To achieve selective leaching of ion adsorption rare earth,it is necessary to thoroughly reveal the differences in the adsorption mechanisms of aluminum and rare earth elements.In this study,we investigated the adsorp...To achieve selective leaching of ion adsorption rare earth,it is necessary to thoroughly reveal the differences in the adsorption mechanisms of aluminum and rare earth elements.In this study,we investigated the adsorption processes of Dy and Al on the surface of K–homoionic kaolinite using batch experiments and sequential chemical extractions.The results revealed that the adsorption of Dy and Al,as well as the desorption of K,followed the Langmuir model.The maximum ion-exchangeable capacity of Dy was higher(9.39 mmol.kg^(-1))than that of Al(6.30 mmol.kg^(-1)).The ion exchange stoichiometry ratios of Dy–K and Al–K derived from the Langmuir model were2.0 and 2.6.The analysis of X-ray absorption fine structure(XAFS)and density functional theory(DFT)revealed that Dy and Al were adsorbed onto kaolinite as outer-sphere hydrated complexes via hydrogen bonds.Dy was adsorbed as[Dy(H_(2)O)_(10)]^(3+),and Al was adsorbed as[Al(OH)_(2)(H_(2)O)_(4)]^(+).In particular,the adsorption of Al resulted in protonation of the hydroxyl groups on the surface of the kaolinite.Based on the above insights,the higher ion exchange stoichiometry ratios are attributed to closer adsorption distances(6.04 A for Dy and 3.69 A for Al)and lower adsorption energies(-223.72 kJ.mol^(-1)for Dy and-268.33 kJ.mol^(-1)for Al).The maximum ionexchangeable capacity is related to the change of the surface electrical properties of kaolinite.The zeta potential was increased to-7.3 mV as the protonation resulted from aluminum adsorption,while Dy adsorption had a minor effect,maintaining a value of-17.5 m V.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
Modifying the surface structures of g-C_(3)N_(4) through interfacial coupling with other semiconductors has been spotlighted as an efficient approach for improving photocatalytic efficiency.With the surge of S-scheme ...Modifying the surface structures of g-C_(3)N_(4) through interfacial coupling with other semiconductors has been spotlighted as an efficient approach for improving photocatalytic efficiency.With the surge of S-scheme heterojunctions,the research is intensified towards designing this kind of composite for energy-environmental-related applications.In this context,a new approach involving surface modifications of g-C_(3)N_(4) through Gd species and integrating with monoclinic-WO_(3) via a wet chemical approach to form S-scheme heterojunctions is investigated.The characterization results attested that the adopted protocol promotes the better dispersion of Gd species over the g-C_(3)N_(4) surface and rigidly integrates with WO_(3).The optical response of the composite spanned a significant portion of the visible region in the solar spec-trum.The computational studies and the findings of the Mott-Schottky plot collectively suggested that the position of band edges qualifies for the formation of S-scheme heterojunction.The results derived from photocurrent response measurements and photoluminescence technique attribute to the effective charge carrier separation in the heterostructure.The rate constant of Gd-g-C_(3)N_(4)/WO_(3) was 1.48×10^(-2) min^(-1) which was approximately 4.35 and 2.27 times greater than that of WO_(3)(0.34×10^(-2) min^(-1))and g-C_(3)N_(4)/WO_(3)(0.65×10^(-2) min^(-1))respectively.Furthermore,RhB degradation in the presence of scav-engers validated the participation of superoxide and hydroxyl radicals in the degradation mechanisms.This was possible only when the conduction band electrons of WO_(3) recombined with the valence band holes of Gd-modified g-C_(3)N_(4).The present work helps to understand the S-scheme heterojunction forma-tion between surface-modified g-C_(3)N_(4) and metal oxides and retain the involvement of energetic charge carriers in the desired redox reactions.展开更多
A corrosion discoloration model for copper-nickel alloys in Cl^(−)environments was established using CIE-Lab,UV-VIS absorption spectroscopy,X-ray diffraction,and X-ray photoelectron spectroscopy.The corrosion discolor...A corrosion discoloration model for copper-nickel alloys in Cl^(−)environments was established using CIE-Lab,UV-VIS absorption spectroscopy,X-ray diffraction,and X-ray photoelectron spectroscopy.The corrosion discoloration process and the corresponding main corrosion products can be summarized as follows:silver-white(Cu+Ni)→green(NiO)→reddishbrown(NiO+Cu_(2)O)→black(NiO+Cu_(2)O+CuO).Density functional theory was employed to explain the corrosion process of copper-nickel alloys and the detrimental effect of Cl^(−).The results indicate that adsorbates preferentially bind to nickel,leading to the preferential formation of NiO,which imparts a green appearance to the surface.Furthermore,the difficulty in forming nickel cation vacancies and the higher diffusion barrier for nickel inhibit the migration of species within the oxide layer.Notably,nickel also suppresses carrier migration within the oxide layer,reducing the charge transfer rate.In contrast,the promotion of corrosion by Cl^(−)is primarily attributed to the reduction in surface work function and the formation energy of cation vacancies.展开更多
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
Pyrrhotite naturally occurs in various superstructures including magnetic(4C)and non-magnetic(5C,6C)types,each with distinct physicochemical properties and flotation behaviors.Challenges in accurately identifying and ...Pyrrhotite naturally occurs in various superstructures including magnetic(4C)and non-magnetic(5C,6C)types,each with distinct physicochemical properties and flotation behaviors.Challenges in accurately identifying and quantifying these superstructures hinder the optimization of pyrrhotite depression in flotation processes.To address this critical issue,synchrotron X-ray powder diffraction(S-XRPD)with Rietveld refinement was employed to quantify the distribution of superstructures in the feed and flotation concentrates of a copper–gold ore.To elucidate the mechanisms influencing depression,density functional theory(DFT)calculations were conducted to explore the electronic structures and surface reactivity of the pyrrhotite superstructures toward the adsorption of water,oxygen and hydroxyl ions(OH-)as dominant species present in the flotation process.S-XRPD analysis revealed that flotation recovery rates of pyrrhotite followed the order of 4C<6C<5C.DFT calculations indicated that the Fe 3d and S 3p orbital band centers exhibited a similar trend relative to the Fermi level with 4C being the closest.The Fe3d band center suggested that the 4C structure possessed a more reactive surface toward the oxygen reduction reaction,promoting the formation of hydrophilic Fe-OH sites.The S 3p band center order also implied that xanthate on the non-magnetic 5C and 6C surfaces could oxidize to dixanthogen,increasing hydrophobicity and floatability,while 4C formed less hydrophobic metal-xanthate complexes.Adsorption energy and charge transfer analyses of water,hydroxyl ions and molecular oxygen further supported the high reactivity and hydrophilic nature of 4C pyrrhotite.The strong bonding with hydroxyl ions indicated enhanced surface passivation by hydrophilic Fe–OOH complexes,aligning with the experimentally observed flotation order(4C<6C<5C).These findings provide a compelling correlation between experimental flotation results and electronic structure calculations,delivering crucial insights for optimizing flotation processes and improving pyrrhotite depression.This breakthrough opens up new opportunities to enhance the efficiency of flotation processes in the mining industry.展开更多
调制解调法是一种常用的微弱信号检测方法,高精度、低复杂度的解调方法的实现对于调制解调法的应用具有重要的意义.传统坐标旋转数字计算(coordinate rotation digital computer,CORDIC)算法具有占用资源多,需要缩放因子补偿等问题.因...调制解调法是一种常用的微弱信号检测方法,高精度、低复杂度的解调方法的实现对于调制解调法的应用具有重要的意义.传统坐标旋转数字计算(coordinate rotation digital computer,CORDIC)算法具有占用资源多,需要缩放因子补偿等问题.因此设计并实现了一种基于改进CORDIC算法的离散傅里叶变换(discrete Fourier transform,DFT)解调方法用于微弱信号的检测.首先改进了传统的CORDIC算法用于正余弦函数值的计算,该方法不仅免除了缩放因子,而且不需要进行旋转角度的判断,降低了算法的资源占用;然后基于该CORDIC算法设计了DFT解调算法,避免了乘法器与大量查找表的使用.最终仿真结果表明,设计的DFT解调方法在整周期采样的情况下能够实现对调制信号的高精度解调,并且具备良好的抗噪声性能,能够满足微弱信号检测的要求.展开更多
Organic semiconductor materials have demonstrated extensive potential in the field of gas sensors due to the advantages including designable chemical structure,tunable physical and chemical properties.Through density ...Organic semiconductor materials have demonstrated extensive potential in the field of gas sensors due to the advantages including designable chemical structure,tunable physical and chemical properties.Through density functional theory(DFT)calculations,researchers can investigate gas sensing mechanisms,optimize,and predict the electronic structures and response characteristics of these materials,and thereby identify candidate materials with promising gas sensing applications for targeted design.This review concentrates on three primary applications of DFT technology in the realm of organic semiconductor-based gas sensors:(1)Investigating the sensing mechanisms by analyzing the interactions between gas molecules and sensing materials through DFT,(2)simulating the dynamic responses of gas molecules,which involves the behavior on the sensing interface using DFT combined with other computational methods to explore adsorption and diffusion processes,and(3)exploring and designing sensitive materials by employing DFT for screening and predicting chemical structures,thereby developing new sensing materials with exceptional performance.Furthermore,this review examines current research outcomes and anticipates the extensive application prospects of DFT technology in the domain of organic semiconductor-based gas sensors.These efforts are expected to provide valuable insights for further indepth exploration of DFT applications in sensor technology,thereby fostering significant advancements and innovations in the field.展开更多
基金financially supported by the National Key Research and Development Program of China(No.2021YFC2902203)the Key Research and Development Program of Guangxi Province(No.Guike-AB22080056)+2 种基金Beijing Nova Program(No.20230484379)the Science and Technology Innovation Fund of GRINM(No.2022PD0102)the Central Government Guides Local Science and Technology Development Fund Project(No.246Z4005G)。
文摘To achieve selective leaching of ion adsorption rare earth,it is necessary to thoroughly reveal the differences in the adsorption mechanisms of aluminum and rare earth elements.In this study,we investigated the adsorption processes of Dy and Al on the surface of K–homoionic kaolinite using batch experiments and sequential chemical extractions.The results revealed that the adsorption of Dy and Al,as well as the desorption of K,followed the Langmuir model.The maximum ion-exchangeable capacity of Dy was higher(9.39 mmol.kg^(-1))than that of Al(6.30 mmol.kg^(-1)).The ion exchange stoichiometry ratios of Dy–K and Al–K derived from the Langmuir model were2.0 and 2.6.The analysis of X-ray absorption fine structure(XAFS)and density functional theory(DFT)revealed that Dy and Al were adsorbed onto kaolinite as outer-sphere hydrated complexes via hydrogen bonds.Dy was adsorbed as[Dy(H_(2)O)_(10)]^(3+),and Al was adsorbed as[Al(OH)_(2)(H_(2)O)_(4)]^(+).In particular,the adsorption of Al resulted in protonation of the hydroxyl groups on the surface of the kaolinite.Based on the above insights,the higher ion exchange stoichiometry ratios are attributed to closer adsorption distances(6.04 A for Dy and 3.69 A for Al)and lower adsorption energies(-223.72 kJ.mol^(-1)for Dy and-268.33 kJ.mol^(-1)for Al).The maximum ionexchangeable capacity is related to the change of the surface electrical properties of kaolinite.The zeta potential was increased to-7.3 mV as the protonation resulted from aluminum adsorption,while Dy adsorption had a minor effect,maintaining a value of-17.5 m V.
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.
基金Department of Chemistry,School of Applied Sciences,REVA University,Bangalore for providing seed money(RU:EST:CH:2022/20).
文摘Modifying the surface structures of g-C_(3)N_(4) through interfacial coupling with other semiconductors has been spotlighted as an efficient approach for improving photocatalytic efficiency.With the surge of S-scheme heterojunctions,the research is intensified towards designing this kind of composite for energy-environmental-related applications.In this context,a new approach involving surface modifications of g-C_(3)N_(4) through Gd species and integrating with monoclinic-WO_(3) via a wet chemical approach to form S-scheme heterojunctions is investigated.The characterization results attested that the adopted protocol promotes the better dispersion of Gd species over the g-C_(3)N_(4) surface and rigidly integrates with WO_(3).The optical response of the composite spanned a significant portion of the visible region in the solar spec-trum.The computational studies and the findings of the Mott-Schottky plot collectively suggested that the position of band edges qualifies for the formation of S-scheme heterojunction.The results derived from photocurrent response measurements and photoluminescence technique attribute to the effective charge carrier separation in the heterostructure.The rate constant of Gd-g-C_(3)N_(4)/WO_(3) was 1.48×10^(-2) min^(-1) which was approximately 4.35 and 2.27 times greater than that of WO_(3)(0.34×10^(-2) min^(-1))and g-C_(3)N_(4)/WO_(3)(0.65×10^(-2) min^(-1))respectively.Furthermore,RhB degradation in the presence of scav-engers validated the participation of superoxide and hydroxyl radicals in the degradation mechanisms.This was possible only when the conduction band electrons of WO_(3) recombined with the valence band holes of Gd-modified g-C_(3)N_(4).The present work helps to understand the S-scheme heterojunction forma-tion between surface-modified g-C_(3)N_(4) and metal oxides and retain the involvement of energetic charge carriers in the desired redox reactions.
基金supported by the Key Program of the National Natural Science Foundation of China(Grant No.51131007)the National Key Research and Development Program of China(Grant No.2021YFC2803102).
文摘A corrosion discoloration model for copper-nickel alloys in Cl^(−)environments was established using CIE-Lab,UV-VIS absorption spectroscopy,X-ray diffraction,and X-ray photoelectron spectroscopy.The corrosion discoloration process and the corresponding main corrosion products can be summarized as follows:silver-white(Cu+Ni)→green(NiO)→reddishbrown(NiO+Cu_(2)O)→black(NiO+Cu_(2)O+CuO).Density functional theory was employed to explain the corrosion process of copper-nickel alloys and the detrimental effect of Cl^(−).The results indicate that adsorbates preferentially bind to nickel,leading to the preferential formation of NiO,which imparts a green appearance to the surface.Furthermore,the difficulty in forming nickel cation vacancies and the higher diffusion barrier for nickel inhibit the migration of species within the oxide layer.Notably,nickel also suppresses carrier migration within the oxide layer,reducing the charge transfer rate.In contrast,the promotion of corrosion by Cl^(−)is primarily attributed to the reduction in surface work function and the formation energy of cation vacancies.
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 Australian Research Council Linkage Project(No.LP200200717)co sponsored by Newmont Corporation(United States)and Vega Industries(India)+1 种基金the Powder Diffraction Beamline at the Australia’s Nuclear Science and Technology Organisation(No.PDR19870),Australiathe Centre for Microscopy and Microanalysis at the University of Queensland(No.1366),Australia。
文摘Pyrrhotite naturally occurs in various superstructures including magnetic(4C)and non-magnetic(5C,6C)types,each with distinct physicochemical properties and flotation behaviors.Challenges in accurately identifying and quantifying these superstructures hinder the optimization of pyrrhotite depression in flotation processes.To address this critical issue,synchrotron X-ray powder diffraction(S-XRPD)with Rietveld refinement was employed to quantify the distribution of superstructures in the feed and flotation concentrates of a copper–gold ore.To elucidate the mechanisms influencing depression,density functional theory(DFT)calculations were conducted to explore the electronic structures and surface reactivity of the pyrrhotite superstructures toward the adsorption of water,oxygen and hydroxyl ions(OH-)as dominant species present in the flotation process.S-XRPD analysis revealed that flotation recovery rates of pyrrhotite followed the order of 4C<6C<5C.DFT calculations indicated that the Fe 3d and S 3p orbital band centers exhibited a similar trend relative to the Fermi level with 4C being the closest.The Fe3d band center suggested that the 4C structure possessed a more reactive surface toward the oxygen reduction reaction,promoting the formation of hydrophilic Fe-OH sites.The S 3p band center order also implied that xanthate on the non-magnetic 5C and 6C surfaces could oxidize to dixanthogen,increasing hydrophobicity and floatability,while 4C formed less hydrophobic metal-xanthate complexes.Adsorption energy and charge transfer analyses of water,hydroxyl ions and molecular oxygen further supported the high reactivity and hydrophilic nature of 4C pyrrhotite.The strong bonding with hydroxyl ions indicated enhanced surface passivation by hydrophilic Fe–OOH complexes,aligning with the experimentally observed flotation order(4C<6C<5C).These findings provide a compelling correlation between experimental flotation results and electronic structure calculations,delivering crucial insights for optimizing flotation processes and improving pyrrhotite depression.This breakthrough opens up new opportunities to enhance the efficiency of flotation processes in the mining industry.
基金supported by National Natural Science Foundation of China(Nos.92263109 and 61904188)the Shanghai Rising-Star Program(No.22QA1410400)。
文摘Organic semiconductor materials have demonstrated extensive potential in the field of gas sensors due to the advantages including designable chemical structure,tunable physical and chemical properties.Through density functional theory(DFT)calculations,researchers can investigate gas sensing mechanisms,optimize,and predict the electronic structures and response characteristics of these materials,and thereby identify candidate materials with promising gas sensing applications for targeted design.This review concentrates on three primary applications of DFT technology in the realm of organic semiconductor-based gas sensors:(1)Investigating the sensing mechanisms by analyzing the interactions between gas molecules and sensing materials through DFT,(2)simulating the dynamic responses of gas molecules,which involves the behavior on the sensing interface using DFT combined with other computational methods to explore adsorption and diffusion processes,and(3)exploring and designing sensitive materials by employing DFT for screening and predicting chemical structures,thereby developing new sensing materials with exceptional performance.Furthermore,this review examines current research outcomes and anticipates the extensive application prospects of DFT technology in the domain of organic semiconductor-based gas sensors.These efforts are expected to provide valuable insights for further indepth exploration of DFT applications in sensor technology,thereby fostering significant advancements and innovations in the field.
