Pt/Al2O3 catalysts with mean Pt particle size ranged from 2.7 to 7.1 nm were synthesized by chemical reduction method,and the sulfated counterparts were prepared by impregnation of sulfuric acid.The turnover frequency...Pt/Al2O3 catalysts with mean Pt particle size ranged from 2.7 to 7.1 nm were synthesized by chemical reduction method,and the sulfated counterparts were prepared by impregnation of sulfuric acid.The turnover frequency of platinum for soot oxidation under loose contact conditions in a feed flow containing NO and O2 are positively correlated with the size of platinum.The sulfated Pt/Al2O3 exhibits higher catalytic activity for soot oxidation in the presence of NO despite their reduced ability for NO2 production.Such a contradiction is more significant for those catalysts with smaller platinum particles.Herein,the catalysts were characterized by X-ray diffraction(XRD),Brunauer-Emmett-Teller(BET),transmission electron microscopy(TEM),inductive coupled plasma(ICP)emission spectrometry,CO chemisorption,thermogravimetric analysis(TGA),NH3 temperature-programmed desorption(NH 3-TPD),NO temperature-programmed oxidation(TPO)and NO x temperatureprogrammed desorption(TPD).Possible effect of Pt particle size for the catalytic oxidation of soot in the presence of NO was presented based primarily on the promoted NO2 transfer efficiency onto the soot pushed by the acidic catalysts.展开更多
Ultrafine particles prepared by evaporating pure Fe in CH4 atmosphere using arc-dischargeheating method, were found to consist of Fe-C solid solution, γ-Fe and Fe3C phases. EfFect of annealing temperature on phase tr...Ultrafine particles prepared by evaporating pure Fe in CH4 atmosphere using arc-dischargeheating method, were found to consist of Fe-C solid solution, γ-Fe and Fe3C phases. EfFect of annealing temperature on phase transformation and hyperfine interactions has been investigated by Mossbauer spectroscopy, X-ray diffraction (XRD), differential thermal analysis and thermogravimetry (DTA-TG), transmission electron microscopy (TEM), oxygen determination and vibrating sample magnetometer (VSM) measurements. It was observed that phase transformation of γ-Fe to α-Fe occurs during annealing in vacuum. The mechanism causing the change of hyperfine interactions with annealing temperature differs for Fe-C solution and interstitial compounds. DifFerence of hyperfine interactions of Fe-C solid solution in the starting sample and its annealed samples is ascribed to the improvement of activation of interstitial carbon atoms. Stress-relieving in structure of annealed Fe3C particle can result in a weak influence on hyperfine interactions. Parameters fitted to the Mossbauer spectra show the existence of superparamagnetism in all the samples. Absorbed and combined oxygen on particle surface of the starting sample were determined.展开更多
Fast ionic conductors are one kind of solid state material with ionic conductivity as high as that of melten salts or liquid electrolytes.Ionic conductivity is one of the important parameters for characterizing a fast...Fast ionic conductors are one kind of solid state material with ionic conductivity as high as that of melten salts or liquid electrolytes.Ionic conductivity is one of the important parameters for characterizing a fast ionic conductor.For a long time materialists and chemists have made great efforts in search of new fast ionic conductors with high ionic conductivity.In view of structure,they have synthesised silver and copper fast ionic conductors with so called open structures.But it is not so successful for searching more applicable alkaline fast ionic conductors.Since polymer has flexibility for making thin film,it concentrates attention on the polymer-alkaline salt complex.Fenton et al.have first reported poly(ethylene oxide) (PEO)-alkaline salt complex.Later on Armard et al.have investigated the electrical property of PEO-NaSCN.展开更多
A reaction-coupling strategy is often employed for CO_(2)hydrogenation to produce fuels and chemicals using oxide/zeolite bifunctional catalysts.Because the oxide components are responsible for CO_(2)activation,unders...A reaction-coupling strategy is often employed for CO_(2)hydrogenation to produce fuels and chemicals using oxide/zeolite bifunctional catalysts.Because the oxide components are responsible for CO_(2)activation,understanding the structural effects of these oxides is crucial,however,these effects still remain unclear.In this study,we combined In_(2)O_(3),with varying particle sizes,and SAPO‐34 as bifunctional catalysts for CO_(2)hydrogenation.The CO_(2)conversion and selectivity of the lower olefins increased as the average In_(2)O_(3)crystallite size decreased from 29 to 19 nm;this trend mainly due to the increasing number of oxygen vacancies responsible for CO_(2) and H_(2) activation.However,In_(2)O_(3)particles smaller than 19 nm are more prone to sintering than those with other sizes.The results suggest that 19 nm is the optimal size of In_(2)O_(3)for CO_(2)hydrogenation to lower olefins and that the oxide particle size is crucial for designing catalysts with high activity,high selectivity,and high stability.展开更多
Ni-Re/SiO2 catalysts with controllable Ni particle sizes(4.5–18.0 nm)were synthesized to investigate the effects of the particle size on the amination of monoethanolamine(MEA).The catalysts were characterized by vari...Ni-Re/SiO2 catalysts with controllable Ni particle sizes(4.5–18.0 nm)were synthesized to investigate the effects of the particle size on the amination of monoethanolamine(MEA).The catalysts were characterized by various techniques and evaluated for the amination reaction in a trickle bed reactor at 170℃,8.0 MPa,and 0.5 h^-1 liquid hourly space velocity of MEA(LHSVMEA)in NH3/H2 atmosphere.The Ni-Re/SiO2 catalyst with the lowest Ni particle size(4.5 nm)exhibited the highest yield(66.4%)of the desired amines(ethylenediamine(EDA)and piperazine(PIP)).The results of the analysis show that the turnover frequency of MEA increased slightly(from 193 to 253 h^-1)as the Ni particle sizes of the Ni-Re/SiO2 catalysts increased from 4.5 to 18.0 nm.Moreover,the product distribution could be adjusted by varying the Ni particle size.The ratio of primary to secondary amines increased from 1.0 to 2.0 upon increasing the Ni particle size from 4.5 to 18.0 nm.Further analyses reveal that the Ni particle size influenced the electronic properties of surface Ni,which in turn affected the adsorption of MEA and the reaction pathway of MEA amination.Compared to those of small Ni particles,large particles possessed a higher proportion of high-coordinated terrace Ni sites and a higher surface electron density,which favored the amination of MEA and NH3 to form EDA.展开更多
Production of’renewable Methane’has attracted renewed research interest as a fundamental probe reaction and process for CO_(2)utilization through potential use in Cl fuel production and even for future space explora...Production of’renewable Methane’has attracted renewed research interest as a fundamental probe reaction and process for CO_(2)utilization through potential use in Cl fuel production and even for future space exploration technologies.CO_(2)methanation is a structure sensitive reaction on Ni/CeO_(2)catalysts.To precisely elucidate the size effect of the Ni metal center on the CO_(2)methanation performance,we prepared2%Ni/CeO_(2)catalysts with pre-synthesized uniform Ni particles(2,4 and 8 nm)on a high surface area CeO_(2)support.Transmission electron microscopy(TEM)and ambient pressure X-ray photo spectroscopy(AP-XPS)characterization have confirmed that the catalyst structure and chemical state was uniform and stable under reaction conditions.The 8 nm sized catalyst showed superior methanation selectivity over the 4 and 2 nm counterparts,and the methanation activity in term of TOF is 10 times and 70 times higher than for the 4 and 2 nm counterparts,respectively.The DRIFTS studies revealed that the larger Ni(8 nm particles)over CeO_(2)efficiently facilitated the hydrogenation of the surface formate intermediates,which is proposed as the rate determining step accounting for the excellent CO_(2)methanation performance.展开更多
Adsorption/desorption in a new Zn（Ⅱ）-TiO2 adsorption system was investigated at different particle concentrations （Cp）. TEM, SEM and XRD analyses revealed that the TiO2 particles were an aggregation of nano-sized...Adsorption/desorption in a new Zn（Ⅱ）-TiO2 adsorption system was investigated at different particle concentrations （Cp）. TEM, SEM and XRD analyses revealed that the TiO2 particles were an aggregation of nano-sized （approximately 10 nm） pure anatase-type TiO2. Adsorption experiments were carried out with particle concentrations of 100, 400 and 1000 mg/L, and their adsorption isotherms were found to decline successively, showing an obvious Cp effect. Desorption experiments indicated that adsorption in this system was irreversible, and the irreversibility increased with increasing Cp. These phenomena could be explained by the MEA （metastable equilibrium adsorption） theory and the Cp effect could be modeled well with an MEA-Freundlich-type Cp effect isotherm equation. This study may heln understand environmental behavior of contaminants on ultrafine natural particles.展开更多
Gold catalysts supported on Mg-Al mixed oxides for oxidative esterification of methacrolein are prepared by impregnation.Effects of the support particle size,concentration of HAuCl4 solution and Mg/Al ratio on gold lo...Gold catalysts supported on Mg-Al mixed oxides for oxidative esterification of methacrolein are prepared by impregnation.Effects of the support particle size,concentration of HAuCl4 solution and Mg/Al ratio on gold loading and catalytic properties are investigated.The catalysts are characterized by CO_(2)-TPD,EDS,XPS,STEM and XRD techniques.Catalysts with smaller support particle size show more uniform gold distribution and higher gold dispersion,resulting in a higher catalytic performance,and the uniformity of gold and the activity of the catalysts with larger support particle size can be improved by decreasing the concentration of HAuCl4 solution.The Mg/Al molar ratio has significant effect on the uniformity of gold and the activity of the catalyst,and the optimum Mg/Al molar ratio is 0.1–0.2.This study underlines the importance of engineering support particle size,concentration of HAuCl4 solution and density of adsorption sites for efficient gold loading on support by impregnation.展开更多
Carbon deposition is sensitive to the metal particle sizes of supported Ni catalysts in CH_4/CO_2 reforming.To explore the reason of this phenomenon,Ni4,Ni8,and Ni12 which re flect the different cluster thicknesses su...Carbon deposition is sensitive to the metal particle sizes of supported Ni catalysts in CH_4/CO_2 reforming.To explore the reason of this phenomenon,Ni4,Ni8,and Ni12 which re flect the different cluster thicknesses supported on the MgO(100) slabs,have been employed to simulate Ni/MgO catalysts,and the reaction pathways of CH_4/CO_2 reforming on Nix/MgO(100) models are investigated by density functional theory.The reforming mechanisms of CH_4/CO_2 on different Nix/MgO(100) indicate the energy barriers of CH_4 dissociated adsorption,CH dissociation,and C oxidation three factors are all declining with the decrease of the Ni cluster sizes.The Hirshfeld charges analyses of three steps as described above show only Ni atoms in bottom two layers can obtain electrons from the MgO supporters,and the main electron transfer occurs between adsorbed species and their directly contacted Ni atoms.Due to more electron-rich Ni atoms in contact with the MgO supporters,the Ni/MgO catalysts with small Ni particles have a strong metal particle size effect and lead to its better catalytic activity.展开更多
The deactivation behavior by crystallite growth of nickel nanoparticles on various supports（carbon nanofibers, zirconia, Si C, α-Al2O3 and γ-Al2O3） was investigated in the aqueous phase reforming of ethylene glyco...The deactivation behavior by crystallite growth of nickel nanoparticles on various supports（carbon nanofibers, zirconia, Si C, α-Al2O3 and γ-Al2O3） was investigated in the aqueous phase reforming of ethylene glycol. Supported Ni catalysts of ~10 wt% were prepared by impregnation of carbon nanofibers（CNF）,Zr O2, SiC, γ-Al2O3 and α-Al2O3. The extent of the Ni nanoparticle growth on various support materials follows the order CNF ~ ZrO2〉 SiC 〉 γ-Al2O3〉〉 α-Al2O3 which sequence, however, was determined by the initial Ni particle size. Based on the observed nickel leaching and the specific growth characteristics; the particle size distribution and the effect of loading on the growth rate, Ostwald ripening is suggested to be the main mechanism contributing to nickel particle growth. Remarkably, initially smaller Ni particles（~12 nm） supported on α-Al2O3 were found to outgrow Ni particles with initially larger size（~20 nm）. It is put forward that the higher susceptibility with respect to oxidation of the smaller Ni nanoparticles and differences in initial particle size distribution are responsible for this behavior.展开更多
We study the transition to turbulence of channel flow of finite-size particle suspensions at low volume fraction, i.e., φ ≈0.001. The critical Reynolds number above which turbulence is sustained reduces to Re ≈ 167...We study the transition to turbulence of channel flow of finite-size particle suspensions at low volume fraction, i.e., φ ≈0.001. The critical Reynolds number above which turbulence is sustained reduces to Re ≈ 1675, in the presence of few particles, independently of the initial condition, a value lower than that of the corresponding single-phase flow, i.e., Re ≈1775. In the dilute suspension, the initial arrangement of the particles is important to trigger the transition at a fixed Reynolds number and particle volume fraction. As in single phase flows, streamwise elongated disturbances are initially induced in the flow. If particles can induce oblique disturbances with high enough energy within a certain time, the streaks breakdown, flow experiences the transition to turbulence and the particle trajectories become chaotic, Otherwise, the streaks decay in time and the particles immigrate towards the channel core in a laminar flow.展开更多
An intensive study of the particle size distribution of four commercial ultrafine alumina powders to obtain information about the powder agglomeration and relate them to the compactibility and the sinterability has be...An intensive study of the particle size distribution of four commercial ultrafine alumina powders to obtain information about the powder agglomeration and relate them to the compactibility and the sinterability has been made.展开更多
The film formation process of micro-PS particles (diameter 742 nm) and nano-PS particles (diameter 29 nm) was studied by atomic force microscopy and differential scanning calorimetry. During a step heating process, th...The film formation process of micro-PS particles (diameter 742 nm) and nano-PS particles (diameter 29 nm) was studied by atomic force microscopy and differential scanning calorimetry. During a step heating process, the particles were annealed for 0.5 h at each selected temperature. It was found that the deformation and interdiffusion temperatures of the micro-PS particles are ca. 120-130degreesC and 140-150degreesC, that of the nano-PS particles are 90degreesC and 100-110degreesC respectively. The DSC traces of nano-PS particles showed that there was an exothermic peak near T-g after annealing for 0.5 h at the selected temperatures below 90degreesC; otherwise, the exothermic peak disappeared after annealing at 100degreesC or above. Compared with the micro-PS particles, the sintering process of nano-PS particles occurs at much lower temperature determined by the confined state of polymer chains with higher conformational energy in nano-particles, and completes in a much narrower temperature range driven mainly by the larger total surface energy.展开更多
This paper represents a review of the recent researches that investigate the behavior of the gas turbulent flow laden with solid particles. The significant parameters that influence the interactions between the both p...This paper represents a review of the recent researches that investigate the behavior of the gas turbulent flow laden with solid particles. The significant parameters that influence the interactions between the both phases, such as particle size, loading ratio and the gas velocity, have been extensively reviewed. Those parameters are presented in dimensionless numbers in which the applicability of studying its effect in terms of all circumstances of the gas turbulent channel flow at different condition is possible. The represented results show that the turbulence degree is proportional to the particle size. It was found that at the most flow conditions even at low mass ratio, the particle shape, density and size significantly alter the turbulence characteristics. However, the results demonstrate that the particle Reynolds number is a vital sign: the turbulence field becomes weaker if particle Reynolds number is lower than the critical limit and vies verse. The gas velocity has a strong effect on the particles settling along the channel flow and as a result, the pressure drop will be affected.展开更多
Effect of the particle number density on the dispersion properties of longitudinal and transverse lattice waves in a two-dimensional Yukawa charged-dust system is investigated using molecular dynamics simulation. The ...Effect of the particle number density on the dispersion properties of longitudinal and transverse lattice waves in a two-dimensional Yukawa charged-dust system is investigated using molecular dynamics simulation. The dispersion relations for the waves are obtained. It is found that the frequencies of both the longitudinal and transverse dust waves increase with the density and when the density is sufficiently high a cutoff region appears at the short wavelength. With the increase of the particle number density, the common frequency tends to increase, and the sound speed of the longitudinal wave also increases, but that of the transverse wave remains low.展开更多
The mechanism of the response motion of a suspended particle to turbulent motion of its surrounding fluid is different according to si:e of turbulent eddies. The particle is dragged by the viscous force of large eddie...The mechanism of the response motion of a suspended particle to turbulent motion of its surrounding fluid is different according to si:e of turbulent eddies. The particle is dragged by the viscous force of large eddies, and meanwhile driven randomly by small eddies. Based on this understanding, the dispersion of a particle with finite size in a homogeneous isotropic turbulence is calculated in this study. Results show that there are two competing effects: when enhanced by the inertia of a particle, the long-term particle diffusivity is reduced by the finite size of the particle.展开更多
Ethanol steam reforming(ESR)represents a promising route for sustainable hydrogen production,leveraging the high hydrogen content,renewability,and logistical advantages of ethanol.Although Ni-based catalysts are leadi...Ethanol steam reforming(ESR)represents a promising route for sustainable hydrogen production,leveraging the high hydrogen content,renewability,and logistical advantages of ethanol.Although Ni-based catalysts are leading non-noble candidates for ESR,their practical deployment is hindered by compromised H_(2) production efficiency and rapid deactivation.In this work,we combined catalyst synthesis,kinetic analysis,and mechanistic investigation to elucidate the effectsof Ni particle size(3-9 nm)on ESR performance of Ni/CeO_(2) catalysts.These Ni/CeO_(2) catalysts were prepared via a citric acid-assisted coprecipitation method,and systematically characterized using complementary techniques,including high-resolution transmission electron microscopy(HRTEM),in situ X-ray photoelectron spectroscopy(XPS),hydrogen temperature-programmed reduction(H_(2)-TPR),Raman spectroscopy,O_(2)/CO chemisorption,and temperature-programmed surface reaction(TPSR)analyses.Mechanistic study revealed that ethanol dehydrogenation to acetaldehyde is the rate-determining step,defining the intrinsic activity of Ni sites,whereas C-C bond cleavage governs H_(2) selectivity in ESR.At smaller Ni sizes(e.g.,3.1 nm),larger CeO_(2) surface was exposed,which promoted acetaldehyde condensation to acetone,and consequently reduced H_(2) production efficiency.The Ni/CeO_(2) catalyst with~5 nm of Ni particles afforded the highest H_(2) yield(66.3%)and outstanding stability by balancing dehydrogenation activity,H_(2) selectivity,and coking resistance.Conversely,larger Ni particles(>6 nm)facilitated methanation reaction and catalyst deactivation.This work reconciles prior inconsistencies in the Ni size effects on ESR and provides guidance for the design of efficient and durable Ni-based catalysts for H_(2) production.展开更多
Effective soil particle size composition can more realistically reflect the particle size sorting process of erosion.To reveal the individual contributions of rainfall intensity and slope to splash erosion,and to dist...Effective soil particle size composition can more realistically reflect the particle size sorting process of erosion.To reveal the individual contributions of rainfall intensity and slope to splash erosion,and to distinguish the enrichment ratio of each size and the critical size in splash,loessial soil collected on the Loess Plateau in May 2019 was tested under different rainfall intensities(60,84,108,132,156 mm h^(-1))and slopes(0°,5°,10°,15°,20°).The results demonstrated that 99%of splash mass was concentrated in 0–0.4 m.Rainfall intensity was the major factor for splash according to the raindrop generation mode by rainfall simulator nozzles.The contributions of rainfall intensity to splash erosion were 82.72%and 93.24%,respectively in upslope and downslope direction.The mass percentages of effective clay and effective silt were positively correlated with rainfall intensity,while the mass percentages of effective very fine sand and effective fine sand were negatively correlated with rainfall intensity.Opposite to effective very fine sand,the mass percentages of effective clay significantly decreased with increasing distance.Rainfall intensity had significant effects on enrichment ratios,positively for effective clay and effective silt and negatively for effective very fine sand and effective fine sand.The critical effective particle size in splash for loessial soil was 50μm.展开更多
Turbulence enhancement by particle wake effect is studied by numerical simulation of gas turbulent flows passing over particle under various particle sizes, inlet gas velocities, gas viscosity, gas density and the dis...Turbulence enhancement by particle wake effect is studied by numerical simulation of gas turbulent flows passing over particle under various particle sizes, inlet gas velocities, gas viscosity, gas density and the distance of particles. By performing dimension analysis and using the form of gas-particle interaction source term for reference, a new semi-empirical turbulence enhancement model by the particle-wake effect is proposed. The turbulence model is then incorporated into second-order moment model for simulating gas-particle flows in a horizontal channel with different wall roughness and a sudden-expansion chamber. The results show that this model is with higher calculating accuracy than another two turbulence models in comparison with the experimental results.展开更多
基金This work was supported by projects of the National Key R&D Program of China(No.2017YFC0211102)the Key Laboratory of Advanced Materials of the Ministry of Education.
文摘Pt/Al2O3 catalysts with mean Pt particle size ranged from 2.7 to 7.1 nm were synthesized by chemical reduction method,and the sulfated counterparts were prepared by impregnation of sulfuric acid.The turnover frequency of platinum for soot oxidation under loose contact conditions in a feed flow containing NO and O2 are positively correlated with the size of platinum.The sulfated Pt/Al2O3 exhibits higher catalytic activity for soot oxidation in the presence of NO despite their reduced ability for NO2 production.Such a contradiction is more significant for those catalysts with smaller platinum particles.Herein,the catalysts were characterized by X-ray diffraction(XRD),Brunauer-Emmett-Teller(BET),transmission electron microscopy(TEM),inductive coupled plasma(ICP)emission spectrometry,CO chemisorption,thermogravimetric analysis(TGA),NH3 temperature-programmed desorption(NH 3-TPD),NO temperature-programmed oxidation(TPO)and NO x temperatureprogrammed desorption(TPD).Possible effect of Pt particle size for the catalytic oxidation of soot in the presence of NO was presented based primarily on the promoted NO2 transfer efficiency onto the soot pushed by the acidic catalysts.
文摘Ultrafine particles prepared by evaporating pure Fe in CH4 atmosphere using arc-dischargeheating method, were found to consist of Fe-C solid solution, γ-Fe and Fe3C phases. EfFect of annealing temperature on phase transformation and hyperfine interactions has been investigated by Mossbauer spectroscopy, X-ray diffraction (XRD), differential thermal analysis and thermogravimetry (DTA-TG), transmission electron microscopy (TEM), oxygen determination and vibrating sample magnetometer (VSM) measurements. It was observed that phase transformation of γ-Fe to α-Fe occurs during annealing in vacuum. The mechanism causing the change of hyperfine interactions with annealing temperature differs for Fe-C solution and interstitial compounds. DifFerence of hyperfine interactions of Fe-C solid solution in the starting sample and its annealed samples is ascribed to the improvement of activation of interstitial carbon atoms. Stress-relieving in structure of annealed Fe3C particle can result in a weak influence on hyperfine interactions. Parameters fitted to the Mossbauer spectra show the existence of superparamagnetism in all the samples. Absorbed and combined oxygen on particle surface of the starting sample were determined.
文摘Fast ionic conductors are one kind of solid state material with ionic conductivity as high as that of melten salts or liquid electrolytes.Ionic conductivity is one of the important parameters for characterizing a fast ionic conductor.For a long time materialists and chemists have made great efforts in search of new fast ionic conductors with high ionic conductivity.In view of structure,they have synthesised silver and copper fast ionic conductors with so called open structures.But it is not so successful for searching more applicable alkaline fast ionic conductors.Since polymer has flexibility for making thin film,it concentrates attention on the polymer-alkaline salt complex.Fenton et al.have first reported poly(ethylene oxide) (PEO)-alkaline salt complex.Later on Armard et al.have investigated the electrical property of PEO-NaSCN.
文摘A reaction-coupling strategy is often employed for CO_(2)hydrogenation to produce fuels and chemicals using oxide/zeolite bifunctional catalysts.Because the oxide components are responsible for CO_(2)activation,understanding the structural effects of these oxides is crucial,however,these effects still remain unclear.In this study,we combined In_(2)O_(3),with varying particle sizes,and SAPO‐34 as bifunctional catalysts for CO_(2)hydrogenation.The CO_(2)conversion and selectivity of the lower olefins increased as the average In_(2)O_(3)crystallite size decreased from 29 to 19 nm;this trend mainly due to the increasing number of oxygen vacancies responsible for CO_(2) and H_(2) activation.However,In_(2)O_(3)particles smaller than 19 nm are more prone to sintering than those with other sizes.The results suggest that 19 nm is the optimal size of In_(2)O_(3)for CO_(2)hydrogenation to lower olefins and that the oxide particle size is crucial for designing catalysts with high activity,high selectivity,and high stability.
基金supported by the National Natural Science Foundation of China(21273227)Strategic Priority Research Program of Chinese Academy of Sciences(XDB17000000)~~
文摘Ni-Re/SiO2 catalysts with controllable Ni particle sizes(4.5–18.0 nm)were synthesized to investigate the effects of the particle size on the amination of monoethanolamine(MEA).The catalysts were characterized by various techniques and evaluated for the amination reaction in a trickle bed reactor at 170℃,8.0 MPa,and 0.5 h^-1 liquid hourly space velocity of MEA(LHSVMEA)in NH3/H2 atmosphere.The Ni-Re/SiO2 catalyst with the lowest Ni particle size(4.5 nm)exhibited the highest yield(66.4%)of the desired amines(ethylenediamine(EDA)and piperazine(PIP)).The results of the analysis show that the turnover frequency of MEA increased slightly(from 193 to 253 h^-1)as the Ni particle sizes of the Ni-Re/SiO2 catalysts increased from 4.5 to 18.0 nm.Moreover,the product distribution could be adjusted by varying the Ni particle size.The ratio of primary to secondary amines increased from 1.0 to 2.0 upon increasing the Ni particle size from 4.5 to 18.0 nm.Further analyses reveal that the Ni particle size influenced the electronic properties of surface Ni,which in turn affected the adsorption of MEA and the reaction pathway of MEA amination.Compared to those of small Ni particles,large particles possessed a higher proportion of high-coordinated terrace Ni sites and a higher surface electron density,which favored the amination of MEA and NH3 to form EDA.
基金supported by the U.S.Department of Energy under contract no.DE-SC0012704supported by a U.S.Department of Energy Early Career Award+2 种基金ICREA Academia program and projects MICINN/FEDER RTI2018093996-B-C31 and GC 2017 SGR 128financial support from the Natural Science Foundation of China(22002140)Young Elite Scientist Sponsorship Program by CAST,NO.2019QNRC001。
文摘Production of’renewable Methane’has attracted renewed research interest as a fundamental probe reaction and process for CO_(2)utilization through potential use in Cl fuel production and even for future space exploration technologies.CO_(2)methanation is a structure sensitive reaction on Ni/CeO_(2)catalysts.To precisely elucidate the size effect of the Ni metal center on the CO_(2)methanation performance,we prepared2%Ni/CeO_(2)catalysts with pre-synthesized uniform Ni particles(2,4 and 8 nm)on a high surface area CeO_(2)support.Transmission electron microscopy(TEM)and ambient pressure X-ray photo spectroscopy(AP-XPS)characterization have confirmed that the catalyst structure and chemical state was uniform and stable under reaction conditions.The 8 nm sized catalyst showed superior methanation selectivity over the 4 and 2 nm counterparts,and the methanation activity in term of TOF is 10 times and 70 times higher than for the 4 and 2 nm counterparts,respectively.The DRIFTS studies revealed that the larger Ni(8 nm particles)over CeO_(2)efficiently facilitated the hydrogenation of the surface formate intermediates,which is proposed as the rate determining step accounting for the excellent CO_(2)methanation performance.
基金Project supported by the National Natural Science Foundation of China(No.20537020)the "Hundred Talent Scientist Program" of the Chinese Academy of Sciences.
文摘Adsorption/desorption in a new Zn（Ⅱ）-TiO2 adsorption system was investigated at different particle concentrations （Cp）. TEM, SEM and XRD analyses revealed that the TiO2 particles were an aggregation of nano-sized （approximately 10 nm） pure anatase-type TiO2. Adsorption experiments were carried out with particle concentrations of 100, 400 and 1000 mg/L, and their adsorption isotherms were found to decline successively, showing an obvious Cp effect. Desorption experiments indicated that adsorption in this system was irreversible, and the irreversibility increased with increasing Cp. These phenomena could be explained by the MEA （metastable equilibrium adsorption） theory and the Cp effect could be modeled well with an MEA-Freundlich-type Cp effect isotherm equation. This study may heln understand environmental behavior of contaminants on ultrafine natural particles.
基金Open Project of Yunnan Precious Metals Laboratory Co.,Ltd(YPML-2023050269)the Fundamental Research Funds for the Central Universities(226-2023-00085,226-2023-00057).
文摘Gold catalysts supported on Mg-Al mixed oxides for oxidative esterification of methacrolein are prepared by impregnation.Effects of the support particle size,concentration of HAuCl4 solution and Mg/Al ratio on gold loading and catalytic properties are investigated.The catalysts are characterized by CO_(2)-TPD,EDS,XPS,STEM and XRD techniques.Catalysts with smaller support particle size show more uniform gold distribution and higher gold dispersion,resulting in a higher catalytic performance,and the uniformity of gold and the activity of the catalysts with larger support particle size can be improved by decreasing the concentration of HAuCl4 solution.The Mg/Al molar ratio has significant effect on the uniformity of gold and the activity of the catalyst,and the optimum Mg/Al molar ratio is 0.1–0.2.This study underlines the importance of engineering support particle size,concentration of HAuCl4 solution and density of adsorption sites for efficient gold loading on support by impregnation.
基金Supported by the National Natural Science Foundation of China(U1361202,51276120)
文摘Carbon deposition is sensitive to the metal particle sizes of supported Ni catalysts in CH_4/CO_2 reforming.To explore the reason of this phenomenon,Ni4,Ni8,and Ni12 which re flect the different cluster thicknesses supported on the MgO(100) slabs,have been employed to simulate Ni/MgO catalysts,and the reaction pathways of CH_4/CO_2 reforming on Nix/MgO(100) models are investigated by density functional theory.The reforming mechanisms of CH_4/CO_2 on different Nix/MgO(100) indicate the energy barriers of CH_4 dissociated adsorption,CH dissociation,and C oxidation three factors are all declining with the decrease of the Ni cluster sizes.The Hirshfeld charges analyses of three steps as described above show only Ni atoms in bottom two layers can obtain electrons from the MgO supporters,and the main electron transfer occurs between adsorbed species and their directly contacted Ni atoms.Due to more electron-rich Ni atoms in contact with the MgO supporters,the Ni/MgO catalysts with small Ni particles have a strong metal particle size effect and lead to its better catalytic activity.
基金the support of the Smart Mix Program of The Netherlands Ministry of Economic Affairs, Agriculture and Innovation and The Netherlands Ministry of Education, Culture and Science (Grant no. 053.70.011)
文摘The deactivation behavior by crystallite growth of nickel nanoparticles on various supports（carbon nanofibers, zirconia, Si C, α-Al2O3 and γ-Al2O3） was investigated in the aqueous phase reforming of ethylene glycol. Supported Ni catalysts of ~10 wt% were prepared by impregnation of carbon nanofibers（CNF）,Zr O2, SiC, γ-Al2O3 and α-Al2O3. The extent of the Ni nanoparticle growth on various support materials follows the order CNF ~ ZrO2〉 SiC 〉 γ-Al2O3〉〉 α-Al2O3 which sequence, however, was determined by the initial Ni particle size. Based on the observed nickel leaching and the specific growth characteristics; the particle size distribution and the effect of loading on the growth rate, Ostwald ripening is suggested to be the main mechanism contributing to nickel particle growth. Remarkably, initially smaller Ni particles（~12 nm） supported on α-Al2O3 were found to outgrow Ni particles with initially larger size（~20 nm）. It is put forward that the higher susceptibility with respect to oxidation of the smaller Ni nanoparticles and differences in initial particle size distribution are responsible for this behavior.
基金supported by the European Research Council Grant No.ERC-2013-CoG-616186,TRITOSthe Swedish Research Council(VR)
文摘We study the transition to turbulence of channel flow of finite-size particle suspensions at low volume fraction, i.e., φ ≈0.001. The critical Reynolds number above which turbulence is sustained reduces to Re ≈ 1675, in the presence of few particles, independently of the initial condition, a value lower than that of the corresponding single-phase flow, i.e., Re ≈1775. In the dilute suspension, the initial arrangement of the particles is important to trigger the transition at a fixed Reynolds number and particle volume fraction. As in single phase flows, streamwise elongated disturbances are initially induced in the flow. If particles can induce oblique disturbances with high enough energy within a certain time, the streaks breakdown, flow experiences the transition to turbulence and the particle trajectories become chaotic, Otherwise, the streaks decay in time and the particles immigrate towards the channel core in a laminar flow.
文摘An intensive study of the particle size distribution of four commercial ultrafine alumina powders to obtain information about the powder agglomeration and relate them to the compactibility and the sinterability has been made.
基金This work was funded by the Special Funds for Major State Basic Research Project (Grant No. 95-12-G1999064800) and National Natural Science Foundation of China (Grant No. 20004011 & 20023003).
文摘The film formation process of micro-PS particles (diameter 742 nm) and nano-PS particles (diameter 29 nm) was studied by atomic force microscopy and differential scanning calorimetry. During a step heating process, the particles were annealed for 0.5 h at each selected temperature. It was found that the deformation and interdiffusion temperatures of the micro-PS particles are ca. 120-130degreesC and 140-150degreesC, that of the nano-PS particles are 90degreesC and 100-110degreesC respectively. The DSC traces of nano-PS particles showed that there was an exothermic peak near T-g after annealing for 0.5 h at the selected temperatures below 90degreesC; otherwise, the exothermic peak disappeared after annealing at 100degreesC or above. Compared with the micro-PS particles, the sintering process of nano-PS particles occurs at much lower temperature determined by the confined state of polymer chains with higher conformational energy in nano-particles, and completes in a much narrower temperature range driven mainly by the larger total surface energy.
文摘This paper represents a review of the recent researches that investigate the behavior of the gas turbulent flow laden with solid particles. The significant parameters that influence the interactions between the both phases, such as particle size, loading ratio and the gas velocity, have been extensively reviewed. Those parameters are presented in dimensionless numbers in which the applicability of studying its effect in terms of all circumstances of the gas turbulent channel flow at different condition is possible. The represented results show that the turbulence degree is proportional to the particle size. It was found that at the most flow conditions even at low mass ratio, the particle shape, density and size significantly alter the turbulence characteristics. However, the results demonstrate that the particle Reynolds number is a vital sign: the turbulence field becomes weaker if particle Reynolds number is lower than the critical limit and vies verse. The gas velocity has a strong effect on the particles settling along the channel flow and as a result, the pressure drop will be affected.
基金Supported by the National Natural Science Foundation of China under Grant Nos 11675261 and 21403297the Scientific Research Foundation of Ludong University under Grant No LY2014010
文摘Effect of the particle number density on the dispersion properties of longitudinal and transverse lattice waves in a two-dimensional Yukawa charged-dust system is investigated using molecular dynamics simulation. The dispersion relations for the waves are obtained. It is found that the frequencies of both the longitudinal and transverse dust waves increase with the density and when the density is sufficiently high a cutoff region appears at the short wavelength. With the increase of the particle number density, the common frequency tends to increase, and the sound speed of the longitudinal wave also increases, but that of the transverse wave remains low.
文摘The mechanism of the response motion of a suspended particle to turbulent motion of its surrounding fluid is different according to si:e of turbulent eddies. The particle is dragged by the viscous force of large eddies, and meanwhile driven randomly by small eddies. Based on this understanding, the dispersion of a particle with finite size in a homogeneous isotropic turbulence is calculated in this study. Results show that there are two competing effects: when enhanced by the inertia of a particle, the long-term particle diffusivity is reduced by the finite size of the particle.
基金supported by the National Key Research and Develop-ment Pr0gram of China(Nos.2021YFA1501104 and 2023YFA1506802)the National Natural Science Foundation of China(No.22032001).
文摘Ethanol steam reforming(ESR)represents a promising route for sustainable hydrogen production,leveraging the high hydrogen content,renewability,and logistical advantages of ethanol.Although Ni-based catalysts are leading non-noble candidates for ESR,their practical deployment is hindered by compromised H_(2) production efficiency and rapid deactivation.In this work,we combined catalyst synthesis,kinetic analysis,and mechanistic investigation to elucidate the effectsof Ni particle size(3-9 nm)on ESR performance of Ni/CeO_(2) catalysts.These Ni/CeO_(2) catalysts were prepared via a citric acid-assisted coprecipitation method,and systematically characterized using complementary techniques,including high-resolution transmission electron microscopy(HRTEM),in situ X-ray photoelectron spectroscopy(XPS),hydrogen temperature-programmed reduction(H_(2)-TPR),Raman spectroscopy,O_(2)/CO chemisorption,and temperature-programmed surface reaction(TPSR)analyses.Mechanistic study revealed that ethanol dehydrogenation to acetaldehyde is the rate-determining step,defining the intrinsic activity of Ni sites,whereas C-C bond cleavage governs H_(2) selectivity in ESR.At smaller Ni sizes(e.g.,3.1 nm),larger CeO_(2) surface was exposed,which promoted acetaldehyde condensation to acetone,and consequently reduced H_(2) production efficiency.The Ni/CeO_(2) catalyst with~5 nm of Ni particles afforded the highest H_(2) yield(66.3%)and outstanding stability by balancing dehydrogenation activity,H_(2) selectivity,and coking resistance.Conversely,larger Ni particles(>6 nm)facilitated methanation reaction and catalyst deactivation.This work reconciles prior inconsistencies in the Ni size effects on ESR and provides guidance for the design of efficient and durable Ni-based catalysts for H_(2) production.
基金Natural Science Foundation of China,No.42077058,No.41601282,No.41867015Young Talent Fund of University Association for Science and Technology in Shaanxi,China,No.20210705+1 种基金Fundamental Research Funds for Central Universities,No.GK202309005Shaanxi Provincial Key Research and Development Program,No.2021ZDLSF05-02。
文摘Effective soil particle size composition can more realistically reflect the particle size sorting process of erosion.To reveal the individual contributions of rainfall intensity and slope to splash erosion,and to distinguish the enrichment ratio of each size and the critical size in splash,loessial soil collected on the Loess Plateau in May 2019 was tested under different rainfall intensities(60,84,108,132,156 mm h^(-1))and slopes(0°,5°,10°,15°,20°).The results demonstrated that 99%of splash mass was concentrated in 0–0.4 m.Rainfall intensity was the major factor for splash according to the raindrop generation mode by rainfall simulator nozzles.The contributions of rainfall intensity to splash erosion were 82.72%and 93.24%,respectively in upslope and downslope direction.The mass percentages of effective clay and effective silt were positively correlated with rainfall intensity,while the mass percentages of effective very fine sand and effective fine sand were negatively correlated with rainfall intensity.Opposite to effective very fine sand,the mass percentages of effective clay significantly decreased with increasing distance.Rainfall intensity had significant effects on enrichment ratios,positively for effective clay and effective silt and negatively for effective very fine sand and effective fine sand.The critical effective particle size in splash for loessial soil was 50μm.
基金the National Natural Science Foundation of China(No.50736006)the Aero-Science Fund(No.2009ZB56004)the Jiangxi Provincial Natural Science Foundation(Nos.2009GZC0100 and 2008GZW0016)
文摘Turbulence enhancement by particle wake effect is studied by numerical simulation of gas turbulent flows passing over particle under various particle sizes, inlet gas velocities, gas viscosity, gas density and the distance of particles. By performing dimension analysis and using the form of gas-particle interaction source term for reference, a new semi-empirical turbulence enhancement model by the particle-wake effect is proposed. The turbulence model is then incorporated into second-order moment model for simulating gas-particle flows in a horizontal channel with different wall roughness and a sudden-expansion chamber. The results show that this model is with higher calculating accuracy than another two turbulence models in comparison with the experimental results.
