The Principle of Introducing Halogen Ions Into β-FeOOH: Controlling Electronic Structure and Electrochemical Performance

Coordination tuning electronic structure of host materials is a quite effective strategy for activating and improving the intrinsic properties.Herein,halogen anion(X-)-incorporated β-FeOOH(β-FeOOH(X),X=F-,Cl-,and Br-) was investigated with a spontaneous adsorption process,which realized a great improvement of supercapacitor performances by adjusting the coordination geometry.Experiments coupled with theoretical calculations demonstrated that the change of Fe-O bond length and structural distortion of β-FeOOH,which is rooted in halogen ions embedment,led to the relatively narrow band gap.Because of the strong electronegativity of X-,the Fe element in β-FeOOH(X)s presented the unexpected high valence state(3+δ),which is facilitating to adsorb S032-species.Consequently,the designed β-FeOOH(X)s exhibited the good electric conductivity and enhanced the contact between electrode and electrolyte.When used as a negative electrode,the β-FeOOH(F) showed the excellent specific capacity of 391.9 F g-1 at 1 A g-1 current density,almost tenfold improvement compared with initial β-FeOOH,with the superior rate capacity and cyclic stability.This combinational design principle of electronic structure and electrochemical performances provides a promising way to develop advanced electrode materials for supercapacitor.

Preliminary Theoretical Studies on the Combination of Halogen Ions with Crown Tetraalanylpeptide

The density functional theory based hybrid-method B3LYP was used to investigate the interaction of the halogen ions with crown tetraalanylpeptide which was the coronary structures of homodetic cyclotetraalapeptide and was represented as the model basic. Many properties including combination energy, optimum geometry structures and population analysis were calculated. It was shown that there was scarcely any change in the coronary structure of C4-Ala after combination with X. The electrons moved from halogen ions to C4-Ala during the combining process. Combination of C4-Ala with F was obviously stronger than that of Cl^- and Br. When the energy of C4-Ala-X was at minimum, the distances between halogen ions and the center of C4-Ala were 0.084 nm, 0.210 nm and 0.200 nm, respectively.

A pillar[5]arene-based side-chain pseudorotaxanes and polypseudorotaxanes as novel fluorescent sensors for the selective detection of halogen ions

A pseudorotaxane and its polypseudorotaxanes formed between pillar[5]arene moieties and noctylpyrazinium cations as novel fluorescent sensors for the selective detection of halogen ions were reported.A collapse of these pillar[5]arene-based pseudorotaxanes and polypseudorotaxanes occurred upon the addition of Cl,Br,and I（tetrabutylammonium salts）,respectively,leading to their fluorescence recovery.The fluorescence enhancement of the pseudorotaxane and the polypseudorotaxanes increases in the order of I

Halide-Anion Water Clusters in Cucurbit[6]uril Supramolecular Systems

Three types of dihalide water clusters [X2（H20）8]2 （X=Cl, Br） and [I2（H20）10]^2- have been observed in cucurbit[6]uril supramolecular systems with same guest. According to the single crystal data and the quantitative theory computation, with the increase of electronegativity of halide ions, dihalide water clusters become more stable. A further comparison of three kinds of guests with different molecule length but the same anions, [p-phenylenediamine salt, hexamethylenediamine salt and N,N＇-hexamethylenebis（pyrazinylbromide）], gives the result that the dihalide water clusters collapse from 2D to 1D with the increase of the lengths.

Energy transfer process of Nd^(3+)/Ho3+co-doped fluoride halide glasses with anion substituted multi-wavelength tunable mid-infrared luminescence

Ho^(3+)doped ZBLAN glass with 2.0 and 2.9μm emission was prepared.In order to further improve the luminescence of Ho^(3+),halogen ions(Cl,Br,1)were introduced to reduce the maximum phonon energy and phonon state density of the sample.At the same time,Nd^(3+)was introduced to transfer the energy to Ho^(3+)pumped with a 793 nm laser(Nd^(3+):4 F5/2,4 F3/2→Ho^(3+):5 I6).The effect of different halogen ion on the luminescent properties of the fluoride halide glass was compared.The results show that the luminescent intensity of infrared increases with the introduction of different halogen ions.By comparison,it is found that the sample with I-has the strongest luminescence of 1064 nm,2.0μm and 2.9μm.This is consistent with the calculated J-O intensity parameters.In addition,the 2.0 and 2.9μm emission of Ho^(3+)pumped with a 450 nm laser will not disappear.A mid-infrared sample with multi-wavelength excitation and multi-wavelength emission can be obtained.Nd^(3+)/Ho^(3+)co-doped fluoride halide glasses with 1064 nm,2.0μm and 2.9μm luminescence were prepared by melt quenching method.The luminescent mechanism and the energy transfer process between the two ions of Nd^(3+)/Ho^(3+)co-doped fluoride halide glass were studied.The J-O parameters,luminescence lifetime and absorption emission cross-sectional area of Ho^(3+)and Nd^(3+)were calculated,respectively.It is found that the value ofΩ2 in the glass matrix increases with the introduction of different halogen ions,whileΩ4 andΩ6 do not change obviously in different glass compositions.This is because the environment of the crystal field around the rare earth ions changes.The crystal phase and phonon energy of the sample were analyzed by X-ray diffraction pattern and a Fourier transform infrared spectrometer,respectively.Based on the above spectra and data(phonon energy is 634.71 cm-1),it can be predicted that Nd^(3+)/Ho^(3+)co-doped fluoride halide glass is a potential mid-infrared luminescent material.