A method to compute the numerical derivative of eigenvalues of parameterized crystal field Hamiltonian matrix is given, based on the numerical derivatives the general iteration methods such as Levenberg-Marquardt, New...A method to compute the numerical derivative of eigenvalues of parameterized crystal field Hamiltonian matrix is given, based on the numerical derivatives the general iteration methods such as Levenberg-Marquardt, Newton method, and so on, can be used to solve crystal field parameters by fitting to experimental energy levels. With the numerical eigenvalue derivative, a detailed iteration algorithm to compute crystal field parameters by fitting experimental energy levels has also been described. This method is used to compute the crystal parameters of Yb^3＋ in Sc2O3 crystal, which is prepared by a co-precipitation method and whose structure was refined by Rietveld method. By fitting on the parameters of a simple overlap model of crystal field, the results show that the new method can fit the crystal field energy splitting with fast convergence and good stability.展开更多
In recent years,researchers have increasingly focused on aqueous rechargeable Zn-ion batteries(AZIBs)as a cost-effective and safe alternative to lithium-ion batteries for energy storage.Nevertheless,the limited revers...In recent years,researchers have increasingly focused on aqueous rechargeable Zn-ion batteries(AZIBs)as a cost-effective and safe alternative to lithium-ion batteries for energy storage.Nevertheless,the limited reversibility of the Zn anode and the low coulombic efficiency of the electroplating process limit the application of AZIBs.In this work,pyrrole is employed as a cost-effective electrolyte additive for stabilizing the Zn anode for the first time.By altering the coordination environment of Zn(H2O)62+,chemical and hydrogen evolution corrosion was reduced,and a molecular interface layer was in-situ constructed on the surface of the metal Zn anode,thus effectively inhibiting the corrosion of Zn anode and the growth of dendrites.In addition,the molecular interface layer based on pyrrole can effectively regulate the uniform deposition of Zn ions and limit the 2D diffusion of Zn ions.Therefore,the electrochemical performance of the metal Zn anode is greatly improved in the pyrrole-based electrolyte.At the current density of 1 mA·cm^(-2),the stable cycle can exceed 1200 h,and the average Coulomb efficiency is as high as 99%.Moreover,the full battery can have more than 400 stable cycles with a reversible capacity 247.9 mAh·g^(-1)at a current density 0.5 A·g^(-1)when assembled with V2O5 cathodes.This work provides a simple and feasible strategy for realizing the high performance of aqueous Zn-ion batteries.展开更多
Non-centrosymmetric(NCS)crystalline structures,critical for second harmonic generation(SHG)in all-solid-state lasers,are far less prevalent than their centrosymmetric(Cs)counterparts.In this study,we report a structur...Non-centrosymmetric(NCS)crystalline structures,critical for second harmonic generation(SHG)in all-solid-state lasers,are far less prevalent than their centrosymmetric(Cs)counterparts.In this study,we report a structural transformation from CS to NCS configuration in benzenesulfonate derivatives via hydroxyl group incorporation,as illustrated by the transition in the newly discovered CN_(3)H_(6)C_(6)H_(5)SO_(3)(CS)and CN_(3)H_(6)C_(6)H_(5)SO_(3)(OH)(NCS).The introduced hydroxyl groups induce hydrogen bond reconstruction,effectively breaking the original centrosymmetry.The resulting NCS compound exhibits remarkable nonlinear optical(NLO)properties,including a strong SHG response(1.6×KDP with the particle sizes of 200250μm),a wide bandgap(UV cutoff at 290 nm,corresponding band gap is 4.37 eV),and a large birefringence(0.21@1064 nm),demonstrating excellent potential as an UV NLO crystal material.展开更多
It is challenging to cooperatively improve the nonlinear optical(NLO)efficiency and the laser-induced damage threshold(LIDT).This work reports a novel IR NLO materials CsInP_(2)S_(7)(CIPS)designed by combination the s...It is challenging to cooperatively improve the nonlinear optical(NLO)efficiency and the laser-induced damage threshold(LIDT).This work reports a novel IR NLO materials CsInP_(2)S_(7)(CIPS)designed by combination the strategies of alkali metals substitution and microscopic NLO units PS4 introduction based on AgGaS_(2).CIPS was composed of strongly distorted[InS_(6)]^(9-)octahedra and[P_(2)S_(7)]4-dimers constructed by corner-sharing[PS_(4)]^(3-),which increase the NLO efficiency and decrease thermal expansion anisotropy simultaneously.Compared with AgGaS_(2),CIPS exhibited strong phase matchable NLO response ca.1.1×AGS@2.1μm,high LIDT ca.20.8×AgGaS_(2),and IR transparency up to 15.3μm.Structural analysis and theoretical investigation confirmed that large SHG effect and ultrahigh LIDT of CIPS originated from the synergistic contribution of[InS_(6)]^(9-)octahedra and[P_(2)S_(7)]4-dimers.These results indicate that CIPS is a promising NLO candidate in the mid-IR region,and this study provides a new approach for developing potential NLO-LIDT compatible materials.展开更多
Deep-ultraviolet (DUV, wavelength λ < 200 nm) nonlinear optical (NLO) crystal is the core component of frequency conversion to generate DUV laser, which plays an important role in cutting-edge laser technology and...Deep-ultraviolet (DUV, wavelength λ < 200 nm) nonlinear optical (NLO) crystal is the core component of frequency conversion to generate DUV laser, which plays an important role in cutting-edge laser technology and fundamental science. Significant progress has been made in both experimental exploration and theoretical design in the field of DUV NLO crystals over the past three decades. In-depth insight into “structure-property correlations”, in particular, allows for rigorous and precise identification of DUV NLO crystals. In this article, we reviewed the current experimental and theoretical research progress while elucidating the core concepts and stringent criteria of qualified DUV phase-matched second-harmonic generation crystals. We also discussed the development of the DUV NLO “structure-property correlations” from first principles and how it has sparked interest in related materials, as well as future directions for obtaining potential DUV NLO crystals.展开更多
Nonlinear optical(NLO)crystals are the key fundamental materials in modern optoelectronic information technology,which play an irre-placeable role in modern quantum optics and photonics in addition to traditional lase...Nonlinear optical(NLO)crystals are the key fundamental materials in modern optoelectronic information technology,which play an irre-placeable role in modern quantum optics and photonics in addition to traditional laser frequency conversion applications[1,2].Especially at a time when the international competition of quantum information tech-nology is becoming increasingly intense,high-performing NLO crystals as the strategic materials for optical quantum technology have received continuous attention from physical chemists and materials scientists.展开更多
The electrochemical nitric oxide reduction reaction(NORR)to NH_(3)represents a promising avenue for NO removal and NH_(3)synthesis.It is essential to develop catalysts with superior performance for this process.We sys...The electrochemical nitric oxide reduction reaction(NORR)to NH_(3)represents a promising avenue for NO removal and NH_(3)synthesis.It is essential to develop catalysts with superior performance for this process.We systematically studied a series of single-atom alloy catalysts(SAACs)with Pd single-atom dopants using density functional theory(DFT)calculations and machine learning(ML).Based on the energetic span model,we take G_(max)(η)as a descriptor to evaluate the reaction activity of SAACs.After comprehensively considering the stability,activity,and NH_(3)selectivity of SAACs,Cu and Pd/Cu SAAC are screened out as candidate NORR to NH_(3)catalysts.To predict the G_(max)(η)descriptor,the extreme gradient boosting regression(XGBR)ML algorithm was adopted with geometric/electronic properties of the SAACs as input features.Additionally,we proposed a mathematical formula to correlate the crucial features and the G_(max)(η)descriptor using the sure independence screening and sparsifying operator(SISSO)approach.This work provides an understanding of the complex NORR mechanisms and offers a strategy to rationally design highly efficient SAACs.展开更多
Aqueous zinc-ion batteries(AZIBs)are regarded as one of the most promising rivals in the upcoming high-energy secondary battery market because of their safety and non-toxicity.However,the zinc dendrites growth and hyd...Aqueous zinc-ion batteries(AZIBs)are regarded as one of the most promising rivals in the upcoming high-energy secondary battery market because of their safety and non-toxicity.However,the zinc dendrites growth and hydrogen evolution corrosion of the Zn anode have seriously restricted the application of AZIBs.Herein,to overcome these constraints,a three-dimensional(3D)porous PFA-COOH-CNT artificial solid electrolyte interface(SEl)film with high hydrophobic and zincophilic properties was constructed on Zn anode surface by in-situ polymerization of furfuryl alcohol(FA)and carboxyl carbon nanotubes(COOH-CNT).A series of in-situ,ex-situ characterizations as well as the density functional theory(DFT)calculations reveal that the formed PFA-COOH-CNT SEI film with an abundant oxygen-containing group can provide abundant zincophilic sites and induce homogeneous deposition of Zn^(2+),as well as the hydrophobic alkyl and carbon skeleton in PFA-COOH-CNT SEI film can isolate the direct contact of H_(2)O with Zn anode,and inhibit the occurrence of hydrogen evolution reaction(HER).Accordingly,the Zn anode with PFA-COOH-CNT layer can attain an ultra-long cycle life of 2200 h at 1 mA·cm^(-2),1 mAh·cm^(-2).Simultaneously,the assembled PFA-COOH-CNT@ZnllV2Os full cell can also achieve a high reversible capacity of up to 150.2 mAh•g^(-1) at 1 A·g^(-1) after 400 cycles,with a high average coulombic efficiency(CE)of 98.8%.The designed PFA-COOH-CNT artificial SEI film provides a broad prospect for highly stable zinc anode,and can also be extended to other energy storage systems based on metal anodes.展开更多
Interlayer sliding modulation in van der Waals(vdW)layered materials opens opportunities to seek tunable applications for photonics and optoelectronics at the nanoscale.In this work,focusing on ternary chalcogenides,d...Interlayer sliding modulation in van der Waals(vdW)layered materials opens opportunities to seek tunable applications for photonics and optoelectronics at the nanoscale.In this work,focusing on ternary chalcogenides,dozens of typical vdW layered materials with the formula of A_(2)MZ_(4)(A,M=metal cation;Z=S/Se)were systematically classified and studied to illustrate the interlayer sliding modulation performance on nonlinear optical(NLO)effect and underlying mechanism.Based on first-principles analysis,the screened Cd_(2)GeSe_(4) exhibits large second harmonic generation(SHG)deviation(>36 times between high-and low-SHG states)under sliding among all studied materials.This phenomenon arises from the polarization modulation induced by the vdW interlayer charge redistribution of two tetrahedral primitives in the ternary edge-sharing tetrahedral structures.Our findings present a strategy to substantially modulate NLO properties by altering the interlayer charge coupling which is commonly thought to be very weak in vdW layered materials.展开更多
基金Project supported by the National Natural Science Foundation of China(Grant Nos.50772112 and 50872135)the Natural Science Foundation of Anhui Province of China(Grant No.08040106820)the Knowledge Innovation Program of the Chinese Academy of Sciences(Grant No.YYYJ-1002)
文摘A method to compute the numerical derivative of eigenvalues of parameterized crystal field Hamiltonian matrix is given, based on the numerical derivatives the general iteration methods such as Levenberg-Marquardt, Newton method, and so on, can be used to solve crystal field parameters by fitting to experimental energy levels. With the numerical eigenvalue derivative, a detailed iteration algorithm to compute crystal field parameters by fitting experimental energy levels has also been described. This method is used to compute the crystal parameters of Yb^3＋ in Sc2O3 crystal, which is prepared by a co-precipitation method and whose structure was refined by Rietveld method. By fitting on the parameters of a simple overlap model of crystal field, the results show that the new method can fit the crystal field energy splitting with fast convergence and good stability.
基金supported by the National Natural Science Foundation of China(No.51902036)the Natural Science Foundation of Chongqing Science&Technology Commission(No.CSTB2022NSCQ-MSX0828)+2 种基金the Venture&Innovation Support Program for Chongqing Overseas Returnees(No.CX2021046)the Science and Technology Research Program of Chongqing Municipal Education Commission(No.KJZD-K202300802)the Research Project of Innovative Talent Training Engineering Program of Chongqing Primary and Secondary School(No.CY230801).
文摘In recent years,researchers have increasingly focused on aqueous rechargeable Zn-ion batteries(AZIBs)as a cost-effective and safe alternative to lithium-ion batteries for energy storage.Nevertheless,the limited reversibility of the Zn anode and the low coulombic efficiency of the electroplating process limit the application of AZIBs.In this work,pyrrole is employed as a cost-effective electrolyte additive for stabilizing the Zn anode for the first time.By altering the coordination environment of Zn(H2O)62+,chemical and hydrogen evolution corrosion was reduced,and a molecular interface layer was in-situ constructed on the surface of the metal Zn anode,thus effectively inhibiting the corrosion of Zn anode and the growth of dendrites.In addition,the molecular interface layer based on pyrrole can effectively regulate the uniform deposition of Zn ions and limit the 2D diffusion of Zn ions.Therefore,the electrochemical performance of the metal Zn anode is greatly improved in the pyrrole-based electrolyte.At the current density of 1 mA·cm^(-2),the stable cycle can exceed 1200 h,and the average Coulomb efficiency is as high as 99%.Moreover,the full battery can have more than 400 stable cycles with a reversible capacity 247.9 mAh·g^(-1)at a current density 0.5 A·g^(-1)when assembled with V2O5 cathodes.This work provides a simple and feasible strategy for realizing the high performance of aqueous Zn-ion batteries.
基金the National Natural Science Foundation of China(Nos.22275201 , 22133004)the Youth Innovation Promotion Association CAS.
文摘Non-centrosymmetric(NCS)crystalline structures,critical for second harmonic generation(SHG)in all-solid-state lasers,are far less prevalent than their centrosymmetric(Cs)counterparts.In this study,we report a structural transformation from CS to NCS configuration in benzenesulfonate derivatives via hydroxyl group incorporation,as illustrated by the transition in the newly discovered CN_(3)H_(6)C_(6)H_(5)SO_(3)(CS)and CN_(3)H_(6)C_(6)H_(5)SO_(3)(OH)(NCS).The introduced hydroxyl groups induce hydrogen bond reconstruction,effectively breaking the original centrosymmetry.The resulting NCS compound exhibits remarkable nonlinear optical(NLO)properties,including a strong SHG response(1.6×KDP with the particle sizes of 200250μm),a wide bandgap(UV cutoff at 290 nm,corresponding band gap is 4.37 eV),and a large birefringence(0.21@1064 nm),demonstrating excellent potential as an UV NLO crystal material.
基金the Natural Science Foundation of China(No.22105218).
文摘It is challenging to cooperatively improve the nonlinear optical(NLO)efficiency and the laser-induced damage threshold(LIDT).This work reports a novel IR NLO materials CsInP_(2)S_(7)(CIPS)designed by combination the strategies of alkali metals substitution and microscopic NLO units PS4 introduction based on AgGaS_(2).CIPS was composed of strongly distorted[InS_(6)]^(9-)octahedra and[P_(2)S_(7)]4-dimers constructed by corner-sharing[PS_(4)]^(3-),which increase the NLO efficiency and decrease thermal expansion anisotropy simultaneously.Compared with AgGaS_(2),CIPS exhibited strong phase matchable NLO response ca.1.1×AGS@2.1μm,high LIDT ca.20.8×AgGaS_(2),and IR transparency up to 15.3μm.Structural analysis and theoretical investigation confirmed that large SHG effect and ultrahigh LIDT of CIPS originated from the synergistic contribution of[InS_(6)]^(9-)octahedra and[P_(2)S_(7)]4-dimers.These results indicate that CIPS is a promising NLO candidate in the mid-IR region,and this study provides a new approach for developing potential NLO-LIDT compatible materials.
基金the National Natural Science Foundation of China(Grant Nos.12174404 and 22133004).
文摘Deep-ultraviolet (DUV, wavelength λ < 200 nm) nonlinear optical (NLO) crystal is the core component of frequency conversion to generate DUV laser, which plays an important role in cutting-edge laser technology and fundamental science. Significant progress has been made in both experimental exploration and theoretical design in the field of DUV NLO crystals over the past three decades. In-depth insight into “structure-property correlations”, in particular, allows for rigorous and precise identification of DUV NLO crystals. In this article, we reviewed the current experimental and theoretical research progress while elucidating the core concepts and stringent criteria of qualified DUV phase-matched second-harmonic generation crystals. We also discussed the development of the DUV NLO “structure-property correlations” from first principles and how it has sparked interest in related materials, as well as future directions for obtaining potential DUV NLO crystals.
基金supported by the National Natural Science Foundation of China(Grat Nos.12174404 and 22133004)the Open Research Fund Program of the State Key Laboratory of Low-Dimensional Quantum Physics
文摘Nonlinear optical(NLO)crystals are the key fundamental materials in modern optoelectronic information technology,which play an irre-placeable role in modern quantum optics and photonics in addition to traditional laser frequency conversion applications[1,2].Especially at a time when the international competition of quantum information tech-nology is becoming increasingly intense,high-performing NLO crystals as the strategic materials for optical quantum technology have received continuous attention from physical chemists and materials scientists.
基金support from the He Bei Natural Science Foundation(Nos.B2022205029 and B2022205013)。
文摘The electrochemical nitric oxide reduction reaction(NORR)to NH_(3)represents a promising avenue for NO removal and NH_(3)synthesis.It is essential to develop catalysts with superior performance for this process.We systematically studied a series of single-atom alloy catalysts(SAACs)with Pd single-atom dopants using density functional theory(DFT)calculations and machine learning(ML).Based on the energetic span model,we take G_(max)(η)as a descriptor to evaluate the reaction activity of SAACs.After comprehensively considering the stability,activity,and NH_(3)selectivity of SAACs,Cu and Pd/Cu SAAC are screened out as candidate NORR to NH_(3)catalysts.To predict the G_(max)(η)descriptor,the extreme gradient boosting regression(XGBR)ML algorithm was adopted with geometric/electronic properties of the SAACs as input features.Additionally,we proposed a mathematical formula to correlate the crucial features and the G_(max)(η)descriptor using the sure independence screening and sparsifying operator(SISSO)approach.This work provides an understanding of the complex NORR mechanisms and offers a strategy to rationally design highly efficient SAACs.
基金This study was funded by the National Natural Science Foundation of China(Nos.51902036,22222902,2263203,and 52111530236)the National Key R&D Program of China(No.2022YFA1203902)+3 种基金the Key Science and Technology Research Program of Chongqing Education Commission(No.KJZD-K202200807)the Natural Science Foundation of Chongqing Science&Technology Commission(No.CSTB2022NSCQ-MSX0828)Chongqing Bayu Scholars Support Program(No.YS2022050)Research Project of Innovative Talent Training Engineering Program of Chongqing Primary and Secondary School(No.CY240806).
文摘Aqueous zinc-ion batteries(AZIBs)are regarded as one of the most promising rivals in the upcoming high-energy secondary battery market because of their safety and non-toxicity.However,the zinc dendrites growth and hydrogen evolution corrosion of the Zn anode have seriously restricted the application of AZIBs.Herein,to overcome these constraints,a three-dimensional(3D)porous PFA-COOH-CNT artificial solid electrolyte interface(SEl)film with high hydrophobic and zincophilic properties was constructed on Zn anode surface by in-situ polymerization of furfuryl alcohol(FA)and carboxyl carbon nanotubes(COOH-CNT).A series of in-situ,ex-situ characterizations as well as the density functional theory(DFT)calculations reveal that the formed PFA-COOH-CNT SEI film with an abundant oxygen-containing group can provide abundant zincophilic sites and induce homogeneous deposition of Zn^(2+),as well as the hydrophobic alkyl and carbon skeleton in PFA-COOH-CNT SEI film can isolate the direct contact of H_(2)O with Zn anode,and inhibit the occurrence of hydrogen evolution reaction(HER).Accordingly,the Zn anode with PFA-COOH-CNT layer can attain an ultra-long cycle life of 2200 h at 1 mA·cm^(-2),1 mAh·cm^(-2).Simultaneously,the assembled PFA-COOH-CNT@ZnllV2Os full cell can also achieve a high reversible capacity of up to 150.2 mAh•g^(-1) at 1 A·g^(-1) after 400 cycles,with a high average coulombic efficiency(CE)of 98.8%.The designed PFA-COOH-CNT artificial SEI film provides a broad prospect for highly stable zinc anode,and can also be extended to other energy storage systems based on metal anodes.
基金This work is supported by the National Natural Science Foundation of China(Grant No.12174404 and 22133004)the Open Research Fund Program of the State Key Laboratory of Low-Dimensional Quantum Physics.The authors thank Dr.Bonan Zhu and Xuanlin Pan for helpful discussion.
文摘Interlayer sliding modulation in van der Waals(vdW)layered materials opens opportunities to seek tunable applications for photonics and optoelectronics at the nanoscale.In this work,focusing on ternary chalcogenides,dozens of typical vdW layered materials with the formula of A_(2)MZ_(4)(A,M=metal cation;Z=S/Se)were systematically classified and studied to illustrate the interlayer sliding modulation performance on nonlinear optical(NLO)effect and underlying mechanism.Based on first-principles analysis,the screened Cd_(2)GeSe_(4) exhibits large second harmonic generation(SHG)deviation(>36 times between high-and low-SHG states)under sliding among all studied materials.This phenomenon arises from the polarization modulation induced by the vdW interlayer charge redistribution of two tetrahedral primitives in the ternary edge-sharing tetrahedral structures.Our findings present a strategy to substantially modulate NLO properties by altering the interlayer charge coupling which is commonly thought to be very weak in vdW layered materials.
