Micro silicon(mSi)is a promising anode candidate for all-solid-state batteries due to its high specific capacity,low side reactions,and high tap density.However,silicon suffers from its poor electronic and ionic condu...Micro silicon(mSi)is a promising anode candidate for all-solid-state batteries due to its high specific capacity,low side reactions,and high tap density.However,silicon suffers from its poor electronic and ionic conductivity,which is particularly severe on a micro scale and in solid-state systems,leading to increased polarization and inferior electrochemical performance.Doping can broaden the transmission pathways and reduce the diffusion energy barrier for electrons and lithium ions.However,achieving effective,uniform doping in mSi is challenging due to its longer diffusion paths and higher energy barriers.Therefore,current doping research is primarily limited to nanosilicon.In this study,we successfully used a Joule-heating activated staged thermal treatment to achieve full-depth doping of germanium(Ge)in the mSi substrate.The Joule-heating process activated the mSi substrate,resulting in abundant vacancy defects that reduced the diffusion barrier of Ge into the silicon lattice and facilitated full-depth Ge doping.Surprisingly,the resulting Si-Ge anode exhibited significantly enhanced electrical conductivity(70 times).Meanwhile,the improved Li-ion conductivity in mSi and the reduced Young’s modulus enhance the electrode reaction kinetics and integrity after cycling.Ge-doped silicon anodes demonstrate excellent electrochemical performance when applied in sulfide solid-state half-cells and full-cells.This work provides substantial insights into the rational structural design of mSi alloyed anode materials,paving the way for the development of high-performance solid-state Li-ion batteries.展开更多
In this study,a straightforward one-step hydrothermal method was successfully utilized to synthesize the solid solution Na_(0.9)Mg_(0.45)Ti_(3.55)O_(8)-Na_(2)Ni_(2)Ti_(6)O_(16)(NNMTO-x),where x denotes the molar perce...In this study,a straightforward one-step hydrothermal method was successfully utilized to synthesize the solid solution Na_(0.9)Mg_(0.45)Ti_(3.55)O_(8)-Na_(2)Ni_(2)Ti_(6)O_(16)(NNMTO-x),where x denotes the molar percentage of Na_(2)Ni_(2)Ti_(6)O_(16)(NNTO)within Na_(0.9)Mg_(0.45)Ti_(3.55)O_(8)(NMTO),with x values of 10,20,30,40,and 50.Both XPS(X-ray Photoelectron Spectroscopy)and EDX(Energy Dispersive X-ray Spectroscopy)analyses unequivocally validated the formation of the NNMTO-x solid solutions.It was observed that when x is below 40,the NNMTO-x solid solution retains the structural characteristics of the original NMTO.However,beyond this threshold,significant alterations in crystal morphology were noted,accompanied by a noticeable decline in photocatalytic activity.Notably,the absorption edge of NNMTO-x(x<40)exhibited a shift towards the visible-light spectrum,thereby substantially broadening the absorption range.The findings highlight that NNMTO-30 possesses the most pronounced photocatalytic activity for the reduction of CO_(2).Specifically,after a 6 h irradiation period,the production rates of CO and CH_(4)were recorded at 42.38 and 1.47μmol/g,respectively.This investigation provides pivotal insights that are instrumental in the advancement of highly efficient and stable photocatalysts tailored for CO_(2)reduction processes.展开更多
Polyethylene oxide(PEO)-based solid polymer electrolytes(SPEs)have long faced limitations due to low ionic conductivity at ambient temperature and poor interfacial stability with lithium metal anodes.Here,we present a...Polyethylene oxide(PEO)-based solid polymer electrolytes(SPEs)have long faced limitations due to low ionic conductivity at ambient temperature and poor interfacial stability with lithium metal anodes.Here,we present a structural engineering strategy to address these challenges through shear-induced crystallization of concentrated PEO-LiTFSI solutions,which self-assemble into flower-like spherulites with radially aligned lamellar crystals.This unique structure creates continuous Li^(+)transport highways through densely packed crystalline domains,achieving a record-high ionic conductivity of 1.70×10^(-4) S/cm at 25℃ for pristine PEO-based systems.Strategic incorporation of lithium montmorillonite(MMTli,10 wt%)further optimizes the composite electrolyte,balancing high ionic conductivity(1.47×10^(-4) S/cm)with enhanced electrochemical stability(4.99 V vs.Li^(+)/Li),elevated Li^(+)transference number(0.62),and mechanical robustness.The composite electrolyte enables stable Li plating/stripping over 800 h in symmetric Li||Li cells and powers LiFePO_(4)||Li solid-state batteries with 82%capacity retention after 200 cycles at 0.2 C under ambient conditions.This work pioneers a scalable processing paradigm for crystalline polymer electrolytes,offering new insights into ion transport mechanisms and validating clay minerals as multifunctional additives for next-generation energy storage systems.展开更多
All-solid-state batteries(ASSBs)represent a next-generation energy storage technology,offering enhanced safety,higher energy density,and improved cycling stability compared to conventional liquid-electrolyte-based lit...All-solid-state batteries(ASSBs)represent a next-generation energy storage technology,offering enhanced safety,higher energy density,and improved cycling stability compared to conventional liquid-electrolyte-based lithium-ion batteries.Understanding and optimizing the complex chemistries and interfaces that underpin ASSB performance present significant challenges from both experimental and modeling perspectives.In particular,atomistic simulations face difficulties in capturing the complex structure,disorder,and dynamic evolution of materials and interfaces under practically relevant conditions.While established methods such as density functional theory and classical force fields have provided valuable insights,some questions remain difficult to address,particularly those involving large system sizes or long timescales.Recently,machine learning interatomic potentials(MLIPs)have emerged as a transformative tool,enabling atomistic simulations at length and time scales that were previously challenging to access with conventional approaches.By delivering near first-principles accuracy with much greater efficiency,MLIPs open new avenues for large-scale,long-timescale,and high-throughput simulations of solid-state battery materials.In this review,we present a comparative overview of density functional theory,classical force fields,and MLIPs,highlighting their respective strengths and limitations in ASSB research.We then discuss how MLIPs enable simulations that reach longer timescales,larger system sizes,and support high-throughput calculations,providing unique insights into ion transport and interfacial evolution in ASSBs.Finally,we conclude with a summary and outlook on current challenges and future opportunities for expanding MLIP capabilities and accelerating their impact in solid-state battery research.展开更多
In the realm of large-scale power system energy storage,sodium-based batteries represent a cost-effective post-lithium energy storage technology,making inorganic solid-state sodium batteries(ISSSB)a critical branch of...In the realm of large-scale power system energy storage,sodium-based batteries represent a cost-effective post-lithium energy storage technology,making inorganic solid-state sodium batteries(ISSSB)a critical branch of this development.Inorganic solid-state electrolytes(ISSEs)are the core components of sodium batteries;however,they face significant challenges such as insufficient ionic conductivity,interfacial instability,and dendrite growth,all of which severely hinder practical application.This review critically assesses experimental protocols and theoretical frameworks related to mainstream ISSEs and systematizes optimization strategies aimed at overcoming these challenges.Leveraging integrated insights from both experimental and computational studies,the review first categorizes and summarizes the primary types of ISSEs,namely oxide-,sulfide-,and halide-based electrolytes.It then details interfacial optimization strategies focused on addressing three core interfacial issues:ion transport barriers resulting from mechanical incompatibility,side reactions stemming from electrochemical mismatch,and dendrite formation.Finally,the review advocates prioritizing in-depth research that integrates experimental and theoretical approaches to establish a closed-loop methodology encompassing predictive design,multiscale investigation,mechanistic exploration,and high-throughput automated experimentation,with feedback-driven refinement.This work serves as a comprehensive reference and systematic roadmap for future research on solid-state electrolytes(SSEs).展开更多
Thermoplastic polyurethane(TPU)consists of a hardsegment and a soft segment,where the former affords mechanical strength and thermalstability,while the latter provides a possibility of good ionic conductivity by promo...Thermoplastic polyurethane(TPU)consists of a hardsegment and a soft segment,where the former affords mechanical strength and thermalstability,while the latter provides a possibility of good ionic conductivity by promoting dissociation of ions from the lithium salt.Thus,TPU attracts a wide interest recently as a promising polymer electrolyte for solid-state lithium batteries.However,the relatively low ionic conductivity of TPU still restricts its actual applications due to the aggregation of polymer chains,which greatly reduces the dissociation of lithium salts.Herein,a strategy to address this challenge was adopted by in situ polymerization poly(ethylene glycol diacrylate)(PEGDA)in fully dispersed TPU.Hence a stretchable solid-state electrolyte(denoted as TELL and the contrast sample was denoted as TLL)with high ionic conductivity of 7.18×10^(-4) S/cm was obtained at room temperature.The Li^(+)transference number is 0.85 in Li|TELL|Li cell and can stably undergo charge-discharge cycles for 1400 h at a current density of O.1 mA/cm^(2),while the contrast sample is short-circuited after 634 h of cycling.The LiFePO_(4)|TELL|Li cell achieves a capacity retention of 78.93%after 200 cycles at 2 C.The LiFePO_(4) TLL Li cellonly gains the capacity retention of 51.9%after 50 cyclesat the same current density.So,the method adopted here may provide a new approach to realize a flexible solid-state electrolyte with high ion-conductivity.展开更多
In this article,we show the existence,uniqueness and stability of bounded solutions to the following quasilinear problems with mean curvature operator(φ'(x′(t)))′=f(t,x),t≥t_(0),lim_(t→∞)x(t)=ψ_(0),lim_(t→...In this article,we show the existence,uniqueness and stability of bounded solutions to the following quasilinear problems with mean curvature operator(φ'(x′(t)))′=f(t,x),t≥t_(0),lim_(t→∞)x(t)=ψ_(0),lim_(t→∞)x′(t)e^(t)=0,where t_(0) and ψ_(0) are real constants,φ(s)=s/√1−s^(2),s∈R with s∈(−1,1),f:[t_(0),∞)×R→R satisfies the Lipschitz or Osgood-type conditions.展开更多
Circumlunar abort trajectories constitute a vital contingency return strategy during the translunar phase of crewed lunar missions.This paper proposes a methodology for constructing the solution set of the circumlunar...Circumlunar abort trajectories constitute a vital contingency return strategy during the translunar phase of crewed lunar missions.This paper proposes a methodology for constructing the solution set of the circumlunar abort trajectory and leverages its advantageous properties to address the optimization design problem of abort trajectories.Initially,a solution set of all feasible abort trajectories,originating from an abort point on the nominal trajectory and complying with fundamental reentry constraints,is formulated through the introduction of two novel design parameters.Subsequently,the geometric characteristics of the solution set,as well as the distributional properties of key iterative constraint responses,including flight time and velocity increment,are analyzed.Finally,the characteristics exhibited in the solution set are employed to directly identify the design parameters of the abort trajectories with minimum flight time and velocity increment,thereby providing solutions to two distinct types of optimization problems.The simulation results for a variety of nominal trajectories,encompassing the reconstruction and redesign of the Apollo13 abort trajectory,validate the proposed method,demonstrating its ability to directly generate optimal abort trajectories.The method proposed in this paper investigates feasible abort trajectories from a global perspective,providing both a framework and convenience for mission planning and iterative optimization in abort trajectory design.展开更多
Strong seismic excitation and fault dislocation are likely to occur simultaneously in high-intensity seismic zones,causing severe damage to tunnels crossing active fault zones.This paper aims to develop a novel analyt...Strong seismic excitation and fault dislocation are likely to occur simultaneously in high-intensity seismic zones,causing severe damage to tunnels crossing active fault zones.This paper aims to develop a novel analytical solution to determine the longitudinal mechanical responses of tunnels subjected to the combined effects of seismic waves and strike-slip faulting.Adopting the elastic springbeam model,the seismic waves are modelled as shear horizontal(SH)waves and the fault dislocation follows an S-shaped pattern;the superposition principle for free-fielddisplacements caused by both effects is assumed.In addition,the transmission and reflectionof seismic waves at the fault-rock geological interface and the tangential contact conditions at the tunnel-rock interface are considered.The analytical model is validated against numerical simulations,confirmingits accuracy in calculating tunnel responses.Moreover,a parametric study is conducted to evaluate the impact of key factors,including fault displacement,fault zone width,fault dip angle,earthquake frequency,rock conditions,tunnel lining stiffness,and tangential contact conditions,on tunnel responses.Compared with each effect alone,the combined effects of seismic waves and strike-slip faulting significantlychange the tunnel deformation and internal forces,leading to increased tunnel responses,especially within the fault zone and near the fault-rock interfaces.Depending on specificparameters,tunnel responses can be classifiedinto seismic-dominated,faulting-dominated,and seismic-faulting coupled responses on the basis of the relative contributions of each effect.The proposed analytical solution can be applied to quickly predict the longitudinal mechanical behaviour of tunnels under such combined effects in engineering applications.展开更多
Substrate and nutrient supply are essential for vegetable cultivation in greenhouse.The strategies for plant nutrient supply vary depending on the cultivation methods or substrate dosages employed.With the development...Substrate and nutrient supply are essential for vegetable cultivation in greenhouse.The strategies for plant nutrient supply vary depending on the cultivation methods or substrate dosages employed.With the development of mechanization,wide-row spacing substrate cultivation became an optimize mode of the greenhouse cucumber cultivation,aligning with the trend of intelligent agriculture.To determine the optimal nutrient solution supply amount(NS)and supply frequency(SF)for promoting the integrated growth of cucumber under wide-row spacing substrate cultivation,we explored the effects of substrate supply amount(SS),NS,and SF on cucumber yield,quality,and element utilization efficiency.A five-level quadratic orthogonal rotation combination design with three experimental factors(NS,SF,and SS)was implemented for 23 coupling treatments over three growing seasons,including spring(2022S and 2023S)and autumn(2022A).The technique for order preference by similarity to ideal solution(TOPSIS)combining weights based on game theory was applied to construct cucumber comprehensive growth evaluation model.Single and two experimental factors analyses revealed significant effects of single factors and the coupling of NS-SS,NS-SF and SS-SF on the integrated growth of cucumber for all three growing seasons.For the NS-SF-SS combination,the optimal parameters for comprehensive cucumber growth were determined as follows:levels of^(-1).68 for NS,-0.7 for SF,and^(-1).682 for SS in 2022A;-0.43 for NS,-0.06 for SF,and 0.34 for SS in 2022S;0.3 for NS,-0.02 for SF,and 0.04 for SS in 2023S.Furthermore,for SS ranges of 2.00-3.01,3.01-4.50,4.50-5.99,5.99-7.00(L·plant^(-1)),the corresponding NS and SF intervals maximizing cucumber integrated growth in spring were:0.28-0.30(L·plant^(-1))and 6(times·d^(-1)),0.26-0.30(L·plant^(-1))and 6(times·d^(-1)),0.25-0.30(L·plant^(-1))and 6(times·d^(-1)),0.23-0.30(L·plant^(-1))and 6(times·d^(-1)),respectively.With the same SS,the corresponding NS and SF intervals that maximized cucumber integrated growth in autumn were:0.10(L·plant^(-1))and 8(times·d^(-1)),0.18(L·plant^(-1))and 7(times·d^(-1)),0.30(L·plant^(-1))and 6(times·d^(-1)),0.49(L·plant^(-1))and 5(times·d^(-1)),respectively.The results provide a theoretical basis for solution management,and further in-depth research on cucumber cultivation.展开更多
Doping in thin-film transistors(TFTs) plays a crucial role in tailoring material properties to enhance device performance, making them essential for advanced electronic applications. This study explores the synthesis ...Doping in thin-film transistors(TFTs) plays a crucial role in tailoring material properties to enhance device performance, making them essential for advanced electronic applications. This study explores the synthesis and characterization of TFTs fabricated using nickel(Ni)-doped indium oxide(In_(2)O_(3)) via a wet-chemical approach. The presented work investigates the effect of "Ni" incorporation in In_(2)O_(3) on the structural and electrical transport properties of In_(2)O_(3), revealing that higher "Ni" content decreases the oxygen vacancies, leading to a reduction in leakage current and a forward shift in threshold potential(V_(th)).Experimental findings reveal that Ni In O-based TFTs(with Ni = 0.5%) showcase enhanced electrical performance, achieving mobility of 7.54 cm^(2)/(V·s), an impressive ON/OFF current ratio of ~10^(7), a V_(th) of 6.26 V, reduced interfacial trap states(D_(it)) of 8.23 ×10^(12) cm^(-2) and enhanced biased stress stability. The efficacy of "Ni" incorporation is attributed to the upgraded Lewis acidity, stable Ni-O bond strength, and small ionic radius of Ni. Negative bias illumination stability(NBIS) measurements further indicate that device stability diminishes with shorter light wavelengths, likely due to the activation of oxygen vacancies. These findings validate the solution-processed techniques' potential for future large-scale, low-cost, energy-efficient, and high-performance electronics.展开更多
In-situ stress is a key parameter for underground mine design and rock stability analysis.The borehole overcoring technique is widely used for in-situ stress measurement,but the rheological recovery deformation of roc...In-situ stress is a key parameter for underground mine design and rock stability analysis.The borehole overcoring technique is widely used for in-situ stress measurement,but the rheological recovery deformation of rocks after stress relief introduces errors.To improve accuracy,this study proposes an in-situ stress solution theory that incorporates time-dependent stress relief effects.Triaxial stepwise loadingunloading rheological tests on granite and siltstone established quantitative relationships between instantaneous elastic recovery and viscoelastic recovery under different stress levels,confirming their impact on measurement accuracy.By integrating a dual-class elastic deformation recovery model,an improved in-situ stress solution theory was derived.Additionally,accounting for the nonlinear characteristics of rock masses,a determination method for time-dependent nonlinear mechanical parameters was proposed.Based on the CSIRO hollow inclusion strain cell,time-dependent strain correction equations and long-term confining pressure calibration equations were formulated.Finally,the proposed theory was successfully applied at one iron mine(736 m depth)in Xinjiang,China,and one coal mine(510 m depth)in Ningxia,China.Compared to classical theory,the calculated mean stress values showed accuracy improvements of 6.0%and 9.4%,respectively,validating the applicability and reliability of the proposed theory.展开更多
Titanium plates with a Ti−O solid solution surface-hardened layer were cold roll-bonded with 304 stainless steel plates with high work hardening rates.The evolution and mechanisms affecting the interfacial bonding str...Titanium plates with a Ti−O solid solution surface-hardened layer were cold roll-bonded with 304 stainless steel plates with high work hardening rates.The evolution and mechanisms affecting the interfacial bonding strength in titanium/stainless steel laminated composites were investigated.Results indicate that the hardened layer reduces the interfacial bonding strength from over 261 MPa to less than 204 MPa.During the cold roll-bonding process,the hardened layer fractures,leading to the formation of multi-scale cracks that are difficult for the stainless steel to fill.This not only hinders the development of an interlocking interface but also leads to the presence of numerous microcracks and hardened blocks along the nearly straight interface,consequently weakening the interfacial bonding strength.In metals with high work hardening rates,the conventional approach of enhancing interface interlocking and improving interfacial bonding strength by using a surface-hardened layer becomes less effective.展开更多
Generalised reduced masses with a set of equations governing the three relative motions between two of 3-bodies in their gravitational field are established,of which the dynamic characteristics of 3-body dynamics,fund...Generalised reduced masses with a set of equations governing the three relative motions between two of 3-bodies in their gravitational field are established,of which the dynamic characteristics of 3-body dynamics,fundamental bases of this paper,are revealed.Based on these findings,an equivalent system is developed,which is a 2-body system with its total mass,constant angular momentum,kinetic and potential energies same as the total ones of three relative motions,so that it can be solved using the well-known theory of the 2-body system.From the solution of an equivalent system with the revealed characteristics of three relative motions,the general theoretical solutions of the 3-body system are obtained in the curve-integration forms along the orbits in the imaged radial motion space.The possible periodical orbits with generalised Kepler’s law are presented.Following the description and mathematical demonstrations of the proposed methods,the examples including Euler’s/Lagrange’s problems,and a reported numerical one are solved to validate the proposed methods.The methods derived from the 3-body system are extended to N-body problems.展开更多
Irbesartan(IBS)is a tetrazole derivative and antihypertensive drug that has two interconvertible structures,1H-and 2H-tautomers.The difference between them lies in the protonation of the tetrazole ring.In the solid-st...Irbesartan(IBS)is a tetrazole derivative and antihypertensive drug that has two interconvertible structures,1H-and 2H-tautomers.The difference between them lies in the protonation of the tetrazole ring.In the solid-state,both tautomers can be isolated as crystal forms A(1H-tautomer)and B(2H-tautomer).Studies have reported that IBS is a polymorphic system and its forms A and B are related monotropically.These reports indicate form B as the most stable and less soluble form.Therefore,the goal of this contribution is to demonstrate through a complete solid-state characterization,thermodynamic study and dissolution properties that the IBS forms are desmotropes that are not related monotropically.However,the intention is also to call attention to the importance of conducting strict chemical and in solid-state quality controls on the IBS raw materials.Hence,powder X-ray diffraction(PXRD)and Raman spectroscopy(RS)at ambient and non-ambient conditions,differential scanning calorimetry(DSC),hot stage microscopy(HSM),Fourier transform infrared(FT-IR)and scanning electron microscopy(SEM)techniques were applied.Furthermore,intrinsic dissolution rate(IDR)and structural stability studies at 98%relative humidity(RH),25℃and 40℃were conducted as well.The results show that in fact,form A is approximately four-fold more soluble than form B.In addition,both IBS forms are stable at ambient conditions.Nevertheless,structural and/or chemical instability was observed in form B at 40℃and 98%RH.IBS has been confirmed as a desmotropic system rather than a polymorphic one.Consequently,forms A and B are not related monotropically.展开更多
An empirical solution to abnormal potential responses, showing peaks of emf, of commercial Cu2+- and Cd2+-selective electrodes with solid-state membranes was proposed for aqueous solutions of CuCl2 and CdI2. The two-s...An empirical solution to abnormal potential responses, showing peaks of emf, of commercial Cu2+- and Cd2+-selective electrodes with solid-state membranes was proposed for aqueous solutions of CuCl2 and CdI2. The two-step processes of Mn+ + Yn? (s: solid phase) MY(s) and MY(s) + 2X? X2MY2?(s) (n = 1, 2) at a test solution/electrode-interface were considered as a model. Here, Mn+, Yn?, and X? refer to a divalent or univalent cation, functional groups of electrode materials, and a halide ion (X? = Cl?, Br?, I?), respectively. By applying electrochemical potentials to these processes at n = 2, we derived an equation. Regression analyses based on the equation reproduced well the plots of emf versus log 2(*[M]t) for the Cd(II) and Cu(II) systems: *[M]t denotes a total concentration of species relevant to M2+ in a bulk of the aqueous solution. Also, we obtained log Ks(CdBr2) = 4.28 ? 0.22, log Ks(CdI2) = 6.98 ? 0.05, log Ks(CuCl2) = 3.96 ? 0.09, and log Ks(CuBr2) = 11.4 at 25?C. The magnitude in ?log Ks reflected that in the logarithmic solubility product, log {*[M2+](*[X?])2}, for bulk water, where *[M2+] or *[X?] denotes a molar concentration of the bulk solu-tion of M2+ or X? at equilibrium, respectively. Moreover, a mixture of CuSO4 with NaCl at the molar ratio of 1:1 yielded a plot similar to that of CuCl2.展开更多
Fe^(3+) substituted ZSM-5 zeolite was studied using EPR and ^(27)A1,^(29)Si MAS-NMR spectroscopy.The results showed that the synthe- sized sample has the typical ZSM-5 structure with Fe^(3+) ionsincorporated in tetrah...Fe^(3+) substituted ZSM-5 zeolite was studied using EPR and ^(27)A1,^(29)Si MAS-NMR spectroscopy.The results showed that the synthe- sized sample has the typical ZSM-5 structure with Fe^(3+) ionsincorporated in tetrahedric sites in the zeolite framework and there are some para- magnetic centers in the samples.展开更多
To characterize the structure and dynamics of metal--organic frameworks(MOFs)indepth at the molecular level,it is necessary to pursue high-resolution solid-state magic angle spinning(MAS)nuclear magnetic resonance(NMR...To characterize the structure and dynamics of metal--organic frameworks(MOFs)indepth at the molecular level,it is necessary to pursue high-resolution solid-state magic angle spinning(MAS)nuclear magnetic resonance(NMR)spectroscopy.Spectral resolution is usually affected by the quality of materials and various experimental conditions,of which magic angle(MA)accuracy is a crucial determinant.The current industrial criteria for MA calibration based on the common standard of KBr were found insufficient in guaranteeing optimal resolution MAS NMR for highly ordered MOFs.To drive towards higher-resolution MAS NMR spectroscopy,we propose_a calibration protocol for more accurate MA with a higher-precision criterion based on 79Br MAS NMR of KBr,where the linewidth ratio of the fifth-order spinning sideband to the central band of KBr should be less than 1.00.As a result,ultrahigh-resolution 13C cross-polarization(CP)MAS NMR of MOF-5 is achieved with minimal linewidths as low as 4 Hz,and therefore MOF-5 can be used as a new standard convenient for verifying MA accuracy and also optimizing 13c CP conditions.Maintaining high-precision MA under variable temperature(VT)was found challenging on certain commercial MAS NMR probes,as was systematically investigated by VT NMR using KBr and MOF-5.Nevertheless,ultrahigh-resolution MAS NMR spectroscopy with stable MA under VT is employed to reveal fine structures and linker dynamics of a series of Zn-based MOFs with highly regulated structures.The ultrahigh-resolution NMR methodcan be generally applied to study a broad range of MOFs and other materials.展开更多
基金financially supported by the National Key Research and Development Program(2022YFE0127400)the National Natural Science Foundation of China(52172040,52202041,and U23B2077)+1 种基金Taishan Scholar Project of Shandong Province(tsqn202211086,ts202208832,tsqnz20221118)the Fundamental Research Funds for the Central Universities(23CX06055A).
文摘Micro silicon(mSi)is a promising anode candidate for all-solid-state batteries due to its high specific capacity,low side reactions,and high tap density.However,silicon suffers from its poor electronic and ionic conductivity,which is particularly severe on a micro scale and in solid-state systems,leading to increased polarization and inferior electrochemical performance.Doping can broaden the transmission pathways and reduce the diffusion energy barrier for electrons and lithium ions.However,achieving effective,uniform doping in mSi is challenging due to its longer diffusion paths and higher energy barriers.Therefore,current doping research is primarily limited to nanosilicon.In this study,we successfully used a Joule-heating activated staged thermal treatment to achieve full-depth doping of germanium(Ge)in the mSi substrate.The Joule-heating process activated the mSi substrate,resulting in abundant vacancy defects that reduced the diffusion barrier of Ge into the silicon lattice and facilitated full-depth Ge doping.Surprisingly,the resulting Si-Ge anode exhibited significantly enhanced electrical conductivity(70 times).Meanwhile,the improved Li-ion conductivity in mSi and the reduced Young’s modulus enhance the electrode reaction kinetics and integrity after cycling.Ge-doped silicon anodes demonstrate excellent electrochemical performance when applied in sulfide solid-state half-cells and full-cells.This work provides substantial insights into the rational structural design of mSi alloyed anode materials,paving the way for the development of high-performance solid-state Li-ion batteries.
基金Supported by the Doctoral Research Start-up Project of Yuncheng University(YQ-2023067)Project of Shanxi Natural Science Foundation(202303021211189)+1 种基金Fund Program for the Scientific Activities of Selected Returned Overseas Professionals in Shanxi Provinces(20220036)Shanxi ProvinceIntelligent Optoelectronic Sensing Application Technology Innovation Center and Shanxi Province Optoelectronic Information Science and TechnologyLaboratory,Yuncheng University.
文摘In this study,a straightforward one-step hydrothermal method was successfully utilized to synthesize the solid solution Na_(0.9)Mg_(0.45)Ti_(3.55)O_(8)-Na_(2)Ni_(2)Ti_(6)O_(16)(NNMTO-x),where x denotes the molar percentage of Na_(2)Ni_(2)Ti_(6)O_(16)(NNTO)within Na_(0.9)Mg_(0.45)Ti_(3.55)O_(8)(NMTO),with x values of 10,20,30,40,and 50.Both XPS(X-ray Photoelectron Spectroscopy)and EDX(Energy Dispersive X-ray Spectroscopy)analyses unequivocally validated the formation of the NNMTO-x solid solutions.It was observed that when x is below 40,the NNMTO-x solid solution retains the structural characteristics of the original NMTO.However,beyond this threshold,significant alterations in crystal morphology were noted,accompanied by a noticeable decline in photocatalytic activity.Notably,the absorption edge of NNMTO-x(x<40)exhibited a shift towards the visible-light spectrum,thereby substantially broadening the absorption range.The findings highlight that NNMTO-30 possesses the most pronounced photocatalytic activity for the reduction of CO_(2).Specifically,after a 6 h irradiation period,the production rates of CO and CH_(4)were recorded at 42.38 and 1.47μmol/g,respectively.This investigation provides pivotal insights that are instrumental in the advancement of highly efficient and stable photocatalysts tailored for CO_(2)reduction processes.
基金supported by the National Natural Science Foundation of China(No.42272044)the High-performance Computing Platform of China University of Geosciences Beijing。
文摘Polyethylene oxide(PEO)-based solid polymer electrolytes(SPEs)have long faced limitations due to low ionic conductivity at ambient temperature and poor interfacial stability with lithium metal anodes.Here,we present a structural engineering strategy to address these challenges through shear-induced crystallization of concentrated PEO-LiTFSI solutions,which self-assemble into flower-like spherulites with radially aligned lamellar crystals.This unique structure creates continuous Li^(+)transport highways through densely packed crystalline domains,achieving a record-high ionic conductivity of 1.70×10^(-4) S/cm at 25℃ for pristine PEO-based systems.Strategic incorporation of lithium montmorillonite(MMTli,10 wt%)further optimizes the composite electrolyte,balancing high ionic conductivity(1.47×10^(-4) S/cm)with enhanced electrochemical stability(4.99 V vs.Li^(+)/Li),elevated Li^(+)transference number(0.62),and mechanical robustness.The composite electrolyte enables stable Li plating/stripping over 800 h in symmetric Li||Li cells and powers LiFePO_(4)||Li solid-state batteries with 82%capacity retention after 200 cycles at 0.2 C under ambient conditions.This work pioneers a scalable processing paradigm for crystalline polymer electrolytes,offering new insights into ion transport mechanisms and validating clay minerals as multifunctional additives for next-generation energy storage systems.
文摘All-solid-state batteries(ASSBs)represent a next-generation energy storage technology,offering enhanced safety,higher energy density,and improved cycling stability compared to conventional liquid-electrolyte-based lithium-ion batteries.Understanding and optimizing the complex chemistries and interfaces that underpin ASSB performance present significant challenges from both experimental and modeling perspectives.In particular,atomistic simulations face difficulties in capturing the complex structure,disorder,and dynamic evolution of materials and interfaces under practically relevant conditions.While established methods such as density functional theory and classical force fields have provided valuable insights,some questions remain difficult to address,particularly those involving large system sizes or long timescales.Recently,machine learning interatomic potentials(MLIPs)have emerged as a transformative tool,enabling atomistic simulations at length and time scales that were previously challenging to access with conventional approaches.By delivering near first-principles accuracy with much greater efficiency,MLIPs open new avenues for large-scale,long-timescale,and high-throughput simulations of solid-state battery materials.In this review,we present a comparative overview of density functional theory,classical force fields,and MLIPs,highlighting their respective strengths and limitations in ASSB research.We then discuss how MLIPs enable simulations that reach longer timescales,larger system sizes,and support high-throughput calculations,providing unique insights into ion transport and interfacial evolution in ASSBs.Finally,we conclude with a summary and outlook on current challenges and future opportunities for expanding MLIP capabilities and accelerating their impact in solid-state battery research.
基金the National Natural Science Foundation of China (52076076, 52006065)Fundamental Research Funds for Central Universities (2025JC003)Beijing Municipal Natural Science Foundation (3242022)
文摘In the realm of large-scale power system energy storage,sodium-based batteries represent a cost-effective post-lithium energy storage technology,making inorganic solid-state sodium batteries(ISSSB)a critical branch of this development.Inorganic solid-state electrolytes(ISSEs)are the core components of sodium batteries;however,they face significant challenges such as insufficient ionic conductivity,interfacial instability,and dendrite growth,all of which severely hinder practical application.This review critically assesses experimental protocols and theoretical frameworks related to mainstream ISSEs and systematizes optimization strategies aimed at overcoming these challenges.Leveraging integrated insights from both experimental and computational studies,the review first categorizes and summarizes the primary types of ISSEs,namely oxide-,sulfide-,and halide-based electrolytes.It then details interfacial optimization strategies focused on addressing three core interfacial issues:ion transport barriers resulting from mechanical incompatibility,side reactions stemming from electrochemical mismatch,and dendrite formation.Finally,the review advocates prioritizing in-depth research that integrates experimental and theoretical approaches to establish a closed-loop methodology encompassing predictive design,multiscale investigation,mechanistic exploration,and high-throughput automated experimentation,with feedback-driven refinement.This work serves as a comprehensive reference and systematic roadmap for future research on solid-state electrolytes(SSEs).
基金financially supported by the National Natural Science Foundation of China(Nos.52263010 and 52372188)2023 Introduction of studying abroad talent program,Henan Provincial Key Scientific Research Project of Collegesand Universities(No.23A150038)+1 种基金Key Scientific Research Project of Education Department of Henan Province(No.22A150042)the National students'platform for innovation and entrepreneurship training program(No.201910476010).
文摘Thermoplastic polyurethane(TPU)consists of a hardsegment and a soft segment,where the former affords mechanical strength and thermalstability,while the latter provides a possibility of good ionic conductivity by promoting dissociation of ions from the lithium salt.Thus,TPU attracts a wide interest recently as a promising polymer electrolyte for solid-state lithium batteries.However,the relatively low ionic conductivity of TPU still restricts its actual applications due to the aggregation of polymer chains,which greatly reduces the dissociation of lithium salts.Herein,a strategy to address this challenge was adopted by in situ polymerization poly(ethylene glycol diacrylate)(PEGDA)in fully dispersed TPU.Hence a stretchable solid-state electrolyte(denoted as TELL and the contrast sample was denoted as TLL)with high ionic conductivity of 7.18×10^(-4) S/cm was obtained at room temperature.The Li^(+)transference number is 0.85 in Li|TELL|Li cell and can stably undergo charge-discharge cycles for 1400 h at a current density of O.1 mA/cm^(2),while the contrast sample is short-circuited after 634 h of cycling.The LiFePO_(4)|TELL|Li cell achieves a capacity retention of 78.93%after 200 cycles at 2 C.The LiFePO_(4) TLL Li cellonly gains the capacity retention of 51.9%after 50 cyclesat the same current density.So,the method adopted here may provide a new approach to realize a flexible solid-state electrolyte with high ion-conductivity.
基金Supported by the National Natural Science Foundation of China(Grant Nos.12361040,12061064)the National Science Foundation of Gansu Province(Grant No.22JR5RA264)State Scholarship Fund(Grant No.20230862021).
文摘In this article,we show the existence,uniqueness and stability of bounded solutions to the following quasilinear problems with mean curvature operator(φ'(x′(t)))′=f(t,x),t≥t_(0),lim_(t→∞)x(t)=ψ_(0),lim_(t→∞)x′(t)e^(t)=0,where t_(0) and ψ_(0) are real constants,φ(s)=s/√1−s^(2),s∈R with s∈(−1,1),f:[t_(0),∞)×R→R satisfies the Lipschitz or Osgood-type conditions.
文摘Circumlunar abort trajectories constitute a vital contingency return strategy during the translunar phase of crewed lunar missions.This paper proposes a methodology for constructing the solution set of the circumlunar abort trajectory and leverages its advantageous properties to address the optimization design problem of abort trajectories.Initially,a solution set of all feasible abort trajectories,originating from an abort point on the nominal trajectory and complying with fundamental reentry constraints,is formulated through the introduction of two novel design parameters.Subsequently,the geometric characteristics of the solution set,as well as the distributional properties of key iterative constraint responses,including flight time and velocity increment,are analyzed.Finally,the characteristics exhibited in the solution set are employed to directly identify the design parameters of the abort trajectories with minimum flight time and velocity increment,thereby providing solutions to two distinct types of optimization problems.The simulation results for a variety of nominal trajectories,encompassing the reconstruction and redesign of the Apollo13 abort trajectory,validate the proposed method,demonstrating its ability to directly generate optimal abort trajectories.The method proposed in this paper investigates feasible abort trajectories from a global perspective,providing both a framework and convenience for mission planning and iterative optimization in abort trajectory design.
基金supported by the National Natural Science Foundation of China(No.41941018)Shanghai Gaofeng Discipline Construction Funding.
文摘Strong seismic excitation and fault dislocation are likely to occur simultaneously in high-intensity seismic zones,causing severe damage to tunnels crossing active fault zones.This paper aims to develop a novel analytical solution to determine the longitudinal mechanical responses of tunnels subjected to the combined effects of seismic waves and strike-slip faulting.Adopting the elastic springbeam model,the seismic waves are modelled as shear horizontal(SH)waves and the fault dislocation follows an S-shaped pattern;the superposition principle for free-fielddisplacements caused by both effects is assumed.In addition,the transmission and reflectionof seismic waves at the fault-rock geological interface and the tangential contact conditions at the tunnel-rock interface are considered.The analytical model is validated against numerical simulations,confirmingits accuracy in calculating tunnel responses.Moreover,a parametric study is conducted to evaluate the impact of key factors,including fault displacement,fault zone width,fault dip angle,earthquake frequency,rock conditions,tunnel lining stiffness,and tangential contact conditions,on tunnel responses.Compared with each effect alone,the combined effects of seismic waves and strike-slip faulting significantlychange the tunnel deformation and internal forces,leading to increased tunnel responses,especially within the fault zone and near the fault-rock interfaces.Depending on specificparameters,tunnel responses can be classifiedinto seismic-dominated,faulting-dominated,and seismic-faulting coupled responses on the basis of the relative contributions of each effect.The proposed analytical solution can be applied to quickly predict the longitudinal mechanical behaviour of tunnels under such combined effects in engineering applications.
基金supported by the China Agriculture Research System(Grant No.CARS-23-D06)the Key Research and Development Program of Shaanxi Province(Grant Nos.2024NC2-GJHX-29 and 2024NC-ZDCYL-05-08)Shaanxi Agricultural Collaborative Innovation and Extension Alliance Project(Grant No.LMZD202202).
文摘Substrate and nutrient supply are essential for vegetable cultivation in greenhouse.The strategies for plant nutrient supply vary depending on the cultivation methods or substrate dosages employed.With the development of mechanization,wide-row spacing substrate cultivation became an optimize mode of the greenhouse cucumber cultivation,aligning with the trend of intelligent agriculture.To determine the optimal nutrient solution supply amount(NS)and supply frequency(SF)for promoting the integrated growth of cucumber under wide-row spacing substrate cultivation,we explored the effects of substrate supply amount(SS),NS,and SF on cucumber yield,quality,and element utilization efficiency.A five-level quadratic orthogonal rotation combination design with three experimental factors(NS,SF,and SS)was implemented for 23 coupling treatments over three growing seasons,including spring(2022S and 2023S)and autumn(2022A).The technique for order preference by similarity to ideal solution(TOPSIS)combining weights based on game theory was applied to construct cucumber comprehensive growth evaluation model.Single and two experimental factors analyses revealed significant effects of single factors and the coupling of NS-SS,NS-SF and SS-SF on the integrated growth of cucumber for all three growing seasons.For the NS-SF-SS combination,the optimal parameters for comprehensive cucumber growth were determined as follows:levels of^(-1).68 for NS,-0.7 for SF,and^(-1).682 for SS in 2022A;-0.43 for NS,-0.06 for SF,and 0.34 for SS in 2022S;0.3 for NS,-0.02 for SF,and 0.04 for SS in 2023S.Furthermore,for SS ranges of 2.00-3.01,3.01-4.50,4.50-5.99,5.99-7.00(L·plant^(-1)),the corresponding NS and SF intervals maximizing cucumber integrated growth in spring were:0.28-0.30(L·plant^(-1))and 6(times·d^(-1)),0.26-0.30(L·plant^(-1))and 6(times·d^(-1)),0.25-0.30(L·plant^(-1))and 6(times·d^(-1)),0.23-0.30(L·plant^(-1))and 6(times·d^(-1)),respectively.With the same SS,the corresponding NS and SF intervals that maximized cucumber integrated growth in autumn were:0.10(L·plant^(-1))and 8(times·d^(-1)),0.18(L·plant^(-1))and 7(times·d^(-1)),0.30(L·plant^(-1))and 6(times·d^(-1)),0.49(L·plant^(-1))and 5(times·d^(-1)),respectively.The results provide a theoretical basis for solution management,and further in-depth research on cucumber cultivation.
基金funded by the research startup funding of National Research Foundation (NRF) of Korea through the Ministry of Science and ICT 2022R1G1A1009887Part of this study was supported by research start-up funding of Anhui University (S202418001/078)。
文摘Doping in thin-film transistors(TFTs) plays a crucial role in tailoring material properties to enhance device performance, making them essential for advanced electronic applications. This study explores the synthesis and characterization of TFTs fabricated using nickel(Ni)-doped indium oxide(In_(2)O_(3)) via a wet-chemical approach. The presented work investigates the effect of "Ni" incorporation in In_(2)O_(3) on the structural and electrical transport properties of In_(2)O_(3), revealing that higher "Ni" content decreases the oxygen vacancies, leading to a reduction in leakage current and a forward shift in threshold potential(V_(th)).Experimental findings reveal that Ni In O-based TFTs(with Ni = 0.5%) showcase enhanced electrical performance, achieving mobility of 7.54 cm^(2)/(V·s), an impressive ON/OFF current ratio of ~10^(7), a V_(th) of 6.26 V, reduced interfacial trap states(D_(it)) of 8.23 ×10^(12) cm^(-2) and enhanced biased stress stability. The efficacy of "Ni" incorporation is attributed to the upgraded Lewis acidity, stable Ni-O bond strength, and small ionic radius of Ni. Negative bias illumination stability(NBIS) measurements further indicate that device stability diminishes with shorter light wavelengths, likely due to the activation of oxygen vacancies. These findings validate the solution-processed techniques' potential for future large-scale, low-cost, energy-efficient, and high-performance electronics.
基金supported by the National Science and Technology Major Project of the Ministry of Science and Technology of China(No.2024ZD1700201)the National Natural Science Foundation of China(Nos.U2034206,51974014 and 51574014)+1 种基金the Guangdong Basic and Applied Basic Research Foundation(No.2024A1515011631)the National Key Research and Development Project of China(No.2022YFC3004601)。
文摘In-situ stress is a key parameter for underground mine design and rock stability analysis.The borehole overcoring technique is widely used for in-situ stress measurement,but the rheological recovery deformation of rocks after stress relief introduces errors.To improve accuracy,this study proposes an in-situ stress solution theory that incorporates time-dependent stress relief effects.Triaxial stepwise loadingunloading rheological tests on granite and siltstone established quantitative relationships between instantaneous elastic recovery and viscoelastic recovery under different stress levels,confirming their impact on measurement accuracy.By integrating a dual-class elastic deformation recovery model,an improved in-situ stress solution theory was derived.Additionally,accounting for the nonlinear characteristics of rock masses,a determination method for time-dependent nonlinear mechanical parameters was proposed.Based on the CSIRO hollow inclusion strain cell,time-dependent strain correction equations and long-term confining pressure calibration equations were formulated.Finally,the proposed theory was successfully applied at one iron mine(736 m depth)in Xinjiang,China,and one coal mine(510 m depth)in Ningxia,China.Compared to classical theory,the calculated mean stress values showed accuracy improvements of 6.0%and 9.4%,respectively,validating the applicability and reliability of the proposed theory.
基金supported by the National Key R&D Program of China(2023YFA1406200)the National Natural Science Foundation of China(T2521005,12174144,12474009,12174146,and 124B2059)the Special Construction Project Fund for Shan-dong Province Taishan Scholars.
文摘Multifunctional optical responsive materials have grown increasingly pivotal in addressingthe escalating demands of sensing,detection,and anti-counterfeiting applications[1,2].These materials exhibit distinct visible optical variations upon exposure to external stimuli,such as pressure,temperature,light,solvents,pH fluctuations,or mechanical force.Fluorescent sensing and anti-counterfeiting technologies leveraging these optical responses have emerged as highly promising solutions.
基金supported by the National Key R&D Program of China (No. 2018YFA0707300)the National Natural Science Foundation of China (No. 52374376)the Introduction Plan for High end Foreign Experts, China (No. G2023105001L)。
文摘Titanium plates with a Ti−O solid solution surface-hardened layer were cold roll-bonded with 304 stainless steel plates with high work hardening rates.The evolution and mechanisms affecting the interfacial bonding strength in titanium/stainless steel laminated composites were investigated.Results indicate that the hardened layer reduces the interfacial bonding strength from over 261 MPa to less than 204 MPa.During the cold roll-bonding process,the hardened layer fractures,leading to the formation of multi-scale cracks that are difficult for the stainless steel to fill.This not only hinders the development of an interlocking interface but also leads to the presence of numerous microcracks and hardened blocks along the nearly straight interface,consequently weakening the interfacial bonding strength.In metals with high work hardening rates,the conventional approach of enhancing interface interlocking and improving interfacial bonding strength by using a surface-hardened layer becomes less effective.
文摘Generalised reduced masses with a set of equations governing the three relative motions between two of 3-bodies in their gravitational field are established,of which the dynamic characteristics of 3-body dynamics,fundamental bases of this paper,are revealed.Based on these findings,an equivalent system is developed,which is a 2-body system with its total mass,constant angular momentum,kinetic and potential energies same as the total ones of three relative motions,so that it can be solved using the well-known theory of the 2-body system.From the solution of an equivalent system with the revealed characteristics of three relative motions,the general theoretical solutions of the 3-body system are obtained in the curve-integration forms along the orbits in the imaged radial motion space.The possible periodical orbits with generalised Kepler’s law are presented.Following the description and mathematical demonstrations of the proposed methods,the examples including Euler’s/Lagrange’s problems,and a reported numerical one are solved to validate the proposed methods.The methods derived from the 3-body system are extended to N-body problems.
基金financial support of FEES-CONARE(Ref 115B5662)the University of Costa Rica(UCR)+1 种基金the Costa Rica Institute of Technology(TEC)the National Laboratory of Nanotechnology(LANOTEC)
文摘Irbesartan(IBS)is a tetrazole derivative and antihypertensive drug that has two interconvertible structures,1H-and 2H-tautomers.The difference between them lies in the protonation of the tetrazole ring.In the solid-state,both tautomers can be isolated as crystal forms A(1H-tautomer)and B(2H-tautomer).Studies have reported that IBS is a polymorphic system and its forms A and B are related monotropically.These reports indicate form B as the most stable and less soluble form.Therefore,the goal of this contribution is to demonstrate through a complete solid-state characterization,thermodynamic study and dissolution properties that the IBS forms are desmotropes that are not related monotropically.However,the intention is also to call attention to the importance of conducting strict chemical and in solid-state quality controls on the IBS raw materials.Hence,powder X-ray diffraction(PXRD)and Raman spectroscopy(RS)at ambient and non-ambient conditions,differential scanning calorimetry(DSC),hot stage microscopy(HSM),Fourier transform infrared(FT-IR)and scanning electron microscopy(SEM)techniques were applied.Furthermore,intrinsic dissolution rate(IDR)and structural stability studies at 98%relative humidity(RH),25℃and 40℃were conducted as well.The results show that in fact,form A is approximately four-fold more soluble than form B.In addition,both IBS forms are stable at ambient conditions.Nevertheless,structural and/or chemical instability was observed in form B at 40℃and 98%RH.IBS has been confirmed as a desmotropic system rather than a polymorphic one.Consequently,forms A and B are not related monotropically.
文摘An empirical solution to abnormal potential responses, showing peaks of emf, of commercial Cu2+- and Cd2+-selective electrodes with solid-state membranes was proposed for aqueous solutions of CuCl2 and CdI2. The two-step processes of Mn+ + Yn? (s: solid phase) MY(s) and MY(s) + 2X? X2MY2?(s) (n = 1, 2) at a test solution/electrode-interface were considered as a model. Here, Mn+, Yn?, and X? refer to a divalent or univalent cation, functional groups of electrode materials, and a halide ion (X? = Cl?, Br?, I?), respectively. By applying electrochemical potentials to these processes at n = 2, we derived an equation. Regression analyses based on the equation reproduced well the plots of emf versus log 2(*[M]t) for the Cd(II) and Cu(II) systems: *[M]t denotes a total concentration of species relevant to M2+ in a bulk of the aqueous solution. Also, we obtained log Ks(CdBr2) = 4.28 ? 0.22, log Ks(CdI2) = 6.98 ? 0.05, log Ks(CuCl2) = 3.96 ? 0.09, and log Ks(CuBr2) = 11.4 at 25?C. The magnitude in ?log Ks reflected that in the logarithmic solubility product, log {*[M2+](*[X?])2}, for bulk water, where *[M2+] or *[X?] denotes a molar concentration of the bulk solu-tion of M2+ or X? at equilibrium, respectively. Moreover, a mixture of CuSO4 with NaCl at the molar ratio of 1:1 yielded a plot similar to that of CuCl2.
文摘Fe^(3+) substituted ZSM-5 zeolite was studied using EPR and ^(27)A1,^(29)Si MAS-NMR spectroscopy.The results showed that the synthe- sized sample has the typical ZSM-5 structure with Fe^(3+) ionsincorporated in tetrahedric sites in the zeolite framework and there are some para- magnetic centers in the samples.
基金supported by the start-up fund(2017F0201-000-10)from ShanghaiTech Universitythe sponsorship by Double First-Class Initiative Fund of ShanghaiTech University(SYLDX0052022)the support from the Analytical Instrumentation Center(SPSTAIC10112914)at ShanghaiTech University.
文摘To characterize the structure and dynamics of metal--organic frameworks(MOFs)indepth at the molecular level,it is necessary to pursue high-resolution solid-state magic angle spinning(MAS)nuclear magnetic resonance(NMR)spectroscopy.Spectral resolution is usually affected by the quality of materials and various experimental conditions,of which magic angle(MA)accuracy is a crucial determinant.The current industrial criteria for MA calibration based on the common standard of KBr were found insufficient in guaranteeing optimal resolution MAS NMR for highly ordered MOFs.To drive towards higher-resolution MAS NMR spectroscopy,we propose_a calibration protocol for more accurate MA with a higher-precision criterion based on 79Br MAS NMR of KBr,where the linewidth ratio of the fifth-order spinning sideband to the central band of KBr should be less than 1.00.As a result,ultrahigh-resolution 13C cross-polarization(CP)MAS NMR of MOF-5 is achieved with minimal linewidths as low as 4 Hz,and therefore MOF-5 can be used as a new standard convenient for verifying MA accuracy and also optimizing 13c CP conditions.Maintaining high-precision MA under variable temperature(VT)was found challenging on certain commercial MAS NMR probes,as was systematically investigated by VT NMR using KBr and MOF-5.Nevertheless,ultrahigh-resolution MAS NMR spectroscopy with stable MA under VT is employed to reveal fine structures and linker dynamics of a series of Zn-based MOFs with highly regulated structures.The ultrahigh-resolution NMR methodcan be generally applied to study a broad range of MOFs and other materials.
