One-photon absorption and two-photon absorption（TPA） properties of three tris（picolyl）amine-based zinc ion sensors are investigated by employing the density functional response theory in combination with the polar...One-photon absorption and two-photon absorption（TPA） properties of three tris（picolyl）amine-based zinc ion sensors are investigated by employing the density functional response theory in combination with the polarizable continuum model.The different isomer and coordination geometry of each probe are taken into account. Special emphasis is placed on the effects of isomerism and the coordination mode on the optical properties. The intra-molecular charge transfer（ICT）properties are specified by natural bond orbital charge analysis. It is shown that the isomerism has non-negligible effects on TPA properties of free ligands. It is found that both the TPA wavelength and the cross section are highly dependent on the coordination mode. When the zinc ion connects with the picolyl unit in the middle of a ligand, the zinc complex has a large TPA intensity in a long wavelength range due to the increased ICT mechanism.展开更多
The influence of rotational isomerism on the two-photon absorption （TPA） of FTC chromophores has been investi- gated using the quadratic response theory with the B3LYP functional. Eight rotamers induced by three rot...The influence of rotational isomerism on the two-photon absorption （TPA） of FTC chromophores has been investi- gated using the quadratic response theory with the B3LYP functional. Eight rotamers induced by three rotatable single bonds in the molecule are fully optimized, and it is found that their conformational energies are nearly degenerate. Our calculations demonstrate that rotational isomerism has an important effect on the TPA cross sections. For a certain rotamer, the maximum TPA cross section is enhanced significantly. In addition, in the longer wavelength region, the rotational isomerism could lead to a large shift of the TPA position.展开更多
Organic additives with multiple functional groups have shown great promise in improving the performance and stability of perovskite solar cells.The functional groups can passivate undercoordinated ions to reduce nonra...Organic additives with multiple functional groups have shown great promise in improving the performance and stability of perovskite solar cells.The functional groups can passivate undercoordinated ions to reduce nonradiative recombination losses.However,how these groups synergistically affect the enhancement beyond passivation is still unclear.Specifically,isomeric molecules with different substitution patterns or molecular shapes remain elusive in designing new organic additives.Here,we report two isomeric carbazolyl bisphosphonate additives,2,7-Cz BP and 3,6-Cz BP.The isomerism effect on passivation and charge transport process was studied.The two molecules have similar passivation effects through multiple interactions,e.g.,P=O···Pb,P=O···H–N and N–H···I.2,7-CzBP can further bridge the perovskite crystallites to facilitates charge transport.Power conversion efficiencies(PCEs)of 25.88%and 21.04%were achieved for 0.09 cm^(2)devices and 14 cm^(2)modules after 2,7-Cz BP treatment,respectively.The devices exhibited enhanced operational stability maintaining 95%of initial PCE after 1000 h of continuous maximum power point tracking.This study of isomerism effect hints at the importance of tuning substitution positions and molecular shapes for organic additives,which paves the way for innovation of next-generation multifunctional aromatic additives.展开更多
Efficient and selective glucose-to-fructose isomerization is a crucial step for production of oxygenated chemicals derived from sugars,which is usually catalyzed by base or Lewis acid heterogeneous catalyst.However,hi...Efficient and selective glucose-to-fructose isomerization is a crucial step for production of oxygenated chemicals derived from sugars,which is usually catalyzed by base or Lewis acid heterogeneous catalyst.However,high yield and selectivity of fructose cannot be simultaneously obtained under mild conditions which hamper the scale of application compared with enzymatic catalysis.Herein,a Li-promoted C_(3)N_(4) catalyst was exploited which afforded an excellent fructose yield(40.3 wt%)and selectivity(99.5%)from glucose in water at 50℃,attributed to the formation of stable Li–N bond to strengthen the basic sites of catalysts.Furthermore,the so-formed N_(6)–Li–H_(2)O active site on Li–C_(3)N_(4) catalyst in aqueous phase changes the local electronic structure and strengthens the deprotonation process during glucose isomerization into fructose.The superior catalytic performance which is comparable to biological pathway suggests promising applications of lithium containing heterogeneous catalyst in biomass refinery.展开更多
The transformation of aldose to ketose or common sugars into rare saccharides,including rare ketoses and aldoses,is of great value and interest to the food industry and for saccharidic biomass utilization,medicine,and...The transformation of aldose to ketose or common sugars into rare saccharides,including rare ketoses and aldoses,is of great value and interest to the food industry and for saccharidic biomass utilization,medicine,and the synthesis of drugs.Nowadays,high-fructose corn syrup(HFCS)is industrially produced in more than 10 million tons annually using immobilized glucose isomerase.Some low-calorie saccharides such as tagatose and psicose,which are becoming popular sweeteners,have also been produced on a pilot scale in order to replace sucrose and HFCS.However,current catalysts and catalytic processes are still difficult to utilize in biomass conversion and also have strong substrate dependence in producing high-value,rare sugars.Considering the specific reaction properties of saccharides and catalysts,since the pioneering discovery by Fischer,various catalysts and catalytic systems have been discovered or developed in attempts to extend the reaction pathways,improve the reaction efficiency,and to potentially produce commercial products.In this review,we trace the history of sugar isomerization/epimerization reactions and summarize the important breakthroughs for each reaction as well as the difficulties that remain unresolved to date.展开更多
5-amino-4-nitrobenzo[1,2-c:3,4-c']bis([1,2,5]oxadiazole)1,6-dioxide(CL-18)exhibits significant potential as an initiating explosive.However,its current synthesis process remains non-scalable due to low yields and ...5-amino-4-nitrobenzo[1,2-c:3,4-c']bis([1,2,5]oxadiazole)1,6-dioxide(CL-18)exhibits significant potential as an initiating explosive.However,its current synthesis process remains non-scalable due to low yields and safety risks.In this study,we have developed a simple and safe synthetic route for CL-18.It was synthesized from 3,5-dihaloanisole in a four-step reaction with an overall yield exceeding 60%,surpassing all reported yields in the literature.Subsequently,recrystallization of CL-18 was successfully achieved by carefully selecting appropriate solvents and antisolvents to reduce its mechanical sensitivity.Ultimately,when DMF-ethanol was employed as the recrystallization solvent system,satisfactory product yield(>90%)and reduced mechanical sensitivity(IS=15 J;FS=216 N)were obtained.Additionally,CL-18 is derived from the rearrangement of oxygen atoms on i-CL-18 furoxan,and a comparative analysis of their physicochemical properties was conducted.The thermal stability of both compounds is similar,with onset decomposition temperatures recorded at 186 and 182℃respectively.Similarly,they exhibit 5 s breaking point temperatures of 236 and 237℃.Additionally,we present novel insights into the positional-isomerization-laser-ignition performance of CL-18 and its isomer i-CL-18 using laser irradiation for the first time.Remarkably,our findings demonstrate that i-CL-18 exhibits enhanced laser sensitivity,as it can be directly ignited by a 1064 nm wavelength laser,whereas CL-18 lacks this characteristic.展开更多
Hydroisomerization of n-heptane is an efficient method for producing gasoline with a high octane number.The focus of this study was to find a highly efficient catalyst that could both promote the conversion of n-hepta...Hydroisomerization of n-heptane is an efficient method for producing gasoline with a high octane number.The focus of this study was to find a highly efficient catalyst that could both promote the conversion of n-heptane and inhibit the cracking side reaction.MIL-101(Cr)is a chromium-based metal-organic framework(MOF)with good hydrothermal stability,and exhibits a three-dimensional pore structure that is similar to that of zeolites.Using phosphomolybdic acid(PMA;H3PMo12O40·xH2O)can increase the number of Brønsted acid sites on MIL-101(Cr),which contributes to improving the catalytic performance during isomerization.In this study,0.4%Pt/PMA-MIL-101(Cr)catalyst was successfully crystallized at 220℃using a hydrothermal synthetic method.The results showed that the synthesized samples were mesoporousmicroporous composite materials with the typical octahedral structure,and the MIL-101(Cr)framework was not damaged following modification with PMA.It was found that 0.4%Pt30%PMA-MIL-101(Cr)exhibited the best performance for isomerization of n-heptane,with a conversion rate and selectivity at 260°C of 47.6%and 96.6%,respectively.After five hours of reaction,the conversion rate and selectivity of the catalyst remained above 38%and 80%,respectively.展开更多
Two pairs of structural isomers isolated from Aconitum nagarum var.lasiandrum have been differentiated by ESI MS using hydroxylamine hydrochloride(NH2OH·HCl) derivative method.
Nobel metallic Pt/ZSM-22 and Pt/ZSM-23 catalysts were prepared for hydroisomerization of normal dodecane and hydrodewaxing of heavy waxy lube base oil.The hydroisomerization performance of n-dodecane indicated that th...Nobel metallic Pt/ZSM-22 and Pt/ZSM-23 catalysts were prepared for hydroisomerization of normal dodecane and hydrodewaxing of heavy waxy lube base oil.The hydroisomerization performance of n-dodecane indicated that the Pt/ZSM-23 catalyst preferred to crack the C-C bond near the middle of n-dodecane chain,while the Pt/ZSM-22 catalyst was favorable for breaking the carbon chain near the end of n-dodecane.As a result,more than 2%of light products(gas plus naphtha)and3%more of heavy lube base oil with low-pour point and high viscosity index were produced on Pt/ZSM-22 than those on Pt/ZSM-23 while using the heavy waxy vacuum distillate oil as feedstock.展开更多
The rate determining step and the energy barrier involved in hydrogen adsorption on Pt/WO3- ZrO2 were studied based on the assumption that the hydrogen adsorption occurs only through Pt sites. The rate of hydrogen ads...The rate determining step and the energy barrier involved in hydrogen adsorption on Pt/WO3- ZrO2 were studied based on the assumption that the hydrogen adsorption occurs only through Pt sites. The rate of hydrogen adsorption on Pt/WOa-ZrO2 was measured in the adsorption temperature range of 323-573 K and an initial hydrogen pressure of 50 Torr. The rates of hydrogen uptake were very high for the initial few minutes and the adsorption continued for more than 5 h below 523 K. The hydrogen uptake far exceeded the H/Pt ratio of unity for all adsorption temperatures, indicating that the adsorption of hydrogen involved the dissociative adsorption of hydrogen on Pt sites to form hydrogen atoms, the spillover of hydrogen atoms onto the surface of the WO3-ZrO2 catalyst, the diffusion of spiltover hydrogen atom over the surface of the WO3-ZrO2 catalyst, and the formation of protonic acid site originated from hydrogen atom by releasing an electron in which the electron may react with a second hydrogen atom to form a hydride near the Lewis acid site. The rate determining step was the spillover with the activation energy of 12.3 kJ/mol. The rate of hydrogen adsorption cannot be expressed by the rate equation based on the assumption that the rate determining step is the surface diffusion. The activity of Pt/WO3-ZrO2 was examined on n-heptane isomerization in which the increase of hydrogen partial pressure provided positive-effect on the conversion of n-heptane and negative-effect on the selectivity towards iso-heptane.展开更多
A novel fibrous silica Y zeolite (HSi@Y) loaded with Pt has been studied based on its ability to produce protonic acid sites originating from molecular hydrogen. The Pt/HSi@Y was prepared using seed assisted crystalli...A novel fibrous silica Y zeolite (HSi@Y) loaded with Pt has been studied based on its ability to produce protonic acid sites originating from molecular hydrogen. The Pt/HSi@Y was prepared using seed assisted crystallization followed by protonation and Pt-loading. The product formed had a spherical morphology with bicontinuous lamellar with a diameter in the range of 500-700 nm. The catalytic activity of the Pt/HSi@Y has been assessed based on light linear alkane (C5-C7) isomerization in a micro-catalytic pulse reactor at 423-623 K. A pyridine IR study confirmed that the introduction of fibrous silica on Y zeolite increased the Lewis acid sites corresponding with the formation of extra-framework Al which led to the generation of more protonic acid sites. A hydrogen adsorbed IR study showed that the protonic acid sites which act as active sites in the isomerization were formed via dissociative-adsorption of molecular hydrogen releasing electrons to the nearby Lewis acid sites. Thus, it is suggested that the presence of Pt and HSi@Y with a high number of Lewis acid as well as weak Bronsted acid sites improved the activity and stability in C5, C6 and C7 isomerization via hydrogen spill-over mechanism.展开更多
Mg-Al hydrotalcites were synthesized using different preparation methods(a co-precipitation method, a urea method, and a simple one) to analyze their effect on the catalytic activity of these solid base catalysts. The...Mg-Al hydrotalcites were synthesized using different preparation methods(a co-precipitation method, a urea method, and a simple one) to analyze their effect on the catalytic activity of these solid base catalysts. The method strongly affected the structure of their layers(e.g., the growth and stacking of the layers, and the type of intercalated anions) and, accordingly, their catalytic activity. The Mg-Al hydrotalcite prepared by co-precipitation showed the best catalytic performance in the isomerization of glucose into fructose, due to the small crystallite size and sand rose morphology enhancing the exposure of surface active sites to reactants.展开更多
In this study,we theoretically investigate the feasibility of using laser-wakefield accelerated(LWFA)electrons for the photonuclear measurement of nuclear isomers according to the characteristics of the electrons obta...In this study,we theoretically investigate the feasibility of using laser-wakefield accelerated(LWFA)electrons for the photonuclear measurement of nuclear isomers according to the characteristics of the electrons obtained from LWFA experiments conducted at the Compact Laser-Plasma Accelerator(CLAPA)laboratory.The experiments at the CLAPA show that a stable electron beam with an energy of 78-135 MeV and a charge of 300-600 pC can be obtained.The bremsstrahlung spectra were simulated using Geant4,which suggests that a bremsstrahlung source with a peak intensity of 10^(19) photons/s can be generated.Theoretical calculations of isomer production cross sections from the photonuclear reactions on six target nuclei,^(197)Au,^(180)Hf,^(159)Tb,^(115)In,^(103)Rh,and ^(90)Zr,were performed and compared with the available experimental data in EXFOR,which suggest that further experiments are required for a series of photonuclear reaction channels.Flux-averaged cross sections and isomer ratios(IR)resulting from such bremsstrahlung sources are theoretically deduced.The results suggest that IR measurements can be used to constrain nuclear components,such asγstrength function and optical model potential.In addition,the detection of the decay characteristics was evaluated with Geant4 simulations.The use of the LWFA electron beam and its bremsstrahlung for photonuclear studies involving nuclear isomers is anticipated.展开更多
The results of commercial application of two types of C_8 aromatics isomerization catalysts under different feed conditions were compared to gain an insight in the techno-economical basis for selecting proper technolo...The results of commercial application of two types of C_8 aromatics isomerization catalysts under different feed conditions were compared to gain an insight in the techno-economical basis for selecting proper technological route at the plant.The comparison reveals differences in every aspect of feed consumption,unit capacity,product output,product distribution,and unit process parameters depending upon which catalyst type is adopted by the integrated PX complex.The type of aromatics isomerization catalyst has its influence on the plant scale,the construction cost,the process unit capacity and the product cost,with the magnitude of its impact varying with changing feed conditions.展开更多
The ionic liquid Et3NHC1-2AIC13 can catalyze the isomerization of n-pentane. This paper investigates the ionic liquid catalyzed isomerization performance of n-pentane with several product distribution improvers in an ...The ionic liquid Et3NHC1-2AIC13 can catalyze the isomerization of n-pentane. This paper investigates the ionic liquid catalyzed isomerization performance of n-pentane with several product distribution improvers in an autoclave. The product distribution of n-pentane isomerization could be improved by such improvers as benzene, cyelohexane, and methyl cyclohexane at the expense of conversion of n-pentane. The optimal product distribution improver was determined to be cyclohexane. The yield of isomerate and the selectivity of liquid isoalkanes increased, whereas the conversion of n-pentane decreased, with increasing cyclohexane amount. At the same conversion of n-pentane, the research octane number （RON） of liquid product, with cyclohexane amount of 0.5 wt%, was about 1.3 higher than that without cyclohexane. At the same reaction conditions, the presence of cyclohexane enhanced the yield of isomerate, the selectivity of liquid isoalkanes, and the RON of the liquid product, but reduced the conversion of n-pentane.展开更多
The catalyst NiW/HSAPO-11 was prepared by impregnating Ni and W onto HSAPO-11 zeolite with two different methods. The isomerization and aromatization properties were investigated with an microreactor using n-octane ...The catalyst NiW/HSAPO-11 was prepared by impregnating Ni and W onto HSAPO-11 zeolite with two different methods. The isomerization and aromatization properties were investigated with an microreactor using n-octane as a feedstock. NiW/HSAPO-11 shows a high hydroconversion activity of n-octane, and the optimum operating parameters for the catalyst to produce high octane number products were: 400℃, 2.0MPa, VH2:Vn-octane= 400:1, liquid hourly space velocity LHSV=1.0h-1. Under the optimum reaction condition, the conversion efficiency, C5 liquid + product selectivity, isomerization and aromatization product selectivity were 69.80%, 56.95%, 79.73% and 1.29% respectively. The catalyst (S1) impregnated with Ni and W after the HSAPO-11 zeolite was combined with Al2O3 matrix, performed better than the catalyst (S2) impregnated with Ni and W before combining with the Al2O3 matrix.展开更多
A lead-shielded HPGe detector and offlineγ-ray spectra of the residual product were used to measure the cross section(CS)and ratios of isomeric CS(σm/σg)in^(134)Xe(n,2n)^(133m),gXe reactions at different energies(1...A lead-shielded HPGe detector and offlineγ-ray spectra of the residual product were used to measure the cross section(CS)and ratios of isomeric CS(σm/σg)in^(134)Xe(n,2n)^(133m),gXe reactions at different energies(13.5 MeV,13.8 MeV,14.1 MeV,14.4 MeV,14.8 MeV)relative to the^(93)Nb(n,2n)^(92)mNb reaction CS.The target was high-purity natural Xe gas under high pressure.The T(d,n)4He reaction produces neutrons.TALYS code(version 1.95)for nuclear reactions was used for calculations,with default parameters and nuclear level density models.The uncertainties in the measured CS data were thoroughly analyzed using the covariance analysis method.The results were compared with theoretical values,evaluation data,and previous experimental findings.CS data of the 134Xe(n,2n)133mXe and 134Xe(n,2n)133gXe reactions and the corresponding isomeric CS ratios at 13.5 MeV,13.8 MeV,and 14.1 MeV neutron energies are reported for the first time.This research advances our knowledge of pre-equilibrium emission in the(n,2n)reaction channel by resolving inconsistencies in the Xe data.展开更多
The metathesis of ethylene and 2-pentene was studied as an alternative route for propylene production over Re2O7/γ-Al2O3 and Re2O7/SiO2-Al2O3 catalysts. Both NH3 temperature-programmed desorption （NH3-TPD） and H2 t...The metathesis of ethylene and 2-pentene was studied as an alternative route for propylene production over Re2O7/γ-Al2O3 and Re2O7/SiO2-Al2O3 catalysts. Both NH3 temperature-programmed desorption （NH3-TPD） and H2 temperature-programmed reduction （H2-TPR） results showed that Re2O7/SiO2-Al2O3 exhibited stronger acidity and weaker metal-support interaction than Re2O7/γ-Al2O3. At 35 60℃, isomerization free metathesis was observed only over Re2O7/γ-Al2O3, suggesting that the formation of metal-carbene metathesis active sites required only weak acidity. Our results suggest that on the Re2O7/SiO2-Al2O3, hydrido-rhenium species （[Re]-H） were formed in addition to the metathesis active sites, resulting in the isomerization of the initial 1-butene product into 2-butenes. A subsequent secondary metathesis reaction between these 2-butenes and the excess ethylene could explain the enhanced yields of propylene observed. The results demonstrate the potential for high yield of propylene from alternative feedstocks.展开更多
Thorium-229 possesses the lowest first nuclear excited state,with an energy of approximately 8 eV.The extremely narrow linewidth of the first nuclear excited state,with an uncertainty of 53 THz,prevents direct laser e...Thorium-229 possesses the lowest first nuclear excited state,with an energy of approximately 8 eV.The extremely narrow linewidth of the first nuclear excited state,with an uncertainty of 53 THz,prevents direct laser excitation and realization of the nuclear clock.We present a proposal using the Coulomb crystal of a linear chain formed by229Th^(3+)ions,where the nuclei of229Th3+ions in the ion trap are excited by the electronic bridge(EB)process.The 7 P1∕2state of the thorium-229 nuclear ground state is chosen for EB excitation.Using the two-level optical Bloch equation under experimental conditions,we calculate that 2 out of 36 prepared thorium ions in the Coulomb crystal can be excited to the first nuclear excited state,and it takes approximately 2 h to scan over an uncertainty of 0.22 eV.Taking advantage of the transition enhancement of EB and the long stability of the Coulomb crystal,the energy uncertainty of the first excited state can be limited to the order of 1 GHz.展开更多
基金Project supported by the Natural Science Foundation of Shandong Province,China(Grant No.ZR2014AM026)the Taishan Scholar Project of Shandong Province,China
文摘One-photon absorption and two-photon absorption（TPA） properties of three tris（picolyl）amine-based zinc ion sensors are investigated by employing the density functional response theory in combination with the polarizable continuum model.The different isomer and coordination geometry of each probe are taken into account. Special emphasis is placed on the effects of isomerism and the coordination mode on the optical properties. The intra-molecular charge transfer（ICT）properties are specified by natural bond orbital charge analysis. It is shown that the isomerism has non-negligible effects on TPA properties of free ligands. It is found that both the TPA wavelength and the cross section are highly dependent on the coordination mode. When the zinc ion connects with the picolyl unit in the middle of a ligand, the zinc complex has a large TPA intensity in a long wavelength range due to the increased ICT mechanism.
基金Project supported by the Young Scientists Fund of the National Natural Science Foundation of China (Grant No. 10904085)
文摘The influence of rotational isomerism on the two-photon absorption （TPA） of FTC chromophores has been investi- gated using the quadratic response theory with the B3LYP functional. Eight rotamers induced by three rotatable single bonds in the molecule are fully optimized, and it is found that their conformational energies are nearly degenerate. Our calculations demonstrate that rotational isomerism has an important effect on the TPA cross sections. For a certain rotamer, the maximum TPA cross section is enhanced significantly. In addition, in the longer wavelength region, the rotational isomerism could lead to a large shift of the TPA position.
基金financially supported by the National Science Foundation of China(62474142)Natural Science Foundation of Shandong Province(No.ZR2024YQ070)。
文摘Organic additives with multiple functional groups have shown great promise in improving the performance and stability of perovskite solar cells.The functional groups can passivate undercoordinated ions to reduce nonradiative recombination losses.However,how these groups synergistically affect the enhancement beyond passivation is still unclear.Specifically,isomeric molecules with different substitution patterns or molecular shapes remain elusive in designing new organic additives.Here,we report two isomeric carbazolyl bisphosphonate additives,2,7-Cz BP and 3,6-Cz BP.The isomerism effect on passivation and charge transport process was studied.The two molecules have similar passivation effects through multiple interactions,e.g.,P=O···Pb,P=O···H–N and N–H···I.2,7-CzBP can further bridge the perovskite crystallites to facilitates charge transport.Power conversion efficiencies(PCEs)of 25.88%and 21.04%were achieved for 0.09 cm^(2)devices and 14 cm^(2)modules after 2,7-Cz BP treatment,respectively.The devices exhibited enhanced operational stability maintaining 95%of initial PCE after 1000 h of continuous maximum power point tracking.This study of isomerism effect hints at the importance of tuning substitution positions and molecular shapes for organic additives,which paves the way for innovation of next-generation multifunctional aromatic additives.
基金The financial support from the National Natural Science Foundation of China(22278419,21978316,22108289,22172188)the Ministry of Science and Technology of China(2018YFB0604700)Suzhou Key Technology Research(Social Development)Project(2023ss06)。
文摘Efficient and selective glucose-to-fructose isomerization is a crucial step for production of oxygenated chemicals derived from sugars,which is usually catalyzed by base or Lewis acid heterogeneous catalyst.However,high yield and selectivity of fructose cannot be simultaneously obtained under mild conditions which hamper the scale of application compared with enzymatic catalysis.Herein,a Li-promoted C_(3)N_(4) catalyst was exploited which afforded an excellent fructose yield(40.3 wt%)and selectivity(99.5%)from glucose in water at 50℃,attributed to the formation of stable Li–N bond to strengthen the basic sites of catalysts.Furthermore,the so-formed N_(6)–Li–H_(2)O active site on Li–C_(3)N_(4) catalyst in aqueous phase changes the local electronic structure and strengthens the deprotonation process during glucose isomerization into fructose.The superior catalytic performance which is comparable to biological pathway suggests promising applications of lithium containing heterogeneous catalyst in biomass refinery.
基金Financial support by Dual Initiative Project of Jiangsu Province and Changzhou University is gratefully acknowledgedSample analysis supported by Analysis and Testing Center,NERC Biomass of Changzhou University was also greatly acknowledged.
文摘The transformation of aldose to ketose or common sugars into rare saccharides,including rare ketoses and aldoses,is of great value and interest to the food industry and for saccharidic biomass utilization,medicine,and the synthesis of drugs.Nowadays,high-fructose corn syrup(HFCS)is industrially produced in more than 10 million tons annually using immobilized glucose isomerase.Some low-calorie saccharides such as tagatose and psicose,which are becoming popular sweeteners,have also been produced on a pilot scale in order to replace sucrose and HFCS.However,current catalysts and catalytic processes are still difficult to utilize in biomass conversion and also have strong substrate dependence in producing high-value,rare sugars.Considering the specific reaction properties of saccharides and catalysts,since the pioneering discovery by Fischer,various catalysts and catalytic systems have been discovered or developed in attempts to extend the reaction pathways,improve the reaction efficiency,and to potentially produce commercial products.In this review,we trace the history of sugar isomerization/epimerization reactions and summarize the important breakthroughs for each reaction as well as the difficulties that remain unresolved to date.
基金support from the National Natural Science Foundation of China(Grant No.22175160)the Science Challenge Project(Grant No.TZ2018004)。
文摘5-amino-4-nitrobenzo[1,2-c:3,4-c']bis([1,2,5]oxadiazole)1,6-dioxide(CL-18)exhibits significant potential as an initiating explosive.However,its current synthesis process remains non-scalable due to low yields and safety risks.In this study,we have developed a simple and safe synthetic route for CL-18.It was synthesized from 3,5-dihaloanisole in a four-step reaction with an overall yield exceeding 60%,surpassing all reported yields in the literature.Subsequently,recrystallization of CL-18 was successfully achieved by carefully selecting appropriate solvents and antisolvents to reduce its mechanical sensitivity.Ultimately,when DMF-ethanol was employed as the recrystallization solvent system,satisfactory product yield(>90%)and reduced mechanical sensitivity(IS=15 J;FS=216 N)were obtained.Additionally,CL-18 is derived from the rearrangement of oxygen atoms on i-CL-18 furoxan,and a comparative analysis of their physicochemical properties was conducted.The thermal stability of both compounds is similar,with onset decomposition temperatures recorded at 186 and 182℃respectively.Similarly,they exhibit 5 s breaking point temperatures of 236 and 237℃.Additionally,we present novel insights into the positional-isomerization-laser-ignition performance of CL-18 and its isomer i-CL-18 using laser irradiation for the first time.Remarkably,our findings demonstrate that i-CL-18 exhibits enhanced laser sensitivity,as it can be directly ignited by a 1064 nm wavelength laser,whereas CL-18 lacks this characteristic.
基金National Natural Science Foundation of China(Grant No.22272129).
文摘Hydroisomerization of n-heptane is an efficient method for producing gasoline with a high octane number.The focus of this study was to find a highly efficient catalyst that could both promote the conversion of n-heptane and inhibit the cracking side reaction.MIL-101(Cr)is a chromium-based metal-organic framework(MOF)with good hydrothermal stability,and exhibits a three-dimensional pore structure that is similar to that of zeolites.Using phosphomolybdic acid(PMA;H3PMo12O40·xH2O)can increase the number of Brønsted acid sites on MIL-101(Cr),which contributes to improving the catalytic performance during isomerization.In this study,0.4%Pt/PMA-MIL-101(Cr)catalyst was successfully crystallized at 220℃using a hydrothermal synthetic method.The results showed that the synthesized samples were mesoporousmicroporous composite materials with the typical octahedral structure,and the MIL-101(Cr)framework was not damaged following modification with PMA.It was found that 0.4%Pt30%PMA-MIL-101(Cr)exhibited the best performance for isomerization of n-heptane,with a conversion rate and selectivity at 260°C of 47.6%and 96.6%,respectively.After five hours of reaction,the conversion rate and selectivity of the catalyst remained above 38%and 80%,respectively.
文摘Two pairs of structural isomers isolated from Aconitum nagarum var.lasiandrum have been differentiated by ESI MS using hydroxylamine hydrochloride(NH2OH·HCl) derivative method.
基金financial supports by National Key R&D Program of China(Grant No.2017YFB0306702)are gratefully acknowledged。
文摘Nobel metallic Pt/ZSM-22 and Pt/ZSM-23 catalysts were prepared for hydroisomerization of normal dodecane and hydrodewaxing of heavy waxy lube base oil.The hydroisomerization performance of n-dodecane indicated that the Pt/ZSM-23 catalyst preferred to crack the C-C bond near the middle of n-dodecane chain,while the Pt/ZSM-22 catalyst was favorable for breaking the carbon chain near the end of n-dodecane.As a result,more than 2%of light products(gas plus naphtha)and3%more of heavy lube base oil with low-pour point and high viscosity index were produced on Pt/ZSM-22 than those on Pt/ZSM-23 while using the heavy waxy vacuum distillate oil as feedstock.
文摘The rate determining step and the energy barrier involved in hydrogen adsorption on Pt/WO3- ZrO2 were studied based on the assumption that the hydrogen adsorption occurs only through Pt sites. The rate of hydrogen adsorption on Pt/WOa-ZrO2 was measured in the adsorption temperature range of 323-573 K and an initial hydrogen pressure of 50 Torr. The rates of hydrogen uptake were very high for the initial few minutes and the adsorption continued for more than 5 h below 523 K. The hydrogen uptake far exceeded the H/Pt ratio of unity for all adsorption temperatures, indicating that the adsorption of hydrogen involved the dissociative adsorption of hydrogen on Pt sites to form hydrogen atoms, the spillover of hydrogen atoms onto the surface of the WO3-ZrO2 catalyst, the diffusion of spiltover hydrogen atom over the surface of the WO3-ZrO2 catalyst, and the formation of protonic acid site originated from hydrogen atom by releasing an electron in which the electron may react with a second hydrogen atom to form a hydride near the Lewis acid site. The rate determining step was the spillover with the activation energy of 12.3 kJ/mol. The rate of hydrogen adsorption cannot be expressed by the rate equation based on the assumption that the rate determining step is the surface diffusion. The activity of Pt/WO3-ZrO2 was examined on n-heptane isomerization in which the increase of hydrogen partial pressure provided positive-effect on the conversion of n-heptane and negative-effect on the selectivity towards iso-heptane.
基金supported by the Universiti Teknologi Malaysia through Research University Grant No. 13H61 and 19H04
文摘A novel fibrous silica Y zeolite (HSi@Y) loaded with Pt has been studied based on its ability to produce protonic acid sites originating from molecular hydrogen. The Pt/HSi@Y was prepared using seed assisted crystallization followed by protonation and Pt-loading. The product formed had a spherical morphology with bicontinuous lamellar with a diameter in the range of 500-700 nm. The catalytic activity of the Pt/HSi@Y has been assessed based on light linear alkane (C5-C7) isomerization in a micro-catalytic pulse reactor at 423-623 K. A pyridine IR study confirmed that the introduction of fibrous silica on Y zeolite increased the Lewis acid sites corresponding with the formation of extra-framework Al which led to the generation of more protonic acid sites. A hydrogen adsorbed IR study showed that the protonic acid sites which act as active sites in the isomerization were formed via dissociative-adsorption of molecular hydrogen releasing electrons to the nearby Lewis acid sites. Thus, it is suggested that the presence of Pt and HSi@Y with a high number of Lewis acid as well as weak Bronsted acid sites improved the activity and stability in C5, C6 and C7 isomerization via hydrogen spill-over mechanism.
基金supported by the Basic Science Research Program through the National Research Foundation of Korea funded by the Ministry of Education (NRF-2015R1D1A1A01059724)
文摘Mg-Al hydrotalcites were synthesized using different preparation methods(a co-precipitation method, a urea method, and a simple one) to analyze their effect on the catalytic activity of these solid base catalysts. The method strongly affected the structure of their layers(e.g., the growth and stacking of the layers, and the type of intercalated anions) and, accordingly, their catalytic activity. The Mg-Al hydrotalcite prepared by co-precipitation showed the best catalytic performance in the isomerization of glucose into fructose, due to the small crystallite size and sand rose morphology enhancing the exposure of surface active sites to reactants.
基金supported by the National Natural Science Foundation of China (Nos.11921006,U2230133)Beijing Outstanding Young Scientists Program+2 种基金National Grand Instrument Project (No.2019YFF01014400)National Key R&D Program of China (No.2022YFA1603303)Open Foundation of Key Laboratory of High Power Laser and Physics,Chinese Academy of Sciences (No.SGKF202104)。
文摘In this study,we theoretically investigate the feasibility of using laser-wakefield accelerated(LWFA)electrons for the photonuclear measurement of nuclear isomers according to the characteristics of the electrons obtained from LWFA experiments conducted at the Compact Laser-Plasma Accelerator(CLAPA)laboratory.The experiments at the CLAPA show that a stable electron beam with an energy of 78-135 MeV and a charge of 300-600 pC can be obtained.The bremsstrahlung spectra were simulated using Geant4,which suggests that a bremsstrahlung source with a peak intensity of 10^(19) photons/s can be generated.Theoretical calculations of isomer production cross sections from the photonuclear reactions on six target nuclei,^(197)Au,^(180)Hf,^(159)Tb,^(115)In,^(103)Rh,and ^(90)Zr,were performed and compared with the available experimental data in EXFOR,which suggest that further experiments are required for a series of photonuclear reaction channels.Flux-averaged cross sections and isomer ratios(IR)resulting from such bremsstrahlung sources are theoretically deduced.The results suggest that IR measurements can be used to constrain nuclear components,such asγstrength function and optical model potential.In addition,the detection of the decay characteristics was evaluated with Geant4 simulations.The use of the LWFA electron beam and its bremsstrahlung for photonuclear studies involving nuclear isomers is anticipated.
文摘The results of commercial application of two types of C_8 aromatics isomerization catalysts under different feed conditions were compared to gain an insight in the techno-economical basis for selecting proper technological route at the plant.The comparison reveals differences in every aspect of feed consumption,unit capacity,product output,product distribution,and unit process parameters depending upon which catalyst type is adopted by the integrated PX complex.The type of aromatics isomerization catalyst has its influence on the plant scale,the construction cost,the process unit capacity and the product cost,with the magnitude of its impact varying with changing feed conditions.
基金support was provided by the National Science Foundation of China(Grant Nos.20806091,20976194,and 21036008)
文摘The ionic liquid Et3NHC1-2AIC13 can catalyze the isomerization of n-pentane. This paper investigates the ionic liquid catalyzed isomerization performance of n-pentane with several product distribution improvers in an autoclave. The product distribution of n-pentane isomerization could be improved by such improvers as benzene, cyelohexane, and methyl cyclohexane at the expense of conversion of n-pentane. The optimal product distribution improver was determined to be cyclohexane. The yield of isomerate and the selectivity of liquid isoalkanes increased, whereas the conversion of n-pentane decreased, with increasing cyclohexane amount. At the same conversion of n-pentane, the research octane number （RON） of liquid product, with cyclohexane amount of 0.5 wt%, was about 1.3 higher than that without cyclohexane. At the same reaction conditions, the presence of cyclohexane enhanced the yield of isomerate, the selectivity of liquid isoalkanes, and the RON of the liquid product, but reduced the conversion of n-pentane.
文摘The catalyst NiW/HSAPO-11 was prepared by impregnating Ni and W onto HSAPO-11 zeolite with two different methods. The isomerization and aromatization properties were investigated with an microreactor using n-octane as a feedstock. NiW/HSAPO-11 shows a high hydroconversion activity of n-octane, and the optimum operating parameters for the catalyst to produce high octane number products were: 400℃, 2.0MPa, VH2:Vn-octane= 400:1, liquid hourly space velocity LHSV=1.0h-1. Under the optimum reaction condition, the conversion efficiency, C5 liquid + product selectivity, isomerization and aromatization product selectivity were 69.80%, 56.95%, 79.73% and 1.29% respectively. The catalyst (S1) impregnated with Ni and W after the HSAPO-11 zeolite was combined with Al2O3 matrix, performed better than the catalyst (S2) impregnated with Ni and W before combining with the Al2O3 matrix.
基金supported by the National Natural science Foundation of China(Nos.11875016,12165006).
文摘A lead-shielded HPGe detector and offlineγ-ray spectra of the residual product were used to measure the cross section(CS)and ratios of isomeric CS(σm/σg)in^(134)Xe(n,2n)^(133m),gXe reactions at different energies(13.5 MeV,13.8 MeV,14.1 MeV,14.4 MeV,14.8 MeV)relative to the^(93)Nb(n,2n)^(92)mNb reaction CS.The target was high-purity natural Xe gas under high pressure.The T(d,n)4He reaction produces neutrons.TALYS code(version 1.95)for nuclear reactions was used for calculations,with default parameters and nuclear level density models.The uncertainties in the measured CS data were thoroughly analyzed using the covariance analysis method.The results were compared with theoretical values,evaluation data,and previous experimental findings.CS data of the 134Xe(n,2n)133mXe and 134Xe(n,2n)133gXe reactions and the corresponding isomeric CS ratios at 13.5 MeV,13.8 MeV,and 14.1 MeV neutron energies are reported for the first time.This research advances our knowledge of pre-equilibrium emission in the(n,2n)reaction channel by resolving inconsistencies in the Xe data.
基金supports from the Thailand Research Fund (TRF)the Office of Higher Education Commission
文摘The metathesis of ethylene and 2-pentene was studied as an alternative route for propylene production over Re2O7/γ-Al2O3 and Re2O7/SiO2-Al2O3 catalysts. Both NH3 temperature-programmed desorption （NH3-TPD） and H2 temperature-programmed reduction （H2-TPR） results showed that Re2O7/SiO2-Al2O3 exhibited stronger acidity and weaker metal-support interaction than Re2O7/γ-Al2O3. At 35 60℃, isomerization free metathesis was observed only over Re2O7/γ-Al2O3, suggesting that the formation of metal-carbene metathesis active sites required only weak acidity. Our results suggest that on the Re2O7/SiO2-Al2O3, hydrido-rhenium species （[Re]-H） were formed in addition to the metathesis active sites, resulting in the isomerization of the initial 1-butene product into 2-butenes. A subsequent secondary metathesis reaction between these 2-butenes and the excess ethylene could explain the enhanced yields of propylene observed. The results demonstrate the potential for high yield of propylene from alternative feedstocks.
基金the National Natural Science Foundation of China(No.11804372).
文摘Thorium-229 possesses the lowest first nuclear excited state,with an energy of approximately 8 eV.The extremely narrow linewidth of the first nuclear excited state,with an uncertainty of 53 THz,prevents direct laser excitation and realization of the nuclear clock.We present a proposal using the Coulomb crystal of a linear chain formed by229Th^(3+)ions,where the nuclei of229Th3+ions in the ion trap are excited by the electronic bridge(EB)process.The 7 P1∕2state of the thorium-229 nuclear ground state is chosen for EB excitation.Using the two-level optical Bloch equation under experimental conditions,we calculate that 2 out of 36 prepared thorium ions in the Coulomb crystal can be excited to the first nuclear excited state,and it takes approximately 2 h to scan over an uncertainty of 0.22 eV.Taking advantage of the transition enhancement of EB and the long stability of the Coulomb crystal,the energy uncertainty of the first excited state can be limited to the order of 1 GHz.
