Polycrystalline perovskite oxide particles are promising candidates for cathode materials in solid oxide fuel cells.However,their limited activity and stability pose significant challenges for practical applications.I...Polycrystalline perovskite oxide particles are promising candidates for cathode materials in solid oxide fuel cells.However,their limited activity and stability pose significant challenges for practical applications.In this study,we demonstrate a novel approach to achieve both high activity and durability in a PrBaCo_(2)O_(5+δ) catalyst through a simple epitaxial layer growth strategy.We found that an amorphous precursor of the highly durable catalyst SmBa_(0.5)Ca_(0.5)CoCuO_(5+δ) can spontaneously adhere to the surface of PrBaCo_(2)O_(5+δ) particles.Upon heat treatment,it grows along the perovskite lattice,forming a heteroepitaxial layer with just a few atomic layers thickness.This heterostructure enhances the operational stability of PrBaCo_(2)O_(5+δ) transforming a 78% decrease over 100 h into a 7% increase.After 100 h,the power output density of the cell with the modified sample is more than 500% higher than that of unmodified PrBaCo_(2)O_(5+δ.)This work presents a new strategy for fabricating heteroepitaxial layers on polycrystalline ceramic catalysts and introduces a pioneering approach for developing high-performance oxygen reduction catalysts and related materials.展开更多
Iron oxide nanoparticles(IONPs)with intrinsic peroxidase(POD)-mimic activity have gained significant attention as nanozymes.Reducing sizes of IONPs is the mostly applied strategy to boost their enzymatic activity due ...Iron oxide nanoparticles(IONPs)with intrinsic peroxidase(POD)-mimic activity have gained significant attention as nanozymes.Reducing sizes of IONPs is the mostly applied strategy to boost their enzymatic activity due to their high specific surface areas.Herein,we synthesized a series of uniformly sized IONPs ranging from3.17 to 21.2 nm,and found that POD activity of IONPs is not monotone increased by reducing their sizes,with the optimal size of 7.82 nm rather than smaller sized 3.17 nm.The reason for this unnormal phenomenon is that electronic structure also had great influence on POD activity,especially at the ultrasmall size region.Since Fe^(2+)are with higher enzymatic activity than Fe^(3+),3.17 nm IONPs although have the largest specific surface area,are prone to be oxidized,which reduced their iron content and ratio of Fe^(2+)to Fe^(3+),and consequently decreased their POD activity.By intentionally oxidized 7.82 nm IONPs in air,POD activity was obviously reduced,illustrating electronic structure cannot be overlooked.At the larger sized region ranging from 7.82 to 21.2 nm,oxidation degree of IONPs is similar,and surface electronic structure had a negligible effect on POD activity,and therefore,POD activity is predominantly influenced by specific surface area.By using the optimized 7.82 nm IONPs,tumor growth was obviously inhibited,demonstrating their potential in cancer therapeutics.Our results reveal that the designing of nanozymes should comprehensively balance their influence of surface electronic structure and specific surface area.展开更多
Nano-scale chemical inhomogeneity in surface oxide films formed on a V-and N-containing martensite stainless steel and tempering heating induced changes are investigated by a combination of synchrotron-based hard X-ra...Nano-scale chemical inhomogeneity in surface oxide films formed on a V-and N-containing martensite stainless steel and tempering heating induced changes are investigated by a combination of synchrotron-based hard X-ray Photoelectron emission spectroscopy(HAXPES)and microscopy(HAXPEEM)as well as microscopic X-ray absorption spectroscopy(μ-XAS)techniques.The results reveal the inhomogeneity in the oxide films on the micron-sized Cr_(2)N-and VN-type particles,while the inhomogeneity on the martensite matrix phase exists due to localised formation of nano-sized tempering nitride particles at 600℃.The oxide film formed on Cr_(2)N-type particles is rich in Cr_(2)O_(3) compared with that on the martensite matrix and VN-type particles.With the increase of tempering temperature,Cr_(2)O_(3) formation is faster for the oxidation of Cr in the martensite matrix than the oxidation of Cr nitride-rich particles.展开更多
Microwave was applied to roasting the zinc oxide fume obtained from fuming furnace for the removal of F and Cl. The effects of important parameters, such as roasting temperature, holding time and stirring speed, were ...Microwave was applied to roasting the zinc oxide fume obtained from fuming furnace for the removal of F and Cl. The effects of important parameters, such as roasting temperature, holding time and stirring speed, were investigated and the process conditions were optimized using response surface methodology (RSM). The results show that the effects of roasting temperature and holding time on the removal rate of F and Cl are the most significant, and the effect of stirring speed is the second. The defluorination rate reaches 92.6% while the dechlorination rate reaches 90.2%, under the process conditions of roasting temperature of 700 °C, holding time of 80 min and stirring speed of 120 r/min. The results indicate that the removal of F and Cl from fuming furnace production of zinc oxide fumes using microwave roasting process is feasible and reliable.展开更多
An important step for achieving the knowledge-based design freedom on nano-and interfacial materials is attained by elucidating the related surface and interface thermodynamics from the first principles so as to allow...An important step for achieving the knowledge-based design freedom on nano-and interfacial materials is attained by elucidating the related surface and interface thermodynamics from the first principles so as to allow engineering the microstructures for desired properties through smartly designing fabrication processing parameters.This is demonstrated for SnO2 nano-particle surfaces and also a technologically important Ag-SnO2 interface fabricated by in-situ internal oxidation.Based on defect thermodynamics,we first modeled and calculated the equilibrium surface and interface structures,and as well corresponding properties,as a function of the ambient temperature and oxygen partial pressure.A series of first principles energetics calculations were then performed to construct the equilibrium surface and interface phase diagrams,to describe the environment dependence of the microstructures and properties of the surfaces and interfaces during fabrication and service conditions.The use and potential application of these phase diagrams as a process design tool were suggested and discussed.展开更多
The poisoning effect of CO2 on the oxygen surface exchange kinetics of BSCF （Ba0.5 Sr0.5 Co0.8 Feo.2O3_δ） is investigated with a novel pulse isotopic exchange technique. The surface exchange rate of BSCF severely d...The poisoning effect of CO2 on the oxygen surface exchange kinetics of BSCF （Ba0.5 Sr0.5 Co0.8 Feo.2O3_δ） is investigated with a novel pulse isotopic exchange technique. The surface exchange rate of BSCF severely decreases after in situ exposure to CO2, which is ascribed to carbonate formation on the material surface. The detrimental effect of CO2 starts at a low temperature of 375 ℃ and concentration as low as 1%, and becomes more pro- nounced at higher temperatures. Degradation of the surface exchange kinetics is associated with a rapid loss of oxygen permeation performance of BSCF in CO2.展开更多
The presence of a surface oxide film(B_(2)O_(3))on boron(B)particles significantly compromises their combustion efficiency and kinetic performance in fuel-rich solid propellants.This study proposes an innovative conti...The presence of a surface oxide film(B_(2)O_(3))on boron(B)particles significantly compromises their combustion efficiency and kinetic performance in fuel-rich solid propellants.This study proposes an innovative continuous modification strategy combining non-thermal plasma(NTP)etching with fluorocarbon passivation.Characterization and kinetic analysis revealed that reactive plasma species—including atomic hydrogen(H),electronically excited molecular hydrogen(H_(2)^(*)),vibrationally excited molecular hydrogen(H_(2)v),and hydrogen ions(H^(+))—dominate the reduction of B_(2)O_(3)through lowering the transition energy barrier and shifting the reaction spontaneity.Subsequent argon plasma fragmentation of C_(8)F_(18)generates fluorocarbon radicals that form conformal passivation coatings(thickness:7 nm)on purified boron surfaces.The modified boron particles exhibit 37.5℃lower exothermic peak temperature and 27.2%higher heat release(14.8 kJ/g vs.11.6 kJ/g)compared to untreated counterparts.Combustion diagnostics reveal 194%increase in maximum flame height(135.10 mm vs.46.03 mm)and 134%enhancement in flame propagation rate(4.44 cm/s vs.1.90 cm/s).This NTP-based surface engineering approach establishes a scalable pathway for developing highperformance boron-based energetic composites.展开更多
The dynamics of Cd scavenging from solutions by Fe/Mn oxides in natural surface coatings （NSCs） was investigated under laboratory conditions. Selective extraction methods were employed to estimate the contributions ...The dynamics of Cd scavenging from solutions by Fe/Mn oxides in natural surface coatings （NSCs） was investigated under laboratory conditions. Selective extraction methods were employed to estimate the contributions of Fe/Mn oxides, where hydroxylamine hydrochloride （0.01 mol/L NH2OH-HCl ＋ 0.01 mol/L HNO3）, sodium dithionite （0.4 mol/L Na2S2O4） and nitric acid （10% HNO3） were used as extraction reagents. The Cd scavenging was accomplished with developing periods of the NSCs （totally 21 data sets）. The resulting process dynamics fitted well to the Elovich equation, demonstrating that the amount of Cd scavenged was proportional to the increments of Fe/Mn oxides that were accumulated in the NSCs. The amount of Cd bound to Fe oxides （MCdFe） and Mn oxides （MCdMn） could be quantified by solving two equations based on the properties of two extraction reagents. The amount of Cd scavenged by Fe/Mn oxides could also be estimated using MCdFe and MCdMn divided by the total amounts of Fe and Mn oxides in the NSCs, respectively. The results indicated that the Cd scavenging by Fe/Mn oxides was dominated by Fe oxides, with less roles attributed to Mn oxides. The estimated levels of Cd scavenging through Fe and Mn oxides agreed well with those predicted through additive-adsorption and linear-regression models.展开更多
Oxidation of Alloy 690 TT samples either manually ground to 400 and 1500 grit, mechanically polished, or electropolished was performed in a solution of 1500 10 6B and 2.3 10 6Li with 2.5 10 6dissolved H2, at 325℃ and...Oxidation of Alloy 690 TT samples either manually ground to 400 and 1500 grit, mechanically polished, or electropolished was performed in a solution of 1500 10 6B and 2.3 10 6Li with 2.5 10 6dissolved H2, at 325℃ and 15.6 MPa for 60 days. The oxide films grown on samples with different surface states were analyzed using various techniques. Results show that a triple-layered structure was formed after immersion： an outermost layer with large scattered oxide particles rich in Fe and Ni, an intermediate layer with small compact oxide particles rich in Cr and Fe for the ground surfaces and loose needle-like oxides rich in Ni for the polished surfaces, and an inner layer with continuous Cr-rich oxides. The surface state was found to affect not only the surface morphology, but also the corrosion rate. Grinding accelerated the growth of protective oxide films such that the ground samples showed a lower oxidation rate than the polished ones.Samples of ground Alloy 690 TT showed superior resistance to intergranular attack（IGA）.展开更多
To reveal the relative contribution of the components, Fe, Mn oxides or organic materials（OMs） in the surficial sediments（SSs）, and the natural surface coating samples（NSCSs） to adsorbing atrazine（AT）, a selec...To reveal the relative contribution of the components, Fe, Mn oxides or organic materials（OMs） in the surficial sediments（SSs）, and the natural surface coating samples（NSCSs） to adsorbing atrazine（AT）, a selective chemical extraction technique was employed, to remove the different components, and the adsorption characteristics of AT on the SSs and the NSCSs were investigated. The observed adsorptions of AT on the original and extracted SSs and NSCSs were analyzed by nonlinear least squares fitting（NLSF） to estimate the relative contribution of the components. The results showed that the maximum adsorption of AT on the NSCSs was greater than that in the SSs, before and after extraction treatments, implying that the NSCSs were more dominant than the SSs for organic pollutant adsorption. It was also found that the Fe oxides, OMs, and residues in SSs（NSCSs） facilitated the adsorption of AT, but Mn oxides directly or indirectly restrained the interaction of AT with SSs（NSCSs） particles. The contribution of the Fe oxides to AT adsorption was more than that of OMs; the greatest contribution to AT adsorption on a molar basis was from the Fe oxides in the nonresidual fractions, indicating that the Fe oxides played an important role in controlling the environmental behavior of AT in an aquatic environment.展开更多
Surface regulation is a crucial technique for improving catalytic performance in heterogeneous catalysis.Although perovskite oxides containing noble metals show good performance and excellent thermal stability,the enc...Surface regulation is a crucial technique for improving catalytic performance in heterogeneous catalysis.Although perovskite oxides containing noble metals show good performance and excellent thermal stability,the encapsulation of noble metals in perovskite lattice restricts the exposure/usage of active sites.Herein,a method of high-temperature calcination coupling with selective dissolution was adopted to tune the physicochemical environment on the LaPd_(0.1)Mn_(0.9)O_(3)catalyst surface.The X-ray diffraction(XRD)and Raman results reveal that more Pd species emerge on the surface by elevating the calcination temperature,resulting in improved catalytic toluene oxidation activity.A further acid-etching of the LPMO-900 catalyst can also boost catalytic performance,being attributed to the enhanced redox ability and abundant surface oxygen vacancies.In addition,the optimized catalyst also exhibits excellent resistance to sintering and water vapor.This study provides new avenues for the rational design of highly efficient perovskite-based catalysts.展开更多
t Molecular dynamics （MD） simulations are carried out to characterize the mechanical and thermal responses of [011^-1]-oriented ZnO nanobelts with lateral dimensions of 21.22A × 18.95 A, 31.02A× 29.42 A, a...t Molecular dynamics （MD） simulations are carried out to characterize the mechanical and thermal responses of [011^-1]-oriented ZnO nanobelts with lateral dimensions of 21.22A × 18.95 A, 31.02A× 29.42 A, and40.81A ×39.89A over the temperature range of 300-1000 K. The Young＇s modulus and thermal conductivity of the nanobelts are evaluated. Significant surface effects on properties due to the highsurface-to-volume ratios of the nanobelts are observed. For the mechanical response, surface-stress-induced internal stress plays an important role. For the thermal response, surface scattering of phonons dominates. Calculations show that the Young＇s modulus is higher than the corresponding value for bulk ZnO and decreases by -33% as the lateral dimensions increase from 21.22 A × 18.95A to 40.81 A × 39.89A. The thermal conductivity is one order of magnitude lower than the corresponding value for bulk ZnO single crystal and decreases with wire size. Specifically, the conductivity of the 21.22 A × 18.95 A belt is approximately （31-18）% lower than that of the 40.81 A × 39.89 A belt over the temperature range analyzed. A significant dependence of properties on temperature is also observed, with the Young＇s modulus decreasing on average by 12% and the conductivity decreasing by 50% as temperature increases from 300 K to 1000 K.展开更多
Solid oxide materials have widespread applications which are often associated with their surface structure and properties. Solid-state nuclear magnetic resonance（NMR） spectroscopy is one of the most powerful methods...Solid oxide materials have widespread applications which are often associated with their surface structure and properties. Solid-state nuclear magnetic resonance（NMR） spectroscopy is one of the most powerful methods that give detailed local structural information of solid materials. Recent developments in dynamic nuclear polarization（DNP） NMR spectroscopy and17 O surface-selective isotopic labeling provide more opportunities in investigations of surface structure and properties of oxide materials. We describe in this review some of the latest progress in this field. DNP NMR can enhance the sensitivity of surface sites on the oxides by one to two order of magnitude, making very low concentrated species on the surface of oxides visible in NMR spectroscopy. On the basis of surface-selective17 O isotopic labeling,17 O NMR spectroscopy is now able to distinguish surface oxygen species on the different facets or different surface layers in oxide nanostructures. The nature of these facets can also be probed with help of31 P NMR spectroscopy along with phosphorous-containing probe molecules.展开更多
In this paper, three kinds of MgO with different specific surface area were prepared, and their effects on the catalytic performance of nickel catalysts for the carbon dioxide reforming of methane were investigated. T...In this paper, three kinds of MgO with different specific surface area were prepared, and their effects on the catalytic performance of nickel catalysts for the carbon dioxide reforming of methane were investigated. The results showed that MgO support with the higher specific surface area led to the higher dispersion of the active metal, which resulted in the higher initial activity. On the other hand, the specific surface area of MgO materials might not be the dominant factor for the basicity of support to chemisorb and activate CO2, which was another important factor for the performance of catalysts. Herein, Ni/MgO(CA) catalyst with proper specific surface area and strong ability to activate CO2exhibited stable catalytic property and the carbon species deposited on the Ni/MgO(CA) catalyst after 10 h of reaction at 650 ?C were mainly activated carbon species.展开更多
The feature of the surface coating can affect important properties of iron oxide nanoparticles(IONPs), it is therefore critical for further understanding how these materials react to physiological conditions, which is...The feature of the surface coating can affect important properties of iron oxide nanoparticles(IONPs), it is therefore critical for further understanding how these materials react to physiological conditions, which is still needed to fully exploit the potential of IONPs for their theranostic applications. In this work, we prepared IONPs which surface were modified with citric acid(CA), chitosan(CS) and folic acid conjugated chitosan(FA-g-CS). respectively. Their physicochemical properties were investigated using FT-IR, TEM,powder XRD, VSM, TGA, DLS and zeta potential. We found that CA-IONP dispersion was composed of monocrystalline particles while CS-IONP and FA-g-CS-IONP were composed of polycrystalline aggregates. All IONPs retained the crystalline structure of magnetite and exhibited the superparamagnetic behavior. Their saturation magnetization decreased with the increase in the amount of their organic coatings. Their drug loading capacities, drug release patterns and in vitro anticancer efficiencies were studied by using doxorubicin(DOX) as a model drug. DOX@CS-IONP and DOX@FA-g-CSIONP exhibited lower drug loading while showing higher water dispersity when compared with DOX@CA-IONP. All IONPs were surface charged and they tended to agglomerate in medium with high pH value and ionic strength. In the presence of chitosan or FA-g-CS coatings, their DOX release rate was slowed down compared with that of DOX@CA-IONP. Unloaded IONPs exhibited nearly no cytotoxicity on both cancer cells and normal cells in the presence of chitosan and FA-g-CS when compared with CA-IONP which presented high cytotoxicity. However, DOX@FA-g-CS-IONP showed significantly cytotoxicity on folate receptors(FRs) positive breast cancer cells while exhibiting nearly no cytotoxicity on FRs negative normal cells. Results presented in this study were valuable to the design and fabrication of IONPs-based system for better theranostic applications.展开更多
The surface chemical properties of CeO2 and Pr6O11 have been investigated with FT-IR spectroscopy. The reactivities of surface hydroxyls were tested through the reaction of CO. Surface formate species are formed on Ce...The surface chemical properties of CeO2 and Pr6O11 have been investigated with FT-IR spectroscopy. The reactivities of surface hydroxyls were tested through the reaction of CO. Surface formate species are formed on CeO2 and Pr6O11 under CO atmosphere at 200℃ . and the reaction becomcs more prevailing at higher temperatures especially for partially reduced samples. The surface formate species are produced via the reaction of CO with surface hydroxyls which was confirmed by the reaction of CO with D2-treated CeO2 and Pr6O11. The Surface formate can be oxidized to carbonate at temperatures exceeding 300 ℃, and the surface hydroxyls could be recovered as the formate species decompose or are oxidized to carbonate species. The roles played by the surface hydroxyls and surface active sites in the CO oxidation are discussed.展开更多
The porous cubic yttrium oxides with high specific surface area were prepared yttrium nitrate and its complex formed with methyl salicylate. The specific surface area by the explosive decomposition of and properties o...The porous cubic yttrium oxides with high specific surface area were prepared yttrium nitrate and its complex formed with methyl salicylate. The specific surface area by the explosive decomposition of and properties of powders synthesized at various temperatures were characterized using BET, X-ray diffraction （XRD）, infrared spectra （IR）, and scanning electron microscopy （SEM）. The results indicate that the highest specific surface area is found to be 65.37 m^2·g^-1 at the calcination temperature of 600 ℃, and then decreases to 20.33 m2· g^- 1 with the calcination temperature rising from 600 to 900 ℃. The powders show strong surface activity for adsorping water and carbon dioxide in air, which also decreases with the rising calcination temperature. The drop both on the surface area and surface activity of samples at higher temperatures may be due to pore-narrowing（sintering） effects.展开更多
The disadvantageous effects of colloidal SiO2 layer and micro-content of metal oxide adsorbed on SiC powder surface on SiC slurry stable dispersion were studied, and the novel method to avoid this disadvantage was pro...The disadvantageous effects of colloidal SiO2 layer and micro-content of metal oxide adsorbed on SiC powder surface on SiC slurry stable dispersion were studied, and the novel method to avoid this disadvantage was proposed. By acidwashing, on the one hand, because the maximum Zeta potential of SiC powder increases to 72.49 mV with the decreasing content of metal oxide adsorbed on the SiC powder surface, the repulsion force between SiC powders that dispersed in slurry is enhanced, thus the SiC powder can be fully dispersed in slurry. On the other hand, after HF acidwashing, with the OH^- group adsorbed on SiC powder surface destroyed and replaced by the Fion, the hydrogen bond adsorbed on the OHgroup is also destroyed. Therefore, the surface property of the SiC powder is changed from hydrophilic to hydrophobic; H2O that adsorbed on SiC powder surface is released and can flow freely, and it actually increases the content of the effective flow phase in the slurry. These changes of SiC powder surface property can be proved by XPS and FTIR analysis. Finally, the viscosity of SiC slurry is decreased greatly, and when the viscosity of the slurry is lower than 1 Pa·s, the solid volume fraction of SiC powder in the slurry is maximized to 61.5 vol.%.展开更多
Iron oxide supported Au nanomaterials are one of the most studied catalysts for low-temperature CO oxidation.Catalytic performance not only critically depends on the size of the supported Au nanoparticles(NPs)but also...Iron oxide supported Au nanomaterials are one of the most studied catalysts for low-temperature CO oxidation.Catalytic performance not only critically depends on the size of the supported Au nanoparticles(NPs)but also strongly on the chemical nature of the iron oxide.In this study,Au NPs supported on iron oxide nanorods with different surface properties throughβ-FeOOH annealing,at varying temperatures,were synthesized,and applied in the CO oxidation.Detailed characterizations of the interactions between Au NPs and iron oxides were obtained by X-ray diffraction,transmission electron microscopy(TEM),and X-ray photoelectron spectroscopy.The results indicate that the surface hydroxyl group on the Au/FeOOH catalyst,before calcination(Au/FeOOH-fresh),could facilitate the oxygen adsorption and dissociation on positively charged Au,thereby contributing to the low-temperature CO oxidation reactivity.After calcination at 200℃,under air exposure,the chemical state of the supported Au NP on varied iron oxides partly changed from metal cation to Au0,along with the disappearance of the surface OH species.Au/FeOOH with the highest Au0 content exhibits the highest activity in CO oxidation,among the as-synthesized catalysts.Furthermore,good durability in CO oxidation was achieved over the Au/FeOOH catalyst for 12 h without observable deactivation.In addition,the advanced identical-location TEM method was applied to the gas phase reaction to probe the structure evolution of the Au/iron oxide series of the catalysts and support structure.A Au NP size-dependent Ostwald ripening process mediated by the transport of Au(CO)x mobile species under certain reaction conditions is proposed,which offers a new insight into the validity of the structure-performance relationship.展开更多
This paper reports that the thermochromic vanadium dioxide films were deposited on various transparent substrates by radio frequency magnetron sputtering, and then aged under circumstance for years. Samples were chara...This paper reports that the thermochromic vanadium dioxide films were deposited on various transparent substrates by radio frequency magnetron sputtering, and then aged under circumstance for years. Samples were characterized with several different techniques such as x-ray diffraction, x-ray photoelectron spectroscopy, and Raman, when they were fresh from sputter chamber and aged after years, respectively, in order to determine their structure and composition. It finds that a small amount of sodium occurred on the surface of vanadium dioxide films, which was probably due to sodium ion diffusion from soda-lime glass when sputtering was performed at high substrate temperature. It also finds that aging for years significantly affected the nonstoichiometry of vanadium dioxide films, thus inducing much change in Raman modes.展开更多
基金financially supported by the National Natural Science Foundation of China (U2032157, 22209061)the Natural Science Foundation of Jiangsu Province (BK20201425)the Start-up Fund for Senior Talents in Jiangsu University(21JDG060)。
文摘Polycrystalline perovskite oxide particles are promising candidates for cathode materials in solid oxide fuel cells.However,their limited activity and stability pose significant challenges for practical applications.In this study,we demonstrate a novel approach to achieve both high activity and durability in a PrBaCo_(2)O_(5+δ) catalyst through a simple epitaxial layer growth strategy.We found that an amorphous precursor of the highly durable catalyst SmBa_(0.5)Ca_(0.5)CoCuO_(5+δ) can spontaneously adhere to the surface of PrBaCo_(2)O_(5+δ) particles.Upon heat treatment,it grows along the perovskite lattice,forming a heteroepitaxial layer with just a few atomic layers thickness.This heterostructure enhances the operational stability of PrBaCo_(2)O_(5+δ) transforming a 78% decrease over 100 h into a 7% increase.After 100 h,the power output density of the cell with the modified sample is more than 500% higher than that of unmodified PrBaCo_(2)O_(5+δ.)This work presents a new strategy for fabricating heteroepitaxial layers on polycrystalline ceramic catalysts and introduces a pioneering approach for developing high-performance oxygen reduction catalysts and related materials.
基金financially supported by the Natural Science Foundation of Zhejiang Province(No.LR22E010001)the National Natural Science Foundation of China(No.52073258)+1 种基金the Fundamental Research Funds for the Provincial Universities of Zhejiang(No.RF-B2022006)the R&D Program of Zhejiang University of Technology(No.KYY-HX-20190730)
文摘Iron oxide nanoparticles(IONPs)with intrinsic peroxidase(POD)-mimic activity have gained significant attention as nanozymes.Reducing sizes of IONPs is the mostly applied strategy to boost their enzymatic activity due to their high specific surface areas.Herein,we synthesized a series of uniformly sized IONPs ranging from3.17 to 21.2 nm,and found that POD activity of IONPs is not monotone increased by reducing their sizes,with the optimal size of 7.82 nm rather than smaller sized 3.17 nm.The reason for this unnormal phenomenon is that electronic structure also had great influence on POD activity,especially at the ultrasmall size region.Since Fe^(2+)are with higher enzymatic activity than Fe^(3+),3.17 nm IONPs although have the largest specific surface area,are prone to be oxidized,which reduced their iron content and ratio of Fe^(2+)to Fe^(3+),and consequently decreased their POD activity.By intentionally oxidized 7.82 nm IONPs in air,POD activity was obviously reduced,illustrating electronic structure cannot be overlooked.At the larger sized region ranging from 7.82 to 21.2 nm,oxidation degree of IONPs is similar,and surface electronic structure had a negligible effect on POD activity,and therefore,POD activity is predominantly influenced by specific surface area.By using the optimized 7.82 nm IONPs,tumor growth was obviously inhibited,demonstrating their potential in cancer therapeutics.Our results reveal that the designing of nanozymes should comprehensively balance their influence of surface electronic structure and specific surface area.
基金supported by the Vinnova(project number 2020-03778)supported by the Swedish Research Council(Vetenskapsradet,project number 2021-04157).
文摘Nano-scale chemical inhomogeneity in surface oxide films formed on a V-and N-containing martensite stainless steel and tempering heating induced changes are investigated by a combination of synchrotron-based hard X-ray Photoelectron emission spectroscopy(HAXPES)and microscopy(HAXPEEM)as well as microscopic X-ray absorption spectroscopy(μ-XAS)techniques.The results reveal the inhomogeneity in the oxide films on the micron-sized Cr_(2)N-and VN-type particles,while the inhomogeneity on the martensite matrix phase exists due to localised formation of nano-sized tempering nitride particles at 600℃.The oxide film formed on Cr_(2)N-type particles is rich in Cr_(2)O_(3) compared with that on the martensite matrix and VN-type particles.With the increase of tempering temperature,Cr_(2)O_(3) formation is faster for the oxidation of Cr in the martensite matrix than the oxidation of Cr nitride-rich particles.
基金Project(51104073)supported by the National Natural Science Foundation of ChinaProject(2013AA064003)supported by the High-tech Research and Development Program of China+1 种基金Project(2014CB643404)supported by the National Basic Research Program of ChinaProject(2012HB008)supported by Yunnan Province Young Academic Technology Leader Reserve Talents,China
文摘Microwave was applied to roasting the zinc oxide fume obtained from fuming furnace for the removal of F and Cl. The effects of important parameters, such as roasting temperature, holding time and stirring speed, were investigated and the process conditions were optimized using response surface methodology (RSM). The results show that the effects of roasting temperature and holding time on the removal rate of F and Cl are the most significant, and the effect of stirring speed is the second. The defluorination rate reaches 92.6% while the dechlorination rate reaches 90.2%, under the process conditions of roasting temperature of 700 °C, holding time of 80 min and stirring speed of 120 r/min. The results indicate that the removal of F and Cl from fuming furnace production of zinc oxide fumes using microwave roasting process is feasible and reliable.
基金Project(51171211) supported by the National Natural Science Foundation of ChinaProject(NCET-10-0837) supported by the Chinese Ministry of Education's Supportive Program for New Century Excellent Talents in UniversitiesProject(2006BAE03B03) supported by the Chinese National Science and Technology Supportive Program
文摘An important step for achieving the knowledge-based design freedom on nano-and interfacial materials is attained by elucidating the related surface and interface thermodynamics from the first principles so as to allow engineering the microstructures for desired properties through smartly designing fabrication processing parameters.This is demonstrated for SnO2 nano-particle surfaces and also a technologically important Ag-SnO2 interface fabricated by in-situ internal oxidation.Based on defect thermodynamics,we first modeled and calculated the equilibrium surface and interface structures,and as well corresponding properties,as a function of the ambient temperature and oxygen partial pressure.A series of first principles energetics calculations were then performed to construct the equilibrium surface and interface phase diagrams,to describe the environment dependence of the microstructures and properties of the surfaces and interfaces during fabrication and service conditions.The use and potential application of these phase diagrams as a process design tool were suggested and discussed.
基金This work was supported by the National Natural Science Foundation of China （No.U1432108）, the Fundamental Research Funds for the Central Universi- ties （No.XDJK2015C002 and No.WK2320000021）, Provincial Natural Science Foundation （No.1408085ME85）, Scientific Research Founda- tion for the Returned Overseas Chinese Scholars, State Education Ministry （No.WF2320000005）, and the Opening Project of CAS Key Laboratory of Materials for Energy Conversion （No.KF2014003）. Professor Henny J. M. Bouwmeester of University at Twente is deeply appreciated for fruitful discussions.
文摘The poisoning effect of CO2 on the oxygen surface exchange kinetics of BSCF （Ba0.5 Sr0.5 Co0.8 Feo.2O3_δ） is investigated with a novel pulse isotopic exchange technique. The surface exchange rate of BSCF severely decreases after in situ exposure to CO2, which is ascribed to carbonate formation on the material surface. The detrimental effect of CO2 starts at a low temperature of 375 ℃ and concentration as low as 1%, and becomes more pro- nounced at higher temperatures. Degradation of the surface exchange kinetics is associated with a rapid loss of oxygen permeation performance of BSCF in CO2.
基金supported by the National Natural Science Foundation of China(Nos.U2341249,12005076,22205112)the Fundamental Research Funds for the Central Universities(No.2025201012)。
文摘The presence of a surface oxide film(B_(2)O_(3))on boron(B)particles significantly compromises their combustion efficiency and kinetic performance in fuel-rich solid propellants.This study proposes an innovative continuous modification strategy combining non-thermal plasma(NTP)etching with fluorocarbon passivation.Characterization and kinetic analysis revealed that reactive plasma species—including atomic hydrogen(H),electronically excited molecular hydrogen(H_(2)^(*)),vibrationally excited molecular hydrogen(H_(2)v),and hydrogen ions(H^(+))—dominate the reduction of B_(2)O_(3)through lowering the transition energy barrier and shifting the reaction spontaneity.Subsequent argon plasma fragmentation of C_(8)F_(18)generates fluorocarbon radicals that form conformal passivation coatings(thickness:7 nm)on purified boron surfaces.The modified boron particles exhibit 37.5℃lower exothermic peak temperature and 27.2%higher heat release(14.8 kJ/g vs.11.6 kJ/g)compared to untreated counterparts.Combustion diagnostics reveal 194%increase in maximum flame height(135.10 mm vs.46.03 mm)and 134%enhancement in flame propagation rate(4.44 cm/s vs.1.90 cm/s).This NTP-based surface engineering approach establishes a scalable pathway for developing highperformance boron-based energetic composites.
基金The National Basic Research Program (973) of China (No. 2004CB3418501)
文摘The dynamics of Cd scavenging from solutions by Fe/Mn oxides in natural surface coatings （NSCs） was investigated under laboratory conditions. Selective extraction methods were employed to estimate the contributions of Fe/Mn oxides, where hydroxylamine hydrochloride （0.01 mol/L NH2OH-HCl ＋ 0.01 mol/L HNO3）, sodium dithionite （0.4 mol/L Na2S2O4） and nitric acid （10% HNO3） were used as extraction reagents. The Cd scavenging was accomplished with developing periods of the NSCs （totally 21 data sets）. The resulting process dynamics fitted well to the Elovich equation, demonstrating that the amount of Cd scavenged was proportional to the increments of Fe/Mn oxides that were accumulated in the NSCs. The amount of Cd bound to Fe oxides （MCdFe） and Mn oxides （MCdMn） could be quantified by solving two equations based on the properties of two extraction reagents. The amount of Cd scavenged by Fe/Mn oxides could also be estimated using MCdFe and MCdMn divided by the total amounts of Fe and Mn oxides in the NSCs, respectively. The results indicated that the Cd scavenging by Fe/Mn oxides was dominated by Fe oxides, with less roles attributed to Mn oxides. The estimated levels of Cd scavenging through Fe and Mn oxides agreed well with those predicted through additive-adsorption and linear-regression models.
基金supported by the Special Funds for the National Basic Research Program of China (No. 2011CB610502)the National Science and Technology Major Project (No. 2011ZX06004-009)the National Natural Science Foundation of China (No. 51025104)
文摘Oxidation of Alloy 690 TT samples either manually ground to 400 and 1500 grit, mechanically polished, or electropolished was performed in a solution of 1500 10 6B and 2.3 10 6Li with 2.5 10 6dissolved H2, at 325℃ and 15.6 MPa for 60 days. The oxide films grown on samples with different surface states were analyzed using various techniques. Results show that a triple-layered structure was formed after immersion： an outermost layer with large scattered oxide particles rich in Fe and Ni, an intermediate layer with small compact oxide particles rich in Cr and Fe for the ground surfaces and loose needle-like oxides rich in Ni for the polished surfaces, and an inner layer with continuous Cr-rich oxides. The surface state was found to affect not only the surface morphology, but also the corrosion rate. Grinding accelerated the growth of protective oxide films such that the ground samples showed a lower oxidation rate than the polished ones.Samples of ground Alloy 690 TT showed superior resistance to intergranular attack（IGA）.
基金Supported by the National Natural Science Foundation of China(No.50879025)the Scientific Start-up Fund from North China Electric Power University, China(No.X60218)the National Basic Research Program of China(No.2004CB3418501).
文摘To reveal the relative contribution of the components, Fe, Mn oxides or organic materials（OMs） in the surficial sediments（SSs）, and the natural surface coating samples（NSCSs） to adsorbing atrazine（AT）, a selective chemical extraction technique was employed, to remove the different components, and the adsorption characteristics of AT on the SSs and the NSCSs were investigated. The observed adsorptions of AT on the original and extracted SSs and NSCSs were analyzed by nonlinear least squares fitting（NLSF） to estimate the relative contribution of the components. The results showed that the maximum adsorption of AT on the NSCSs was greater than that in the SSs, before and after extraction treatments, implying that the NSCSs were more dominant than the SSs for organic pollutant adsorption. It was also found that the Fe oxides, OMs, and residues in SSs（NSCSs） facilitated the adsorption of AT, but Mn oxides directly or indirectly restrained the interaction of AT with SSs（NSCSs） particles. The contribution of the Fe oxides to AT adsorption was more than that of OMs; the greatest contribution to AT adsorption on a molar basis was from the Fe oxides in the nonresidual fractions, indicating that the Fe oxides played an important role in controlling the environmental behavior of AT in an aquatic environment.
基金Project supported by the National Key R&D Program of China(2023YFC3710300)the National Natural Science Foundation of China(U23A2099,22276111)+1 种基金the Taishan Scholar Project of Shandong Province(202306031)the Natural Science Foundation of Shandong Province(2023HWYQ-024)。
文摘Surface regulation is a crucial technique for improving catalytic performance in heterogeneous catalysis.Although perovskite oxides containing noble metals show good performance and excellent thermal stability,the encapsulation of noble metals in perovskite lattice restricts the exposure/usage of active sites.Herein,a method of high-temperature calcination coupling with selective dissolution was adopted to tune the physicochemical environment on the LaPd_(0.1)Mn_(0.9)O_(3)catalyst surface.The X-ray diffraction(XRD)and Raman results reveal that more Pd species emerge on the surface by elevating the calcination temperature,resulting in improved catalytic toluene oxidation activity.A further acid-etching of the LPMO-900 catalyst can also boost catalytic performance,being attributed to the enhanced redox ability and abundant surface oxygen vacancies.In addition,the optimized catalyst also exhibits excellent resistance to sintering and water vapor.This study provides new avenues for the rational design of highly efficient perovskite-based catalysts.
基金The project supported by the US National Science Foundation through CAREER grant no. CMS9984298the National Natural Science Foundation of China (10528205)
文摘t Molecular dynamics （MD） simulations are carried out to characterize the mechanical and thermal responses of [011^-1]-oriented ZnO nanobelts with lateral dimensions of 21.22A × 18.95 A, 31.02A× 29.42 A, and40.81A ×39.89A over the temperature range of 300-1000 K. The Young＇s modulus and thermal conductivity of the nanobelts are evaluated. Significant surface effects on properties due to the highsurface-to-volume ratios of the nanobelts are observed. For the mechanical response, surface-stress-induced internal stress plays an important role. For the thermal response, surface scattering of phonons dominates. Calculations show that the Young＇s modulus is higher than the corresponding value for bulk ZnO and decreases by -33% as the lateral dimensions increase from 21.22 A × 18.95A to 40.81 A × 39.89A. The thermal conductivity is one order of magnitude lower than the corresponding value for bulk ZnO single crystal and decreases with wire size. Specifically, the conductivity of the 21.22 A × 18.95 A belt is approximately （31-18）% lower than that of the 40.81 A × 39.89 A belt over the temperature range analyzed. A significant dependence of properties on temperature is also observed, with the Young＇s modulus decreasing on average by 12% and the conductivity decreasing by 50% as temperature increases from 300 K to 1000 K.
基金supported by the National Natural Science Foundation of China (NSFC, Nos. 21573103 and 91745202)NSFC–Royal Society Joint Program (No. 21661130149)+1 种基金Royal Society and Newton Fund for Royal Society–Newton Advanced Fellowshipsupported by a Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions
文摘Solid oxide materials have widespread applications which are often associated with their surface structure and properties. Solid-state nuclear magnetic resonance（NMR） spectroscopy is one of the most powerful methods that give detailed local structural information of solid materials. Recent developments in dynamic nuclear polarization（DNP） NMR spectroscopy and17 O surface-selective isotopic labeling provide more opportunities in investigations of surface structure and properties of oxide materials. We describe in this review some of the latest progress in this field. DNP NMR can enhance the sensitivity of surface sites on the oxides by one to two order of magnitude, making very low concentrated species on the surface of oxides visible in NMR spectroscopy. On the basis of surface-selective17 O isotopic labeling,17 O NMR spectroscopy is now able to distinguish surface oxygen species on the different facets or different surface layers in oxide nanostructures. The nature of these facets can also be probed with help of31 P NMR spectroscopy along with phosphorous-containing probe molecules.
基金supported by the South-Central University for Nationalities(CZZ12002)
文摘In this paper, three kinds of MgO with different specific surface area were prepared, and their effects on the catalytic performance of nickel catalysts for the carbon dioxide reforming of methane were investigated. The results showed that MgO support with the higher specific surface area led to the higher dispersion of the active metal, which resulted in the higher initial activity. On the other hand, the specific surface area of MgO materials might not be the dominant factor for the basicity of support to chemisorb and activate CO2, which was another important factor for the performance of catalysts. Herein, Ni/MgO(CA) catalyst with proper specific surface area and strong ability to activate CO2exhibited stable catalytic property and the carbon species deposited on the Ni/MgO(CA) catalyst after 10 h of reaction at 650 ?C were mainly activated carbon species.
基金supported by the State Key Basic Research Program of the PRC(No.2014CB744501)the National Key Research and Development Program of China(No.2017YFA0205301)+1 种基金the National Natural Science Foundation of China(Nos.61527806,61471168 and 61871180)Open Funding of State Key Laboratory of Oral Diseases(No.SKLOD2018OF02)
文摘The feature of the surface coating can affect important properties of iron oxide nanoparticles(IONPs), it is therefore critical for further understanding how these materials react to physiological conditions, which is still needed to fully exploit the potential of IONPs for their theranostic applications. In this work, we prepared IONPs which surface were modified with citric acid(CA), chitosan(CS) and folic acid conjugated chitosan(FA-g-CS). respectively. Their physicochemical properties were investigated using FT-IR, TEM,powder XRD, VSM, TGA, DLS and zeta potential. We found that CA-IONP dispersion was composed of monocrystalline particles while CS-IONP and FA-g-CS-IONP were composed of polycrystalline aggregates. All IONPs retained the crystalline structure of magnetite and exhibited the superparamagnetic behavior. Their saturation magnetization decreased with the increase in the amount of their organic coatings. Their drug loading capacities, drug release patterns and in vitro anticancer efficiencies were studied by using doxorubicin(DOX) as a model drug. DOX@CS-IONP and DOX@FA-g-CSIONP exhibited lower drug loading while showing higher water dispersity when compared with DOX@CA-IONP. All IONPs were surface charged and they tended to agglomerate in medium with high pH value and ionic strength. In the presence of chitosan or FA-g-CS coatings, their DOX release rate was slowed down compared with that of DOX@CA-IONP. Unloaded IONPs exhibited nearly no cytotoxicity on both cancer cells and normal cells in the presence of chitosan and FA-g-CS when compared with CA-IONP which presented high cytotoxicity. However, DOX@FA-g-CS-IONP showed significantly cytotoxicity on folate receptors(FRs) positive breast cancer cells while exhibiting nearly no cytotoxicity on FRs negative normal cells. Results presented in this study were valuable to the design and fabrication of IONPs-based system for better theranostic applications.
文摘The surface chemical properties of CeO2 and Pr6O11 have been investigated with FT-IR spectroscopy. The reactivities of surface hydroxyls were tested through the reaction of CO. Surface formate species are formed on CeO2 and Pr6O11 under CO atmosphere at 200℃ . and the reaction becomcs more prevailing at higher temperatures especially for partially reduced samples. The surface formate species are produced via the reaction of CO with surface hydroxyls which was confirmed by the reaction of CO with D2-treated CeO2 and Pr6O11. The Surface formate can be oxidized to carbonate at temperatures exceeding 300 ℃, and the surface hydroxyls could be recovered as the formate species decompose or are oxidized to carbonate species. The roles played by the surface hydroxyls and surface active sites in the CO oxidation are discussed.
文摘The porous cubic yttrium oxides with high specific surface area were prepared yttrium nitrate and its complex formed with methyl salicylate. The specific surface area by the explosive decomposition of and properties of powders synthesized at various temperatures were characterized using BET, X-ray diffraction （XRD）, infrared spectra （IR）, and scanning electron microscopy （SEM）. The results indicate that the highest specific surface area is found to be 65.37 m^2·g^-1 at the calcination temperature of 600 ℃, and then decreases to 20.33 m2· g^- 1 with the calcination temperature rising from 600 to 900 ℃. The powders show strong surface activity for adsorping water and carbon dioxide in air, which also decreases with the rising calcination temperature. The drop both on the surface area and surface activity of samples at higher temperatures may be due to pore-narrowing（sintering） effects.
基金This work was financially supported by the Doctoral Foundation of Xi'an Jiaotong University (No. DFXJTU2004-04).
文摘The disadvantageous effects of colloidal SiO2 layer and micro-content of metal oxide adsorbed on SiC powder surface on SiC slurry stable dispersion were studied, and the novel method to avoid this disadvantage was proposed. By acidwashing, on the one hand, because the maximum Zeta potential of SiC powder increases to 72.49 mV with the decreasing content of metal oxide adsorbed on the SiC powder surface, the repulsion force between SiC powders that dispersed in slurry is enhanced, thus the SiC powder can be fully dispersed in slurry. On the other hand, after HF acidwashing, with the OH^- group adsorbed on SiC powder surface destroyed and replaced by the Fion, the hydrogen bond adsorbed on the OHgroup is also destroyed. Therefore, the surface property of the SiC powder is changed from hydrophilic to hydrophobic; H2O that adsorbed on SiC powder surface is released and can flow freely, and it actually increases the content of the effective flow phase in the slurry. These changes of SiC powder surface property can be proved by XPS and FTIR analysis. Finally, the viscosity of SiC slurry is decreased greatly, and when the viscosity of the slurry is lower than 1 Pa·s, the solid volume fraction of SiC powder in the slurry is maximized to 61.5 vol.%.
基金supported by the National Natural Science Foundation of China(21773269,21761132025,91545119,21703262)the Youth Innovation Promotion Association CAS(2015152)+1 种基金the Joint Foundation of Liaoning Province Natural Science FoundationShenyang National Laboratory for Materials Science(20180510047)~~
文摘Iron oxide supported Au nanomaterials are one of the most studied catalysts for low-temperature CO oxidation.Catalytic performance not only critically depends on the size of the supported Au nanoparticles(NPs)but also strongly on the chemical nature of the iron oxide.In this study,Au NPs supported on iron oxide nanorods with different surface properties throughβ-FeOOH annealing,at varying temperatures,were synthesized,and applied in the CO oxidation.Detailed characterizations of the interactions between Au NPs and iron oxides were obtained by X-ray diffraction,transmission electron microscopy(TEM),and X-ray photoelectron spectroscopy.The results indicate that the surface hydroxyl group on the Au/FeOOH catalyst,before calcination(Au/FeOOH-fresh),could facilitate the oxygen adsorption and dissociation on positively charged Au,thereby contributing to the low-temperature CO oxidation reactivity.After calcination at 200℃,under air exposure,the chemical state of the supported Au NP on varied iron oxides partly changed from metal cation to Au0,along with the disappearance of the surface OH species.Au/FeOOH with the highest Au0 content exhibits the highest activity in CO oxidation,among the as-synthesized catalysts.Furthermore,good durability in CO oxidation was achieved over the Au/FeOOH catalyst for 12 h without observable deactivation.In addition,the advanced identical-location TEM method was applied to the gas phase reaction to probe the structure evolution of the Au/iron oxide series of the catalysts and support structure.A Au NP size-dependent Ostwald ripening process mediated by the transport of Au(CO)x mobile species under certain reaction conditions is proposed,which offers a new insight into the validity of the structure-performance relationship.
基金supported by the National Natural Science Foundation of China (Grant No 60776039)China Agricultural University Foundation (Grant No 2007037)
文摘This paper reports that the thermochromic vanadium dioxide films were deposited on various transparent substrates by radio frequency magnetron sputtering, and then aged under circumstance for years. Samples were characterized with several different techniques such as x-ray diffraction, x-ray photoelectron spectroscopy, and Raman, when they were fresh from sputter chamber and aged after years, respectively, in order to determine their structure and composition. It finds that a small amount of sodium occurred on the surface of vanadium dioxide films, which was probably due to sodium ion diffusion from soda-lime glass when sputtering was performed at high substrate temperature. It also finds that aging for years significantly affected the nonstoichiometry of vanadium dioxide films, thus inducing much change in Raman modes.
