Separation of ternary C6 cyclic hydrocarbons,i.e.,benzene/cyclohexene/cyclohexane mixtures,is crucial but challenging in the petrochemical industry due to their extremely similar molecular sizes and physical propertie...Separation of ternary C6 cyclic hydrocarbons,i.e.,benzene/cyclohexene/cyclohexane mixtures,is crucial but challenging in the petrochemical industry due to their extremely similar molecular sizes and physical properties.Here,we design and synthesize a new Zn-based metal azolate framework(MAF),MAF-40,with a threedimensional(3D)honeycomb-like framework and 1D sugar-coated-berry type pore channels.By virtue of the strong coordination bonds and abundant trifluoromethyl groups embedded in the pores,MAF-40 exhibits excellent thermal stability(up to 400℃)and acid-base stability(within a pH range of 3–11).Moreover,MAF-40 shows ultrahigh benzene selectivity(38.8)from the ternary benzene/cyclohexene/cyclohexane mixtures,attributed to the strong adsorption affinity from fluorine for benzene and markedly different vip diffusion limited by the small aperture,which are confirmed by computational simulations and infrared spectra.Thus,the results indicated that MAF-40 would be a candidate adsorbent for the separation and purification of benzene from C6 cyclic hydrocarbons,and this work provides a new insight of synthesizing stable MOF materials for separating multicomponent chemical mixtures.展开更多
Adsorptive separation of light hydrocarbons by porous solids provides an energy-efficient alternative to state-of-the-art cryogenic distillation.However,an optimal balance between the cost,performance and stability of...Adsorptive separation of light hydrocarbons by porous solids provides an energy-efficient alternative to state-of-the-art cryogenic distillation.However,an optimal balance between the cost,performance and stability of the sorbent material is yet to be achieved for industrial applications.Here,we report the efficient separation of C2 and C3 hydrocarbons by a faujasite zeolite(Na-X,Si/Al=1.23).A tandem configuration of two fixed-beds packed with Na-X affords complete dynamic separation of the ternary mixture of C_(2)H_(2)/C_(2)H_(4)/C_(2)H_(6)(1/49.5/49.5;v/v/v)under ambient conditions.Pressure-swing desorption on the latter fixed-bed gives ethylene(>99.50%,1.80 mmol g^(-1))and ethane(>99.99%,1.41 mmol g^(-1)).In situ synchrotron X-ray powder diffraction revealed the binding sites for C_(2)H_(2)and C_(2)H_(4)in Na-X.This study highlights the potential application of commercial zeolites for challenging industrial separations.展开更多
The use of polar organic solvents for the separations of rare earth elements (Ⅲ) is effective especially for their extensive separations despite the solubility limitations. The study shows that polyacrylate anion exc...The use of polar organic solvents for the separations of rare earth elements (Ⅲ) is effective especially for their extensive separations despite the solubility limitations. The study shows that polyacrylate anion exchangers, particularly the weakly basic, gel anion exchanger Amberlite IRA 68, can be applied to the separation of rare earth complexes with EDTA in H_2O-methanol and H_2O-ethanol systems. In most cases the determined distribution coefficients of Ln^(3+) complexes with EDTA in mixed media like water-methanol on polyacrylate anion exchangers are larger than those in pure water (media.)展开更多
The efficient limitation of the"shuttle effect"of polysulfide from the rational construction of electrocatalysts to accelerate the redox kinetics of polysulfides is extremely important.In this work,the cobal...The efficient limitation of the"shuttle effect"of polysulfide from the rational construction of electrocatalysts to accelerate the redox kinetics of polysulfides is extremely important.In this work,the cobalt/Nickel bimetallic alloy polyhedrons decorated on layered TiO_(2)heterostructure(Co Ni@TiO_(2)/C)derived from MXene and bimetallic metal-organic framework have been prepared through liquid-phase deposition and high-temperature annealing processes.This heterostructure presents excellent electrical conductivity,which facilitates ion diffusion and electron transfer within the battery.Besides,the heterostructure from anchoring the Co Ni bimetallic alloy on the layered TiO_(2)ensures the full exposure of active sites and accelerates polysulfide redox kinetics through chemisorption and catalytic conversion.Considering these advantages mentioned above,when applied as the lithium-sulfur batteries(LSBs)separator modifier,the cell assembled from the Co Ni@TiO_(2)/C modified separator demonstrates high specific capacity(1481.7 mAh/g at 0.5 C),superior rate capability(855.5 mAh/g at 3 C)and excellent cycling performance,which can maintain the high capacity of 856.09 mAh/g after 300 cycles with low capacity decay rate of 0.09%per cycle.Even under a high sulfur loading of 4.4 mg/cm^(2),the cell can still present excellent cycling stability.This study paves the way for the design of novel material for the construction of an outstanding functional separator layer and shines the light on the effective and feasible way for the inhibition of shuttle effect in lithium-sulfur batteries.展开更多
Y chromosome microdeletions are an important cause of male infertility.At present,research on the Y chromosome is mainly focused on analyzing the loss of large segments of the azoospermia factor a/b/c(AZFa/b/c)gene,an...Y chromosome microdeletions are an important cause of male infertility.At present,research on the Y chromosome is mainly focused on analyzing the loss of large segments of the azoospermia factor a/b/c(AZFa/b/c)gene,and few studies have reported the impact of unit point deletion in the AZF band on fertility.This study analyzed the effect of sperm quality after sY1192 loss in 116 patients.The sY1192-independent deletion accounted for 41.4%(48/116).Eight patterns were found in the deletions associated with sY1192.The rate of sperm detection was similar in the semen of patients with the independent sY1192 deletion and the combined sY1192 deletions(52.1%vs 50.0%).The patients with only sY1192 gene loss had a higher probability of sperm detection than the patients whose sY1192 gene locus existed,but other gene loci were lost(52.1%vs 32.0%).The hormone levels were similar in patients with sY1192 deletion alone and in those with sY1192 deletion and other types of microdeletions in the presence of the sY1192 locus.After multiple intracytoplasmic sperm injection(ICSI)attempts,the pregnancy rate of spouses of men with sY1192-independent deletions was similar to that of other types of microdeletions,but the fertilization and cleavage rates were higher.We observed that eight deletion patterns were observed for sY1192 microdeletions of AZFb/c,dominated by the independent deletion of sY1192.After ICSI,the fertilization rate and cleavage rate of the sY1192-independent microdeletion were higher than those of other Y chromosome microdeletion types,but there was no significant difference in pregnancy outcomes.展开更多
Photocatalytic oxidation of toluene to valuable benzaldehyde offers a promising pathway for sustainable production of fine chemicals and pharmaceuticals.In this process,photogenerated holes play a crucial role in C(sp...Photocatalytic oxidation of toluene to valuable benzaldehyde offers a promising pathway for sustainable production of fine chemicals and pharmaceuticals.In this process,photogenerated holes play a crucial role in C(sp^(3))-H bond dissociation.However,the photocatalytic performance of current photocatalysts is often hindered by the low separation and transfer efficiency of photogenerated charges.In this work,we presented a perovskite-based heterostructure via in situ growth of defective WO_(3-x)nanosheets on Cs_(2)AgBiBr_(6)nanoparticles for photocatalytic toluene transformation.In situ Fourier transform infrared spectroscopy tests proved the introduction of oxygen-deficient WO_(3)-xcomponent enhanced the chemisorption of molecular oxygen.The in situ electron paramagnetic resonance and 4-chloro-7-nitro-1,2,3-benzoxadiazole fluorescence measurements further confirmed the presence of oxygen vacancies,and the formation of heterostructure synergistically accelerated the formation of the superoxide radicals and the transfer of photogenerated charge carriers.Under visible light irradiation,Cs_(2)AgBiBr_(6)/WO_(3-x)photocatalyst could effectively oxidize toluene toward benzaldehyde with a conversion rate of 9020μmol g^(-1)h^(-1),which was a 3.5-fold increase over that of the unmodified Cs_(2)AgBiBr_(6).展开更多
With the increasing demand for synthetic rubber,the purification of 1,3-butadiene(C_(4)H_(6))is of great industrial significance.Herein,the successful removal of n-butene(n-C_(4)H_(8))and iso-butene(iso-C_(4)H_(8))fro...With the increasing demand for synthetic rubber,the purification of 1,3-butadiene(C_(4)H_(6))is of great industrial significance.Herein,the successful removal of n-butene(n-C_(4)H_(8))and iso-butene(iso-C_(4)H_(8))from 1,3-butadiene(C_(4)H_(6))was realized by synthesizing a novel TaOF_(5)^(2-) anion-pillared ultramicroporous material TaOFFIVE-3-Ni(also referred to as ZU-96,TaOFFIVE=TaOF_(5)^(2-),3=pyrazine).Single-component adsorption isotherms show that TaOFFIVE-3-Ni can achieve the exclusion of n-C_(4)H_(8) and iso-C_(4)H_(8) in the low pressure region(0–30 kPa),and uptake C_(4)H_(6) with a high capacity of 92.78 cm^(3)·cm^(-3)(298 K and 100 kPa).The uptake ratio of C_(4)H_(6)/iso-C_(4)H_(8) on TaOFFIVE-3-Ni was 20.83(298 K and 100 kPa),which was the highest among the state-of-the-art adsorbents reported so far.With the rotation of anion and pyrazine ring,the pore size changes continuously,which makes smaller-size C_(4)H_(6) enter the channel while larger-size n-C_(4)H_(8) and iso-C_(4)H_(8) are completely blocked.The excellent breakthrough performance of TaOFFIVE-3-Ni shows great potential in industrial separation of C4 olefins.The specific adsorption binding sites within ZU-96 was further revealed through the modeling calculation.展开更多
The valence state of C atoms and the structure of molecular orbitals of the (Buckminster)Fullerene C_(60)have been demonstrated. It has been shown that when a motion-coordinate system is adopted, in which the coordina...The valence state of C atoms and the structure of molecular orbitals of the (Buckminster)Fullerene C_(60)have been demonstrated. It has been shown that when a motion-coordinate system is adopted, in which the coordinate origin is at every C atom, the z axis is in the direction of the normal and the (x,y) axes are in the direction of tangents of C_(60)'s spherical surface, 240 valence atomic orbitals of C_(60) can be divided into two groups. All (P_x, P_y)atomic orbitals named as Pt ones and all the other P_z atomic orbitals named as p. ones, That is to say that if we name the molecular orbital linearly combined of P_t atomic orbitals as σ_t and the molecular orbital linearly combined of P_n atomic orbitals as π_n, the 240 valence molecular orbitals are of the property of σ_t-π_n separability. It has also been shown that the frontier and nearby frontier molecular orbitals are π_n ones, and therefore the essential physical and chemical properties of C_(60) are determined by its π_n molecular orbitals.展开更多
The effects of directional solidification parameters and the coupling of directional solidification parameters and alternating electromagnetic fields on separation and enrichment of the C54–TiSi2 phase were investiga...The effects of directional solidification parameters and the coupling of directional solidification parameters and alternating electromagnetic fields on separation and enrichment of the C54–TiSi2 phase were investigated in a directionally solidified hypoeutectic Ti–65 wt.%Si alloy.The results indicated that by increasing the pull-down velocity at a given position within the ingot,the cooling rate,growth rate,and temperature gradient of ingot could be increased.At a pull-down velocity near 5μm/s,the temperature gradient,cooling rate,and growth rate decreased with increasing the thickness of the C54–TiSi2-rich layer.Electromagnetic fields enhanced mass transfer at pull-down velocities of 5,10,15,and 20μm/s,with resulting enriched layer thicknesses of 15,10,10,and 5 mm,respectively.By increasing the percentage of Ti in the Ti–Si alloy from 25 to 35 wt.%,the thickness of the C54–TiSi2-rich layer was increased from 2.5 to 3.3 cm.However,the maximum C54–TiSi2 content obtained experimentally in this layer decreased from 92.06 to 79.49 mass%.展开更多
基金supported by the National Natural Science Foundation of China(Nos.22090061,22488101,22475240,and 22231012)the State Key Laboratory of Catalysis(No.2024SKL-A-010).
文摘Separation of ternary C6 cyclic hydrocarbons,i.e.,benzene/cyclohexene/cyclohexane mixtures,is crucial but challenging in the petrochemical industry due to their extremely similar molecular sizes and physical properties.Here,we design and synthesize a new Zn-based metal azolate framework(MAF),MAF-40,with a threedimensional(3D)honeycomb-like framework and 1D sugar-coated-berry type pore channels.By virtue of the strong coordination bonds and abundant trifluoromethyl groups embedded in the pores,MAF-40 exhibits excellent thermal stability(up to 400℃)and acid-base stability(within a pH range of 3–11).Moreover,MAF-40 shows ultrahigh benzene selectivity(38.8)from the ternary benzene/cyclohexene/cyclohexane mixtures,attributed to the strong adsorption affinity from fluorine for benzene and markedly different vip diffusion limited by the small aperture,which are confirmed by computational simulations and infrared spectra.Thus,the results indicated that MAF-40 would be a candidate adsorbent for the separation and purification of benzene from C6 cyclic hydrocarbons,and this work provides a new insight of synthesizing stable MOF materials for separating multicomponent chemical mixtures.
基金supported by the National Natural Science Fund of China(22121005,22025203)the University of Manchester,and Haihe Laboratory of Sustainable Chemical Transformations,Tianjin。
文摘Adsorptive separation of light hydrocarbons by porous solids provides an energy-efficient alternative to state-of-the-art cryogenic distillation.However,an optimal balance between the cost,performance and stability of the sorbent material is yet to be achieved for industrial applications.Here,we report the efficient separation of C2 and C3 hydrocarbons by a faujasite zeolite(Na-X,Si/Al=1.23).A tandem configuration of two fixed-beds packed with Na-X affords complete dynamic separation of the ternary mixture of C_(2)H_(2)/C_(2)H_(4)/C_(2)H_(6)(1/49.5/49.5;v/v/v)under ambient conditions.Pressure-swing desorption on the latter fixed-bed gives ethylene(>99.50%,1.80 mmol g^(-1))and ethane(>99.99%,1.41 mmol g^(-1)).In situ synchrotron X-ray powder diffraction revealed the binding sites for C_(2)H_(2)and C_(2)H_(4)in Na-X.This study highlights the potential application of commercial zeolites for challenging industrial separations.
文摘The use of polar organic solvents for the separations of rare earth elements (Ⅲ) is effective especially for their extensive separations despite the solubility limitations. The study shows that polyacrylate anion exchangers, particularly the weakly basic, gel anion exchanger Amberlite IRA 68, can be applied to the separation of rare earth complexes with EDTA in H_2O-methanol and H_2O-ethanol systems. In most cases the determined distribution coefficients of Ln^(3+) complexes with EDTA in mixed media like water-methanol on polyacrylate anion exchangers are larger than those in pure water (media.)
基金supported by National Natural Science Foundation of China(Nos.52472194,52101243)Natural Science Foundation of Guangdong Province,China(No.2023A1515012619)the Science and Technology Planning Project of Guangzhou(No.202201010565)。
文摘The efficient limitation of the"shuttle effect"of polysulfide from the rational construction of electrocatalysts to accelerate the redox kinetics of polysulfides is extremely important.In this work,the cobalt/Nickel bimetallic alloy polyhedrons decorated on layered TiO_(2)heterostructure(Co Ni@TiO_(2)/C)derived from MXene and bimetallic metal-organic framework have been prepared through liquid-phase deposition and high-temperature annealing processes.This heterostructure presents excellent electrical conductivity,which facilitates ion diffusion and electron transfer within the battery.Besides,the heterostructure from anchoring the Co Ni bimetallic alloy on the layered TiO_(2)ensures the full exposure of active sites and accelerates polysulfide redox kinetics through chemisorption and catalytic conversion.Considering these advantages mentioned above,when applied as the lithium-sulfur batteries(LSBs)separator modifier,the cell assembled from the Co Ni@TiO_(2)/C modified separator demonstrates high specific capacity(1481.7 mAh/g at 0.5 C),superior rate capability(855.5 mAh/g at 3 C)and excellent cycling performance,which can maintain the high capacity of 856.09 mAh/g after 300 cycles with low capacity decay rate of 0.09%per cycle.Even under a high sulfur loading of 4.4 mg/cm^(2),the cell can still present excellent cycling stability.This study paves the way for the design of novel material for the construction of an outstanding functional separator layer and shines the light on the effective and feasible way for the inhibition of shuttle effect in lithium-sulfur batteries.
基金supported by the funding from the Joint Funds for the Innovation of Science and Technology,Fujian Province(Grant No.2023Y9385)Major Scientific Research Program for Young and Middleaged Health Professionals of Fujian Province,China(Grant No.2022ZQNZD010).
文摘Y chromosome microdeletions are an important cause of male infertility.At present,research on the Y chromosome is mainly focused on analyzing the loss of large segments of the azoospermia factor a/b/c(AZFa/b/c)gene,and few studies have reported the impact of unit point deletion in the AZF band on fertility.This study analyzed the effect of sperm quality after sY1192 loss in 116 patients.The sY1192-independent deletion accounted for 41.4%(48/116).Eight patterns were found in the deletions associated with sY1192.The rate of sperm detection was similar in the semen of patients with the independent sY1192 deletion and the combined sY1192 deletions(52.1%vs 50.0%).The patients with only sY1192 gene loss had a higher probability of sperm detection than the patients whose sY1192 gene locus existed,but other gene loci were lost(52.1%vs 32.0%).The hormone levels were similar in patients with sY1192 deletion alone and in those with sY1192 deletion and other types of microdeletions in the presence of the sY1192 locus.After multiple intracytoplasmic sperm injection(ICSI)attempts,the pregnancy rate of spouses of men with sY1192-independent deletions was similar to that of other types of microdeletions,but the fertilization and cleavage rates were higher.We observed that eight deletion patterns were observed for sY1192 microdeletions of AZFb/c,dominated by the independent deletion of sY1192.After ICSI,the fertilization rate and cleavage rate of the sY1192-independent microdeletion were higher than those of other Y chromosome microdeletion types,but there was no significant difference in pregnancy outcomes.
基金supported by the National Key Research and Development Program of China(No.2021YFA1600800)the National Natural Science Foundation of China(Nos.22102102,22372102,22101185 and 22402122)+8 种基金Shenzhen Science and Technology Program(No.20231122120657001)the City University of Hong Kong Start-Up Fund(No.9020003)ITFRTH-Global STEM Professorship(No.9446006)Guangdong Basic and Applied Basic Research Foundation(No.2020A1515010982)Research Team Cultivation Program of Shenzhen University(No.2023QNT013)Scientific Foundation for Youth Scholars of Shenzhen University(868-000001032185)Shenzhen Peacock Plan(Nos.20210308299C,RCJC20200714114434086 and 20231121175024001)Shenzhen Key Laboratory of 2D Metamaterials for Information Technology(No.ZDSYS201707271014468)China Postdoctoral Science Foundation(No.2023M742395)
文摘Photocatalytic oxidation of toluene to valuable benzaldehyde offers a promising pathway for sustainable production of fine chemicals and pharmaceuticals.In this process,photogenerated holes play a crucial role in C(sp^(3))-H bond dissociation.However,the photocatalytic performance of current photocatalysts is often hindered by the low separation and transfer efficiency of photogenerated charges.In this work,we presented a perovskite-based heterostructure via in situ growth of defective WO_(3-x)nanosheets on Cs_(2)AgBiBr_(6)nanoparticles for photocatalytic toluene transformation.In situ Fourier transform infrared spectroscopy tests proved the introduction of oxygen-deficient WO_(3)-xcomponent enhanced the chemisorption of molecular oxygen.The in situ electron paramagnetic resonance and 4-chloro-7-nitro-1,2,3-benzoxadiazole fluorescence measurements further confirmed the presence of oxygen vacancies,and the formation of heterostructure synergistically accelerated the formation of the superoxide radicals and the transfer of photogenerated charge carriers.Under visible light irradiation,Cs_(2)AgBiBr_(6)/WO_(3-x)photocatalyst could effectively oxidize toluene toward benzaldehyde with a conversion rate of 9020μmol g^(-1)h^(-1),which was a 3.5-fold increase over that of the unmodified Cs_(2)AgBiBr_(6).
基金supported by Natural Science Foundation of Zhejiang Province(LR20B060001 and LZ18B060001)the National Natural Science Foundation of China(21725603,21938011),the Entrepreneur Team Introduction Program of Zhejiang(2019R01006)the Research Computing Center in College of Chemical and Biological Engineering at Zhejiang University.
文摘With the increasing demand for synthetic rubber,the purification of 1,3-butadiene(C_(4)H_(6))is of great industrial significance.Herein,the successful removal of n-butene(n-C_(4)H_(8))and iso-butene(iso-C_(4)H_(8))from 1,3-butadiene(C_(4)H_(6))was realized by synthesizing a novel TaOF_(5)^(2-) anion-pillared ultramicroporous material TaOFFIVE-3-Ni(also referred to as ZU-96,TaOFFIVE=TaOF_(5)^(2-),3=pyrazine).Single-component adsorption isotherms show that TaOFFIVE-3-Ni can achieve the exclusion of n-C_(4)H_(8) and iso-C_(4)H_(8) in the low pressure region(0–30 kPa),and uptake C_(4)H_(6) with a high capacity of 92.78 cm^(3)·cm^(-3)(298 K and 100 kPa).The uptake ratio of C_(4)H_(6)/iso-C_(4)H_(8) on TaOFFIVE-3-Ni was 20.83(298 K and 100 kPa),which was the highest among the state-of-the-art adsorbents reported so far.With the rotation of anion and pyrazine ring,the pore size changes continuously,which makes smaller-size C_(4)H_(6) enter the channel while larger-size n-C_(4)H_(8) and iso-C_(4)H_(8) are completely blocked.The excellent breakthrough performance of TaOFFIVE-3-Ni shows great potential in industrial separation of C4 olefins.The specific adsorption binding sites within ZU-96 was further revealed through the modeling calculation.
文摘The valence state of C atoms and the structure of molecular orbitals of the (Buckminster)Fullerene C_(60)have been demonstrated. It has been shown that when a motion-coordinate system is adopted, in which the coordinate origin is at every C atom, the z axis is in the direction of the normal and the (x,y) axes are in the direction of tangents of C_(60)'s spherical surface, 240 valence atomic orbitals of C_(60) can be divided into two groups. All (P_x, P_y)atomic orbitals named as Pt ones and all the other P_z atomic orbitals named as p. ones, That is to say that if we name the molecular orbital linearly combined of P_t atomic orbitals as σ_t and the molecular orbital linearly combined of P_n atomic orbitals as π_n, the 240 valence molecular orbitals are of the property of σ_t-π_n separability. It has also been shown that the frontier and nearby frontier molecular orbitals are π_n ones, and therefore the essential physical and chemical properties of C_(60) are determined by its π_n molecular orbitals.
基金This research was supported by the National Natural Science Foundation of China(No.U1702251)Special Funds of State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization(Grant No.CNMRCUTS1604)+2 种基金the Program for Innovative Research Team in University of Ministry of Education of China(No.IRT_17R48)Key Laboratory of Comprehensive Utilization of Vanadium and Titanium Resources in Sichuan Province(2019FTSZ06)the PhD Fund of Panzhihua University,and Funded by the State Key Laboratory of Vanadium and Titanium Resources Comprehensive Utilization.
文摘The effects of directional solidification parameters and the coupling of directional solidification parameters and alternating electromagnetic fields on separation and enrichment of the C54–TiSi2 phase were investigated in a directionally solidified hypoeutectic Ti–65 wt.%Si alloy.The results indicated that by increasing the pull-down velocity at a given position within the ingot,the cooling rate,growth rate,and temperature gradient of ingot could be increased.At a pull-down velocity near 5μm/s,the temperature gradient,cooling rate,and growth rate decreased with increasing the thickness of the C54–TiSi2-rich layer.Electromagnetic fields enhanced mass transfer at pull-down velocities of 5,10,15,and 20μm/s,with resulting enriched layer thicknesses of 15,10,10,and 5 mm,respectively.By increasing the percentage of Ti in the Ti–Si alloy from 25 to 35 wt.%,the thickness of the C54–TiSi2-rich layer was increased from 2.5 to 3.3 cm.However,the maximum C54–TiSi2 content obtained experimentally in this layer decreased from 92.06 to 79.49 mass%.
