Two pairs of novel 6/6/6/9 tetracyclic merosesquiterpenoid enantiomers,dauroxonanols A(1)and B(2),possessing an unprecedented 9,15-dioxatetracyclo[8.5.3.0^(4.17).0^(14.18)]octadecane core skeleton,were isolated from R...Two pairs of novel 6/6/6/9 tetracyclic merosesquiterpenoid enantiomers,dauroxonanols A(1)and B(2),possessing an unprecedented 9,15-dioxatetracyclo[8.5.3.0^(4.17).0^(14.18)]octadecane core skeleton,were isolated from Rhododendron dauricum.The nuclear magnetic resonance(NMR)spectra of 1 and 2 showed very broad resonances,and^(13)C NMR spectrum of 1 exhibited only 13 instead of 22 carbon resonances.These broadening or missing NMR resonances led to a great challenge to elucidate their structures using NMR data analysis.Their structures and absolute configurations of 1 and 2 were finally determined by single crystal X-ray diffraction analysis,chiral separation,and electronic circular dichroism(ECD)calculations.Plausible biosynthetic pathways for 1 and 2 are proposed.Conformational analysis,density functional theory(DFT)calculations,and dynamic NMR assigned the coalescent NMR phenomena of 1 and 2 to the conformational changes of the flexible oxonane ring.Dauroxonanols A(1)and B(2)showed potentα-glucosidase inhibitory activities,2-8 times potent than acarbose,an antidiabetic drug targetingα-glucosidase in clinic.展开更多
Effectively separating bastnaesite from calcium-bearing gangue minerals(particularly calcite)presents a formidable challenge,making the development of efficient collectors crucial.To achieve this,we have designed and ...Effectively separating bastnaesite from calcium-bearing gangue minerals(particularly calcite)presents a formidable challenge,making the development of efficient collectors crucial.To achieve this,we have designed and synthesized a novel,highly efficient,water-soluble cationic collector,N-dodecylisopropanolamine(NDIA),for use in the bastnaesite-calcite flotation process.Density functional theory(DFT)calculations identified the amine nitrogen atom in NDIA as the site most susceptible to electrophilic attack and electron loss.By introducing an OH group into the traditional collector dodecylamine(DDA)structure,NDIA provided additional adsorption sites,enabling synergistic adsorption on the surface of bastnaesite,thereby significantly enhancing both the floatability and selectivity of these minerals.The recovery of bastnaesite was 76.02%,while the calcite was 1.26%.The NDIA markedly affected the zeta potential of bastnaesite,while its impact on calcite was relatively minor.Detailed Fourier-transform infrared spectroscopy(FTIR)and X-ray photoelectron spectroscopy(XPS)results elucidated that the―NH―and―OH groups in NDIA anchored onto the bastnaesite surface through robust electrostatic and hydrogen bonding interactions,thereby enhancing bastnaesite's affinity for NDIA.Furthermore,in situ atomic force microscopy(AFM)provided conclusive evidence of NDIA aggregation on the bastnaesite surface,improving contact angle and hydrophobicity,and significantly boosting the flotation recovery of bastnaesite.展开更多
Water contamination by tetracycline(TC)has emerged as an environmental concern owing to its widespread use and antibiotic resistance.Application of peracetic acid(PAA)in the water and wastewater treatment has recently...Water contamination by tetracycline(TC)has emerged as an environmental concern owing to its widespread use and antibiotic resistance.Application of peracetic acid(PAA)in the water and wastewater treatment has recently been proposed and demonstrated to be effective for TC abatement,yet the underlying reaction kinetics between the PAA and TC are not yet clear.To explore the reaction kinetics,the effect of solution pH on TC abatement by PAA is studied and the species-specific rate constants are calculated.The ability to donate and accept electrons for different species of TC and PAA is evaluated via density functional theory(DFT)calculations.The pH-dependent apparent second-order rate constants of TC abatement by PAA exhibits the parabolic shape with the maximum at p H 8.5(9.75 L mol^(-1)s^(-1)).This phenomenon is closely related to the speciation of TC and PAA,in which the reaction between PAAH and TTC^(2-)possesses the highest species-specific rate constants according to the kinetic simulation.Further DFT calculations suggest that the HOMO of TTCH^(+),TTC,TTC^(-),TTC^(2-)and the LUMO of PAAH and PAA-are–6.40,–6.26,–5.10,–4.94 e V and–0.24,0.60 e V,respectively.According to the DFT calculations,deprotonation of TC and PAA leads to an increase of the HOMO value of TC and the LUMO value of PAA.Furthermore,the HOMOTC–LUMOPAAvalues is in good agreement with the trend of species-specific rate constants,which can be used to evaluate the reactivity between PAA and TC with different species.This study provides the kinetic data and theoretical basis for the reaction of PAA and TC,which is critical for the application of PAA in the treatment of water and wastewater.展开更多
Fire retardant CNTs/WPP/Gel composite papers were fabricated by incorporating bio-based carbon nanotubes(CNTs)recycled from mature beech pinewood sawdust(MB)and cellulosic waste printed paper(WPP)into a gelatin soluti...Fire retardant CNTs/WPP/Gel composite papers were fabricated by incorporating bio-based carbon nanotubes(CNTs)recycled from mature beech pinewood sawdust(MB)and cellulosic waste printed paper(WPP)into a gelatin solution(Gel)and allowing the mixture to dry at room temperature.The CNTs within the WPP matrix formed a network,enhancing the mechanical and thermal properties of the resulting CNTs paper sheet.In comparison to pure WPP/Gel,CNTs/WPP/Gel exhibited superior flexibility,mechanical toughness,and notable flame retardancy characteristics.This study provides a unique and practical method for producing flame-retardant CNTs/WPP/Gel sheets,suitable for diverse industrial applications,especially packaging,where used paper materials pose a significant fire risk.Bio-CNT-based fire-resistant packaging offers enhanced safety during transportation and storage.The sheets demonstrated increased strength and stiffness,with optimal mechanical properties achieved at a 20%CNTs loading.Additionally,thermal stability was improved,as confirmed by thermogravimetric analysis(TGA)and differential thermogravimetry(DTG).Flame retardancy tests revealed a rise in LOI(Limiting Oxygen Index)values with increasing CNTs content,indicating the CNTs’effectiveness in inhibiting combustion.The compatibility of recycled paper,CNTs,and Gel suggests potential applications in industrial fields,capitalizing on the biocompatible and biodegradable nature of cellulose.Density functional theory(DFT)calculations using the B3LYP with the 6-31G(d)basis set were employed to optimize the stability of these compounds and elucidate their chemical interactions.展开更多
Carbon-based single-atom catalysts(SACs) with atomic sizes of active sites have become the promising candidates for a variety of catalytic systems because of their high atom utilization, and unique electronic structur...Carbon-based single-atom catalysts(SACs) with atomic sizes of active sites have become the promising candidates for a variety of catalytic systems because of their high atom utilization, and unique electronic structures. Different types of single-atom sites can be fabricated via multiple preparation strategies, which would demonstrate distinct different coordination configurations and electronic features, and ultimately affected the structure-catalysis relationship of SACs in targeted reactions. As a result, it is necessary to identify the active sites of SACs and understand the structure-catalysis relationship of SACs at the atomic scale. In this review, a variety of preparation strategies of carbon-based SACs were documented. Then, the recent development on versatile characterization techniques and computational achievements were summarized regarding in understanding the electronic and geometric characteristics of carbon-based SACs.Finally, major challenges and development directions concerning single-atom sites identification and advanced tools development are discussed to shed light on future research of carbon-based SACs.展开更多
The relationships between the structure of oxime compounds(R^(1)R^(2)C=NOH,R^(1)/R^(2)=alkyl groups) with different substituents and their corresponding flotation performances were studied. The analyses of density fun...The relationships between the structure of oxime compounds(R^(1)R^(2)C=NOH,R^(1)/R^(2)=alkyl groups) with different substituents and their corresponding flotation performances were studied. The analyses of density functional theory(DFT) calculations illustrated that the introduced phenyl group at the R^(1) position could enhance the acidity,while the heptyl group could effectively increase the hydrophobicity and benefit van der Waals interactions. Meanwhile,the introduced amino group at the R^(2) position could provide cationic sites to interact with negatively charged surfaces of minerals, while the introduced hydroxyl group could provide additional action sites to form stable chelates with metal ions. Based on the structure-activity relationships, structural optimization was carried out to obtain three efficient collectors, which possessed superior flotation separation performances, proving the effectiveness of the structural modification to oxime compounds in this work.展开更多
In this work,the impact of the doping process on the photoluminescence emission of CaWO_(4) as a function of the concentration of Eu^(3+) cation(0.01 mol%,0.02 mol%,0.04 mol%,0.06 mol%,0.08 mol%,and 0.10 mol%) is disc...In this work,the impact of the doping process on the photoluminescence emission of CaWO_(4) as a function of the concentration of Eu^(3+) cation(0.01 mol%,0.02 mol%,0.04 mol%,0.06 mol%,0.08 mol%,and 0.10 mol%) is discussed in detail.Ca_(1-x)WO~4:xEu^(3+) samples were successfully synthesized by a simple coprecipitation method followed by microwave irradiation.The blue shift in the absorption edge confirms the quantum confinement effect and the band gap energy covers the range from 3.91 to 4.18 eV,as the amount of Eu^(3+) cations increases.The experimental results are sustained by first-principles calculations,at the density functional theory level,to decipher the geometry and electronic properties,thereby enabling a more accurate and direct comparison between theory and experiment for the Ca_(1-x)WO_(4):xEu^(3+) structure.展开更多
Acetaminophen(ACE)is commonly used in analgesic and antipyretic drug,which is hardly removed by traditional wastewater treatment processes.Herein,amorphous Co(OH)_(2)nanocages were explored as peroxymonosulfate(PMS)ac...Acetaminophen(ACE)is commonly used in analgesic and antipyretic drug,which is hardly removed by traditional wastewater treatment processes.Herein,amorphous Co(OH)_(2)nanocages were explored as peroxymonosulfate(PMS)activator for efficient degradation of ACE.In the presence of amorphous Co(OH)_(2)nanocages,100%of ACE removal was reached within 2 min with a reaction rate constant k_(1)=3.68 min 1 at optimum pH 5,which was much better than that of crystallineβ-Co(OH)_(2)and Co_(3)O_(4).Amorphous materials(disorder atom arrangement)with hollow structures possess large specific surface area,more reactive sites,and abundant vacancies structures,which could efficiently facilitate the catalytic redox reactions.The radicals quenching experiment demonstrated that SO_(4)^(·-)radicals dominated the ACE degradation rather than^(·)OH radicals.The mechanism of ACE degradation was elucidated by the an alysis of degradation in termediates and theoretical calculation,indicating that the electrophilic SO_(4)^(·-)and^(·)OH tend to attack the atoms of ACE with high Fukui index(f).Our finding highlights the remarkable advantages of amorphous materials as heterogeneous catalysts in sulfate radicals-based AOPs and sheds new lights on water treatment for the degradation of emerging organic contaminants.展开更多
A novel neonicotinoid analogue（C13H19N5O5,3a）had been synthesized,the structure was characterized by elemental analysis,IR and 1H NMR spectra,and the S-（＋）-（E）-configuration was confirmed by single-crystal X-ra...A novel neonicotinoid analogue（C13H19N5O5,3a）had been synthesized,the structure was characterized by elemental analysis,IR and 1H NMR spectra,and the S-（＋）-（E）-configuration was confirmed by single-crystal X-ray diffraction.The crystal belongs to monoclinic,space group P21 with a = 8.7076（17）,b = 8.3211（17）,c = 10.642（2）,β = 92.370（3）o,V = 770.4（3）3,Z = 2,Dc = 1.402 g/cm3,μ = 0.110 mm-1,Mr = 325.33,F（000）= 344,S = 1.027,R = 0.0543 and wR = 0.1229 for 3601 unique reflections with 2919 observed ones（I 2σ（I））.Compound 3a is stabilized by intramolecular hydrogen bonds and intermolecular force.In addition,the structure of compound 3a was optimized by the B3LYP/6-31G（d,p）.DFT/B3LYP optimizations were performed based on X-ray geometries applying 6-31G（d,p）basis set.The optimized structure of compound 3a by the B3LYP/6-31G（d,p）method is more bent than in the crystal.IR spectrum of the solid compound is consistent with the X-ray structure.The HOMO-LUMO gap in 3a（5.3 eV）indicates high kinetic stabilities of compound 3a.The preliminary bioassay test showed that 3a exhibited good activities against Nilaparvata legen,Pseudaletia separate Walker and Aphis medicagini at 500 mg/L.展开更多
Two new fluorinated phenylisoquinoline-based iridium（Ⅲ） complexes,[Ir（f2piq）2（bipy）][PF6]（3a） and[Ir（fmpiq）2（bipy）][PF6]（3b）（f2piq = l-（2,4-difluorophenyl）isoquinoline,fmpiq = 1-（4-fluoro-2-methylph...Two new fluorinated phenylisoquinoline-based iridium（Ⅲ） complexes,[Ir（f2piq）2（bipy）][PF6]（3a） and[Ir（fmpiq）2（bipy）][PF6]（3b）（f2piq = l-（2,4-difluorophenyl）isoquinoline,fmpiq = 1-（4-fluoro-2-methylphenyl）isoquinoline,bipy = 2,2＇-bipyridine）,have been synthesized and fully characterized.Single crystal X-ray diffraction study has been undertaken on complexes 3a and 3b,which show that each adopts the distorted octahedral coordination geometry with the cis-C,C＇ and trans-N,N＇ configuration.The photoluminescence spectra of 3a and 3b exhibit yellow and orange emission maxima at 584 and 600 nm,respectively.The frontier molecular orbital diagrams and the lowest-energy electronic transitions of 3a-3b have been calculated with density functional theory（DFT） and time-dependent DFT（TD-DFT）.The absorption and emission spectra of complex 3b is red-shifted relative to those of complex 3a,as a consequence of the nature of the methyl group.展开更多
We have prepared the 2-（quinolin-8-yloxy）-acetic acid and characterized it by infrared and Raman spectroscopies in the solid phase. The Density Functional Theory （DFT） method, together with the 6-31G^＊ and 6-311...We have prepared the 2-（quinolin-8-yloxy）-acetic acid and characterized it by infrared and Raman spectroscopies in the solid phase. The Density Functional Theory （DFT） method, together with the 6-31G^＊ and 6-311＋＋ G^＊＊ basis sets, show that three stable molecules, for the anhydrous and monohydrated compounds were theoretically determined in the gas phase, and that probably the two more stable conformations are present in the solid phase of the monohydrated compound. The harmonic vibrational wavenumbers for the optimized geometries were calculated at B3LYP/6-31G^＊and B3LYP/6-311＋＋G^＊＊ levels. For a complete assignment of all the observed bands in the vibrational spectra the DFT calculations were combined with Pulay＇s scaled quantum mechanical force field （SQMFF） methodology in order to fit the theoretical Wavenumber values to the experimental ones. The characteristics of the electronic delocalization of all structures of both forms were performed by using natural bond orbital （NBO）, while the corresponding topological properties of electronic charge density are analysed by employing Bader＇s atoms in molecules theory （AIM）.展开更多
A novel copper（Ⅱ） complex with tert-butyl 2-[N-（tert-butyloxycarbonylmethyl）-2-picolyamino]acetate（ampy） was synthesized and structurally characterized by elemental analysis, FT-IR spectrum, electrospray ioniza...A novel copper（Ⅱ） complex with tert-butyl 2-[N-（tert-butyloxycarbonylmethyl）-2-picolyamino]acetate（ampy） was synthesized and structurally characterized by elemental analysis, FT-IR spectrum, electrospray ionization-mass spectrometry, UV-vis spectrum and single-crystal X-ray diffraction, respectively. A mononuclear copper（II） complex with ampy, [Cu（ampy）Cl2]（1）, was formed irrespective of the metal-to-ligand molar ratios（[Cu2＋]：[ampy] = 0.5：1, 1：1, and 2：1） as a single product. Complex 1 crystallizes in the orthorhombic system, space group Pbca with a = 12.343（2）, b = 18.928（3）, c = 20.058（4） A, V = 4686.1（14） A3, Z = 8, Dc = 1.3349（4） g/cm3, F（000） = 1920, S = 1.016, R = 0.0693 and w R = 0.1721 for 3151 observed reflections with I 〉 2σ（I）. X-ray diffraction analysis reveals that the central copper（II） ion is bound by pyridyl N, tertiary amine N and carbonyl O atoms of the quadridentate ampy as well as two Cl anions, constructing a slightly distorted octahedral geometry. Complex 1 further constructs a stable 3D supramolecular architecture by intermolecular C–H…Cl hydrogen bonds. In addition, the molecular geometry was calculated by density functional theory（DFT/B3LYP） method with the basis sets（6-31＋G（d,p） for H, C, N, O and Cl atoms, and LANL2 DZ for Cu atom, respectively）. The calculated results show that the optimized geometrical parameters are in good agreement with the experimental data. Natural bond orbital（NBO） analysis and frontier molecular orbitals（FMOs） analysis were investigated at the same level.展开更多
Theoretical study on the supramolecular complexes formed between boron-doped het- erofullerene （C59B） and zinc porphine （ZnF）, namely C59B-ZnP and its anion species C59B-ZnP, was performed by density functional th...Theoretical study on the supramolecular complexes formed between boron-doped het- erofullerene （C59B） and zinc porphine （ZnF）, namely C59B-ZnP and its anion species C59B-ZnP, was performed by density functional theory calculation at wB97XD/6-31G（d） level. Strong interaction between porphyrin and heterofullerene moiety was predicted for these complexes based on geometry and electronic structure analysis. Especially, pseudobonding interaction occurring between the B atom of fullerene and the N atom of porphyrin was predicted to occur in C59B-ZnP complex, but be broken in C59B-ZnP complex. Time-dependent density functional theory calculation manifests the redshift of electron absorption for ZnP upon the interaction with heterofullerene.展开更多
We studied the first oxidation product of vitamin C, the dehydro-L-ascorbic acid dimer and characterized it by infrared and Raman spectroscopies in the solid phase. The Density functional theory was used to study its ...We studied the first oxidation product of vitamin C, the dehydro-L-ascorbic acid dimer and characterized it by infrared and Raman spectroscopies in the solid phase. The Density functional theory was used to study its structure and vibrational properties. These calculations gave us a precise knowledge of the normal modes of vibration taking into account that the molecule comprises a system of five fused rings; non planar γ-lactone and furonose rings are attached to a central dioxan ring in the twisted boat conformation. The calculated harmonic vibrational frequencies are consistent with the experimental vibrational spectra. An assignment of the observed spectral features is proposed. The shift of the band located in the infrared spectrum of the ascorbic acid from 3409 cm^-1 to 3299 cml and the remarkable increase in the band intensity at 1784 cm^-1 evidences the acid decomposition into its first product, the dehydro-L-ascorbic acid. The theoretical vibrational calculations allowed us to obtain a set of scaled force constants. The nature of the different -γ-lactone, furanose and dioxan rings and their topological properties were investigated by means of natural bond orbital and Bader＇s atoms in the molecule theory, respectively.展开更多
Electrochromic materials are of great interest for their potential in eyewear protection and data storage devices, as they change colors in response to electrochemical switching. While many of the systems currently us...Electrochromic materials are of great interest for their potential in eyewear protection and data storage devices, as they change colors in response to electrochemical switching. While many of the systems currently used are based on inorganic materials, organic materials such as triazenes have emerged as viable alternatives due to their unique properties, including optical properties. Triazenes are a class of organic compounds with three consecutive nitrogen atoms in an acyclic arrangement, and they have been used for a variety of applications in medicinal and synthetic chemistry. However, the effects of solvents on the UV-visible absorption spectrum of triazenes have not been fully investigated. The neutral molecules of 3,3-diisopropyl-1-phenyltriazene and 1-(4-chlorophenyl)-3-cyclopentyltriazene in acetonitrile, the UV-visible spectra corresponded respectively to HOMO → LUMO transitions with a large maximum absorption at 299.74 nm (4.1364 eV) and 299.57 nm (4.1387 eV) and the most intense oscillator strength (f = 0.6988) and (f = 0.7372). These results suggest that the electronic transitions of the compounds are highly influenced by the nature of the substituents on the triazene unit, as well as the solvent used in the experiment. The redox couple 0.92 and -0.44 V/Ag/AgCl is attributed to the phenyl group. Compound III showed an oxidation and reduction peak respectively -0.27 and -0.8 V/Ag/AgCl attributed to the phenyl molecule. The study concluded that all three compounds were electroactive and exhibited reversible characteristics with oxidizing/reducing couples. This study aims to contribute to research on the optical properties of triazenes compounds and the application of quantum chemical calculation methods for understanding their molecular structures. By investigating the solute-solvent interactions occurring in the solvation shell of the solutes, we aim to gain insights into the effects of solvents on the UV-visible absorption spectrum of triazenes. Our findings may have implications for the development of functionalized triazenes as potential electrochromic materials.展开更多
First-principles calculations are performed to investigate the relaxation and electronic properties of sulfide minerals surfaces(MoS2, Sb2S3, Cu2 S, ZnS, PbS and FeS2) in presence of H2 O molecule. The calculated resu...First-principles calculations are performed to investigate the relaxation and electronic properties of sulfide minerals surfaces(MoS2, Sb2S3, Cu2 S, ZnS, PbS and FeS2) in presence of H2 O molecule. The calculated results show that the structure and electronic properties of sulfide minerals surfaces have been influenced in presence of H2 O molecule. The adsorption of the flotation reagent at the interface of mineral-water would be different from that of mineral surface due to the changes of surface structures and electronic properties caused by H2 O molecule. Hence, the influence of H2 O molecule on the reaction of flotation reagent with sulfide mineral surface will attract more attention.展开更多
P-xylene(p-C_(8)H_(10))is extremely harmful and dangerous to human health due to high toxicity and strong carcinogenicity.Exploring sensitive material to effectively detect p-xylene is of importance.In this paper,pero...P-xylene(p-C_(8)H_(10))is extremely harmful and dangerous to human health due to high toxicity and strong carcinogenicity.Exploring sensitive material to effectively detect p-xylene is of importance.In this paper,perovskite single crystal(C_(4)H_(9)NH_(3))_(2)PbI_(4) has been successfully synthesized via solution method.The obtained product was analyzed by single crystal X-ray diffraction.With the space group Pbca,orthorhombic(C_(4)H_(9)NH_(3))_(2)PbI_(4) layered perovskite structure consists of an extended two-dimensional network of corner-sharing PbI_(6) octahedron.Single layer perovskite sheets of distorted PbI_(6) octahedron alternated with protonated n-butylammonium cation bilayers,which offers many advantages and provides the possibility of forming a gas sensor device based on the change of resistances.Density functional theory(DFT)simulations regarding the adsorption energy revealed that this organicinorganic hybrid perovskite compound has excellent selectivity toward p-xylene compared with other gases including C_(2)H_(5)OH,C_(6)H_(6),CH_(2)Cl_(2),HCHO,CH_(3)COCH_(3) and C_(7)H_(8).The calculation of electron density,density of states and electron density difference showed the sensing mechanism of p-C_(8)H_(10) is mainly derived from physical adsorption-desorption in view of electron transfer.展开更多
The detrimental Fe element in Al-Si cast alloy can be effectively removed by Fecontaining intermetallics separation.However,the formation temperature of Fecontaining intermetallics can be further improved to increase ...The detrimental Fe element in Al-Si cast alloy can be effectively removed by Fecontaining intermetallics separation.However,the formation temperature of Fecontaining intermetallics can be further improved to increase the removal efficiency of Fe element.The effects of the Cr/Mn atomic ratio on the stability,theoretical melting point,elastic modulus,and thermal properties were calculated with the aim of improving the stability of theα-Al(FeMnCr)Si phase.An increased Cr/Mn atomic ratio effectively increased the stability,theoretical melting point,elastic modulus,isobaric heat capacity,and reduced the volumetric thermal expansion coefficient ofα-Al(FeMnCr)Si phase,which can be explained by the strengthened Al-Cr and Si-Cr chemical bonds.The experimental study results revealed that the formation temperature and Young's modulus of theα-Al(FeMnCr)Si phase increase from 673.0°C and 228.5 GPa to 732.0°C and 272.1 GPa with the Cr/Mn atomic ratio increasing from 0.11 to 0.8,which better validates the thermodynamic stability,theoretical melting point and elastic modulus calculation results.These results provide a new strategy for designing Fecontaining intermetallics with the desired properties,which contributes to guiding the development of high-performance recycled Al-Si alloys.展开更多
The Co^(2+)and Peroxymonosulfate(PMS)reaction is a highly regarded advanced oxidation process(AOP)that has been extensively researched.The consensus regarding the relative contribution of reactive species in the Co2+/...The Co^(2+)and Peroxymonosulfate(PMS)reaction is a highly regarded advanced oxidation process(AOP)that has been extensively researched.The consensus regarding the relative contribution of reactive species in the Co2+/PMS system under different pH conditions has not been established.In this study,quenching experiments and electron spin resonance(ESR)tests demonstrated the coexistence of Co(IV),sulfate radical(SO_(4)^(•-)),hydroxyl radical(•OH),and singlet oxygen(1O2),and there fell to CBZ degradation were Co(IV)>SO_(4)^(•-)->•OH≈1O2 in the optimal conditions,where almost 100%of CBZ was degraded in the Co2+/PMS system within 30 min.Furthermore,Cl−would suppress the formation of Co(IV),SO_(4)^(•-),and•OH but enhance the yield of 1O2,thereby showing a trend of inhibiting CBZ degradation.The probe compound used in this study was Methyl Phenyl Sulfoxide(PMSO),while methyl phenyl sulfone(PMSO_(2))as the indicator of Co(IV),the generation efficiency of PMSO_(2)(η'[PMSO_(2)])increased with reaction time and reached 70%–98%at 40 min at all set pH values(3,4,6,and 8).These results suggest that Co(IV)played a significant role in the Co^(2+)/PMS system and its importance became more pronounced as the reaction progressed.PMSO probe and SO_(4)^(•-)quantification experiments jointly revealed that Co(IV)had the greatest performance at pH 4,and compared to other pH values,SO_(4)^(•-)had the largest contribution in the initial stage of the reaction at pH 6.The Ecological Structure Activity Relationships(ECOSAR)software was utilized to predict the toxicity of the degradation by-products.Additionally,luminescent bacteria experiments were conducted to assess the acute toxicity of the reaction solution.The results of these experiments demonstrated that the Co^(2+)/PMS process exhibited a remarkable ability to detoxify the solution.展开更多
Spintronic technology and energy applications benefit greatly from the exceptional characteristics of rare-earth-based spinel chalcogenides.Examining the electrical,magnetic and thermoelectric properties of HgNd_(2)Z_...Spintronic technology and energy applications benefit greatly from the exceptional characteristics of rare-earth-based spinel chalcogenides.Examining the electrical,magnetic and thermoelectric properties of HgNd_(2)Z_(4)(Z=S,Se)in a systematic manner is essential for the strategic advancement of spin polarized current in a spintronic device.In this recent study,the WIEN2K code was employed to comprehensively analyze these properties.The calculated lattice constants,obtained using the generalized gradient approximation(GGAsol-PBE),closely match experimental findings of the similar family compounds.The examination of the stability of ferromagnetic states in the ground state involves comparing energies between anti-ferromagnetic and ferromagnetic states.Moreover,an assessment of the stability of the cubic phase in both spinels was conducted using analyses of the phonon dispersion curve,formation energy and Born stability criteria.The ductility characteristics were examined through the calculation of Poisson's and Pugh's ratios.Furthermore,details regarding the density of states,spin polarization,ex-change coupling and Curie temperature were provided to explore the characteristics associated with ferromagnetism.Potential optoelectronic applications were proposed,leveraging the direct band gaps of 1.4 and 1.0 eV for HgNd_(2)Z_(4)(Z=S,Se)respectively,within the visible spectrum.Particularly noteworthy is the effective light absorption of HgNd2Se4 in the visible range,characterized by prominent peaks that facilitate the transition of electrons from the valence band(VB)to the conduction band(CB).Additionally,the study extends to thermoelectric characteristics,determining various factors such as Seebeck coef-ficient(S),figure of merit(ZT),electrical and thermal conductivities of the evaluated spinels.展开更多
基金supported by the National Natural Science Foundation of China(Nos.22207036,22277034,22477034,and 22107033)Interdisciplinary Research Program of Huazhong University of Science and Technology(No.2023JCYJ037)International Cooperation Project of Hubei Provincial Key R&D Plan(No.2023EHA040)。
文摘Two pairs of novel 6/6/6/9 tetracyclic merosesquiterpenoid enantiomers,dauroxonanols A(1)and B(2),possessing an unprecedented 9,15-dioxatetracyclo[8.5.3.0^(4.17).0^(14.18)]octadecane core skeleton,were isolated from Rhododendron dauricum.The nuclear magnetic resonance(NMR)spectra of 1 and 2 showed very broad resonances,and^(13)C NMR spectrum of 1 exhibited only 13 instead of 22 carbon resonances.These broadening or missing NMR resonances led to a great challenge to elucidate their structures using NMR data analysis.Their structures and absolute configurations of 1 and 2 were finally determined by single crystal X-ray diffraction analysis,chiral separation,and electronic circular dichroism(ECD)calculations.Plausible biosynthetic pathways for 1 and 2 are proposed.Conformational analysis,density functional theory(DFT)calculations,and dynamic NMR assigned the coalescent NMR phenomena of 1 and 2 to the conformational changes of the flexible oxonane ring.Dauroxonanols A(1)and B(2)showed potentα-glucosidase inhibitory activities,2-8 times potent than acarbose,an antidiabetic drug targetingα-glucosidase in clinic.
基金supported by the the National Key R&D Program of China(No.2021YFC2900800)National Natural Science Foundation of China(Nos.52425406,51874247,51922091,and 52204285)+4 种基金the Open Research Fund of State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization(No.CNMRCUKF2001)Science and Technology Major Project of Ordos City-Iconic Innovation Team and “Rejuvenating Inner Mongolia through Science and Technology”(No.202204/2023)Yueqi Outstanding Scholar Award of CUMTB(No.202022)Funded by Open Foundation of State Key Laboratory of Mineral Processing(No.BGRIMM-KJSKL-2023-05)Fundamental Research Funds for the Central Universities(Ph.D.Top Innovative Talents Fund of CUMT BBJ2024048)。
文摘Effectively separating bastnaesite from calcium-bearing gangue minerals(particularly calcite)presents a formidable challenge,making the development of efficient collectors crucial.To achieve this,we have designed and synthesized a novel,highly efficient,water-soluble cationic collector,N-dodecylisopropanolamine(NDIA),for use in the bastnaesite-calcite flotation process.Density functional theory(DFT)calculations identified the amine nitrogen atom in NDIA as the site most susceptible to electrophilic attack and electron loss.By introducing an OH group into the traditional collector dodecylamine(DDA)structure,NDIA provided additional adsorption sites,enabling synergistic adsorption on the surface of bastnaesite,thereby significantly enhancing both the floatability and selectivity of these minerals.The recovery of bastnaesite was 76.02%,while the calcite was 1.26%.The NDIA markedly affected the zeta potential of bastnaesite,while its impact on calcite was relatively minor.Detailed Fourier-transform infrared spectroscopy(FTIR)and X-ray photoelectron spectroscopy(XPS)results elucidated that the―NH―and―OH groups in NDIA anchored onto the bastnaesite surface through robust electrostatic and hydrogen bonding interactions,thereby enhancing bastnaesite's affinity for NDIA.Furthermore,in situ atomic force microscopy(AFM)provided conclusive evidence of NDIA aggregation on the bastnaesite surface,improving contact angle and hydrophobicity,and significantly boosting the flotation recovery of bastnaesite.
基金National Natural Science Foundation of China(No.52170088)Natural Science Foundation of Fujian Province(No.2022J05064)the Fundamental Research Funds for the Central Universities(No.ZQN-1118)。
文摘Water contamination by tetracycline(TC)has emerged as an environmental concern owing to its widespread use and antibiotic resistance.Application of peracetic acid(PAA)in the water and wastewater treatment has recently been proposed and demonstrated to be effective for TC abatement,yet the underlying reaction kinetics between the PAA and TC are not yet clear.To explore the reaction kinetics,the effect of solution pH on TC abatement by PAA is studied and the species-specific rate constants are calculated.The ability to donate and accept electrons for different species of TC and PAA is evaluated via density functional theory(DFT)calculations.The pH-dependent apparent second-order rate constants of TC abatement by PAA exhibits the parabolic shape with the maximum at p H 8.5(9.75 L mol^(-1)s^(-1)).This phenomenon is closely related to the speciation of TC and PAA,in which the reaction between PAAH and TTC^(2-)possesses the highest species-specific rate constants according to the kinetic simulation.Further DFT calculations suggest that the HOMO of TTCH^(+),TTC,TTC^(-),TTC^(2-)and the LUMO of PAAH and PAA-are–6.40,–6.26,–5.10,–4.94 e V and–0.24,0.60 e V,respectively.According to the DFT calculations,deprotonation of TC and PAA leads to an increase of the HOMO value of TC and the LUMO value of PAA.Furthermore,the HOMOTC–LUMOPAAvalues is in good agreement with the trend of species-specific rate constants,which can be used to evaluate the reactivity between PAA and TC with different species.This study provides the kinetic data and theoretical basis for the reaction of PAA and TC,which is critical for the application of PAA in the treatment of water and wastewater.
基金The research received funding from the PRIMA International Project,between the Academy of Scientific Research and Technology(ASRT)and PRIMA,through the Joint Agreement Project“Sustainable Antimicrobial Packaging Based on a Healthy Intelligent Renewable Approach”with acronym“SAPHIRA”.
文摘Fire retardant CNTs/WPP/Gel composite papers were fabricated by incorporating bio-based carbon nanotubes(CNTs)recycled from mature beech pinewood sawdust(MB)and cellulosic waste printed paper(WPP)into a gelatin solution(Gel)and allowing the mixture to dry at room temperature.The CNTs within the WPP matrix formed a network,enhancing the mechanical and thermal properties of the resulting CNTs paper sheet.In comparison to pure WPP/Gel,CNTs/WPP/Gel exhibited superior flexibility,mechanical toughness,and notable flame retardancy characteristics.This study provides a unique and practical method for producing flame-retardant CNTs/WPP/Gel sheets,suitable for diverse industrial applications,especially packaging,where used paper materials pose a significant fire risk.Bio-CNT-based fire-resistant packaging offers enhanced safety during transportation and storage.The sheets demonstrated increased strength and stiffness,with optimal mechanical properties achieved at a 20%CNTs loading.Additionally,thermal stability was improved,as confirmed by thermogravimetric analysis(TGA)and differential thermogravimetry(DTG).Flame retardancy tests revealed a rise in LOI(Limiting Oxygen Index)values with increasing CNTs content,indicating the CNTs’effectiveness in inhibiting combustion.The compatibility of recycled paper,CNTs,and Gel suggests potential applications in industrial fields,capitalizing on the biocompatible and biodegradable nature of cellulose.Density functional theory(DFT)calculations using the B3LYP with the 6-31G(d)basis set were employed to optimize the stability of these compounds and elucidate their chemical interactions.
基金supported by Tai Shan Scholar Foundation (No.ts201511003)financial support from the Australian Research Council via Discovery Projects (Nos.DE210100253 and DP190103548)。
文摘Carbon-based single-atom catalysts(SACs) with atomic sizes of active sites have become the promising candidates for a variety of catalytic systems because of their high atom utilization, and unique electronic structures. Different types of single-atom sites can be fabricated via multiple preparation strategies, which would demonstrate distinct different coordination configurations and electronic features, and ultimately affected the structure-catalysis relationship of SACs in targeted reactions. As a result, it is necessary to identify the active sites of SACs and understand the structure-catalysis relationship of SACs at the atomic scale. In this review, a variety of preparation strategies of carbon-based SACs were documented. Then, the recent development on versatile characterization techniques and computational achievements were summarized regarding in understanding the electronic and geometric characteristics of carbon-based SACs.Finally, major challenges and development directions concerning single-atom sites identification and advanced tools development are discussed to shed light on future research of carbon-based SACs.
基金the support of the National Natural Science Foundation of China(Nos.51774329 and 51904337)the High Performance Computing Center of Central South University,China。
文摘The relationships between the structure of oxime compounds(R^(1)R^(2)C=NOH,R^(1)/R^(2)=alkyl groups) with different substituents and their corresponding flotation performances were studied. The analyses of density functional theory(DFT) calculations illustrated that the introduced phenyl group at the R^(1) position could enhance the acidity,while the heptyl group could effectively increase the hydrophobicity and benefit van der Waals interactions. Meanwhile,the introduced amino group at the R^(2) position could provide cationic sites to interact with negatively charged surfaces of minerals, while the introduced hydroxyl group could provide additional action sites to form stable chelates with metal ions. Based on the structure-activity relationships, structural optimization was carried out to obtain three efficient collectors, which possessed superior flotation separation performances, proving the effectiveness of the structural modification to oxime compounds in this work.
基金Project supported in part by Fundacao de AmparoàPesquisa do Estado de Sao Paulo-FAPESP(2013/07296-2,2016/23891-6,2017/26105-4,2019/01732-1)Financiadora de Estudos e Projetos-FINEP,Conselho Nacional de Desenvolvimento Científico e Tecnológico-CNPQ(166281/2017-4,305792/2020-2)CAPES。
文摘In this work,the impact of the doping process on the photoluminescence emission of CaWO_(4) as a function of the concentration of Eu^(3+) cation(0.01 mol%,0.02 mol%,0.04 mol%,0.06 mol%,0.08 mol%,and 0.10 mol%) is discussed in detail.Ca_(1-x)WO~4:xEu^(3+) samples were successfully synthesized by a simple coprecipitation method followed by microwave irradiation.The blue shift in the absorption edge confirms the quantum confinement effect and the band gap energy covers the range from 3.91 to 4.18 eV,as the amount of Eu^(3+) cations increases.The experimental results are sustained by first-principles calculations,at the density functional theory level,to decipher the geometry and electronic properties,thereby enabling a more accurate and direct comparison between theory and experiment for the Ca_(1-x)WO_(4):xEu^(3+) structure.
基金Financial supports from China Postdoctoral Science Foundation (Nos.2019M650007 and 2020M670088)National NaturalScience Foundation of China (Nos.21906001,51721006)the Beijing Nova Program (No. Z19111000110000)
文摘Acetaminophen(ACE)is commonly used in analgesic and antipyretic drug,which is hardly removed by traditional wastewater treatment processes.Herein,amorphous Co(OH)_(2)nanocages were explored as peroxymonosulfate(PMS)activator for efficient degradation of ACE.In the presence of amorphous Co(OH)_(2)nanocages,100%of ACE removal was reached within 2 min with a reaction rate constant k_(1)=3.68 min 1 at optimum pH 5,which was much better than that of crystallineβ-Co(OH)_(2)and Co_(3)O_(4).Amorphous materials(disorder atom arrangement)with hollow structures possess large specific surface area,more reactive sites,and abundant vacancies structures,which could efficiently facilitate the catalytic redox reactions.The radicals quenching experiment demonstrated that SO_(4)^(·-)radicals dominated the ACE degradation rather than^(·)OH radicals.The mechanism of ACE degradation was elucidated by the an alysis of degradation in termediates and theoretical calculation,indicating that the electrophilic SO_(4)^(·-)and^(·)OH tend to attack the atoms of ACE with high Fukui index(f).Our finding highlights the remarkable advantages of amorphous materials as heterogeneous catalysts in sulfate radicals-based AOPs and sheds new lights on water treatment for the degradation of emerging organic contaminants.
基金supported by the National Natural Science Foundation of China (21042010)the Key Laboratory of Rare Earth Functional Materials of Shanghai (07dz22303)the Key Scientific and Technological Project of Shanghai (09391912100)
文摘A novel neonicotinoid analogue（C13H19N5O5,3a）had been synthesized,the structure was characterized by elemental analysis,IR and 1H NMR spectra,and the S-（＋）-（E）-configuration was confirmed by single-crystal X-ray diffraction.The crystal belongs to monoclinic,space group P21 with a = 8.7076（17）,b = 8.3211（17）,c = 10.642（2）,β = 92.370（3）o,V = 770.4（3）3,Z = 2,Dc = 1.402 g/cm3,μ = 0.110 mm-1,Mr = 325.33,F（000）= 344,S = 1.027,R = 0.0543 and wR = 0.1229 for 3601 unique reflections with 2919 observed ones（I 2σ（I））.Compound 3a is stabilized by intramolecular hydrogen bonds and intermolecular force.In addition,the structure of compound 3a was optimized by the B3LYP/6-31G（d,p）.DFT/B3LYP optimizations were performed based on X-ray geometries applying 6-31G（d,p）basis set.The optimized structure of compound 3a by the B3LYP/6-31G（d,p）method is more bent than in the crystal.IR spectrum of the solid compound is consistent with the X-ray structure.The HOMO-LUMO gap in 3a（5.3 eV）indicates high kinetic stabilities of compound 3a.The preliminary bioassay test showed that 3a exhibited good activities against Nilaparvata legen,Pseudaletia separate Walker and Aphis medicagini at 500 mg/L.
基金supported by the National Natural Science Foundation of China(No.21501037)the Natural Science Foundation of Hainan Province(No.20152017)the Science and Research Project of Education Department of Hainan Province(Nos.Hjkj2013-25 and Hnky2015-27)
文摘Two new fluorinated phenylisoquinoline-based iridium（Ⅲ） complexes,[Ir（f2piq）2（bipy）][PF6]（3a） and[Ir（fmpiq）2（bipy）][PF6]（3b）（f2piq = l-（2,4-difluorophenyl）isoquinoline,fmpiq = 1-（4-fluoro-2-methylphenyl）isoquinoline,bipy = 2,2＇-bipyridine）,have been synthesized and fully characterized.Single crystal X-ray diffraction study has been undertaken on complexes 3a and 3b,which show that each adopts the distorted octahedral coordination geometry with the cis-C,C＇ and trans-N,N＇ configuration.The photoluminescence spectra of 3a and 3b exhibit yellow and orange emission maxima at 584 and 600 nm,respectively.The frontier molecular orbital diagrams and the lowest-energy electronic transitions of 3a-3b have been calculated with density functional theory（DFT） and time-dependent DFT（TD-DFT）.The absorption and emission spectra of complex 3b is red-shifted relative to those of complex 3a,as a consequence of the nature of the methyl group.
文摘We have prepared the 2-（quinolin-8-yloxy）-acetic acid and characterized it by infrared and Raman spectroscopies in the solid phase. The Density Functional Theory （DFT） method, together with the 6-31G^＊ and 6-311＋＋ G^＊＊ basis sets, show that three stable molecules, for the anhydrous and monohydrated compounds were theoretically determined in the gas phase, and that probably the two more stable conformations are present in the solid phase of the monohydrated compound. The harmonic vibrational wavenumbers for the optimized geometries were calculated at B3LYP/6-31G^＊and B3LYP/6-311＋＋G^＊＊ levels. For a complete assignment of all the observed bands in the vibrational spectra the DFT calculations were combined with Pulay＇s scaled quantum mechanical force field （SQMFF） methodology in order to fit the theoretical Wavenumber values to the experimental ones. The characteristics of the electronic delocalization of all structures of both forms were performed by using natural bond orbital （NBO）, while the corresponding topological properties of electronic charge density are analysed by employing Bader＇s atoms in molecules theory （AIM）.
基金supported by the National Basic Research Program of China(No.2014CB643401)the National Natural Science Foundation of China(Nos.51134007 and 51474256)
文摘A novel copper（Ⅱ） complex with tert-butyl 2-[N-（tert-butyloxycarbonylmethyl）-2-picolyamino]acetate（ampy） was synthesized and structurally characterized by elemental analysis, FT-IR spectrum, electrospray ionization-mass spectrometry, UV-vis spectrum and single-crystal X-ray diffraction, respectively. A mononuclear copper（II） complex with ampy, [Cu（ampy）Cl2]（1）, was formed irrespective of the metal-to-ligand molar ratios（[Cu2＋]：[ampy] = 0.5：1, 1：1, and 2：1） as a single product. Complex 1 crystallizes in the orthorhombic system, space group Pbca with a = 12.343（2）, b = 18.928（3）, c = 20.058（4） A, V = 4686.1（14） A3, Z = 8, Dc = 1.3349（4） g/cm3, F（000） = 1920, S = 1.016, R = 0.0693 and w R = 0.1721 for 3151 observed reflections with I 〉 2σ（I）. X-ray diffraction analysis reveals that the central copper（II） ion is bound by pyridyl N, tertiary amine N and carbonyl O atoms of the quadridentate ampy as well as two Cl anions, constructing a slightly distorted octahedral geometry. Complex 1 further constructs a stable 3D supramolecular architecture by intermolecular C–H…Cl hydrogen bonds. In addition, the molecular geometry was calculated by density functional theory（DFT/B3LYP） method with the basis sets（6-31＋G（d,p） for H, C, N, O and Cl atoms, and LANL2 DZ for Cu atom, respectively）. The calculated results show that the optimized geometrical parameters are in good agreement with the experimental data. Natural bond orbital（NBO） analysis and frontier molecular orbitals（FMOs） analysis were investigated at the same level.
文摘Theoretical study on the supramolecular complexes formed between boron-doped het- erofullerene （C59B） and zinc porphine （ZnF）, namely C59B-ZnP and its anion species C59B-ZnP, was performed by density functional theory calculation at wB97XD/6-31G（d） level. Strong interaction between porphyrin and heterofullerene moiety was predicted for these complexes based on geometry and electronic structure analysis. Especially, pseudobonding interaction occurring between the B atom of fullerene and the N atom of porphyrin was predicted to occur in C59B-ZnP complex, but be broken in C59B-ZnP complex. Time-dependent density functional theory calculation manifests the redshift of electron absorption for ZnP upon the interaction with heterofullerene.
文摘We studied the first oxidation product of vitamin C, the dehydro-L-ascorbic acid dimer and characterized it by infrared and Raman spectroscopies in the solid phase. The Density functional theory was used to study its structure and vibrational properties. These calculations gave us a precise knowledge of the normal modes of vibration taking into account that the molecule comprises a system of five fused rings; non planar γ-lactone and furonose rings are attached to a central dioxan ring in the twisted boat conformation. The calculated harmonic vibrational frequencies are consistent with the experimental vibrational spectra. An assignment of the observed spectral features is proposed. The shift of the band located in the infrared spectrum of the ascorbic acid from 3409 cm^-1 to 3299 cml and the remarkable increase in the band intensity at 1784 cm^-1 evidences the acid decomposition into its first product, the dehydro-L-ascorbic acid. The theoretical vibrational calculations allowed us to obtain a set of scaled force constants. The nature of the different -γ-lactone, furanose and dioxan rings and their topological properties were investigated by means of natural bond orbital and Bader＇s atoms in the molecule theory, respectively.
文摘Electrochromic materials are of great interest for their potential in eyewear protection and data storage devices, as they change colors in response to electrochemical switching. While many of the systems currently used are based on inorganic materials, organic materials such as triazenes have emerged as viable alternatives due to their unique properties, including optical properties. Triazenes are a class of organic compounds with three consecutive nitrogen atoms in an acyclic arrangement, and they have been used for a variety of applications in medicinal and synthetic chemistry. However, the effects of solvents on the UV-visible absorption spectrum of triazenes have not been fully investigated. The neutral molecules of 3,3-diisopropyl-1-phenyltriazene and 1-(4-chlorophenyl)-3-cyclopentyltriazene in acetonitrile, the UV-visible spectra corresponded respectively to HOMO → LUMO transitions with a large maximum absorption at 299.74 nm (4.1364 eV) and 299.57 nm (4.1387 eV) and the most intense oscillator strength (f = 0.6988) and (f = 0.7372). These results suggest that the electronic transitions of the compounds are highly influenced by the nature of the substituents on the triazene unit, as well as the solvent used in the experiment. The redox couple 0.92 and -0.44 V/Ag/AgCl is attributed to the phenyl group. Compound III showed an oxidation and reduction peak respectively -0.27 and -0.8 V/Ag/AgCl attributed to the phenyl molecule. The study concluded that all three compounds were electroactive and exhibited reversible characteristics with oxidizing/reducing couples. This study aims to contribute to research on the optical properties of triazenes compounds and the application of quantum chemical calculation methods for understanding their molecular structures. By investigating the solute-solvent interactions occurring in the solvation shell of the solutes, we aim to gain insights into the effects of solvents on the UV-visible absorption spectrum of triazenes. Our findings may have implications for the development of functionalized triazenes as potential electrochromic materials.
基金Project(51164001)supported by the National Natural Science Foundation of China
文摘First-principles calculations are performed to investigate the relaxation and electronic properties of sulfide minerals surfaces(MoS2, Sb2S3, Cu2 S, ZnS, PbS and FeS2) in presence of H2 O molecule. The calculated results show that the structure and electronic properties of sulfide minerals surfaces have been influenced in presence of H2 O molecule. The adsorption of the flotation reagent at the interface of mineral-water would be different from that of mineral surface due to the changes of surface structures and electronic properties caused by H2 O molecule. Hence, the influence of H2 O molecule on the reaction of flotation reagent with sulfide mineral surface will attract more attention.
基金financially supported by the Natural Science Foundation of Hebei(Nos.F2020202027 and F2020202067)the Major National Science and Technology Special Projects(No.2016ZX02301003-004-007)+1 种基金the National Natural Science Foundation of China(No.21271139)the Natural Science Foundation of Tianjin(No.17JCTPJC54500)。
文摘P-xylene(p-C_(8)H_(10))is extremely harmful and dangerous to human health due to high toxicity and strong carcinogenicity.Exploring sensitive material to effectively detect p-xylene is of importance.In this paper,perovskite single crystal(C_(4)H_(9)NH_(3))_(2)PbI_(4) has been successfully synthesized via solution method.The obtained product was analyzed by single crystal X-ray diffraction.With the space group Pbca,orthorhombic(C_(4)H_(9)NH_(3))_(2)PbI_(4) layered perovskite structure consists of an extended two-dimensional network of corner-sharing PbI_(6) octahedron.Single layer perovskite sheets of distorted PbI_(6) octahedron alternated with protonated n-butylammonium cation bilayers,which offers many advantages and provides the possibility of forming a gas sensor device based on the change of resistances.Density functional theory(DFT)simulations regarding the adsorption energy revealed that this organicinorganic hybrid perovskite compound has excellent selectivity toward p-xylene compared with other gases including C_(2)H_(5)OH,C_(6)H_(6),CH_(2)Cl_(2),HCHO,CH_(3)COCH_(3) and C_(7)H_(8).The calculation of electron density,density of states and electron density difference showed the sensing mechanism of p-C_(8)H_(10) is mainly derived from physical adsorption-desorption in view of electron transfer.
基金supported by the National Natural Science Foundation of China(Grants no.52304369)the Open Research Fund from the State Key Laboratory of Rolling and Automation,Northeastern University(Grant no.2022RALKFKT008)+1 种基金the Open Fund for the State Key Laboratory of Advanced Design and Manufacturing for Vehicle Body(Grants no.32115007)Aluminum-based Transportation Lightweighting Technology Demonstration Project(Grants no.2021SFGC1001).
文摘The detrimental Fe element in Al-Si cast alloy can be effectively removed by Fecontaining intermetallics separation.However,the formation temperature of Fecontaining intermetallics can be further improved to increase the removal efficiency of Fe element.The effects of the Cr/Mn atomic ratio on the stability,theoretical melting point,elastic modulus,and thermal properties were calculated with the aim of improving the stability of theα-Al(FeMnCr)Si phase.An increased Cr/Mn atomic ratio effectively increased the stability,theoretical melting point,elastic modulus,isobaric heat capacity,and reduced the volumetric thermal expansion coefficient ofα-Al(FeMnCr)Si phase,which can be explained by the strengthened Al-Cr and Si-Cr chemical bonds.The experimental study results revealed that the formation temperature and Young's modulus of theα-Al(FeMnCr)Si phase increase from 673.0°C and 228.5 GPa to 732.0°C and 272.1 GPa with the Cr/Mn atomic ratio increasing from 0.11 to 0.8,which better validates the thermodynamic stability,theoretical melting point and elastic modulus calculation results.These results provide a new strategy for designing Fecontaining intermetallics with the desired properties,which contributes to guiding the development of high-performance recycled Al-Si alloys.
基金This study was supported by the Youth Science and Technology Fund Gansu Provincial(Project No.22JR5RA515)the“double first-class”guidance project of Lanzhou University(Project No.561120206).
文摘The Co^(2+)and Peroxymonosulfate(PMS)reaction is a highly regarded advanced oxidation process(AOP)that has been extensively researched.The consensus regarding the relative contribution of reactive species in the Co2+/PMS system under different pH conditions has not been established.In this study,quenching experiments and electron spin resonance(ESR)tests demonstrated the coexistence of Co(IV),sulfate radical(SO_(4)^(•-)),hydroxyl radical(•OH),and singlet oxygen(1O2),and there fell to CBZ degradation were Co(IV)>SO_(4)^(•-)->•OH≈1O2 in the optimal conditions,where almost 100%of CBZ was degraded in the Co2+/PMS system within 30 min.Furthermore,Cl−would suppress the formation of Co(IV),SO_(4)^(•-),and•OH but enhance the yield of 1O2,thereby showing a trend of inhibiting CBZ degradation.The probe compound used in this study was Methyl Phenyl Sulfoxide(PMSO),while methyl phenyl sulfone(PMSO_(2))as the indicator of Co(IV),the generation efficiency of PMSO_(2)(η'[PMSO_(2)])increased with reaction time and reached 70%–98%at 40 min at all set pH values(3,4,6,and 8).These results suggest that Co(IV)played a significant role in the Co^(2+)/PMS system and its importance became more pronounced as the reaction progressed.PMSO probe and SO_(4)^(•-)quantification experiments jointly revealed that Co(IV)had the greatest performance at pH 4,and compared to other pH values,SO_(4)^(•-)had the largest contribution in the initial stage of the reaction at pH 6.The Ecological Structure Activity Relationships(ECOSAR)software was utilized to predict the toxicity of the degradation by-products.Additionally,luminescent bacteria experiments were conducted to assess the acute toxicity of the reaction solution.The results of these experiments demonstrated that the Co^(2+)/PMS process exhibited a remarkable ability to detoxify the solution.
基金the Deanship of Scientific Research at King Khalid University for funding this work through large group Research Project under grant number RGP2/450/44。
文摘Spintronic technology and energy applications benefit greatly from the exceptional characteristics of rare-earth-based spinel chalcogenides.Examining the electrical,magnetic and thermoelectric properties of HgNd_(2)Z_(4)(Z=S,Se)in a systematic manner is essential for the strategic advancement of spin polarized current in a spintronic device.In this recent study,the WIEN2K code was employed to comprehensively analyze these properties.The calculated lattice constants,obtained using the generalized gradient approximation(GGAsol-PBE),closely match experimental findings of the similar family compounds.The examination of the stability of ferromagnetic states in the ground state involves comparing energies between anti-ferromagnetic and ferromagnetic states.Moreover,an assessment of the stability of the cubic phase in both spinels was conducted using analyses of the phonon dispersion curve,formation energy and Born stability criteria.The ductility characteristics were examined through the calculation of Poisson's and Pugh's ratios.Furthermore,details regarding the density of states,spin polarization,ex-change coupling and Curie temperature were provided to explore the characteristics associated with ferromagnetism.Potential optoelectronic applications were proposed,leveraging the direct band gaps of 1.4 and 1.0 eV for HgNd_(2)Z_(4)(Z=S,Se)respectively,within the visible spectrum.Particularly noteworthy is the effective light absorption of HgNd2Se4 in the visible range,characterized by prominent peaks that facilitate the transition of electrons from the valence band(VB)to the conduction band(CB).Additionally,the study extends to thermoelectric characteristics,determining various factors such as Seebeck coef-ficient(S),figure of merit(ZT),electrical and thermal conductivities of the evaluated spinels.
