Mineralogical characterization applied to mineral processing is now widespread. The first step for a mineralogi- cal characterization study is usually size fractionation. Preparation of polished sections is done on si...Mineralogical characterization applied to mineral processing is now widespread. The first step for a mineralogi- cal characterization study is usually size fractionation. Preparation of polished sections is done on size fractions to reduce complications in making representative cross sections of particles with large size differences. A sample is commonly fractionated into five or six size intervals. The drawback of this procedure is that it makes liberation studies more expensive, because one sample actually produces five or six sub-samples that need to be studied, i.e. one from each size interval. Thus to reduce cost of liberation studies, it would be desirable to study the un-sized sample. This paper provides a comparative liberation study of a set of samples both using size fractions and using the un-sized samples. The samples studied are the feed, the concentrate and the tails of a lead rougher flotation circuit. The results consistently show significant differences between the sized and the un-sized samples. Nevertheless, the results indicate that un-corrected liberation data from un-sized samples can be used for comparative studies that involve several related samples. Thus, it is possible to improve (or further understand) a concentrator circuit by using mineralogical data from un-sized samples around such circuit.展开更多
The coupling reactions of methanol and long-chain alkanes(n-dodecane,n-tetradecane and n-hexadecane)over CHA-type molecular sieves were studied in a fixed bed reactor.Over SAPO-34 and SSZ-13,it was found that the indu...The coupling reactions of methanol and long-chain alkanes(n-dodecane,n-tetradecane and n-hexadecane)over CHA-type molecular sieves were studied in a fixed bed reactor.Over SAPO-34 and SSZ-13,it was found that the induction period of methanol conversion was shortened by the introduction of long-chain alkanes.However,the addition of long-chain alkanes had little influence on the product distribution.Polymethylbenzenes and the derivatives were the main retained species on spent SSZ-13 catalyst,while adamantanes were the main retained species on SAPO-34.This indicates that coking species formation was mainly related to the further transformation of long-chain alkane/methanol coupling products at acid sites of the molecular sieve.These findings provide valuable information of long chain alkanes conversion and methanol reaction behavior of induction period over small pore CHA molecular sieves.展开更多
Significant increase of specific target olefin selectivity in CO_(2)hydrogenation is not only scientifically interesting but also practically valuable because of the reduction of separation cost.Here,a new composite c...Significant increase of specific target olefin selectivity in CO_(2)hydrogenation is not only scientifically interesting but also practically valuable because of the reduction of separation cost.Here,a new composite catalyst is fabricated with surface oxygen vacancy-abundant ZnZrO_(x)(H)solid solution and ultra-small H-SAPO-34(US)molecular sieve crystals.This catalyst shows a propene selectivity in hydrocarbons of 51.2%that accounts for about 63%of light olefins,along with a CO_(2)conversion of 13.5%,at 350°C and 3.0 MPa.A combination of in situ spectroscopy,isotope-labelled experiments,DFT calculations,and AIMD simulations reveals that an increase of surface oxygen vacancies in ZnZrO_(x)(H)induces formation of a coordinatively unsaturated(Zr-O)_(n)-Zn-(Ov)_(m)configuration,which elevates Zn site electron density and enhances the electronic interaction of Zn-3d and H-1s orbitals.This promotes the H_(2)dissociation and facilitates methanol intermediate formation.The ultra-small H-SAPO-34(US)crystals with a size of 100–200 nm effectively suppresses alkenes hydrogenation and subsequent aromatization in the methanol conversion process.As a result,more propene was produced.展开更多
由于传统求解时间序列自回归(auto-regressive,AR)模型的最小二乘方法无法顾及设计矩阵误差,现有的AR模型迭代解法难以应用协方差传播率给出较为精确的精度评定公式。将块自助采样方法引入到AR模型精度评定研究中,并在其基础上借助Siev...由于传统求解时间序列自回归(auto-regressive,AR)模型的最小二乘方法无法顾及设计矩阵误差,现有的AR模型迭代解法难以应用协方差传播率给出较为精确的精度评定公式。将块自助采样方法引入到AR模型精度评定研究中,并在其基础上借助Sieve自助法的思想,定义了顾及设计矩阵误差AR模型精度评定的Sieve块自助采样方法。根据不同的分块准则和采样策略,给出了4种方法的重采样步骤。模拟实验结果表明,精度评定的Sieve块自助采样方法能够得到比最小二乘法、经典的AR模型迭代解法更加可靠的自回归系数标准差,具有更强的适用性。同时,北斗卫星精密钟差真实案例表明,所提出的Sieve移动块自助法、Sieve非重叠块自助法、Sieve圆形块自助法以及Sieve静止块自助法的均方根(root mean square,RMS)比总体最小二乘的RMS分别减小了70.25%、78.65%、70.89%和79.24%,进一步验证了所提算法的有效性和可靠性,为时间序列AR模型的精度评定问题提供了一种采样思路。展开更多
Carbon capture is an important strategy and is implemented to achieve the goals of CO_(2)reduction and carbon neutrality.As a high energy-efficient technology,membrane-based separation plays a crucial role in CO_(2)ca...Carbon capture is an important strategy and is implemented to achieve the goals of CO_(2)reduction and carbon neutrality.As a high energy-efficient technology,membrane-based separation plays a crucial role in CO_(2)capture.It is urgently needed for membrane-based CO_(2)capture to develop the high-performance membrane materials with high permeability,selectivity,and stability.Herein,ultrapermeable carbon molecular sieve(CMS)membranes are fabricated by py roly zing a finely-engineered benzoxazole-containing copolyimide precursor for efficient CO_(2)capture.The microstructure of CMS membrane has been optimized by initially engineering the precursor-chemistry and subsequently tuning the pyrolysis process.Deep insights into the structure-property relationship of CMSs are provided in detail by a combination of experimental characterization and molecular simulations.We demonstrate that the intrinsically high free volume environment of the precursor,coupled with the steric hindrance of thermostable contorted fragments,promotes the formation of loosely packed and ultramicroporous carbon structures within the resultant CMS membrane,thereby enabling efficient CO_(2)discrimination via size sieving and affinity.The membrane achieves an ultrahigh CO_(2)permeability,good selectivity,and excellent stability.After one month of long-term operation,the CO_(2)permeability in the mixed gas is maintained at 11,800 Barrer,with a CO_(2)/N_(2)selectivity exceeding 60.This study provides insights into the relationship between precursor-chemistry and CMS performance,and our ultrapermeable CMS membrane,which is scalable using thin film manufacturing,holds great potential for industrial CO_(2)capture.展开更多
Let Pr denote an almost-prime with at most r prime factors,counted according to multiplicity.In this paper,it is proved that,for every sufficiently large even integer N,the equation N=x^(2)+p_(2)^(2)+p_(3)^(3)+p_(4)^(...Let Pr denote an almost-prime with at most r prime factors,counted according to multiplicity.In this paper,it is proved that,for every sufficiently large even integer N,the equation N=x^(2)+p_(2)^(2)+p_(3)^(3)+p_(4)^(3)+p_(5)^(5)+_6^(5)is solvable with being an almost-prime P_(6) and the other variables primes.This result constitutes an enhancement upon the previous result of Hooley[Recent Progress in Analytic Number Theory,Vol.1(Durham,1979),London:Academic Press,1981,127-191].展开更多
Porous molecular sieve catalysts,including aluminosilicate zeolites and silicoaluminophosphate(SAPO)molecular sieves,have found widespread use in heterogeneous catalysis and are expected to play a key role in advancin...Porous molecular sieve catalysts,including aluminosilicate zeolites and silicoaluminophosphate(SAPO)molecular sieves,have found widespread use in heterogeneous catalysis and are expected to play a key role in advancing carbon neutrality and sustainable development.Given the ubiquitous presence of water during catalyst synthesis,storage,and application,the interactions between water and molecular sieves as well as their consequent effects on frameworks and catalytic reactions have attracted considerable attention.These effects are inherently complex and highly dependent on various factors such as temperature,water phase,and partial pressure.In this review,we provide a comprehensive overview of the current understanding of water-molecular sieve interactions and their roles in catalysis,based on both experimental and theoretical calculation results.Special attention is paid to water-induced reversible and irreversible structural changes in aluminosilicate and SAPO frameworks at the atomic level,underscoring the dynamic and labile nature of these frameworks in water environments.The influence of water on catalytic performance and reaction kinetics in molecular sieve-catalyzed reactions is discussed from two perspectives:(1)its participation in reaction through hydrogen bonding interactions,such as competitive adsorption at active sites,stabilization of ground and transition states,and proton transfer bridge;(2)its role as a direct reactant forming new species via reactions with other vip molecules.Recent advancements in this area provide valuable insights for the rational design and optimization of catalysts for water-involved reactions.展开更多
SAPO-5 zeolite supported RuMn was a highly efficient catalyst for the aqueous-phase selective hydrodeoxygenation of guaiacol to cyclohexanol.The optimal catalyst achieved a high cyclohexanol yield of 93.7%at full guai...SAPO-5 zeolite supported RuMn was a highly efficient catalyst for the aqueous-phase selective hydrodeoxygenation of guaiacol to cyclohexanol.The optimal catalyst achieved a high cyclohexanol yield of 93.7%at full guaiacol conversion under mild conditions,with a high TOF of 920 h^(-1).Moreover,the catalyst displayed remarkable performance for the hydrogenation of phenol to cyclohexanol,where a 100%yield of cyclohexanol was obtained at a phenol-to-Ru molar ratio of about 17900.In particular,the catalyst exhibited excellent recyclability and could be recycled for 20 times without obvious activity loss.The as-prepared RuMn/SAPO-5 catalyst exhibited higher performance than most of the reported Rubased catalysts.展开更多
Lithium metal batteries,with their light mass anode and high theoretical specific capacity of 3860 m Ah/g,have great potential for development in achieving high energy density.However,the generation of lithium dendrit...Lithium metal batteries,with their light mass anode and high theoretical specific capacity of 3860 m Ah/g,have great potential for development in achieving high energy density.However,the generation of lithium dendrites and the loss of dead lithium pose a serious threat to the safety and long-cycle stability of batteries.Herein,we utilize the Lewis acid-base interaction principle for lithium-ion migration regulation.Through loading solid-acids onto molecular sieves to immobilize Lewis base(PF_(6^(-))),we achieve accelerated dissociation of lithium salts and successfully increase the lithium ion transference number to 0.44.Lewis acid-base interaction helps lithium metal batteries achieve more uniform lithium deposition,with an average CE improved to 92.8%.The symmetrical cells can be plated/stripped stably for more than 800 h of cycling.Full cell with high surface-loaded LFP cathode(14 mg/cm^(2))exhibits impressively high capacity retention of 90.7%after 120 cycles at 0.5 C.展开更多
Pseudomonas syringae pv.actinidiae(Psa)causes destructive kiwifruit bacterial canker by invading vascular tissues across multiple plant organs.However,the cellular mechanism underlying its systemic transmission and ce...Pseudomonas syringae pv.actinidiae(Psa)causes destructive kiwifruit bacterial canker by invading vascular tissues across multiple plant organs.However,the cellular mechanism underlying its systemic transmission and cell-to-cell movement within these specialized vascular conduits remains unclear.In this study,a Psa-GFP strain and various microscopic techniques were used to investigate the interaction between kiwifruit and Psa.Our results reveal that Psa strategically exploits host vascular conduits for systemic movement,with the xylem vessel being the predominant avenue.In the phloem,Psa exhibits adaptive alteration in bacterial shape to traverse sieve pores,facilitating its systemic spread along sieve tubes and inducing phloem necrosis.Within the xylem,Psa breaches pit membranes to migrate between adjacent vessels.Furthermore,phloem fibers act as an initial barrier at the early stages of infection,delaying Psa's entry into vascular tissues during its journey to the xylem.Additionally,at the junctions of stem-stem or stem-leaf,branch trace or leaf trace mediates the bacterial organ-to-organ translocation,thus facilitating the systemic progression of disease.In conclusion,our findings shed light on the cellular mechanism employed by Psa to exploit the woody plant's vascular network for infection,thereby enhancing a better understanding of the biology of this poorly defined bacterium.These insights carry implications for the pathogenesis of Psa and other vascular pathogens,offering theoretical guidance for effective control strategies.展开更多
Silicoaluminophosphate(SAPO)molecular sieves possess diverse architectures and exceptional high-temperature hydrothermal stability,rendering them important acid catalysts.However,enhancing acid concentration of certai...Silicoaluminophosphate(SAPO)molecular sieves possess diverse architectures and exceptional high-temperature hydrothermal stability,rendering them important acid catalysts.However,enhancing acid concentration of certain SAPO materials remains challenging,which limits their catalytic applications.Here,we report the synthesis of a series of SAPO materials using a developed SAPO precursor plus dual template(SPDT)strategy.A variety of SAPO materials characterized by high silica content and enhanced acidity,such as SAPO-34/56 intergrowths,SAPO-56,and SAPO-17,have been synthesized and thoroughly characterized using various techniques including integrated differential phase-contrast scanning transmission electron microscopy,two-dimensional solid-state nuclear magnetic resonance spectroscopy,and continuous rotation electron diffraction.The use of silica-enriched SAPO precursor combined with the flexible selection of the second template enables the crystalline phase regulation and improves the Si atoms incorporation into the framework.Notably,the synthesized SAPO-17 with abundant Si(4Al)species and unprecedentedly high acid density exhibits exceptional DeNO_(x)activity after Cu loading,with NO_(x)conversion exceeding 90%at 175–700℃.This outstanding performance can be attributed to the unique ERI structure and the increased acidity of SAPO-17.This work not only presents an effective method for synthesizing SAPO molecular sieves with enhanced acidity but also offers a new perspective for expanding the active temperature range of the ammonia selective catalytic reduction reaction.展开更多
In order to address challenges posed by the reduction in transistor size,researchers are concentrating on two-dimensional(2D)materials with high dielectric constants and large band gaps.Monoclinic ZrO_(2)(m-ZrO_(2))ha...In order to address challenges posed by the reduction in transistor size,researchers are concentrating on two-dimensional(2D)materials with high dielectric constants and large band gaps.Monoclinic ZrO_(2)(m-ZrO_(2))has emerged as a promising gate dielectric material due to its suitable dielectric constant,wide band gap,ideal valence-band offset,and good thermodynamic stability.However,current deposition methods face compatibility issues with 2D semiconductors,highlighting the need for high-quality dielectrics and interfaces.Here,high-quality 2D m-ZrO_(2)single crystals are successfully prepared using a onestep chemical vapor deposition(CVD)method,aided by 5A molecular sieves for oxygen supply.The prepared ZrO_(2)is utilized as a gate dielectric in the construction of MoS2 field-effect transistors(FETs)to investigate its electrical property.The FETs exhibit a high carrier mobility of up to 5.50 cm^(2)·V^(−1)·s^(−1),and a current switching ratio(Ion/off)of approximately 10^(4),which aligns with the current standards of logic circuits,indicating that ZrO_(2)has application value as a gate dielectric.The successful onestep preparation of single-crystal ZrO_(2)paves the way for the utilization of high-κgate dielectrics and creates favorable conditions for the development of high-performance semiconductor devices,offering new possibilities for transistor miniaturization.展开更多
The nine typical Shanghai soils are usually silty clay or clay,which appears inconsistent with their low clay content in the relevant publications.The literature review shows that the documented clay content of Shangh...The nine typical Shanghai soils are usually silty clay or clay,which appears inconsistent with their low clay content in the relevant publications.The literature review shows that the documented clay content of Shanghai soils ranges from 0%to 30.8%by weight.This inconsistency may stem from two factors:(1)the Shanghai soil classification system relies solely on the plasticity index for soil naming;and(2)the conventional steel sieving method cannot separate the clay from the fine soils(clay and silt mixtures).This paper aims to accurately determine the clay content in Shanghai soils.It uses nylon cloth sieves with apertures ranging from 0.063 mm to 0.0008 mm and completely separates the clay particles from the fine soils.The nine typical Shanghai soils are tested and sieved into distinct subgroups of clay,silt,sand,and gravel particles.Results demonstrate clay content ranges from 18.99%to 79.33%,substantially higher than literature values and consistent with their names of either silty clay or clay.Macro,micro,and scanning electron microscope(SEM)images reveal effective separation of clay,silt,sand,and gravel particles.The clay exhibits cohesive properties,while the silt,sand,and gravel comprise clean,non-cohesive individual particles.The clay and silt fractions are confirmed to be within their respective sieving limits by SEM-based particle size measurements.Additionally,Atterberg limits testing highlights the high plasticity of the clay particles and the non-plastic nature of the silt particles.展开更多
As an important chemical product,propylene(C_(3)H_(6))is widely used in production of many crucial chemical products such as polypropylene.Propane(C_(3)H_(8))is introduced as an inevitable gas impurity during the naph...As an important chemical product,propylene(C_(3)H_(6))is widely used in production of many crucial chemical products such as polypropylene.Propane(C_(3)H_(8))is introduced as an inevitable gas impurity during the naphtha cracking in propylene production.At present,thermal-driven energy-intensive cryogenic distillation is the most common purification method in industry.An energy-efficient,cost-effective and environmental-friendly separation technology is required to get polymer grade C_(3)H_(6)(higher than 99.5%).In face of the increasing demand of propylene,new separation technology based on porous adsorbents is expected to be a promising alternative.In recent years,metal-organic frameworks(MOFs)have obtained attention by their high porosity,regular adjustable pore shape and pore environment and keep making breakthroughs in separation and purification of many industrial gas mixtures,and are thus considered as one of the most potential types of adsorbents.The physical properties of C_(3)H_(6)and C_(3)H_(8),such as boiling point,size and kinetic diameter,are close to each other,making their separation a challenge.Most C_(3)H_(6)/C_(3)H_(8)sieving MOFs based on narrow sieving channels that restrict the access of molecules larger than their confined entrance purify mixtures at the cost of diffusion and capacity.To improve the adsorption of MOFs based on molecular sieving,a novel‘pearl-necklace’strategy was designed,which was named for its connected channel and molecular pocket vividly,but the diffusion limitation remains unsolved.展开更多
Micro-mesoporous ZK-1 molecular sieves with different Si/Al ratios were used as supports for binary Co-Mo hydrodesulfurization（HDS） catalysts.The CoMo/ZK-1 catalysts were prepared using an over-loading impregnation ...Micro-mesoporous ZK-1 molecular sieves with different Si/Al ratios were used as supports for binary Co-Mo hydrodesulfurization（HDS） catalysts.The CoMo/ZK-1 catalysts were prepared using an over-loading impregnation method,and characterized using N2 physisorption,X-ray diffraction,temperature-programmed NH3 desorption,temperature-programmed reduction（TPR）,ultraviolet-visible diffuse reflectance spectroscopy,and high-resolution transmission electron microscopy（HRTEM）.The results show that the CoMo/ZK-1 catalysts have high surface areas（～700 m^2/g）,large pore volumes,and hierarchical porous structures,which promote the dispersion of Co and Mo oxide phases on the ZK-1 supports.The TPR results show that the interactions between the Co and Mo oxide phases and the ZK-1 support are weaker than those in the CoMo/γ-Al2O3 catalyst.The HRTEM results show that the CoMo/ZK-1 catalysts have better MoS2 dispersion and more active edge sites.The catalysts were tested in HDS of dibenzothiophene.Under mild reaction conditions,the activity of Co and Mo sulfides supported on ZK-1 was higher than those of Co and Mo sulfides supported on ZSM-5,A1KIT-1,and γ-Al2O3.展开更多
Small-crystal TS-1 was synthesized via a seed-induced approach using ammonia as the alkali source and tetrapropylammonium bromide as an auxiliary structure-directing agent. The TS-1 samples were characterized using X-...Small-crystal TS-1 was synthesized via a seed-induced approach using ammonia as the alkali source and tetrapropylammonium bromide as an auxiliary structure-directing agent. The TS-1 samples were characterized using X-ray diffraction, N2 adsorption-desorption, Fourier-transform infrared spectroscopy, inductively coupled plasma atomic emission spectroscopy, scanning electron microscopy, and ultraviolet-visible spectroscopy. The use of the colloidal seed reduced the crystal size, and an appropriate amount of silicalite-1 seed assisted Ti incorporation into the TS-1 framework. This method reduces the cost of TS- 1 synthesis because a significantly smaller amount of tetrapropylammonium hydroxide is used. The catalytic performance of the synthesized small-crystal TS-1 samples in cyclohexanone ammoximation was better than that of bulk TS-1 as a result of improved diffusion and a larger number of active tetrahedral Ti centers.展开更多
The ultrastructures of the root protophleom sieve element at different developmental stages of Arabidopsis thaliana L. were investigated using the technique of high pressure freezing and freeze substitution fixing spe...The ultrastructures of the root protophleom sieve element at different developmental stages of Arabidopsis thaliana L. were investigated using the technique of high pressure freezing and freeze substitution fixing specimen. The results show that in the development of the sieve elements, the nuclei undergo typical characteristics of the programmed cell death (PCD): the nuclear envelopes form emboli, the chromatin condenses and aggregates towards the nuclear envelope, which degrades and fully disappears later. Before the nucleus degradation, neither the nuclear envelope undulation, nucleus lobe nor marked dilation (or bleb) of perinuclear space could be observed. In the cytoplasm of the mature sieve element, there are starch-like granules separately sheathed with a layer of membrane and usually with mitochondria around. These gnanules seem to provide substrates to mitochondria in their function. Small vacuoles originate from endoplasmic reticulum (ER), and no bigger vacuole was found.展开更多
n-Alkanes is widely used in the study of geologic body, which occupies 50%-80% of the saturated hydrocarbons commonly. The biogenetic implication of these compounds hold a very important value for the evaluation of al...n-Alkanes is widely used in the study of geologic body, which occupies 50%-80% of the saturated hydrocarbons commonly. The biogenetic implication of these compounds hold a very important value for the evaluation of all source rock, so it is used as biomarker to backward the biogenetic source of deposit organic matter. In order to find the difference of the isotopic composition of different organic compounds before and after complexion the oil shale in Yaojie, Gansu sample was performed by 5 molecular sieve adsorptipon to study the variation of the isotope compositions of n-alkanes, isoalkanes and cyclanes. On the basis of the previous work, the mini-sized Soxhlet extraction set with a hot reflux device was adopted to enhance the recovery of samples and diminish the loss of light components in the tested samples.展开更多
文摘Mineralogical characterization applied to mineral processing is now widespread. The first step for a mineralogi- cal characterization study is usually size fractionation. Preparation of polished sections is done on size fractions to reduce complications in making representative cross sections of particles with large size differences. A sample is commonly fractionated into five or six size intervals. The drawback of this procedure is that it makes liberation studies more expensive, because one sample actually produces five or six sub-samples that need to be studied, i.e. one from each size interval. Thus to reduce cost of liberation studies, it would be desirable to study the un-sized sample. This paper provides a comparative liberation study of a set of samples both using size fractions and using the un-sized samples. The samples studied are the feed, the concentrate and the tails of a lead rougher flotation circuit. The results consistently show significant differences between the sized and the un-sized samples. Nevertheless, the results indicate that un-corrected liberation data from un-sized samples can be used for comparative studies that involve several related samples. Thus, it is possible to improve (or further understand) a concentrator circuit by using mineralogical data from un-sized samples around such circuit.
基金Supported by National Natural Science Foundation of China(21991093)。
文摘The coupling reactions of methanol and long-chain alkanes(n-dodecane,n-tetradecane and n-hexadecane)over CHA-type molecular sieves were studied in a fixed bed reactor.Over SAPO-34 and SSZ-13,it was found that the induction period of methanol conversion was shortened by the introduction of long-chain alkanes.However,the addition of long-chain alkanes had little influence on the product distribution.Polymethylbenzenes and the derivatives were the main retained species on spent SSZ-13 catalyst,while adamantanes were the main retained species on SAPO-34.This indicates that coking species formation was mainly related to the further transformation of long-chain alkane/methanol coupling products at acid sites of the molecular sieve.These findings provide valuable information of long chain alkanes conversion and methanol reaction behavior of induction period over small pore CHA molecular sieves.
基金supported by the National Key R&D Program of China(2023YFB4103102)National Natural Science Foundation of China(21991090,21991092,22322208,22272195,U22A20431)+2 种基金the Basic Research Program of Shanxi Province of China(202203021224009)Innovation foundation of Institute of Coal Chemistry,Chinese Academy of Sciences(SCJC-DT-2023-06)Youth Innovation Promotion Association of Chinese Academy of Sciences(CAS)(2021172).
文摘Significant increase of specific target olefin selectivity in CO_(2)hydrogenation is not only scientifically interesting but also practically valuable because of the reduction of separation cost.Here,a new composite catalyst is fabricated with surface oxygen vacancy-abundant ZnZrO_(x)(H)solid solution and ultra-small H-SAPO-34(US)molecular sieve crystals.This catalyst shows a propene selectivity in hydrocarbons of 51.2%that accounts for about 63%of light olefins,along with a CO_(2)conversion of 13.5%,at 350°C and 3.0 MPa.A combination of in situ spectroscopy,isotope-labelled experiments,DFT calculations,and AIMD simulations reveals that an increase of surface oxygen vacancies in ZnZrO_(x)(H)induces formation of a coordinatively unsaturated(Zr-O)_(n)-Zn-(Ov)_(m)configuration,which elevates Zn site electron density and enhances the electronic interaction of Zn-3d and H-1s orbitals.This promotes the H_(2)dissociation and facilitates methanol intermediate formation.The ultra-small H-SAPO-34(US)crystals with a size of 100–200 nm effectively suppresses alkenes hydrogenation and subsequent aromatization in the methanol conversion process.As a result,more propene was produced.
文摘由于传统求解时间序列自回归(auto-regressive,AR)模型的最小二乘方法无法顾及设计矩阵误差,现有的AR模型迭代解法难以应用协方差传播率给出较为精确的精度评定公式。将块自助采样方法引入到AR模型精度评定研究中,并在其基础上借助Sieve自助法的思想,定义了顾及设计矩阵误差AR模型精度评定的Sieve块自助采样方法。根据不同的分块准则和采样策略,给出了4种方法的重采样步骤。模拟实验结果表明,精度评定的Sieve块自助采样方法能够得到比最小二乘法、经典的AR模型迭代解法更加可靠的自回归系数标准差,具有更强的适用性。同时,北斗卫星精密钟差真实案例表明,所提出的Sieve移动块自助法、Sieve非重叠块自助法、Sieve圆形块自助法以及Sieve静止块自助法的均方根(root mean square,RMS)比总体最小二乘的RMS分别减小了70.25%、78.65%、70.89%和79.24%,进一步验证了所提算法的有效性和可靠性,为时间序列AR模型的精度评定问题提供了一种采样思路。
基金financial support from the National Key R&D Program of China(2021YFB3801200)the National Natural Science Foundation of China(22278051,22178044,22308043)CNPC Innovation Found(2022DQ02-0608)。
文摘Carbon capture is an important strategy and is implemented to achieve the goals of CO_(2)reduction and carbon neutrality.As a high energy-efficient technology,membrane-based separation plays a crucial role in CO_(2)capture.It is urgently needed for membrane-based CO_(2)capture to develop the high-performance membrane materials with high permeability,selectivity,and stability.Herein,ultrapermeable carbon molecular sieve(CMS)membranes are fabricated by py roly zing a finely-engineered benzoxazole-containing copolyimide precursor for efficient CO_(2)capture.The microstructure of CMS membrane has been optimized by initially engineering the precursor-chemistry and subsequently tuning the pyrolysis process.Deep insights into the structure-property relationship of CMSs are provided in detail by a combination of experimental characterization and molecular simulations.We demonstrate that the intrinsically high free volume environment of the precursor,coupled with the steric hindrance of thermostable contorted fragments,promotes the formation of loosely packed and ultramicroporous carbon structures within the resultant CMS membrane,thereby enabling efficient CO_(2)discrimination via size sieving and affinity.The membrane achieves an ultrahigh CO_(2)permeability,good selectivity,and excellent stability.After one month of long-term operation,the CO_(2)permeability in the mixed gas is maintained at 11,800 Barrer,with a CO_(2)/N_(2)selectivity exceeding 60.This study provides insights into the relationship between precursor-chemistry and CMS performance,and our ultrapermeable CMS membrane,which is scalable using thin film manufacturing,holds great potential for industrial CO_(2)capture.
基金Supported by NSFC (Nos.12471009,12301006,12001047,11901566)Beijing Natural Science Foundation (No.1242003)National Training Program of Innovation and Entrepreneurship for Undergraduates(No.202307011)。
文摘Let Pr denote an almost-prime with at most r prime factors,counted according to multiplicity.In this paper,it is proved that,for every sufficiently large even integer N,the equation N=x^(2)+p_(2)^(2)+p_(3)^(3)+p_(4)^(3)+p_(5)^(5)+_6^(5)is solvable with being an almost-prime P_(6) and the other variables primes.This result constitutes an enhancement upon the previous result of Hooley[Recent Progress in Analytic Number Theory,Vol.1(Durham,1979),London:Academic Press,1981,127-191].
文摘Porous molecular sieve catalysts,including aluminosilicate zeolites and silicoaluminophosphate(SAPO)molecular sieves,have found widespread use in heterogeneous catalysis and are expected to play a key role in advancing carbon neutrality and sustainable development.Given the ubiquitous presence of water during catalyst synthesis,storage,and application,the interactions between water and molecular sieves as well as their consequent effects on frameworks and catalytic reactions have attracted considerable attention.These effects are inherently complex and highly dependent on various factors such as temperature,water phase,and partial pressure.In this review,we provide a comprehensive overview of the current understanding of water-molecular sieve interactions and their roles in catalysis,based on both experimental and theoretical calculation results.Special attention is paid to water-induced reversible and irreversible structural changes in aluminosilicate and SAPO frameworks at the atomic level,underscoring the dynamic and labile nature of these frameworks in water environments.The influence of water on catalytic performance and reaction kinetics in molecular sieve-catalyzed reactions is discussed from two perspectives:(1)its participation in reaction through hydrogen bonding interactions,such as competitive adsorption at active sites,stabilization of ground and transition states,and proton transfer bridge;(2)its role as a direct reactant forming new species via reactions with other vip molecules.Recent advancements in this area provide valuable insights for the rational design and optimization of catalysts for water-involved reactions.
基金supported by the Zhejiang Provincial Natural Science Foundation of China(LY23B060006 and LY18B060016).
文摘SAPO-5 zeolite supported RuMn was a highly efficient catalyst for the aqueous-phase selective hydrodeoxygenation of guaiacol to cyclohexanol.The optimal catalyst achieved a high cyclohexanol yield of 93.7%at full guaiacol conversion under mild conditions,with a high TOF of 920 h^(-1).Moreover,the catalyst displayed remarkable performance for the hydrogenation of phenol to cyclohexanol,where a 100%yield of cyclohexanol was obtained at a phenol-to-Ru molar ratio of about 17900.In particular,the catalyst exhibited excellent recyclability and could be recycled for 20 times without obvious activity loss.The as-prepared RuMn/SAPO-5 catalyst exhibited higher performance than most of the reported Rubased catalysts.
基金supported by the National Natural Science Foundation of China(No.22179007)。
文摘Lithium metal batteries,with their light mass anode and high theoretical specific capacity of 3860 m Ah/g,have great potential for development in achieving high energy density.However,the generation of lithium dendrites and the loss of dead lithium pose a serious threat to the safety and long-cycle stability of batteries.Herein,we utilize the Lewis acid-base interaction principle for lithium-ion migration regulation.Through loading solid-acids onto molecular sieves to immobilize Lewis base(PF_(6^(-))),we achieve accelerated dissociation of lithium salts and successfully increase the lithium ion transference number to 0.44.Lewis acid-base interaction helps lithium metal batteries achieve more uniform lithium deposition,with an average CE improved to 92.8%.The symmetrical cells can be plated/stripped stably for more than 800 h of cycling.Full cell with high surface-loaded LFP cathode(14 mg/cm^(2))exhibits impressively high capacity retention of 90.7%after 120 cycles at 0.5 C.
基金supported by grants from the National Key Research and Development Program of China(Grant No.2022YFD1400200)the Special Support Plan for High-Level Talent of Shaanxi Provincethe First-Class Universities and Academic Programs of Northwest A&F University.
文摘Pseudomonas syringae pv.actinidiae(Psa)causes destructive kiwifruit bacterial canker by invading vascular tissues across multiple plant organs.However,the cellular mechanism underlying its systemic transmission and cell-to-cell movement within these specialized vascular conduits remains unclear.In this study,a Psa-GFP strain and various microscopic techniques were used to investigate the interaction between kiwifruit and Psa.Our results reveal that Psa strategically exploits host vascular conduits for systemic movement,with the xylem vessel being the predominant avenue.In the phloem,Psa exhibits adaptive alteration in bacterial shape to traverse sieve pores,facilitating its systemic spread along sieve tubes and inducing phloem necrosis.Within the xylem,Psa breaches pit membranes to migrate between adjacent vessels.Furthermore,phloem fibers act as an initial barrier at the early stages of infection,delaying Psa's entry into vascular tissues during its journey to the xylem.Additionally,at the junctions of stem-stem or stem-leaf,branch trace or leaf trace mediates the bacterial organ-to-organ translocation,thus facilitating the systemic progression of disease.In conclusion,our findings shed light on the cellular mechanism employed by Psa to exploit the woody plant's vascular network for infection,thereby enhancing a better understanding of the biology of this poorly defined bacterium.These insights carry implications for the pathogenesis of Psa and other vascular pathogens,offering theoretical guidance for effective control strategies.
文摘Silicoaluminophosphate(SAPO)molecular sieves possess diverse architectures and exceptional high-temperature hydrothermal stability,rendering them important acid catalysts.However,enhancing acid concentration of certain SAPO materials remains challenging,which limits their catalytic applications.Here,we report the synthesis of a series of SAPO materials using a developed SAPO precursor plus dual template(SPDT)strategy.A variety of SAPO materials characterized by high silica content and enhanced acidity,such as SAPO-34/56 intergrowths,SAPO-56,and SAPO-17,have been synthesized and thoroughly characterized using various techniques including integrated differential phase-contrast scanning transmission electron microscopy,two-dimensional solid-state nuclear magnetic resonance spectroscopy,and continuous rotation electron diffraction.The use of silica-enriched SAPO precursor combined with the flexible selection of the second template enables the crystalline phase regulation and improves the Si atoms incorporation into the framework.Notably,the synthesized SAPO-17 with abundant Si(4Al)species and unprecedentedly high acid density exhibits exceptional DeNO_(x)activity after Cu loading,with NO_(x)conversion exceeding 90%at 175–700℃.This outstanding performance can be attributed to the unique ERI structure and the increased acidity of SAPO-17.This work not only presents an effective method for synthesizing SAPO molecular sieves with enhanced acidity but also offers a new perspective for expanding the active temperature range of the ammonia selective catalytic reduction reaction.
基金support from the National Natural Science Foundation of China(No.21975067)Shenzhen Science and Technology Program(No.JCYJ20220530160407016).
文摘In order to address challenges posed by the reduction in transistor size,researchers are concentrating on two-dimensional(2D)materials with high dielectric constants and large band gaps.Monoclinic ZrO_(2)(m-ZrO_(2))has emerged as a promising gate dielectric material due to its suitable dielectric constant,wide band gap,ideal valence-band offset,and good thermodynamic stability.However,current deposition methods face compatibility issues with 2D semiconductors,highlighting the need for high-quality dielectrics and interfaces.Here,high-quality 2D m-ZrO_(2)single crystals are successfully prepared using a onestep chemical vapor deposition(CVD)method,aided by 5A molecular sieves for oxygen supply.The prepared ZrO_(2)is utilized as a gate dielectric in the construction of MoS2 field-effect transistors(FETs)to investigate its electrical property.The FETs exhibit a high carrier mobility of up to 5.50 cm^(2)·V^(−1)·s^(−1),and a current switching ratio(Ion/off)of approximately 10^(4),which aligns with the current standards of logic circuits,indicating that ZrO_(2)has application value as a gate dielectric.The successful onestep preparation of single-crystal ZrO_(2)paves the way for the utilization of high-κgate dielectrics and creates favorable conditions for the development of high-performance semiconductor devices,offering new possibilities for transistor miniaturization.
基金supported by the Research Grant Council of the Hong Kong Special Administrative Region,China(Grant Nos.HKU 17207518 and R5037-18).
文摘The nine typical Shanghai soils are usually silty clay or clay,which appears inconsistent with their low clay content in the relevant publications.The literature review shows that the documented clay content of Shanghai soils ranges from 0%to 30.8%by weight.This inconsistency may stem from two factors:(1)the Shanghai soil classification system relies solely on the plasticity index for soil naming;and(2)the conventional steel sieving method cannot separate the clay from the fine soils(clay and silt mixtures).This paper aims to accurately determine the clay content in Shanghai soils.It uses nylon cloth sieves with apertures ranging from 0.063 mm to 0.0008 mm and completely separates the clay particles from the fine soils.The nine typical Shanghai soils are tested and sieved into distinct subgroups of clay,silt,sand,and gravel particles.Results demonstrate clay content ranges from 18.99%to 79.33%,substantially higher than literature values and consistent with their names of either silty clay or clay.Macro,micro,and scanning electron microscope(SEM)images reveal effective separation of clay,silt,sand,and gravel particles.The clay exhibits cohesive properties,while the silt,sand,and gravel comprise clean,non-cohesive individual particles.The clay and silt fractions are confirmed to be within their respective sieving limits by SEM-based particle size measurements.Additionally,Atterberg limits testing highlights the high plasticity of the clay particles and the non-plastic nature of the silt particles.
基金support of the National Natural Science Foundation of China(Nos.22378369 and 22205207)Major Project of Natural Science Foundation of Zhejiang Province(LD24B060001).
文摘As an important chemical product,propylene(C_(3)H_(6))is widely used in production of many crucial chemical products such as polypropylene.Propane(C_(3)H_(8))is introduced as an inevitable gas impurity during the naphtha cracking in propylene production.At present,thermal-driven energy-intensive cryogenic distillation is the most common purification method in industry.An energy-efficient,cost-effective and environmental-friendly separation technology is required to get polymer grade C_(3)H_(6)(higher than 99.5%).In face of the increasing demand of propylene,new separation technology based on porous adsorbents is expected to be a promising alternative.In recent years,metal-organic frameworks(MOFs)have obtained attention by their high porosity,regular adjustable pore shape and pore environment and keep making breakthroughs in separation and purification of many industrial gas mixtures,and are thus considered as one of the most potential types of adsorbents.The physical properties of C_(3)H_(6)and C_(3)H_(8),such as boiling point,size and kinetic diameter,are close to each other,making their separation a challenge.Most C_(3)H_(6)/C_(3)H_(8)sieving MOFs based on narrow sieving channels that restrict the access of molecules larger than their confined entrance purify mixtures at the cost of diffusion and capacity.To improve the adsorption of MOFs based on molecular sieving,a novel‘pearl-necklace’strategy was designed,which was named for its connected channel and molecular pocket vividly,but the diffusion limitation remains unsolved.
基金financially supported by the National Natural Science Foundation of China (NNSFC,21206017)~~
文摘Micro-mesoporous ZK-1 molecular sieves with different Si/Al ratios were used as supports for binary Co-Mo hydrodesulfurization（HDS） catalysts.The CoMo/ZK-1 catalysts were prepared using an over-loading impregnation method,and characterized using N2 physisorption,X-ray diffraction,temperature-programmed NH3 desorption,temperature-programmed reduction（TPR）,ultraviolet-visible diffuse reflectance spectroscopy,and high-resolution transmission electron microscopy（HRTEM）.The results show that the CoMo/ZK-1 catalysts have high surface areas（～700 m^2/g）,large pore volumes,and hierarchical porous structures,which promote the dispersion of Co and Mo oxide phases on the ZK-1 supports.The TPR results show that the interactions between the Co and Mo oxide phases and the ZK-1 support are weaker than those in the CoMo/γ-Al2O3 catalyst.The HRTEM results show that the CoMo/ZK-1 catalysts have better MoS2 dispersion and more active edge sites.The catalysts were tested in HDS of dibenzothiophene.Under mild reaction conditions,the activity of Co and Mo sulfides supported on ZK-1 was higher than those of Co and Mo sulfides supported on ZSM-5,A1KIT-1,and γ-Al2O3.
基金supported by the National Natural Science Foundation of China(21403070 and 21373088)Innovation Program of Shanghai Municipal Education Commission(13zz038)+2 种基金Key Project of the Shanghai Committee of Science and Technology(12JC1403600)National Key Technology R&D Program(2012BAE05B02)Shanghai Leading Academic Discipline Project(B409)~~
文摘Small-crystal TS-1 was synthesized via a seed-induced approach using ammonia as the alkali source and tetrapropylammonium bromide as an auxiliary structure-directing agent. The TS-1 samples were characterized using X-ray diffraction, N2 adsorption-desorption, Fourier-transform infrared spectroscopy, inductively coupled plasma atomic emission spectroscopy, scanning electron microscopy, and ultraviolet-visible spectroscopy. The use of the colloidal seed reduced the crystal size, and an appropriate amount of silicalite-1 seed assisted Ti incorporation into the TS-1 framework. This method reduces the cost of TS- 1 synthesis because a significantly smaller amount of tetrapropylammonium hydroxide is used. The catalytic performance of the synthesized small-crystal TS-1 samples in cyclohexanone ammoximation was better than that of bulk TS-1 as a result of improved diffusion and a larger number of active tetrahedral Ti centers.
文摘The ultrastructures of the root protophleom sieve element at different developmental stages of Arabidopsis thaliana L. were investigated using the technique of high pressure freezing and freeze substitution fixing specimen. The results show that in the development of the sieve elements, the nuclei undergo typical characteristics of the programmed cell death (PCD): the nuclear envelopes form emboli, the chromatin condenses and aggregates towards the nuclear envelope, which degrades and fully disappears later. Before the nucleus degradation, neither the nuclear envelope undulation, nucleus lobe nor marked dilation (or bleb) of perinuclear space could be observed. In the cytoplasm of the mature sieve element, there are starch-like granules separately sheathed with a layer of membrane and usually with mitochondria around. These gnanules seem to provide substrates to mitochondria in their function. Small vacuoles originate from endoplasmic reticulum (ER), and no bigger vacuole was found.
文摘n-Alkanes is widely used in the study of geologic body, which occupies 50%-80% of the saturated hydrocarbons commonly. The biogenetic implication of these compounds hold a very important value for the evaluation of all source rock, so it is used as biomarker to backward the biogenetic source of deposit organic matter. In order to find the difference of the isotopic composition of different organic compounds before and after complexion the oil shale in Yaojie, Gansu sample was performed by 5 molecular sieve adsorptipon to study the variation of the isotope compositions of n-alkanes, isoalkanes and cyclanes. On the basis of the previous work, the mini-sized Soxhlet extraction set with a hot reflux device was adopted to enhance the recovery of samples and diminish the loss of light components in the tested samples.
