Wide-angle light scattering(WALS)was used for in situ measurements of droplet and nanoparticle size distributions during the synthesis of titania and iron oxide particles from liquid precursor solutions in the standar...Wide-angle light scattering(WALS)was used for in situ measurements of droplet and nanoparticle size distributions during the synthesis of titania and iron oxide particles from liquid precursor solutions in the standardized SpraySyn burner for spray flame synthesis.Titania was synthesized from titanium tetraisopropoxide(TTIP)and iron oxide from iron(II)nitrate nonahydrate(INN)using ethanol(EtOH)as solvent.Scattering images were taken at heights up to 120 mm above the burner surface and classified into droplet and particle scattering.Droplet size distributions were derived from a sequential analysis of scattering data containing the oscillating Mie pattern,the lognormal size distribution parameters for spherical and fractal particle fractions from a multivariate approach on averaged particle scattering data.The results show that the precursor addition leads to altered evaporation behavior and even droplet disruption probably induced by puffing or micro-explosions compared to pure EtOH.In the case of TTIP(a hygroscopic alkoxide),the synthesis of a large fraction of spheres was observed,while the nitrate INN leads to the formation of mostly fractal aggregates.展开更多
Tuning the surface acidity of ZSM-5 catalyst is essential to achieve desired propene selectivity and yield.Here several ratios of Zr were utilized to modify ZSM-5 via flame spray pyrolysis technique coupled with a pul...Tuning the surface acidity of ZSM-5 catalyst is essential to achieve desired propene selectivity and yield.Here several ratios of Zr were utilized to modify ZSM-5 via flame spray pyrolysis technique coupled with a pulse spray evaporation system.The interaction between Zr and ZSM-5 in the flame influenced the physicochemical and acidity properties of the Zr/ZSM-5.The increasing Zr ratio in ZSM-5 shows coated layers of irregular nano-sized Zr with an increase in crystallite sizes due to the synergetic effect between Zr and ZSM-5.The surface chemical analysis revealed increased lattice oxygen on the Zr modified ZSM-5(1:4) sample compared to other catalysts.The acidity analysis revealed the Lewis and Br?nsted acid distribution in the weak and medium acid sites on the catalyst surface.However,the increase in Zr loading decreased the concentration of Br?nsted acid sites and tuned the catalyst surface to more Lewis acidity,promoting propene selectivity and hindering the over-oxidation of propene.The modified ZSM-5 catalysts were examined in a fixed bed reactor within 300℃-700℃ at a gas hourly space velocity(GHSV) of 6000 mL·g(catalysts)^(-1)·h^(-1) for the oxidative dehydrogenation of propane(ODHP) to propene.Among the catalysts,Zr/ZSM-5(1:4) exhibited the best propene yield, with 57.19% propane conversion and 75.54% selectivity to propene and the highest stability.This work provides a promising strategy for tuning the surface acidity of ZSM-5 with Zr for ODHP applications.展开更多
Flame spray synthesis (FSS), a combination of the flame spray technology and Self-propagation High-temperature Synthesis (SHS) was developed for preparing fine-ceramic-containing composite coatings. It can simplify th...Flame spray synthesis (FSS), a combination of the flame spray technology and Self-propagation High-temperature Synthesis (SHS) was developed for preparing fine-ceramic-containing composite coatings. It can simplify the preparations of powder to synthesize and deposit the desired materials in one step. The preliminary results obtained from TiC-Fe cermet coatings by FSS process are reported. The peculiar microstructure of the composite coatings, which contains very fine (<1m) and round TiC and alternate TiC-rich (Hv=11€*13GPa) and TiC-poor layers (Hv=3.0 -6.0GPa), is expected to play an important role in their tribological properties.展开更多
Eight dialkyl tetrabromophthalates (DATBPs) were synthesized by reacting tetrabromophthalic anhydride with excess alcohols which were used not only as a reactant but also as a solvent and using a quaternary ammonium s...Eight dialkyl tetrabromophthalates (DATBPs) were synthesized by reacting tetrabromophthalic anhydride with excess alcohols which were used not only as a reactant but also as a solvent and using a quaternary ammonium salt as a phase transfer catalyst (PTC). The yields were found to be between 85-93%. Their structures were characterized by IR, NMR and elementary analysis. The flame retardant properties of the compounds were also studied.展开更多
The surface properties of oxidic supports and their interaction with the supported metals play critical roles in governing the catalytic activities of oxide‐supported metal catalysts.When metals are supported on redu...The surface properties of oxidic supports and their interaction with the supported metals play critical roles in governing the catalytic activities of oxide‐supported metal catalysts.When metals are supported on reducible oxides,dynamic surface reconstruction phenomena,including strong metal–support interaction(SMSI)and oxygen vacancy formation,complicate the determination of the structural–functional relationship at the active sites.Here,we performed a systematic investigation of the dynamic behavior of Au nanocatalysts supported on flame‐synthesized TiO_(2),which takes predominantly a rutile phase,using CO oxidation above room temperature as a probe reaction.Our analysis conclusively elucidated a negative correlation between the catalytic activity of Au/TiO_(2) and the oxygen vacancy at the Au/TiO_(2) interface.Although the reversible formation and retracting of SMSI overlayers have been ubiquitously observed on Au/TiO_(2) samples,the catalytic consequence of SMSI remains inconclusive.Density functional theory suggests that the electron transfer from TiO_(2) to Au is correlated to the presence of the interfacial oxygen vacancies,retarding the catalytic activation of CO oxidation.展开更多
One-dimensional carbon nano-materials (ODCNMs) synthesized from ethanol flames exhibit various agglomerated morphologies, such as "chrysanthemum-like", "hairball-like" or "orange-peel-like", "vertically alig...One-dimensional carbon nano-materials (ODCNMs) synthesized from ethanol flames exhibit various agglomerated morphologies, such as "chrysanthemum-like", "hairball-like" or "orange-peel-like", "vertically aligned" and "wrinkling-pileup". The present work studied the agglomerating process and the growth mechanism by using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). It is thought that the size and distribution of the catalyst particles produced from pretreatment of the substrates play a key role during the formation of agglomerations. It is expected that the steady growth of ODCNMs in flames will be improved through the preparation of the catalysts.展开更多
In this study, factors affecting the crystal structure of flame-synthesized Y2O3 :Eu particles were investigated, especially the particle size effect and its interaction with Eu doping concentration, Polydisperse Y2O...In this study, factors affecting the crystal structure of flame-synthesized Y2O3 :Eu particles were investigated, especially the particle size effect and its interaction with Eu doping concentration, Polydisperse Y2O3:Eu (size range 200 nm to 3μm) powder samples with Eu doping concentrations from 2,5 mol% to 25 mol% were generated in either H2/air or H2/O2 substrate-free flames. The crystal structure of the powder samples was determined by powder X-ray diffraction (XRD), which was complemented by pho- toluminescence (PL) measurements. Single particle crystal structure was determined by single particle selected area electron diffraction (SAED), and for the first time, by electron backscatter diffraction (EBSD). H2/air flames resulted in cubic phase Y2O3:Eu particles with hollow morphology and irregular shapes, Particles from H2/O2 flames had dense and spherical morphology; samples with lower Eu doping concen- trations had mixed cubic/monoclinic phases; samples with the highest Eu doping concentrations were phase-pure monoclinic. For samples generated from H2/02 flames, a particle size effect and its interaction with Eu doping concentration were found: particles smaller than a critical diameter had the monoclinic phase, and this critical diameter increased with increasing Eu doping concentration, These findings suggest that the formation of monoclinic Y2O3:Eu is inevitable when extremely hot substrate-free flames are used, because typical flame-synthesized Y203 :Eu particle sizes are well below the critical diameter, However, it may be possible to generate particles with dense, spherical morphology and the desired cubic structure by using a moderately high flame temperature that enables fast sintering without melting the particles.展开更多
The flame technology has been employed broadly for large-scale manufacture of carbon blacks, fumed silica, pigmentary titania, and also ceramic commodities such as SiO2, Ti02, and A1203. A deeper understanding of the ...The flame technology has been employed broadly for large-scale manufacture of carbon blacks, fumed silica, pigmentary titania, and also ceramic commodities such as SiO2, Ti02, and A1203. A deeper understanding of the process also made it possible for production of novel nanomaterials with high functionality--various novel nanomaterials such as nanorods, nanowires, nanotubes, nanocoils, and nanocomposites with core/shell, hollow and ball-in-shell structures, have been synthesized recently via gas combustion technology, while the mechanisms of the material formation were investigated based on the nucleation-growth and chemical engineering principles. Studies of the fluid flow and mass mixing, supported by principles of chemical reaction engineering, could provide knowledge for better understanding of the process, and thus make rational manipulation of the products possible.展开更多
A phosphorus-nitrogen containing flame retardant additive of poly(phosphoric acid piperazine), defined as PPAP, was synthesized by the salt-forming reaction between anhydrous piperazine and phosphoric acid, and the ...A phosphorus-nitrogen containing flame retardant additive of poly(phosphoric acid piperazine), defined as PPAP, was synthesized by the salt-forming reaction between anhydrous piperazine and phosphoric acid, and the dehydration polymerization under heating in nitrogen atmosphere. Its chemical structure was well characterized by Fourier transform infrared(FTIR) spectroscopy, ^(13)C and ^(31)P solid-state nuclear magnetic resonance measurements. The synthesized PPAP and curing agent m-phenylenediamine were blended into epoxy resin(EP) to prepare flame retardant EP thermosets. The effects of PPAP on the fire retardancy and thermal degradation behavior of cured EP/PPAP composites were investigated by limiting oxygen index(LOI), vertical burning(UL-94), thermogravimetric analysis/infrared spectrometry(TG-IR) and cone calorimeter tests. The morphologies and chemical compositions of char residues for cured epoxy resin were investigated by scanning electron microscopy(SEM) and X-ray photoelectron spectroscopy(XPS), respectively. The results demonstrated that the flame retardant EP thermosets successfully passed UL-94 V-0 flammability rating and the LOI value was as high as 30.8% when incorporating 5 wt% PPAP into the EP thermosets. The TGA results indicated that the synthesized PPAP flame retardant additive possessed high thermal stability and excellent charring capability. Meanwhile, the incorporation of PPAP stimulated the epoxy resin matrix to decompose and charring ahead of time due to its catalytic decomposition effect, which led to a higher char yield at high temperature. The morphological structures and the analysis results of XPS for char residues of EP thermosets revealed that the introduction of PPAP benefited the formation of a sufficient, more compact and homogeneous char layer containing phosphorus-nitrogen flame retardant elements on the material surface during combustion. The formed char layer with high quality effectively prevented the heat transmission and diffusion, limited the production of combustible gases, and inhibited the emission of smoke, leading to the reduction of heat and smoke release.展开更多
Doping is a reasonable solution to improve the electronic structure and surface properties of nanomaterials.Herein,we propose a rapid and simple methodology,flame synthesis,as an effective preparation strategy for inc...Doping is a reasonable solution to improve the electronic structure and surface properties of nanomaterials.Herein,we propose a rapid and simple methodology,flame synthesis,as an effective preparation strategy for incorporating high-valence metal ions(Ti^(4+),Sn^(4+),and Zr^(4+))into ultrasmall Fe_(2)O_(3)on carbon nanotube support(i.e.,M-FeO-CNT).The resulting materials exhibit not only a boosted Na+adsorption as shown by density functional theory(DFT)calculations,but also display an increased oxygen deficiency.The electrochemical activity and charge transfer efficiency of Fe 2 O 3 can be improved by reasonably sub-stituting Fe 3+with Ti^(4+),Sn^(4+),and Zr^(4+).The electrochemical investigation of Ti-doped Fe 2 O 3(Ti-FeO-CNT)electrode demonstrates a splendid specific capacitance of 1.25 F cm^(−2)at 1 mA cm^(−2)in 1 M Na_(2)SO_(4).This is significantly higher as compared to the capacitance of 0.48 F cm^(−2).Flexible solid-state asymmetric su-percapacitor Ti-FeO-CNT//MnO_(2)is verified with operating voltage of 2.0 V and stability over 3000 cycles,and delivers a high energy density of 2.14 mWh cm^(−3)at power density of 25 mW cm−3.The flame synthesis is expected to be widely applicable for the preparation of high-valence metal ions doped nanosized Fe_(2)O_(3)functionalized materials,thus opening up new avenues for energy and catalysis research.展开更多
基金funded by the German Research Foundation DFG under grants WI1602/16-1 and WI1602/16-2.
文摘Wide-angle light scattering(WALS)was used for in situ measurements of droplet and nanoparticle size distributions during the synthesis of titania and iron oxide particles from liquid precursor solutions in the standardized SpraySyn burner for spray flame synthesis.Titania was synthesized from titanium tetraisopropoxide(TTIP)and iron oxide from iron(II)nitrate nonahydrate(INN)using ethanol(EtOH)as solvent.Scattering images were taken at heights up to 120 mm above the burner surface and classified into droplet and particle scattering.Droplet size distributions were derived from a sequential analysis of scattering data containing the oscillating Mie pattern,the lognormal size distribution parameters for spherical and fractal particle fractions from a multivariate approach on averaged particle scattering data.The results show that the precursor addition leads to altered evaporation behavior and even droplet disruption probably induced by puffing or micro-explosions compared to pure EtOH.In the case of TTIP(a hygroscopic alkoxide),the synthesis of a large fraction of spheres was observed,while the nitrate INN leads to the formation of mostly fractal aggregates.
基金financial support from the National Natural Science Foundation of China (No. 52161145105/51888103/51976216)Ministry of Science and Technology of China (2017YFA0402800)+5 种基金Beijing Municipal Natural Science Foundation (JQ20017)K.C. Wong Education Foundation (GJTD-2020-07)Recruitment of Global Youth Expertsthe financial support of the Belt and Road scholarshipthe financial support of the ANSO scholarshipthe support of the Chinese Academy of Sciences for the CAS project (Grant No.2018/43)。
文摘Tuning the surface acidity of ZSM-5 catalyst is essential to achieve desired propene selectivity and yield.Here several ratios of Zr were utilized to modify ZSM-5 via flame spray pyrolysis technique coupled with a pulse spray evaporation system.The interaction between Zr and ZSM-5 in the flame influenced the physicochemical and acidity properties of the Zr/ZSM-5.The increasing Zr ratio in ZSM-5 shows coated layers of irregular nano-sized Zr with an increase in crystallite sizes due to the synergetic effect between Zr and ZSM-5.The surface chemical analysis revealed increased lattice oxygen on the Zr modified ZSM-5(1:4) sample compared to other catalysts.The acidity analysis revealed the Lewis and Br?nsted acid distribution in the weak and medium acid sites on the catalyst surface.However,the increase in Zr loading decreased the concentration of Br?nsted acid sites and tuned the catalyst surface to more Lewis acidity,promoting propene selectivity and hindering the over-oxidation of propene.The modified ZSM-5 catalysts were examined in a fixed bed reactor within 300℃-700℃ at a gas hourly space velocity(GHSV) of 6000 mL·g(catalysts)^(-1)·h^(-1) for the oxidative dehydrogenation of propane(ODHP) to propene.Among the catalysts,Zr/ZSM-5(1:4) exhibited the best propene yield, with 57.19% propane conversion and 75.54% selectivity to propene and the highest stability.This work provides a promising strategy for tuning the surface acidity of ZSM-5 with Zr for ODHP applications.
文摘Flame spray synthesis (FSS), a combination of the flame spray technology and Self-propagation High-temperature Synthesis (SHS) was developed for preparing fine-ceramic-containing composite coatings. It can simplify the preparations of powder to synthesize and deposit the desired materials in one step. The preliminary results obtained from TiC-Fe cermet coatings by FSS process are reported. The peculiar microstructure of the composite coatings, which contains very fine (<1m) and round TiC and alternate TiC-rich (Hv=11€*13GPa) and TiC-poor layers (Hv=3.0 -6.0GPa), is expected to play an important role in their tribological properties.
文摘Eight dialkyl tetrabromophthalates (DATBPs) were synthesized by reacting tetrabromophthalic anhydride with excess alcohols which were used not only as a reactant but also as a solvent and using a quaternary ammonium salt as a phase transfer catalyst (PTC). The yields were found to be between 85-93%. Their structures were characterized by IR, NMR and elementary analysis. The flame retardant properties of the compounds were also studied.
基金Science and Technology Innovation Program of Hunan Province,Grant/Award Numbers:2020GK2070,2021RC4006Innovation‐Driven Project of Central South University,Grant/Award Number:2020CX008+3 种基金China Scholarship Council(CSC)National Key R&D Program of China,Grant/Award Number:2022YFE0105900National Natural Science Foundation of China,Grant/Award Number:52276093National Research Foundation Singapore,Grant/Award Number:CREATE。
文摘The surface properties of oxidic supports and their interaction with the supported metals play critical roles in governing the catalytic activities of oxide‐supported metal catalysts.When metals are supported on reducible oxides,dynamic surface reconstruction phenomena,including strong metal–support interaction(SMSI)and oxygen vacancy formation,complicate the determination of the structural–functional relationship at the active sites.Here,we performed a systematic investigation of the dynamic behavior of Au nanocatalysts supported on flame‐synthesized TiO_(2),which takes predominantly a rutile phase,using CO oxidation above room temperature as a probe reaction.Our analysis conclusively elucidated a negative correlation between the catalytic activity of Au/TiO_(2) and the oxygen vacancy at the Au/TiO_(2) interface.Although the reversible formation and retracting of SMSI overlayers have been ubiquitously observed on Au/TiO_(2) samples,the catalytic consequence of SMSI remains inconclusive.Density functional theory suggests that the electron transfer from TiO_(2) to Au is correlated to the presence of the interfacial oxygen vacancies,retarding the catalytic activation of CO oxidation.
基金Supported by the Scientific Research Foundationfor the Returned Overseas Chinese Scholars of Chinese Ministry Edu-cation (200233)
文摘One-dimensional carbon nano-materials (ODCNMs) synthesized from ethanol flames exhibit various agglomerated morphologies, such as "chrysanthemum-like", "hairball-like" or "orange-peel-like", "vertically aligned" and "wrinkling-pileup". The present work studied the agglomerating process and the growth mechanism by using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). It is thought that the size and distribution of the catalyst particles produced from pretreatment of the substrates play a key role during the formation of agglomerations. It is expected that the steady growth of ODCNMs in flames will be improved through the preparation of the catalysts.
基金Financial support for this work was provided by Texas A&M University and Texas Engineering Experiment Station
文摘In this study, factors affecting the crystal structure of flame-synthesized Y2O3 :Eu particles were investigated, especially the particle size effect and its interaction with Eu doping concentration, Polydisperse Y2O3:Eu (size range 200 nm to 3μm) powder samples with Eu doping concentrations from 2,5 mol% to 25 mol% were generated in either H2/air or H2/O2 substrate-free flames. The crystal structure of the powder samples was determined by powder X-ray diffraction (XRD), which was complemented by pho- toluminescence (PL) measurements. Single particle crystal structure was determined by single particle selected area electron diffraction (SAED), and for the first time, by electron backscatter diffraction (EBSD). H2/air flames resulted in cubic phase Y2O3:Eu particles with hollow morphology and irregular shapes, Particles from H2/O2 flames had dense and spherical morphology; samples with lower Eu doping concen- trations had mixed cubic/monoclinic phases; samples with the highest Eu doping concentrations were phase-pure monoclinic. For samples generated from H2/02 flames, a particle size effect and its interaction with Eu doping concentration were found: particles smaller than a critical diameter had the monoclinic phase, and this critical diameter increased with increasing Eu doping concentration, These findings suggest that the formation of monoclinic Y2O3:Eu is inevitable when extremely hot substrate-free flames are used, because typical flame-synthesized Y203 :Eu particle sizes are well below the critical diameter, However, it may be possible to generate particles with dense, spherical morphology and the desired cubic structure by using a moderately high flame temperature that enables fast sintering without melting the particles.
基金support of the National Natural Science Foundation of China(20925621,20906027,20706015)the Program of Shanghai Subject Chief Scientist(08XD1401500)+3 种基金the Shanghai Shuguang Scholars Tracking Program(08GG09)the Special Projects for Key Laboratories in Shanghai(09DZ2202000)the Special Projects for Nanotechnology of Shanghai(0852nm02000,0952nm02100,0952nm02100)the Shanghai Pujiang Program(09PJ1403200)
文摘The flame technology has been employed broadly for large-scale manufacture of carbon blacks, fumed silica, pigmentary titania, and also ceramic commodities such as SiO2, Ti02, and A1203. A deeper understanding of the process also made it possible for production of novel nanomaterials with high functionality--various novel nanomaterials such as nanorods, nanowires, nanotubes, nanocoils, and nanocomposites with core/shell, hollow and ball-in-shell structures, have been synthesized recently via gas combustion technology, while the mechanisms of the material formation were investigated based on the nucleation-growth and chemical engineering principles. Studies of the fluid flow and mass mixing, supported by principles of chemical reaction engineering, could provide knowledge for better understanding of the process, and thus make rational manipulation of the products possible.
基金financially supported by the Fundamental Research Funds for the Central Universities (No.2572014EB06-02)National Natural Science Foundation of China (No.51673035)Heilongjiang Major Research Projects (No.GA15A101)
文摘A phosphorus-nitrogen containing flame retardant additive of poly(phosphoric acid piperazine), defined as PPAP, was synthesized by the salt-forming reaction between anhydrous piperazine and phosphoric acid, and the dehydration polymerization under heating in nitrogen atmosphere. Its chemical structure was well characterized by Fourier transform infrared(FTIR) spectroscopy, ^(13)C and ^(31)P solid-state nuclear magnetic resonance measurements. The synthesized PPAP and curing agent m-phenylenediamine were blended into epoxy resin(EP) to prepare flame retardant EP thermosets. The effects of PPAP on the fire retardancy and thermal degradation behavior of cured EP/PPAP composites were investigated by limiting oxygen index(LOI), vertical burning(UL-94), thermogravimetric analysis/infrared spectrometry(TG-IR) and cone calorimeter tests. The morphologies and chemical compositions of char residues for cured epoxy resin were investigated by scanning electron microscopy(SEM) and X-ray photoelectron spectroscopy(XPS), respectively. The results demonstrated that the flame retardant EP thermosets successfully passed UL-94 V-0 flammability rating and the LOI value was as high as 30.8% when incorporating 5 wt% PPAP into the EP thermosets. The TGA results indicated that the synthesized PPAP flame retardant additive possessed high thermal stability and excellent charring capability. Meanwhile, the incorporation of PPAP stimulated the epoxy resin matrix to decompose and charring ahead of time due to its catalytic decomposition effect, which led to a higher char yield at high temperature. The morphological structures and the analysis results of XPS for char residues of EP thermosets revealed that the introduction of PPAP benefited the formation of a sufficient, more compact and homogeneous char layer containing phosphorus-nitrogen flame retardant elements on the material surface during combustion. The formed char layer with high quality effectively prevented the heat transmission and diffusion, limited the production of combustible gases, and inhibited the emission of smoke, leading to the reduction of heat and smoke release.
基金supported by the National Natu-ral Science Foundation of China(No.21978182)the Miaozi Project in Science and Technology Innovation Program of Sichuan Province(No.21-YCG021).
文摘Doping is a reasonable solution to improve the electronic structure and surface properties of nanomaterials.Herein,we propose a rapid and simple methodology,flame synthesis,as an effective preparation strategy for incorporating high-valence metal ions(Ti^(4+),Sn^(4+),and Zr^(4+))into ultrasmall Fe_(2)O_(3)on carbon nanotube support(i.e.,M-FeO-CNT).The resulting materials exhibit not only a boosted Na+adsorption as shown by density functional theory(DFT)calculations,but also display an increased oxygen deficiency.The electrochemical activity and charge transfer efficiency of Fe 2 O 3 can be improved by reasonably sub-stituting Fe 3+with Ti^(4+),Sn^(4+),and Zr^(4+).The electrochemical investigation of Ti-doped Fe 2 O 3(Ti-FeO-CNT)electrode demonstrates a splendid specific capacitance of 1.25 F cm^(−2)at 1 mA cm^(−2)in 1 M Na_(2)SO_(4).This is significantly higher as compared to the capacitance of 0.48 F cm^(−2).Flexible solid-state asymmetric su-percapacitor Ti-FeO-CNT//MnO_(2)is verified with operating voltage of 2.0 V and stability over 3000 cycles,and delivers a high energy density of 2.14 mWh cm^(−3)at power density of 25 mW cm−3.The flame synthesis is expected to be widely applicable for the preparation of high-valence metal ions doped nanosized Fe_(2)O_(3)functionalized materials,thus opening up new avenues for energy and catalysis research.