2/1 catalyst also exhibits excellent stability for chlorinated and other non-chlorinated VOCs oxidation, making it very promising for real application under various operating conditions.
基金supported by the National Natural Science Foundation of China(21975207,52202303)the Westlake Education Foundation,and the Zhejiang Provincial Natural Science Foundation of China(LQ21B030006)。
文摘The solid electrolyte interphase(SEI)with strong mechanical strength and high ion conductivity is highly desired for Li metal batteries,especially for harsh anode-free batteries.Herein,we report a pragmatic approach to the in-situ construction of high-quality SEI by applying synergistic additives of Li NO_(3)and ethylene sulfite(ES)in the electrolyte.The obtained SEI exhibits a high average Young’s modulus(9.02GPa)and exchanging current density(4.59 mA cm^(-2)),which are 3.0 and 1.2 times as large as those using the sole additive of LiNO_(3),respectively.With this improved SEI,Li-dendrite growth and side reactions are effectively suppressed,leading to an ultra-high Coulombic efficiency(CE)of 99.7%for Li plating and stripping.When applying this improved electrolyte in full cells,it achieves a high capacity retention of 89.7%for over 150 cycles in a LiFePO_(4)||Li battery(~12 mg cm^(-2)cathode,50μm Li)and of 44.5%over 100 cycles in a LiFePO_(4)||Cu anode-free battery.
基金support from the National Natural Science Foundation of China(21802120,21872121,and 21908189)the National Key R&D Program of China(2016YFA0202900)+3 种基金the Key R&D Project of Zhejiang Province(2020C01133)the Fundamental Research Funds for the Central Universities(G2019KY05119)the China Postdoctoral Science Foundation(2021 M692634)the Natural Science Basic Research Program of Shaanxi Province(2022JQ-118)are greatly appreciated.
文摘The surface properties of catalysts determine the intrinsic activity and adaptability.Ruthenium is regarded as a potential candidate to substitute platinum for water electrolysis due to the low cost and analogous electronic structures while it suffers from severe dissolution and stability problems.Herein,the modification of Ru/C with atomically dispersed cobalt atoms is achieved via a simple thermal doping method.The newly formed amorphous shell with Ru-Co sites on the Ru/C catalyst improved the hydrogen evolution reaction activity and stability significantly.Impressively,the obtained Co1Ru@Ru/CN_(x)catalyst exhibited an overpotential as low as 30 mV at 10 mA cm^(-2)in an alkaline medium,which is among the best HER catalysts reported so far.The oxygen oxophile Co prevents the fast oxidation and dissolution of Ru species,ensuring outstanding long-term durability up to 70 h.Theoretical calculations reveal that the Ru-Co coordination acts as a more active site for water dissociation than the Ru-Ru.Meanwhile,the"Ru-Co shell/Ru core"structures show high adaptability for the reaction conditions.This simple doping strategy offers prospects for scalable preparation of highly active electrocatalysts.
基金This work was supported by Financial support from the National Natural Science Foundation of China(21908189,21872121)the National Key R&D Program of China(2016YFA0202900)+1 种基金the Key Program supportedby theNaturalScience Foundationof ZhejiangProvince,China(LZ18B060002)the Key R&D Project of Zhejiang Province(2020C01133).
文摘Selective hydrogenation of phenol to cyclohexanone is intriguing in chemical industry.Though a few catalysts with promising performances have been developed in recent years,the basic principle for catalyst design is still missing owing to the unclear catalytic mechanism.This work tries to unravel the mechanism of phenol hydro-genation and the reasons causing the selectivity discrepancy on noble metal catalysts under mild conditions.Results show that different reaction pathways always firstly converge to the formation of cyclohexanone under mild conditions.The selectivity discrepancy mainly depends on the activity for cyclohexanone sequential hy-drogenation,in which two factors are found to be responsible,i.e.the hydrogenation energy barrier and the competitive chemisorption between phenol and cyclohexanone,if the specific co-catalyzing effect of H 2 O on Ru is not considered.Based on the above results,a quantitative descriptor,E b(one/pl)/E a,in which E a can be further correlated to the d band center of the noble metal catalyst,is proposed by the first time to roughly evaluate and predict the selectivity to cyclohexanone for catalyst screening.
基金National Natural Science Foundation of China 22275159 and 22072133.Leading Innovation and Entrepreneurship Team of Zhejiang Province 2020R01003.
文摘^(23)Na is a nuclear magnetic resonance(NMR)-active isotope with a nuclear spin quantum number of 3/2.^(23)Na relaxation phenomenon is at the core of ^(23)Na NMR measurement and analysis.Due to the dominance of quadrupolar interaction,the relaxation behavior of ^(23)Na is physically and mathematically more complex than that of a typical spin-1/2 isotope.In this review,we overview the semi-classical Redfield theory for deriving the formulations of ^(23)Na relaxation.We show that the relaxation behaviors of ^(23)Na can be quantitatively described by constructing the spectral density functions based on the second-order perturbation theory.In addition,we summarize the applications of ^(23)Na relaxometry in different research fields,including biomedicine,sodium ion batteries,and quantum information processing.Because sodium is an essential element in our body,food and industrial materials,the research on sodium by ^(23)Na NMR emerges as important future directions.The theoretical and practical understandings on ^(23)Na relaxation are the step stones for mastering advanced ^(23)Na NMR techniques.
基金Project(50471043) supported by the National Natural Science Foundation of China
文摘The corrosion behaviours of four kinds of rolled magnesium alloys of AZ31, AZ91, AM60 and ZK60 were studied in 1 mol/L sodium chloride solution. The results of EIS and potentiodynamic polarization show that the corrosion resistance of the four materials is ranked as ZK60>AM60>AZ31>AZ91. The corrosion processes of the four magnesium alloys were also analyzed by SEM and energy dispersive spectroscopy(EDS). The results show that the corrosion patterns of the four alloys are localized corrosion and the galvanic couples formed by the second phase particles and the matrix are the main source of the localized corrosion of magnesium alloys. The corrosion resistance of the different magnesium alloys has direct relationship with the concentration of alloying elements and microstructure of magnesium alloys. The ratio of the β phase in AZ91 is higher than that in AZ31 and the β phase can form micro-galvanic cell with the alloy matrix, as a result, the corrosion resistance of AZ31 will be higher than AZ91. The manganese element in AM60 magnesium alloy can form the second phase particle of AlMnFe, which can reduce the Fe content in magnesium alloy matrix, purifying the microstructure of alloy, as a result, the corrosion resistance of AM60 is improved. However, due to the more noble galvanic couples of AlMnFe and matrix, the microscopic corrosion morphology of AM60 is more localized. The zirconium element in ZK60 magnesium alloy can refine grain, form stable compounds with Fe and Si, and purify the composition of alloy, which results in the good corrosion resistance of ZK60 magnesium alloy.
基金supported by the National Natural Science Foundation of China(21773208,21473155)the Natural Science Foundation of Zhejiang Province(L12B03001)~~
文摘Catalytic transformation of glycerol to value-added products has attracted the attention of scientists all over the world. Among various transformations, selective oxidation of glycerol with molecular oxygen to dihydroxyacetone, glyceric acid, glyceraldehydes, and tartronic acid is challenging both from the viewpoint of academic research and industrial application. Herein, we review the recent progresses in the selective oxidation of glycerol under base-free conditions. Those catalysts widely reported for the selective oxidation of the terminal hydroxyl and secondary hydroxyl groups in glycerol, such as monometallic Au, Pt, and Pd NPs, and bimetallic Au-Pt, Au-Pd, Pt-Bi, Pt-Sb, and Pt-Cu, were compared and discussed in detail. The reaction mechanism over Pt-based catalysts, possible catalyst deactivation, and the corresponding improvements are presented. Further, the recent progresses in the continuous oxidation of glycerol in fixed bed reactors and its excellent selectivity in the formation of dihydroxyacetone are highlighted.
基金Project supported by the Bureau of Science and Technology of Zhejiang Province (No. 2004201), China and the Youth Fund of Ningbo City (No. 2004A620008), China
文摘The effects of dietary supplementation with Clostridium butyricum on growth performance and humoral immune response in Miichthys miiuy were evaluated. One hundred and fifty Miichthys miiuy weighing approximately 200-260 g were divided into five groups and reared in 15 tanks with closed circuiting culture system. The animals were fed 5 diets： basal diet only （control） or supplemented of the basal diet with C. butyricum at doses of 10^3 （CB1）, 10^5 （CB2）, 10^7 （CB3） or 10^9 （CB4） CFU/g. Compared with the control, the serum phenoloxidase activity was significantly increased by the supplementation （P〈0.05）, acid phosphatases activity was increased significantly （P〈0.05） at the doses of 10^9 CFU/g. Serum lysozyme activity peaked at dose of 10^7 CFU/g and in the skin mucus at dose of 10^9 CFU/g. Immunoglobulin M level in the serum and skin mucus was increased except at dose of 10^3 CFU/g （P〈0.05）. The growth at the dose of 10^9 CFU/g was higher than that of the control （P〈0.05）. It is concluded that supplementation of C. butyricum can mediate the humoral immune responses and improve the growth performance in Miichthys miiuy.
基金Project(50471043,50671095)supported by the National Natural Science Foundation of ChinaProject(2005DKA10400-Z5)supportedby the Natural Science Foundation of Ministry of Science and Technology of China
文摘Plasma electrolytic oxidation of Mg-based AM60 alloys was investigated using 50 Hz AC anodizing technique in an alkaline borate solution,which contained a new kind of organic.The anodic film is relatively smooth with some micro pores and cracks,while the anodic film consists of MgO,MgAl2O4 and MgSiO3.The electrochemical behavior of anodic film was studied by electrochemical impedance spectroscopy and potentiodynamic polarization.Polarization results indicate the PEO treatment can decrease corrosion current by 3-4 magnitude compared with blank AM60 alloy.The anodic film presents a good level of corrosion protection for AM60 magnesium alloy,over 272 h of the salt spray test based on ASTM B117.The effect of micro-structure and composition on corrosion protection efficiency was also investigated.
基金Project supported by the Scientific Research Foundation for Re-turned Overseas Scholars and the National Natural Science Founda-tion of China (No. 40576080)
文摘Bentonite is a kind of natural clay with good exchanging ability. By exchanging its interlamellar cations with various soluble cations, such as quaternary ammonium cations and inorganic metal ions, the properties of natural bentonite can be greatly improved. In this study, hexadecyltrimethylammonium bromide (HDTMA), CaCl2, MgCl2, FeCl3, AlCl3 were used as organic and inorganic pillared materials respectively to produce several kinds of Ca-, Mg-, Fe-, Al-organo pillared bentonites. Sorption of reactive red X-3B on them was studied to determine their potential application as sorbents in wastewater treatment. The results showed that these pillared bentonites had much improved sorption properties, and that the dye solutions’ pH value had some effect on the performance of these inorgano-organo pillared bentonites. Isotherms of reactive X-3B on these pillared bentonites sug-gested a Langmuir-type sorption mechanism.
基金Project(50471043) supported by the National Natural Science Foundation of China
文摘Abstract: The anodization of AZ91 magnesium alloy in an alkaline electrolyte of 100 g/L NaOH+20 g/L Na2B4O7·10H2O+50 g/L C6H5Na3O7·2H2O+60 g/L Na2SiO3·9H2O was studied. The corrosion resistance of the anodized films was studied by electrochemical impedance spectroscopy(EIS) and potentiodynamic polarization techniques. The microstructure of the films was examined with scanning electronic microscope(SEM) and X-ray diffractometer(XRD). The results show that, under the experimental conditions, the optimum anodizing time and the optimum anodizing current density are 40 min and 20 mA/cm2 respectively for obtaining the anodic film with high corrosion resistance. The XRD pattern shows that the components of the anodized film consist of MgO and Mg2(SiO4).
基金Projects(50471043, 50771092) supported by the National Natural Science Foundation of ChinaProject(2005DKA10400-Z15) supported by the National R&D Infrastructure and Facility Development Program of ChinaProject supported by Key Laboratory for Ultra-light Materials and Surface-treatment Technology of Education Ministry of China
文摘The corrosion process of AZ91D magnesium alloy in neutral 1%(mass fraction) sodium chloride aqueous solution was investigated by electrochemical noise(EN),SEM and EDX. Fractal theory was primarily used to depict the corrosion process of the alloy. The fast wavelet transform(FWT),as well as the fast Fourier transform(FFT),was employed to analyze the EN data. The results show that the overall corrosion process can be described by three stages. The first stage corresponds to the pit nucleation and growth; the second stage involves the growth of a passive oxide layer; and the third stage involves reactivation. With increasing immersion time,fractal dimension increases fast initially,fluctuates in the medium and increases again at last. Pitting corrosion and fractal dimension increase due to the initiation and formation of pits in the initial and the end of immersion,while depresses due to the passivation in the medium period. The results of SEM and EDX support the above conclusions.
文摘The absorption, fluorescence and Raman spectra of Ce(NO3)(3)(phen)(2) complex were assigned and the crystal structure of the complex was studied. Meanwhile the interactions between Cc (NO3)(3) (phen)(2) and DNA were studied by spectrum methods. As DNA was added, it is found that both the UV absorption bands of Ce(NO3)(3)(phen)(2) and the SERS bands of Ce(NO3)(3)(phen)(2) weaken evidently, while the fluorescence intensity of Ce(NO3)(3)(phen)(2) enhance dramatically. The complex compete against EB on the reaction with DNA. It is indicated by this spectrum methods that there are strong interactions between Ce(NO3)(3)(phen)(2) and DNA, and the bond mode is intercalation. The bond constant of the complex with DNA is determined to be 1.7 x 10(5).
基金Project(20203015) supported by the National Natural Science Foundation of ChinaProject supported by the State Key Laboratory for Corrosion and Protection of China
文摘The point of zero charge(PZC) of SiC nanoparticles was determined by means of standard potentiometric titration method, while the influences of the main technological parameters on the microstructure of electrodeposited Ni-SiC composite film were studied and optimized. The results show that high bath pH value favors SiC nanoparticles negatively charged and high bath temperature promotes them positively charged. Under the experimental conditions, sodium dodecyl-glycol is proven to be an effective surface modification anionic surfactant for SiC nanoparticles. The results also show that the optimized Ni-SiC composite film is composed of the nanoparticles with the average grain size in the nanometer range (100 nm), and SiC nanoparticles disperse into the nickel matrix uniformly.
基金supported by Zhejiang Provincial Natural Science Foundation of China(LR19B020001)the National Natural Science Foundation of China(21472162,21772171)the National Basic Research Program of China(2015CB856600)~~
文摘Visible light promoted difunctionalization of alkynes is reviewed. The difunctionalization reaction is achieved by different reagents. Radicals such as carbon(sp3), carbon(sp2), and other heteroatom(P, S, N, Se, O, and halide) radicals initiated by visible light can undergo radical addition to a carbon-carbon triple bond. Upon further transformation, the desired difunctionalized products are obtained. Some organometallic complexes can be activated by visible light;the difunctionalization of alkynes is catalyzed by these species. Other reagents like 1,3-dipole precursors could also react with alkynes to give difunctionalization products;here, the 1,3-dipole derivatives are obtained by visible light photocatalysis. So far, the strategy has been succeeded in the formation of C–C bonds and C–X bonds. Several valuable chemical skeletons have been constructed under mild conditions. However, high regio-and stereoselectivities in some direct difunctionalization methodologies are yet to be achieved.
文摘A cyclomaltoheptaose--cyclodextrin (-CD) crosslinked chitosan derivative via glyoxal or glutaraldehyde was prepared. The structures of -CD crosslined chitosan with glyoxal or glutaraldehyde were characterized by IR spectra. The surface morphology of the -CD crosslinked chitosan particles was examined using a scanning electron microscope. The immobilization capacity of ?CD on chitosan was affected on the weight ratio of -CD/chitosan, the utilization amount of crosslinking agent, the acidity of the reaction system and the temperature. The adsorption for nicotine indicated that the chitosan--CD was a good adsorbent.
文摘pH-responsive-chitosan nanoparticles for the control release of protein drug were prepared by combining two-step crosslinking method, in which chitosan was subsequently crosslinked by sodium tripolyphosphate （TPP） and glycidoxypropyltrimethoxysilane （GPTMS）. Compared with TPP crosslinked chitosan particles, the two-step crosslinked nanoparticles were not only pH-responsive but also more stable in wide pH range. Fluorescein isothiocyanate （FITC） labeled anti-human-IgG antibody was used as a model protein drug for evaluating the control release profile of the nano-carrier. The amount of released antibody increased from 5.6% to 50% when the pH of solution shifted from 7.4 to 6.0. The results suggest the possible application of the nanoparticles as pH- responsive drug delivery materials.
