CHEMISTRY OF MATERIALS
·
2021
·
IF 9.811
Da Chen,Shiqiang Hao,Liubing Fan,Yangwu Guo,Jiyong Yao,Christopher Wolverton,Mercouri G. Kanatzidis,Jing Zhao,Quanlin Liu
Recent discoveries in organic−inorganic metal halides reveal superior semiconducting and polarization properties. Herein, we report three organic–inorganic metal halides, (PBA)4BiBr7·H2O, (PBA)4BiI7·H2O, and (PBA)4InBr7·H2O [(PBA)+ = C6H5(CH2)4NH3+], with band gaps of ∼3.52, ∼2.29, and ∼4.05 eV, respectively. They possess zero-dimensional structures containing the inorganic octahedra [MX6]3– (M = Bi, In, X = Br, I) and unbound X– ions and crystallize in the C2 space group. (PBA)4BiI7·H2O shows a second-harmonic-generation (SHG) response in the infrared region, approximately 1.3 times that of AgGaS2; (PBA)4BiBr7·H2O and (PBA)4InBr7·H2O show SHG responses in the ultraviolet region, approximately 0.4 and 0.6 times that of KH2PO4, respectively. The large SHG responses are attributed to the synergistic contribution of the octahedral distortion of [MX6]3– (M = Bi, In, X = Br, I) and the ordered arrangement of the benzene ring-containing organic cation PBA+. Upon ultraviolet and visible-light excitations at room temperature, (PBA)4BiBr7·H2O, (PBA)4BiI7·H2O, and (PBA)4InBr7·H2O exhibit broad red-light luminescence with large Stokes shifts of 290, 237, and 360 nm, respectively, due to self-trapped exciton emission. All of these properties demonstrate that this series of metal halides are potential multifunctional optoelectronic materials.
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高影响因子
JOURNAL OF CHEMICAL THERMODYNAMICS
·
2021
·
IF 3.178
Qi-Chao Yang,Dong-Fang Qiu,Yuan-Lin Dang,Zhan-Ping Qiao,Zhi-wei Xu
Two equilibrium diagrams of the ternary system (CsX + MnX 2 + H 2 O, X = Cl, Br) at 298.15 K are reported in this paper. Each system has two double salts (CsMnX 3 ·2H 2 O and Cs 2 MnX 4 ·2H 2 O X = Cl, Br) in it and the elements of all double salts in phase diagrams are confirmed by Schreinemaker method. Equilibrium phase diagrams show that the chloride double salts are congruently soluble compounds in water, however that the bromide double salts are incongruently soluble compounds in water. All the double salts are characterized by titrimetric analysis, powder X-ray diffraction, thermogravimetric and differential thermalanalysis. The enthalpies of formation of these double salts are first calculated by measuring their enthalpies of dissolution.
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高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Shuailong Shen,Ziyi Guo,Wanmei Zhong,Jilin Zhang,Wenli Zhou,Liping Yu,Shixun Lian
All inorganic CsPbX 3 (X = Cl, Br, I) perovskite quantum dots (QDs) have excellent optical properties, and show great potential in optoelectronic devices, information storage, wide color gamut backlight display and other fields. In previous work, embedding CsPbBr 3 QDs into glass matrix through in-situ crystallization has become an important strategy to improve the stability of quantum dots. However, few reports have been made on the synthesis of high-quality whole family CsPbX 3 QDs glass by melt-quenching method. Herein, CsPbX 3 QDs glasses with full visible spectrum were synthesized by a closed melt-quenching technique. And the precise content of GeO 2 was used to regulate the size of glass network gaps to accommodate different sizes of CsPbX 3 QDs. The deconvoluted infrared spectra confirmed that the introduction of GeO 2 was beneficial to the increase of non-bridging oxygen in the rigid structure, the number and percentage of [BO 3 ] triangular units increased correspondingly, and the glass network changed in a three-dimensional and looser benign way, which was beneficial to the growth of large-size QDs. Finally, the luminescent properties of CsPbCl 2 Br, CsPbBr 3 and CsPbBrI 2 QDs glasses were improved respectively. The optimized CsPbX 3 QDs glasses have tunable luminescence in the full visible spectrum (414–692 nm), improved photoluminescence quantum yield (PLQY, ∼53.06 %) and longer decay lifetime, and excellent stability. Finally, the construction of a white light-emitting diode (WLED) device shows that CsPbX 3 QDs glass has potential applications in solid-state lighting.
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高影响因子
JOURNAL OF CHEMICAL THERMODYNAMICS
·
2024
·
IF 2.2
Yufeng Tang,Qichao Yang,Zhanping Qiao
The phase equilibrium of ternary systems RbX/CsX + CuX 2 + H 2 O (X = Cl, Br) at T = 298.15 K were investigated by the isothermal dissolution equilibrium method, in which the composition of equilibrium solid phases was determined by the Schreinemaker’s wet residue method. In the system RbCl + CuCl 2 + H 2 O, there were three crystallization regions corresponding to RbCl, Rb 2 CuCl 4 ·2H 2 O and CuCl 2 ·2H 2 O, respectively. Five crystallization fields corresponding to CsCl, CsCuCl 3 , Cs 3 Cu 2 Cl 7 ·2H 2 O, Cs 2 CuCl 4 and CuCl 2 ·2H 2 O were formed in the system CsCl + CuCl 2 + H 2 O. The ternary system RbBr + CuBr 2 + H 2 O had three crystalline regions corresponding to RbBr, Rb 2 CuBr 4 ·2H 2 O and CuBr 2 . In the system CsBr + CuBr 2 + H 2 O, the solid-phases of CsCuBr 3 , Cs 2 CuBr 4 , besides CsBr and CuBr 2 , were discovered. The results were compared with available literature data for cesium bromide/copper bromide salt-water system. The seven new solid phase were characterized using the X-ray diffraction method and thermogravimetric/differential analysis. The dissolution enthalpies of Rb 2 CuCl 4 ·2H 2 O, Rb 2 CuBr 4 ·2H 2 O, CsCuCl 3 , Cs 3 Cu 2 Cl 7 ·2H 2 O, Cs 2 CuCl 4 , CsCuBr 3 and Cs 2 CuBr 4 at T = 298.15 K were measured. Their standard enthalpies of formation were obtained, and the results were in order with −(1714.4 ± 3.2) kJ·mol −1 , −(1533.6 ± 3.3) kJ·mol −1 , −(697.8 ± 3.1) kJ·mol −1 , −(2418.9 ± 6.1) kJ·mol −1 , −(1134.8 ± 3.2) kJ·mol −1 , −(563.5 ± 3.2) kJ·mol −1 and −(966.2 ± 3.3) kJ·mol −1 , respectively.
研究领域:
物理化学
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无机化学
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热力学
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高影响因子
Advanced Science
·
2023
·Vol. 10
·期 13
·2207630
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IF 15.1
Wen-Fa Chen,Bin-Wen Liu,Shao-Min Pei,Xiao-Ming Jiang,Guo-Cong Guo
In contrast to anionic group theory of nonlinear optical (NLO) materials that second-harmonic generation (SHG) responses mainly originate from anionic groups, structural regulation on the cationic groups of salt-inclusion chalcogenides (SICs) is performed to make them also contribute to the NLO effects. Herein, the stereochemically active lone–electron-pair Pb 2+ cation is first introduced to the cationic groups of NLO SICs, and the resultant [K 2 PbX][Ga 7 S 12 ] (X = Cl, Br, I) are isolated via solid-state method. The features of their three-dimensional structures comprise highly oriented [Ga 7 S 12 ] 3− and [K 2 PbX] 3+ frameworks derived from AgGaS 2 , which display the largest phase-matching SHG intensities (2.5−2.7 × AgGaS 2 @1800 nm) among all SICs. Concurrently, three compounds manifest band gap values of 2.54, 2.49, and 2.41 eV (exceeding the criterion of 2.33 eV), which can avoid two-photon absorption under the fundamental laser of 1064 nm, along with the relatively low anisotropy of thermal expansion coefficients, leading to improved laser-induced damage thresholds (LIDTs) values of 2.3, 3.8, and 4.0 times that of AgGaS 2 . In addition, the density of states and SHG coefficient calculations demonstrate that the Pb 2+ cations narrow the band gaps and benefit SHG responses.
研究领域:
材料科学
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光学
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高影响因子
DALTON TRANSACTIONS
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2021
·Vol. 50
·期 33
·11555-11561
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IF 4.39
Jinhui Wang,Xinyuan Zhang,Fei Liang,Zhanggui Hu,Yicheng Wu
Birefringent crystals with strong anisotropy are important components in modern optical devices. The newly discovered planar π-conjugated cyanurate group (HxC3N3O3)x−3 (x = 0–3) has been demonstrated as an effective functional motif for improving birefringence in the ultraviolet region. Here, single co-crystals of alkali halide cyanurates, RbBr·(H3C3N3O3) (I), RbI·(H3C3N3O3) (II), and CsBr·(H3C3N3O3) (III) were synthesized by the ethanol solution method, and NaBr·(H3C3N3O3) (IV) was obtained via the solvent-drop grinding method. These four co-crystals feature a planar (H3C3N3O3) arrangement and exhibit wide band gaps (> 4.90 eV), tunable birefringence (Δnexp ∼ 0.124–0.256), and high thermal stability (156 °C–349 °C). In addition, first principles calculations were also carried out to evaluate the relationship between molecule density, spatial arrangement and optical birefringence, and suggested a great tailoring effect of the alkali metal and halogen species on regulating the optical anisotropy of co-crystal cyanurates.
研究领域:
材料科学
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晶体工程
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光学材料
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无机化学
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功能材料
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DOI
高影响因子
JOURNAL OF CHEMICAL THERMODYNAMICS
·
2021
·
IF 3.178
Yaqi Ding,Neng Gao,Nian Li,Guangming Chen,Yongmei Xuan
The vapour-liquid equilibrium (VLE) data of four ternary solutions HCOOK + [Emim]Ac /[Emim]Br / [Emim]Cl / [Emim]NO 3 + H 2 O were measured using the boiling method at the temperatures from 305.78 K to 387.08 K, at solute (HCOOK + IL) mass fractions ( w ) between 0.2 and 0.5. A total of 234 data points ( w = 0 included) were obtained and correlated with empirical Antoine-type equations. The absolute average relative deviations (AARD %) between calculated and measured vapour pressures were 0.58%, 0.50%, 0.49%, 0.63%, respectively, which showed good agreement. The comparison of the experimental and standard data and combined uncertainties of the experimental data confirmed good reliability of the experimental method and apparatus. The four ternary solutions with ILs as additives have lower vapour pressure compared to the corresponding binary solutions without ILs. The results showed that the four ternary solutions of HCOOK + [Emim]Ac / [Emim]Br / [Emim]Cl / [Emim]NO 3 + H 2 O can be the alternatives for traditional dehumidification and absorption media. [Emim]Cl has the best ability to reduce the vapour pressure of HCOOK + H 2 O at the solute (HCOOK + IL) mass fraction of 0.4 and 0.5. The [Emim]Ac has the most effect reducing the vapour pressure of HCOOK + H 2 O at the solute (HCOOK + IL) mass fraction of 0.3.
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高影响因子
JOURNAL OF CHEMICAL THERMODYNAMICS
·
2020
·
IF 2.888
Zhan-Ping Qiao,Tian Yang,Shu-Zhi Cao,Yu-Feng Tang,Qi-Chao Yang
Solid-liquid equilibria in the ternary systems RbX + CdX 2 + H 2 O (X = Cl, Br) at T = 298.15 K and under 101.3 kPa were investigated by the method of isothermal solution saturation, and the corresponding phase diagrams were constructed. It was found that there were five crystallization regions corresponding to CdCl 2 ·2.5H 2 O, RbCd 2 Cl 5 ·H 2 O, RbCdCl 3 , Rb 4 CdCl 6 and RbCl in the system (RbCl + CdCl 2 + H 2 O). Four crystallization regions corresponding to CdBr 2 ·4H 2 O, RbCdBr 3 , Rb 4 CdBr 6 and RbBr were found in the system (RbBr + CdBr 2 + H 2 O). The new solid compounds RbCdCl 3 , RbCdBr 3 and Rb 4 CdBr 6 were congruently soluble in water, and new double salts RbCd 2 Cl 5 ·H 2 O and Rb 4 CdCl 6 were incongruently soluble in water. The new solid-phase compounds RbCd 2 Cl 5 ·H 2 O, RbCdCl 3 , Rb 4 CdCl 6 , RbCdBr 3 and Rb 4 CdBr 6 were characterized by chemical analysis, XRD and TG-DTG techniques. The standard molar enthalpies of solution of RbCd 2 Cl 5 ·H 2 O, RbCdCl 3 , Rb 4 CdCl 6 , RbCdBr 3 and Rb 4 CdBr 6 in water were measured to be (20.74 ± 0.16) kJ·mol −1 , (28.00 ± 0.39) kJ·mol −1 , (96.56 ± 0.50) kJ·mol −1 , (35.38 ± 0.33) kJ·mol −1 and (110.64 ± 0.62) kJ·mol −1 by microcalorimetry in the condition of infinite dilution, and their standard molar enthalpies of formation were determined to be −(1545.3 ± 0.6) kJ·mol −1 , −(856.5 ± 0.7) kJ·mol −1 , −(2180.1 ± 1.3) kJ·mol −1 , −(727.1 ± 0.7) kJ·mol −1 and −(1920.5 ± 1.3) kJ·mol −1 , respectively.
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高影响因子
INORGANIC CHEMISTRY
·
2025
·
IF 4.7
Jiantao Yuan,Nan Zhang,Jian Zhang,Xian-Ming Zhang
Single-crystal-to-single-crystal (SCSC) transformation materials are of great research interest because of their promising applications, among which multifunctional switching as next-generation intelligent materials in photoelectric devices is rare, and the corresponding mechanism remains unclear. Herein, we present two organic–inorganic hybrid antimony halides, namely (H2dach)2Sb2Br10·4H2O (1) and (H2dach)SbBr5 (2) (dach = 1,2-diaminocyclohexane) and their reversible mutual SCSC transformation. 1 and 2 adopt zero-dimensional discrete butterfly-like [Sb2Br10]4– dimers and one-dimensional infinite [SbBr5]n2n– chains, respectively, possessing abundant Sb···Br secondary bonds due to the strong stereochemical activity of 5s2 lone-pair electrons in Sb(III). Detailed structural analyses reveal that the reversible SCSC transformation is triggered by the rearrangement of Sb···Br secondary bonds, which enables the 25-time modulation of electron self-trapped photoluminescence with broadband orange emission. Humidity-dependent photoluminescence behavior of dehydrated 2 was also observed, which can be used to sense trace amounts of water. Furthermore, SCSC transformation via dehydration–rehydration could tailor hydrogen-bonding networks, resulting in switchable proton conductivity. The simulated kinetic mechanism of SCSC transformation by DFT is in agreement with the experimentally observed rearrangement of Sb···Br secondary bonds. This work demonstrates that the rearrangement of Sb···Br in hybrid halide systems is beneficial for elucidating dynamic transformation processes and promoting the development of multifunctional materials.
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PubMed
高影响因子
INORGANIC CHEMISTRY
·
2024
·
IF 4.3
Mengmeng Zhu,Junbo Wang,Lei Hou,Yiwen Yuan,Lili Liu,Yaoqing Chu,Chunmei Huang
The design and syntheses of new birefringent crystals will be of great importance in commercial applications and materials science. A series of ultraviolet (UV) birefringent crystals, AX·(H2SeO3)n (A = K, Cs; X = Cl, Br; n = 1, 2), with large sizes up to 23 × 6 × 3 mm3, was successfully synthesized by simple aqueous solution method. These four compounds belong to three different space groups. Isomorphic KCl·(H2SeO3)2 and CsCl·(H2SeO3)2 crystallize in the P1¯ space group, while CsBr·(H2SeO3)2 and CsCl·H2SeO3 crystallize in the P21/m and P21/c space groups, respectively. They exhibit cocrystal structures composed of [2(H2SeO3)]∞ and [AX]∞ frameworks, ingeniously inheriting the large optical anisotropy of selenite and the wide band gap of alkali metal halide. And it proves that these compounds indeed possess large birefringence (0.1–0.17 at 532 nm) and short UV cutoff edges (227–239 nm), achieving a balance of optical properties. This research affords a simple and viable strategy for the design and syntheses of new UV birefringent crystals. Besides, it is also found that the n value and ionic size (A and X ions) have important influences on the crystal structures and optical properties of AX·(H2SeO3)n. And this will promote further understanding of the alkali metal halide selenite family.
研究领域:
材料科学
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晶体工程
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光学材料
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无机化学
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高影响因子
CHEMISTRY OF MATERIALS
·
2024
·
IF 7.2
Yan Guo,Bin-Wen Liu,Chao-Hong Xie,Wen-Fa Chen,Ming-Xin Li,Xiao-Ming Jiang,Guo-Cong Guo
Rare-earth infrared nonlinear optical (IR NLO) compounds have garnered significant attention due to their abundant electronic structures. However, their NLO efficiency has been relatively modest, attributed to the localization of valence electron shells in rare-earth metals. Traditional design strategies for IR NLO materials have predominantly focused on MQ4 (M = metal, Q = S or Se) tetrahedra, with limited exploration of MQ6 octahedra. We introduce a novel approach to enhance NLO effects by incorporating distorted mixed anionic octahedral M(S/X)6 groups. To illustrate this strategy, we undertake structure modification and optimization of IR NLO performance using the Y–Ga–Ge–S system as an example. The synthesis of a new rare-earth chalcogenide, Y6Ga2GeS14 (1), serves as a foundation. Further halogen atom substitution yields Y6Ga4.2S13.6Cl3.4 (2), Y6Ga2.83Ge2S16.75Cl (3), and Y6Ga2.83Ge2S16.5Br1.5 (4). All compounds demonstrate remarkable NLO performance, including moderate NLO coefficients (0.17–0.70 × AgGaS2), large laser-induced damage thresholds (LIDTs) (3.78–6.19 × AgGaS2), and a broader transmission range (0.5–14.9 μm). The incremental enhancement of NLO efficiency in compounds 1–4 can be attributed to symmetry breaking induced by halogen atom substitution and increased distortion of the octahedral M(S/X)6 motifs in their structures, validating the effectiveness of our strategy. Notably, this strategy concurrently increases the band gap and LIDT, overcoming the NLO–LIDT incompatibility, being strikingly different from other reported approaches. This work provides new insights into optimizing the NLO performance of rare-earth IR NLO compounds through the modulation of octahedral motifs.
研究领域:
材料科学
·
光学
·
化学
·
物理学
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高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2022
·
IF 4.326
Heng Ban,Youwei Cheng,Lijun Wang,Xi Li
2,5-Furandicarboxylic acid (FDCA) derived from biomass is a versatile platform chemical for producing various degradable polymers, especially polyethylene 2,5-furandicarboxylate (PEF). To reduce the high cost of feedstock, fructose instead of expensive 5-hydroxymethylfurfural (HMF) was used as the feedstock for producing FDCA in the acetic acid (HOAc) solvent by a one-pot, two-step method. Fructose was first catalytically converted into HMF and 5-acetoxymethylfurfural (AMF) in HOAc over the Amberlyst-15 catalyst. After the separation of only Amberlyst-15, the in situ-formed HMF and AMF were further catalytically oxidized to FDCA by air (oxygen) over homogeneous Co/Mn/Br catalysts following the free-radical chain reaction mechanism. HOAc was not only used as the solvent for the dehydration and following oxidation process but also served as the effective co-catalyst for the dehydration of fructose. The effects of catalyst species, dosage, and reaction temperature on the dehydration process and oxidation temperature on FDCA yield and purity were evaluated systematically. Under the optimized reaction conditions, a total yield of HMF and AMF of 50% and a final FDCA yield of 35% were achieved. Combined with experimental results and theoretical calculation, the reaction mechanism for fructose dehydration side reactions and the HMF and AMF oxidation reactions was proposed correspondingly. The proposed two-step, one-pot method using fructose as the starting material is a promising route for the commercial production of FDCA with the simple operation and viable yield.
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