A solubility limited pyrene-4,5,9,10-tetraone-based covalent organic framework for high-performance aqueous zinc-organic batteries

Pyrene-4,5,9,10-tetraone(PTO),with a high theoretical capacity of 408 mAh·g^(−1),is a promising candidate for rechargeable aqueous zinc-ion batteries(RAZIBs),but its zincated products during discharge process suffer from high solubility in electrolytes.Herein,aβ-ketoenamine-linked two-dimensional(2D)covalent organic framework(COF)based on a 2,7-diaminopyrene-4,5,9,10-tetraone(4KT-BD)monomer and a 2,4,6-trihydroxy-benzene-1,3,5-tricarbaldehyde(Tp)node(4KT-Tp-COF)is synthesized to address the above issue.The well-designed 4KT-Tp-COF displays low solubility in 3 M Zn(CF3SO3)2 owing to the favorableπ-πstacking as well as extended structure.Besides,the ingenious structural design of the active molecule and the long-range ordered nano-channels alter the intramolecular electron distribution,which facilitates the ionic diffusion.Consequently,the 4KT-Tp-COF cathode exhibits a stable capacity of 181 mAh·g^(−1)at 0.2 A·g^(−1),superior rate capability of 139 mAh·g^(−1)at 20 A·g^(−1),and a long lifetime of 1000 cycles without capacity loss at 30 A·g^(−1).Even at a low temperature of−20°C,the electrode also performs an ultralong cycling life of 9000 cycles with a capacity of 106 mAh·g^(−1)at 5 A·g^(−1).The comprehensive characterizations of ex-situ analyses together with the theoretical calculations validate that the groups of C=O can contribute highly accessible redox-active sites for Zn^(2+)storage.The ultra-stable 4KT-Tp-COF cathode provides important insights for designing robust organic electrodes for sustainable and large-scale electrochemical energy storage.

Insights into grain boundary segregation and solubility limit of Cr in(TiZrNbTaCr)C

Dense(TiZrNbTaCr)C with Cr segregation along grain boundaries(GBs)has been first proposed and fabri-cated by pressureless sintering at 1800-2000℃,utilizing the self-synthesized carbide powders obtained by carbothermal reduction.Cr segregation along GBs is successfully realized as expected via optimizing the initial Cr content.When Cr content is more than 11.12 at.%,Cr addition is excessive and results in Cr-rich second phase formation at triple junctions.To analyze the Cr solubility dependence on tempera-ture and initial Cr content,the Cr content in(TiZrNbTaCr)C grains is investigated by EDS.The solubility limit of Cr in(TiZrNbTaCr)C is about 3.8 at.%at 1900℃.Finally,Vickers hardness of all the samples is measured to assess the mechanical property of(TiZrNbTaCr)C ceramics.The basic understanding of the Cr solubility limit and GB segregation feature in(TiZrNbTaCr)C have been preliminarily clarified,which may pave a potential way to design and tailor microstructure and GB feature of(TiZrNbTaCr)C for the purpose of enhancing its properties in the future.

On the Numerical Modeling of the Deep Mantle Water Cycle in Global-Scale Mantle Dynamics:The Effects of the Water Solubility Limit of Lower Mantle Minerals

Water is the most important component in Earth system evolution. Here, I review the current understanding of the fate of water in the mantle dynamics system based on high-pressure and temperature experiments, geochemical analyses, seismological and geomagnetic observations, and nu- merical modeling of both regional- and giobal-scale mantle dynamics. In addition, as a numerical ex- ample, I show that the water solubility of the deep mantle is strongly sensitive to global-scale water cir- culation in the mantle. In a numerical example shown here, water solubility maps as functions of tem- perature and pressure are extremely important for revealing the hydrous structures in both the mantle transition zone and the deep mantle. Particularly, the water solubility limit of lower mantle minerals should be not so large as ~100 ppm for the mantle transition zone to get the largest hydrous reservoir in the giobal-scale mantle dynamics system. This result is consistent with the current view of mantle water circulation provided by mineral physics, which is also found as a hydrous basaltic crust in the deep mantle and the water enhancement of the mantle transition zone simultaneously. In this paper, I also discuss some unresolved issues associated with mantle water circulation, its influence on the onset and stability of plate motion, and the requirements for developing Earth system evolution in mantle dy- namics simulations.

Improved microwave dielectric properties of MgAl_(2)O_(4)spinel ceramics through(Li_(1/3)Ti_(2/3))^(3+)doping

A series of nominal compositions MgAl_(2-x)(Li_(1/3)Ti_(2/3))_(x)O_(4)(x=0,0.04,0.08,0.12,0.16,and 0.20)ceramics were successfully prepared via the conventional solid-state reaction route.The phase compositions,microstructures,and microwave dielectric properties were investigated.The results of x-ray diffraction(XRD)and scanning electron microscopy(SEM)showed that a single phase of MgAl_(2-x)(Li_(1/3)Ti_(2/3))_(x)O_(4)ceramics with a spinel structure was obtained at x≤0.12,whereas the second phase of MgTi_(2)O_(5)appeared when x>0.12.The cell parameters were obtained by XRD refinement.As the x values increased,the unit cell volume kept expanding.This phenomenon could be attributed to the partial substitution of(Li_(1/3)Ti_(2/3))^(3+)for Al^(3+).Results showed that(Li_(1/3)Ti_(2/3))^(3+)doping into MgAl_(2)O_(4)spinel ceramics effectively reduced the sintering temperature and improved the quality factor(Q_f)values.Good microwave dielectric properties were achieved for a sample at x=0.20 sintering at 1500℃in air for 4 h:dielectric constantε_(r)=8.78,temperature coefficient of resonant frequencyτ_(f)=-85 ppm/℃,and Q_(f)=62300 GHz.The Q_(f)value of the x=0.20 sample was about 2 times higher than that of pure MgAl_(2)O_(4)ceramics(31600 GHz).Thus,MgAl_(2-x)(Li_(1/3)Ti_(2/3))_(x)O_(4)ceramics with excellent microwave dielectric properties can be applied to 5G communications.

Preparation of Fe_x Ce_(1-x) O_y solid solution and its application in Pd-only three-way catalysts

FeOx-CeO2 mixed oxides with increasing Fe/（Ce＋Fe） atomic ratio （1-20 mol%） were prepared by sol-gel method and characterized by X-ray powder diffraction （XRD）, Brunauer-Emrnett-Teller （BET） and Hydrogen temperature-programmed reduction （H2-TPR） techniques. The dynamic oxygen storage capacity （DOSC） was investigated by mass spectrometry with CO/O2 transient pulses. The powder XRD data following Rietveld refinement revealed that the solubility limit of iron oxides in the CeO2 was 5 mol% based on Fe/（Ce＋Fe）. The lattice parameters experienced a decrease followed by an increase due to the influence of the maximum solubility limit of iron oxides in the CeO2. TPR analysis revealed that Fe introduction into ceria strongly modified the textual and structural properties, which influenced the oxygen handling properties. DOSC results revealed that Ce-based materials containing Fe oxides with multiple valences contribute to the majority of DOSC. The kinetic analysis indicated that the calculated apparent kinetic parameters obey the compensation effect. The three-way catalytic performance for Pd-only catalysts based on the Fe doping support exhibited the redundant iron species separated out of the CeO2 and interacted with the ceria and Pd species on the surface, which seriously influenced the catalytic properties, especially after hydrothermal aging treatment.