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JOURNAL OF CHEMICAL THERMODYNAMICS · 2024 · IF 2.2

Phase equilibria in the RbX/CsX + CuX2 + H2O (X = Cl, Br) systems at T = 298.15 K and the standard enthalpies of formation of seven double salts

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 · 无机化学 · 热力学
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Inorganic Chemistry Frontiers · 2023 ·Vol. 10 ·期 11 ·3319-3325 · IF 7

Quasi-linear CuX2 (X = Cl, Br) motif-built hybrid copper halides realizing encouraging nonlinear optical activities

Jing-Li Qi,Jiajing Wu,Yue Guo,Zhong-Ping Xu,Wenlong Liu,Sheng-Ping Guo

The emerging organic–inorganic hybrid metal halides feature unique optical and electronic properties, are easily grown and have flexible crystal structures, making them a class of promising next-generation nonlinear optical (NLO) and ferroelectric materials. Herein, we successfully synthesized two centimeter-level zero-dimensional copper halide organic–inorganic hybrids (C20H20P)CuX2 (X = Cl, Br) that are crystallized in the monoclinic noncentrosymmetric P21 space group. Their structures contain rare quasi-linear [CuX2]– anions and [C20H20P]+ cations. (C20H20P)CuCl2 and (C20H20P)CuBr2 crystals show phase-matchable NLO effects around 1.1 and 0.87 times that of benchmark KDP, respectively. These (C20H20P)CuX2 materials are the first NLO-active examples in the hybrid copper(I) halide family containing a quasi-linear CuX2 unit.

研究领域: 材料科学 · 光学
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Small · 2023 · IF 13.3

Synthesis-Kinetics of Violet- and Blue-Emitting Perovskite Nanocrystals with High Brightness and Superior Stability toward Flexible Conversion Layer

Cong Xie,Xiao Zhang,Hsueh Shih Chen,Ping Yang

The low photoluminescence (PL) efficiency and unstable features of small blue-emitting CsPbX 3 nanocrystals (NCs) greatly limit their applications in optoelectronics field. Herein, the synergistic and post-treatment kinetics are studied to create highly bright and anomalous stable violet (peak position of ≈408 nm) and blue (peak position of ∼ 466 nm) emitting perovskite NCs. Ligand and ion exchange mechanism are systematic studied by the evolution of absorption, PL, and fluorescence lifetime to evaluate ligand bonding, defect engineering, and non-radiative recombination. Didodecyl dimethyl mmonium chloride (DDAC) and CuX 2 post-synergistic treatment created DDAC-CsPbCl 3 -CuCl 2 and DDAC-CsPbCl 3 -CuBr 2 NCs that remained the phase composition, morphology, and size of CsPbCl 3 NCs. The PL efficiencies are drastically increased to 42 and 85% for violet- and blue-emitting NCs, respectively. The stability test indicated that the NCs enable against various harsh conditions (e.g., ultraviolet light irradiation and heat-treatment). The NCs retained their initial PL efficiency after 2 months under ambient conditions and UV light irradiation. These NCs also exhibited high stability after heat-treatment at 120 °C. The emitting NCs embedded in flexible films still revealed bright PL and high stability, suggesting current results provide a new avenue for the application in the field of optoelectronics.

研究领域: 材料科学 · 光电 · 纳米技术
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Communications Chemistry · 2025 ·Vol. 8 ·期 1 ·1-11 · IF 6.2

Soda lignin as a sustainable photosensitive component for conventional and controlled radical photopolymerization

Wang Min,Luo Xiongfei,Wang Qunying,Strehmel Veronika,Chen Zhijun,Li Shujun,Strehmel Bernd

Valorization of waste for chemical processes addresses a challenging task for the society. Soda lignin ( AL ) available in the pulp industry operated in a photocatalytic cycle CuX 2 / L (X: Br, Cl; L : Me 6 TREN: Tris[2-(dimethylamino)ethyl]amine) and to initiate radical photopolymerization of methyl methacrylate (MMA) with α-bromophenylacetate (EBPA) by exposure at 420 nm. This resulted in poly(methyl methacrylate) (PMMA ) exhibiting a dispersity <1.3 with CuX 2 /L loading of ≲ 52 ppm. Deactivator reduction increased dispersity. MMA, styrene, and benzyl methacrylate successfully served as monomers for chain extension and block copolymerization experiments. This worked with CuX 2 /L ≥ 6.5 ppm, although conventional radical polymerization additionally competed. Adding of sodium pyruvate enabled radical photopolymerization under air. Modification of lignin with an aryl sulfonate group resulted in a one-component photoinitiator. It successfully initiated radical photopolymerization of a monomer mixture of (hydroxyethyl)methacrylate (HEMA) and urethane dimethacrylate (UDMA). Scale-up experiments approved practicability of photo-ATRP.

研究领域: 高分子化学 · 绿色化学 · 光催化 · 材料科学 · 可持续化学 · 工业化学
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