Ring-opening copolymerization of CO_(2) and epoxides is a promising way to manufacture high value-added materials.Despite a variety of catalyst systems have been reported,the reaction is still limited by low activity ...Ring-opening copolymerization of CO_(2) and epoxides is a promising way to manufacture high value-added materials.Despite a variety of catalyst systems have been reported,the reaction is still limited by low activity and polymer selectivity.Herein,a strategy of polymerization-enhanced Lewis acidity is reported to construct a series of highly efficient polymeric aluminum porphyrin catalysts(PAPCs).The characterization of the coordination equilibrium constant(K_(eq))showed significantly enhanced Lewis acidity of PAPC(K_(eg)=18.2 L/mol)compared to the monomeric counterpart(K_(eq)=6.4 L/mol),accompanied with increased turnover frequency(TOF)from 136 h^(-1) to 5500 h^(-1).Through detailed regulation of Lewis acidity,the highly Lewis acidic PAPC-OTs displayed a record high TOF of 30,200 h^(-1) with polymer selectivity of up to 99%.展开更多
The Lewis acidity scale of boron trihalides BX3 (X=F, Cl, Br, I) and character of the boron-halogen bonds have been studied by means of DV-Xa approach. Present results show that the acid strength of boron trihalides i...The Lewis acidity scale of boron trihalides BX3 (X=F, Cl, Br, I) and character of the boron-halogen bonds have been studied by means of DV-Xa approach. Present results show that the acid strength of boron trihalides increases in the order BF3<BCl3<BBr3<BI3, in excellent agreement with experiments. Based on boron-halogen bonding character, the valence of boron atom in boron compounds can be considered as equal to five instead of three which seems to be more reasonable.展开更多
Since the discovery in 2011,MXenes have become the rising star in the field of two-dimensional materials.Benefiting from the metallic-level conductivity,large and adjustable gallery spacing,low ion diffusion barrier,r...Since the discovery in 2011,MXenes have become the rising star in the field of two-dimensional materials.Benefiting from the metallic-level conductivity,large and adjustable gallery spacing,low ion diffusion barrier,rich surface chemistry,superior mechanical strength,MXenes exhibit great application prospects in energy storage and conversion,sensors,optoelectronics,electromagnetic interference shielding and biomedicine.Nevertheless,two issues seriously deteriorate the further development of MXenes.One is the high experimental risk of common preparation methods such as HF etching,and the other is the difficulty in obtaining MXenes with controllable surface groups.Recently,Lewis acidic etching,as a brand-new preparation strategy for MXenes,has attracted intensive attention due to its high safety and the ability to endow MXenes with uniform terminations.However,a comprehensive review of Lewis acidic etching method has not been reported yet.Herein,we first introduce the Lewis acidic etching from the following four aspects:etching mechanism,terminations regulation,in-situ formed metals and delamination of multi-layered MXenes.Further,the applications of MXenes and MXene-based hybrids obtained by Lewis acidic etching route in energy storage and conversion,sensors and microwave absorption are carefully summarized.Finally,some challenges and opportunities of Lewis acidic etching strategy are also presented.展开更多
Novel Lewis acidic ionic liquids containing thionyl cations and chloroaluminate anions were obtained by one-pot synthesis for the first time. Their acidities were determined by acetonitrile probe on IR spectrography. ...Novel Lewis acidic ionic liquids containing thionyl cations and chloroaluminate anions were obtained by one-pot synthesis for the first time. Their acidities were determined by acetonitrile probe on IR spectrography. The ionic liquids were used as catalyst for Friedel-Crafts alkylation of benzene and 1-dodecene. The turnovers of l-dodecene were higher than 99%. Monoalkylbenzene selectivity was 98%, while the 2-substituent product selectivity was 45%.展开更多
An experimental investigation was conducted to understand the roles of the Br?nsted acid H2SO4 and Lewis acid Al2(SO4)3 in methyl levulinate(ML) production from biomass carbohydrates, including glucose,fructose a...An experimental investigation was conducted to understand the roles of the Br?nsted acid H2SO4 and Lewis acid Al2(SO4)3 in methyl levulinate(ML) production from biomass carbohydrates, including glucose,fructose and cellulose. The product distributions with different catalysts revealed that the Lewis acid was responsible for the isomerization of methyl glucoside(MG), producing a significant amount of the subsequent product 5-methoxymethylfurfural(MMF), while the Br?nsted acid facilitated the production of ML from MMF. Al2(SO4)3 was efficient for monosaccharide conversion but not for cellulose. Using ball-milled cellulose with Al2(SO4)3 resulted in a desired ML yield within a reasonable reaction time. The significant catalysis performances of two types of acids will guide the design of efficient catalytic processes for the selective conversion of biomass into levulinate esters.展开更多
Carbon materials have shown remarkable usefulness in facilitating the performance of insulating sulfur cathode for lithium–sulfur batteries owing to their excellent conductivity and porous structure. However,the anxi...Carbon materials have shown remarkable usefulness in facilitating the performance of insulating sulfur cathode for lithium–sulfur batteries owing to their excellent conductivity and porous structure. However,the anxiety is the poor affinity toward polar polysulfides due to the intrinsic nonpolar surface of carbon.Herein, we report a direct pyrolysis of the mixture urea and boric acid to synthesize B/N–codoped hierarchically porous carbon nanosheets(B–N–CSs) as efficient sulfur host for lithium–sulfur battery. The graphene–like B–N–CSs provides high specific surface area and porous structure with abundant micropores(1.1 nm) and low–range mesopores(2.3 nm), thereby constraining the sulfur active materials within the pores. More importantly, the codoped B/N elements can further enhance the polysulfide confinement through strong Li–N and B–S interaction based on the Lewis acid–base theory. These structural superiorities significantly suppress the shuttle effect by both physical confinement and chemical interaction, and promote the redox kinetics of polysulfide conversion. When evaluated as the cathode host, the S/B–N–CSs composite displays the excellent performance with a high reversible capacity up to 772 m A h g–1 at 0.5 C and a low fading rate of ^0.09% per cycle averaged upon 500 cycles. In particular, remarkable stability with a high capacity retention of 87.1% can be realized when augmenting the sulfur loading in the cathode up to 4.6 mg cm^(-2).展开更多
CeO_(2)-based catalysts are emerging as novel candidates for catalyzing nitrogen reduction reaction(NRR).However, despite the increasing amount of experimental and theoretical research, the design of more efficient ce...CeO_(2)-based catalysts are emerging as novel candidates for catalyzing nitrogen reduction reaction(NRR).However, despite the increasing amount of experimental and theoretical research, the design of more efficient ceria catalysts for NRR remains a challenge due to the poor knowledge of the catalytic mechanism, particularly the nature of the active sites and how they catalyze NRR. Here, using first-principle calculations, we investigated the NRR catalysis process involving adjacent Ce Lewis acid clusters formed on(111),(110), and(100) facets of CeO_(2) as active sites. Our results revealed that the assembled structures of the Ce Lewis acid as active centers after the oxygen vacancies(Ovs) were opened. The exposed Ce sites on CeO_(2)(111), CeO_(2)(110), and CeO_(2)(100) can cause N_(2) to be adsorbed in a ‘‘lying-down" manner, which facilitates the N2 activation and thus leads to much higher NRR activity. Furthermore, from the perspective of electronic structure, we establish two useful descriptors for assessing the NRR activity on ceria with Ovs:The N–N bond strength of the adsorbed N_(2) and the adsorption energy of the *N_(2)H intermediate. This work thus provides direct guidance for the design of more-effective oxide catalysts without the use of scarce metals.展开更多
The azides were reduced to the corresponding amines by two new metal/Lewis acid systems in water or in aqueous EtOH in yields ranging from 80%-95%. The reaction rates were faster in water than in aqueous EtOH in most...The azides were reduced to the corresponding amines by two new metal/Lewis acid systems in water or in aqueous EtOH in yields ranging from 80%-95%. The reaction rates were faster in water than in aqueous EtOH in most cases. All 16 azides with different functional groups were well reduced to the corresponding amines in excellent yields and reaction rates.展开更多
The incorporation of boron into carbon material can significantly enhance its capacity performances.However,the origin of the promotion effect of boron doping on electrochemical performances is still unclear,in part d...The incorporation of boron into carbon material can significantly enhance its capacity performances.However,the origin of the promotion effect of boron doping on electrochemical performances is still unclear,in part due to the inadequate exposure of boron configurations resulting from the complexity of traditional carbon materials.To overcome this issue,herein,a series of boron-doped graphene with highly-exposed boron configurations are prepared by tuning annealing temperature.Then the correlation between boron configurations and the electrochemical performances is investigated.The combination of density-functional theory(DFT)computation and NH3-TPD/Py-FTIR indicates that the BCO_(2)configuration formed on the surface of graphene is easier to accept lone-pair electrons than BC_(2)O and BC_(3)configurations due to the stronger Lewis acidity.Such an electronic structure can effectively reduce the number of unstable electron donors and stabilize the electrochemical interface,which is proved by NMR,and critical for improving the electrochemical performances.Further experiments confirm that the optimized BG800 with the largest amount of BCO_(2)configuration presents ultralow leak current,improved cyclic stability,and better rate performance in SBPBF4/PC.This work would provide an insight into the design of high-performance boron-doped carbon materials towards energy storage.展开更多
Treatment of steroidal sapogenin diosgenin 1 with Lewis acid ethereal trifluoroborane in acetic anhydride at room temperature afforded a new type of pseudosapugenin 23, 26-diacetyl-△22(23)- pseudo-sapogenin 3 and its...Treatment of steroidal sapogenin diosgenin 1 with Lewis acid ethereal trifluoroborane in acetic anhydride at room temperature afforded a new type of pseudosapugenin 23, 26-diacetyl-△22(23)- pseudo-sapogenin 3 and its C-20 isomer 4 in 54% and 19% yield respectively.The possible mechanism was also suggested.展开更多
Chloro(5,10,15,20-tetraphenyl-porphyrinato)-aluminum/tetraethylammonium bromide(Et4NBr)in combination with bulky Lewis acid was used for the copolymerization of CO_2 and cyclohexene oxide(CHO).Bulky Lewis acid having ...Chloro(5,10,15,20-tetraphenyl-porphyrinato)-aluminum/tetraethylammonium bromide(Et4NBr)in combination with bulky Lewis acid was used for the copolymerization of CO_2 and cyclohexene oxide(CHO).Bulky Lewis acid having substituents at the ortho positions of the phenolate ligands,like methylaluminum bis(2,6-di-tert-butyl-4-methylphenolate), significantly shortened the induction period and raised the catalytic activity,the corresponding turnover frequency reached 44.9 h^(-1)in 9 h,which was 23.8% higher than th...展开更多
Ratio of Lewis/Brfnsted acid sites (Cl/Cb) on the surface of nano-sized HZSM-5 was successfully manipulated by means of steaming and acid leaching. Significant enhancement of the deactivation durability of nano-sized...Ratio of Lewis/Brfnsted acid sites (Cl/Cb) on the surface of nano-sized HZSM-5 was successfully manipulated by means of steaming and acid leaching. Significant enhancement of the deactivation durability of nano-sized HZSM-5 in the aromatization of fluid catalytic cracking (FCC) gasoline olefins seems to be closely related to the increase of Lewis/Brfnsted acid sites ratio.展开更多
This paper reports the kinetics of group transfer polymerization (GTP)of ethyl acrylate (EA)with zinc iodide catalyst in 1,2-dichloroethane using dimethyl ketene methyl trimethylsilyl acetal (MTS) as initiator at 0℃ ...This paper reports the kinetics of group transfer polymerization (GTP)of ethyl acrylate (EA)with zinc iodide catalyst in 1,2-dichloroethane using dimethyl ketene methyl trimethylsilyl acetal (MTS) as initiator at 0℃ and above 0℃. The amount of catalyst used was studied. When zinc iodide catalyst used is more than 10mol% relative to monomer, the rate of polymerization is proportional to the concentration of monomer, whereas zinc iodide catalyst used is less than 10 mol% of the monomer, the rate of polymerization is independent of the monomer concentration.In the GTP of EA an induction period was observed when the zinc iodide contents are less than l0mol%. If the reaction temperature is over 0℃, living species become unstable and diminish, leading to incomplete monomer conversion. The reaction curves equations are obtained. The polymers have narrow molecular weight distributions which are not changed as decreasing zinc iodide contents. The polydispersity is about 1.2.展开更多
Lewis acidic guanidinium ionic liquid(LAGIL) 2c was used as a novel, efficient and recyclable catalyst for aminolysis of epoxides under solvent-free and room temperature conditions, giving the corresponding β-amino...Lewis acidic guanidinium ionic liquid(LAGIL) 2c was used as a novel, efficient and recyclable catalyst for aminolysis of epoxides under solvent-free and room temperature conditions, giving the corresponding β-amino alcohols with moderate to excellent regioselectivity(up to 91:9) in high yields(up to 97%). In addition, LAGIL 2c was recycled three times without any loss of catalytic activity and selectivity to the product.展开更多
A polystyrene-bonded stannic chloride catalyst was synthesized by the method of lithium polystyryl combined with stannic chloride. This catalyst is a polymeric organometallic compound containing 0.25 mmol Sn (Ⅳ)/g ca...A polystyrene-bonded stannic chloride catalyst was synthesized by the method of lithium polystyryl combined with stannic chloride. This catalyst is a polymeric organometallic compound containing 0.25 mmol Sn (Ⅳ)/g catalyst. The catalyst showed sufficient stability and catalytic activity in organic reaction such as esterification, acetalation and ketal formation, and it could be reused many times without losing its catalytic activity.展开更多
Rechargeable magnesium batteries(RMBs)are considered the promising candidates for post lithium-ion batteries due to the abundant storage,high capacity,and dendrite-rare characteristic of Mg anode.However,the lack of p...Rechargeable magnesium batteries(RMBs)are considered the promising candidates for post lithium-ion batteries due to the abundant storage,high capacity,and dendrite-rare characteristic of Mg anode.However,the lack of practical electrolytes impedes the development and application of RMBs.Here,through a one-step reaction of LiCl congenital-containing Knochel–Hauser base TMPL(2,2,6,6-tetrame thylpiperidinylmagnesium chloride lithium chloride complex)with Lewis acid AlCl_(3),we successfully synthesized an efficient amino-magnesium halide TMPLA electrolyte.Raman and mass spectroscopy identified that the electrolyte comprises the typical di-nuclear copolymer[Mg_(2)Cl_(3)·6THF]+cation group and[(TMP)2AlCl_(2)]-anion group,further supported by the results of density functional theory calculations(DFT)and the Molecular dynamics(MD)simulations.The TMPLA electrolyte exhibits promising electrochemical performance,including available anodic stability(>2.65 V vs.SS),high ionic conductivity(6.05mS cm^(-1)),and low overpotential(<0.1 V)as well as appropriate Coulombic efficiency(97.3%)for Mg plating/stripping.Both the insertion Mo6S8cathode and conversion Cu S cathode delivered a desirable electrochemical performance with high capacity and good cycling stability based on the TMPLA electrolyte.In particular,when compatible with low cost and easily synthesized Cu S,the Cu S||Mg cell displayed an extremely high discharge capacity of 458.8 mAh g^(-1)for the first cycle and stabilized at 170.2 mAh g^(-1)with high Coulombic efficiency(99.1%)after 50 cycles at 0.05 C.Our work proposes an efficient electrolyte with impressive compatibility with Mg anode and insertion/conversion cathode for practical RMBs and provides a more profound knowledge of the Lewis acid–base reaction mechanisms.展开更多
The fluorine-free MXene was prepared by Lewis acid salt etching of ternary layered ceramic MAX phase material.The structure of fluorine-free MXene was characterized by scanning electron microscopy(SEM)and X-ray diffra...The fluorine-free MXene was prepared by Lewis acid salt etching of ternary layered ceramic MAX phase material.The structure of fluorine-free MXene was characterized by scanning electron microscopy(SEM)and X-ray diffractometry(XRD).The study finds that the layer spacing of fluorine-free MXene is approximately twice that of MXene etched by the liquid-phase method,compared to the conventional liquidphase method.It also has greater capacitive properties.Therefore,the MXene prepared by this method shows a great potential for application in the field of capacitors.展开更多
This review divides the acidic deep eutectic solvents(ADES) into Br?nsted and Lewis DES according to their diversity of acidic character.The hydrogen bond donors and halide salts for formulating an ADES are classified...This review divides the acidic deep eutectic solvents(ADES) into Br?nsted and Lewis DES according to their diversity of acidic character.The hydrogen bond donors and halide salts for formulating an ADES are classified, the synthesis methods are described, and the physicochemical properties including freezing point, acidity, density, viscosity and conductivity are presented. Furthermore, the applications of Br?nsted acidic deep eutectic solvents(BADES) and Lewis acidic deep eutectic solvents(LADES) are overviewed, respectively, covering the fields in dissolution, extraction, organic reaction and metal electrodeposition. It is expected that the ADES has great potential to replace the pollutional mineral acid, expensive and unstable solid acid, and costly ionic liquid in many acid-employed chemical processes, thus meeting the demands of green chemistry.展开更多
A series of heterogeneous catalysts with Cp2TiCl2 supported on palygorskite were prepared and evaluated by ethylene slurry polymerizations. The so-called direct supported catalyst, for which the pretreatment of palygo...A series of heterogeneous catalysts with Cp2TiCl2 supported on palygorskite were prepared and evaluated by ethylene slurry polymerizations. The so-called direct supported catalyst, for which the pretreatment of palygorskite with MAO or Al(i-Bu)3 was not necessary, gave the highest activity among these supported catalysts and could be more robust than homogeneous Cp2TiCl2. With the direct supported catalyst, no significant activity loss was observed under low Al/Ti molar ratios (Al/Ti=300) and the decay of polymerization rate was slower when compared to the other supported catalysts. It was found that the surface Lewis acidity of palygorskite after thermal treatment played an important role in activation of metallocene compound and resulted in high catalyst activity.展开更多
Probiotics are live microorganisms which when administered in adequate amounts confer a health benefit on the host. Human-origin <i>Lactobacillus</i> is a preferable source of probiotic bacteria. This stud...Probiotics are live microorganisms which when administered in adequate amounts confer a health benefit on the host. Human-origin <i>Lactobacillus</i> is a preferable source of probiotic bacteria. This study screened 14 vaginal <i>Lactobacillus</i> strains as probiotic candidates by investigating probiotic-related cell surface characteristics including cell surface hydrophobicity (CSH), Lewis acidity/basicity, autoaggregation, and biofilm formation. Moderate to high CSH and autoaggregation, high basicity and low acidity were prevalent in the 14 tested strains. Biofilm formation varied in a large range among the 14 tested strains. CSH showed a high correlation with Lewis acidity and autoaggregation, while Lewis acidity was highly correlated with autoaggregation and biofilm formation. Four strains were selected as promising probiotic strains. This study was the first one to compare antibiotic sensitivity between biofilm-forming cells and planktonic cells of <i>Lactobacillus</i> species, and found that biofilm-forming cells of a <i>L. fermentum</i> strain had a significantly higher survival rate than planktonic cells in cefotaxime, cefmetazole and tetracycline, but were as sensitive to oxacillin and ampicillin as planktonic cells were.展开更多
基金supported by National Natural Science Foundation of China(Nos.51988102,22271275,22201280,22101277)Special Project of High-tech Industrialization of Cooperation between Jilin Province and Chinese Academy of Sciences(No.2022SYHz0004)Changchun Science and Technology Development Plan Funding Project(No.21ZY10).
文摘Ring-opening copolymerization of CO_(2) and epoxides is a promising way to manufacture high value-added materials.Despite a variety of catalyst systems have been reported,the reaction is still limited by low activity and polymer selectivity.Herein,a strategy of polymerization-enhanced Lewis acidity is reported to construct a series of highly efficient polymeric aluminum porphyrin catalysts(PAPCs).The characterization of the coordination equilibrium constant(K_(eq))showed significantly enhanced Lewis acidity of PAPC(K_(eg)=18.2 L/mol)compared to the monomeric counterpart(K_(eq)=6.4 L/mol),accompanied with increased turnover frequency(TOF)from 136 h^(-1) to 5500 h^(-1).Through detailed regulation of Lewis acidity,the highly Lewis acidic PAPC-OTs displayed a record high TOF of 30,200 h^(-1) with polymer selectivity of up to 99%.
基金Project supported by the National Natural Science Foundation of China.
文摘The Lewis acidity scale of boron trihalides BX3 (X=F, Cl, Br, I) and character of the boron-halogen bonds have been studied by means of DV-Xa approach. Present results show that the acid strength of boron trihalides increases in the order BF3<BCl3<BBr3<BI3, in excellent agreement with experiments. Based on boron-halogen bonding character, the valence of boron atom in boron compounds can be considered as equal to five instead of three which seems to be more reasonable.
基金supported by the Highstar Corporation HSD20210118Taihu Electric Corporation 0001。
文摘Since the discovery in 2011,MXenes have become the rising star in the field of two-dimensional materials.Benefiting from the metallic-level conductivity,large and adjustable gallery spacing,low ion diffusion barrier,rich surface chemistry,superior mechanical strength,MXenes exhibit great application prospects in energy storage and conversion,sensors,optoelectronics,electromagnetic interference shielding and biomedicine.Nevertheless,two issues seriously deteriorate the further development of MXenes.One is the high experimental risk of common preparation methods such as HF etching,and the other is the difficulty in obtaining MXenes with controllable surface groups.Recently,Lewis acidic etching,as a brand-new preparation strategy for MXenes,has attracted intensive attention due to its high safety and the ability to endow MXenes with uniform terminations.However,a comprehensive review of Lewis acidic etching method has not been reported yet.Herein,we first introduce the Lewis acidic etching from the following four aspects:etching mechanism,terminations regulation,in-situ formed metals and delamination of multi-layered MXenes.Further,the applications of MXenes and MXene-based hybrids obtained by Lewis acidic etching route in energy storage and conversion,sensors and microwave absorption are carefully summarized.Finally,some challenges and opportunities of Lewis acidic etching strategy are also presented.
基金the grant from the National Natural Science Foundation of China (Key Program 20533010).
文摘Novel Lewis acidic ionic liquids containing thionyl cations and chloroaluminate anions were obtained by one-pot synthesis for the first time. Their acidities were determined by acetonitrile probe on IR spectrography. The ionic liquids were used as catalyst for Friedel-Crafts alkylation of benzene and 1-dodecene. The turnovers of l-dodecene were higher than 99%. Monoalkylbenzene selectivity was 98%, while the 2-substituent product selectivity was 45%.
基金supported by the National Key R&D Program of China (No. 2016YFE0112800)the European Union’s Horizon 2020 research and innovation programme (No. 690142)+1 种基金the project Agro Cycle (Sustainable techno-economic solutions for the agricultural value chain)the National Natural Science Foundation of China (No. 31671572)
文摘An experimental investigation was conducted to understand the roles of the Br?nsted acid H2SO4 and Lewis acid Al2(SO4)3 in methyl levulinate(ML) production from biomass carbohydrates, including glucose,fructose and cellulose. The product distributions with different catalysts revealed that the Lewis acid was responsible for the isomerization of methyl glucoside(MG), producing a significant amount of the subsequent product 5-methoxymethylfurfural(MMF), while the Br?nsted acid facilitated the production of ML from MMF. Al2(SO4)3 was efficient for monosaccharide conversion but not for cellulose. Using ball-milled cellulose with Al2(SO4)3 resulted in a desired ML yield within a reasonable reaction time. The significant catalysis performances of two types of acids will guide the design of efficient catalytic processes for the selective conversion of biomass into levulinate esters.
基金financial support of the National Natural Science Foundation of China (Grant No. 21263016, 21363015, 51662029, 21863006)the Youth Science Foundation of Jiangxi Province (Grant No. 20192BAB216001)the Key Laboratory of Jiangxi Province for Environment and Energy Catalysis (20181BCD40004)。
文摘Carbon materials have shown remarkable usefulness in facilitating the performance of insulating sulfur cathode for lithium–sulfur batteries owing to their excellent conductivity and porous structure. However,the anxiety is the poor affinity toward polar polysulfides due to the intrinsic nonpolar surface of carbon.Herein, we report a direct pyrolysis of the mixture urea and boric acid to synthesize B/N–codoped hierarchically porous carbon nanosheets(B–N–CSs) as efficient sulfur host for lithium–sulfur battery. The graphene–like B–N–CSs provides high specific surface area and porous structure with abundant micropores(1.1 nm) and low–range mesopores(2.3 nm), thereby constraining the sulfur active materials within the pores. More importantly, the codoped B/N elements can further enhance the polysulfide confinement through strong Li–N and B–S interaction based on the Lewis acid–base theory. These structural superiorities significantly suppress the shuttle effect by both physical confinement and chemical interaction, and promote the redox kinetics of polysulfide conversion. When evaluated as the cathode host, the S/B–N–CSs composite displays the excellent performance with a high reversible capacity up to 772 m A h g–1 at 0.5 C and a low fading rate of ^0.09% per cycle averaged upon 500 cycles. In particular, remarkable stability with a high capacity retention of 87.1% can be realized when augmenting the sulfur loading in the cathode up to 4.6 mg cm^(-2).
基金supported by the National Natural Science Foundation of China (21973013 and 21673040 to S.L, and 21962007 to S.Z)the Natural Science Foundation of Fujian Province of China (2020J02025 to S.L)+2 种基金the Natural Science Foundation of Jiangxi Province (2020BABL203009 to S.Z)the Foundation of Jiangxi Educational Committee (GJJ190697 to S.Z)the Qishan Scholarship Program of Fuzhou University (XRC-17055 to S.L)。
文摘CeO_(2)-based catalysts are emerging as novel candidates for catalyzing nitrogen reduction reaction(NRR).However, despite the increasing amount of experimental and theoretical research, the design of more efficient ceria catalysts for NRR remains a challenge due to the poor knowledge of the catalytic mechanism, particularly the nature of the active sites and how they catalyze NRR. Here, using first-principle calculations, we investigated the NRR catalysis process involving adjacent Ce Lewis acid clusters formed on(111),(110), and(100) facets of CeO_(2) as active sites. Our results revealed that the assembled structures of the Ce Lewis acid as active centers after the oxygen vacancies(Ovs) were opened. The exposed Ce sites on CeO_(2)(111), CeO_(2)(110), and CeO_(2)(100) can cause N_(2) to be adsorbed in a ‘‘lying-down" manner, which facilitates the N2 activation and thus leads to much higher NRR activity. Furthermore, from the perspective of electronic structure, we establish two useful descriptors for assessing the NRR activity on ceria with Ovs:The N–N bond strength of the adsorbed N_(2) and the adsorption energy of the *N_(2)H intermediate. This work thus provides direct guidance for the design of more-effective oxide catalysts without the use of scarce metals.
文摘The azides were reduced to the corresponding amines by two new metal/Lewis acid systems in water or in aqueous EtOH in yields ranging from 80%-95%. The reaction rates were faster in water than in aqueous EtOH in most cases. All 16 azides with different functional groups were well reduced to the corresponding amines in excellent yields and reaction rates.
基金the National Science Foundation for Excellent Young Scholars of China(21922815)the Key Research and Development(R&D)Projects of Shanxi Province(201903D121007)+3 种基金the Natural Science Foundations of Shanxi Province(201801D221156)the DNL Cooperation Fund of CAS(DNL180308)the Science and Technology Service Network Initiative of CAS(KFJ-STS-ZDTP-068)the Youth Innovation Promotion Association of CAS。
文摘The incorporation of boron into carbon material can significantly enhance its capacity performances.However,the origin of the promotion effect of boron doping on electrochemical performances is still unclear,in part due to the inadequate exposure of boron configurations resulting from the complexity of traditional carbon materials.To overcome this issue,herein,a series of boron-doped graphene with highly-exposed boron configurations are prepared by tuning annealing temperature.Then the correlation between boron configurations and the electrochemical performances is investigated.The combination of density-functional theory(DFT)computation and NH3-TPD/Py-FTIR indicates that the BCO_(2)configuration formed on the surface of graphene is easier to accept lone-pair electrons than BC_(2)O and BC_(3)configurations due to the stronger Lewis acidity.Such an electronic structure can effectively reduce the number of unstable electron donors and stabilize the electrochemical interface,which is proved by NMR,and critical for improving the electrochemical performances.Further experiments confirm that the optimized BG800 with the largest amount of BCO_(2)configuration presents ultralow leak current,improved cyclic stability,and better rate performance in SBPBF4/PC.This work would provide an insight into the design of high-performance boron-doped carbon materials towards energy storage.
文摘Treatment of steroidal sapogenin diosgenin 1 with Lewis acid ethereal trifluoroborane in acetic anhydride at room temperature afforded a new type of pseudosapugenin 23, 26-diacetyl-△22(23)- pseudo-sapogenin 3 and its C-20 isomer 4 in 54% and 19% yield respectively.The possible mechanism was also suggested.
基金The work was financially supported by the National Natural Science Foundation of China(No.20634040).
文摘Chloro(5,10,15,20-tetraphenyl-porphyrinato)-aluminum/tetraethylammonium bromide(Et4NBr)in combination with bulky Lewis acid was used for the copolymerization of CO_2 and cyclohexene oxide(CHO).Bulky Lewis acid having substituents at the ortho positions of the phenolate ligands,like methylaluminum bis(2,6-di-tert-butyl-4-methylphenolate), significantly shortened the induction period and raised the catalytic activity,the corresponding turnover frequency reached 44.9 h^(-1)in 9 h,which was 23.8% higher than th...
文摘Ratio of Lewis/Brfnsted acid sites (Cl/Cb) on the surface of nano-sized HZSM-5 was successfully manipulated by means of steaming and acid leaching. Significant enhancement of the deactivation durability of nano-sized HZSM-5 in the aromatization of fluid catalytic cracking (FCC) gasoline olefins seems to be closely related to the increase of Lewis/Brfnsted acid sites ratio.
文摘This paper reports the kinetics of group transfer polymerization (GTP)of ethyl acrylate (EA)with zinc iodide catalyst in 1,2-dichloroethane using dimethyl ketene methyl trimethylsilyl acetal (MTS) as initiator at 0℃ and above 0℃. The amount of catalyst used was studied. When zinc iodide catalyst used is more than 10mol% relative to monomer, the rate of polymerization is proportional to the concentration of monomer, whereas zinc iodide catalyst used is less than 10 mol% of the monomer, the rate of polymerization is independent of the monomer concentration.In the GTP of EA an induction period was observed when the zinc iodide contents are less than l0mol%. If the reaction temperature is over 0℃, living species become unstable and diminish, leading to incomplete monomer conversion. The reaction curves equations are obtained. The polymers have narrow molecular weight distributions which are not changed as decreasing zinc iodide contents. The polydispersity is about 1.2.
文摘Lewis acidic guanidinium ionic liquid(LAGIL) 2c was used as a novel, efficient and recyclable catalyst for aminolysis of epoxides under solvent-free and room temperature conditions, giving the corresponding β-amino alcohols with moderate to excellent regioselectivity(up to 91:9) in high yields(up to 97%). In addition, LAGIL 2c was recycled three times without any loss of catalytic activity and selectivity to the product.
文摘A polystyrene-bonded stannic chloride catalyst was synthesized by the method of lithium polystyryl combined with stannic chloride. This catalyst is a polymeric organometallic compound containing 0.25 mmol Sn (Ⅳ)/g catalyst. The catalyst showed sufficient stability and catalytic activity in organic reaction such as esterification, acetalation and ketal formation, and it could be reused many times without losing its catalytic activity.
基金financial support from the National Natural Science Foundation of China(Nos.21975159,2157316)the Shanghai Aerospace Science and Technology Innovation Fund(No.SAST2018-117)the Oceanic Interdisciplinary Program of Shanghai Jiao Tong University(No.WH410260401/006)。
文摘Rechargeable magnesium batteries(RMBs)are considered the promising candidates for post lithium-ion batteries due to the abundant storage,high capacity,and dendrite-rare characteristic of Mg anode.However,the lack of practical electrolytes impedes the development and application of RMBs.Here,through a one-step reaction of LiCl congenital-containing Knochel–Hauser base TMPL(2,2,6,6-tetrame thylpiperidinylmagnesium chloride lithium chloride complex)with Lewis acid AlCl_(3),we successfully synthesized an efficient amino-magnesium halide TMPLA electrolyte.Raman and mass spectroscopy identified that the electrolyte comprises the typical di-nuclear copolymer[Mg_(2)Cl_(3)·6THF]+cation group and[(TMP)2AlCl_(2)]-anion group,further supported by the results of density functional theory calculations(DFT)and the Molecular dynamics(MD)simulations.The TMPLA electrolyte exhibits promising electrochemical performance,including available anodic stability(>2.65 V vs.SS),high ionic conductivity(6.05mS cm^(-1)),and low overpotential(<0.1 V)as well as appropriate Coulombic efficiency(97.3%)for Mg plating/stripping.Both the insertion Mo6S8cathode and conversion Cu S cathode delivered a desirable electrochemical performance with high capacity and good cycling stability based on the TMPLA electrolyte.In particular,when compatible with low cost and easily synthesized Cu S,the Cu S||Mg cell displayed an extremely high discharge capacity of 458.8 mAh g^(-1)for the first cycle and stabilized at 170.2 mAh g^(-1)with high Coulombic efficiency(99.1%)after 50 cycles at 0.05 C.Our work proposes an efficient electrolyte with impressive compatibility with Mg anode and insertion/conversion cathode for practical RMBs and provides a more profound knowledge of the Lewis acid–base reaction mechanisms.
基金Funded by the National Natural Science Foundation of China Youth Program (51302073)the Green Light Materials Hubei Key Laboratory Open Fund (202027B11)。
文摘The fluorine-free MXene was prepared by Lewis acid salt etching of ternary layered ceramic MAX phase material.The structure of fluorine-free MXene was characterized by scanning electron microscopy(SEM)and X-ray diffractometry(XRD).The study finds that the layer spacing of fluorine-free MXene is approximately twice that of MXene etched by the liquid-phase method,compared to the conventional liquidphase method.It also has greater capacitive properties.Therefore,the MXene prepared by this method shows a great potential for application in the field of capacitors.
基金The financial support from National Natural Science Foundation of China(21776074,21576081,and 2181101120)is greatly acknowledged
文摘This review divides the acidic deep eutectic solvents(ADES) into Br?nsted and Lewis DES according to their diversity of acidic character.The hydrogen bond donors and halide salts for formulating an ADES are classified, the synthesis methods are described, and the physicochemical properties including freezing point, acidity, density, viscosity and conductivity are presented. Furthermore, the applications of Br?nsted acidic deep eutectic solvents(BADES) and Lewis acidic deep eutectic solvents(LADES) are overviewed, respectively, covering the fields in dissolution, extraction, organic reaction and metal electrodeposition. It is expected that the ADES has great potential to replace the pollutional mineral acid, expensive and unstable solid acid, and costly ionic liquid in many acid-employed chemical processes, thus meeting the demands of green chemistry.
基金supported by the National Natural Science Foundation of China(No.20376069).
文摘A series of heterogeneous catalysts with Cp2TiCl2 supported on palygorskite were prepared and evaluated by ethylene slurry polymerizations. The so-called direct supported catalyst, for which the pretreatment of palygorskite with MAO or Al(i-Bu)3 was not necessary, gave the highest activity among these supported catalysts and could be more robust than homogeneous Cp2TiCl2. With the direct supported catalyst, no significant activity loss was observed under low Al/Ti molar ratios (Al/Ti=300) and the decay of polymerization rate was slower when compared to the other supported catalysts. It was found that the surface Lewis acidity of palygorskite after thermal treatment played an important role in activation of metallocene compound and resulted in high catalyst activity.
文摘Probiotics are live microorganisms which when administered in adequate amounts confer a health benefit on the host. Human-origin <i>Lactobacillus</i> is a preferable source of probiotic bacteria. This study screened 14 vaginal <i>Lactobacillus</i> strains as probiotic candidates by investigating probiotic-related cell surface characteristics including cell surface hydrophobicity (CSH), Lewis acidity/basicity, autoaggregation, and biofilm formation. Moderate to high CSH and autoaggregation, high basicity and low acidity were prevalent in the 14 tested strains. Biofilm formation varied in a large range among the 14 tested strains. CSH showed a high correlation with Lewis acidity and autoaggregation, while Lewis acidity was highly correlated with autoaggregation and biofilm formation. Four strains were selected as promising probiotic strains. This study was the first one to compare antibiotic sensitivity between biofilm-forming cells and planktonic cells of <i>Lactobacillus</i> species, and found that biofilm-forming cells of a <i>L. fermentum</i> strain had a significantly higher survival rate than planktonic cells in cefotaxime, cefmetazole and tetracycline, but were as sensitive to oxacillin and ampicillin as planktonic cells were.