JOURNAL OF CHEMICAL AND ENGINEERING DATA
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2023
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IF 2.6
Yanfei Fan,Ziyu Zhuang,Dandan Gao,Dongdong Li,Dewen Zeng
Solid–liquid phase equilibrium data of the Li2SO4 + Rb2SO4 + H2O and Li2SO4 + Cs2SO4 + H2O systems are of importance for the design of alkali metal element extraction processes from sulfate leaching solution of lepidolite. Considering the serious inconsistency of the reported solid phases, especially double salts and solid solutions, phase diagrams of the two systems were reinvestigated experimentally. The results on the Li2SO4 + Rb2SO4 + H2O system at 298.15 K show five solids, i.e., Rb2SO4, Rb2SO4·Li2SO4, Rb2SO4·3Li2SO4·2H2O, Rb2SO4·5Li2SO4·4H2O, and a solid solution with the end members Rb2SO4·5Li2SO4·4H2O and Li2SO4·H2O. For the Li2SO4 + Cs2SO4 + H2O system at 298.15 K, the results also show five solids, i.e., Cs2SO4, Cs2SO4·Li2SO4, Cs2SO4·3Li2SO4·2H2O, Cs2SO4·5Li2SO4·4H2O, and Li2SO4·H2O, while there is no solid solution phase with the end members Cs2SO4·5Li2SO4·4H2O and Li2SO4·H2O. Moreover, the single crystal structures of Rb2SO4·3Li2SO4·2H2O and Cs2SO4·3Li2SO4·2H2O were determined.
研究领域:
化学工程
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材料科学
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高影响因子
JOURNAL OF CHEMICAL THERMODYNAMICS
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2019
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IF 2.29
Yanfei Fan,Dongdong Li,Dandan Gao,Dewen Zeng,Wu Li
Specific heat capacity of Rb 2 SO 4 (aq) and Cs 2 SO 4 (aq) solutions was determined using a Calvet-type calorimeter from 288.15 K to 338.15 K and from about 0.25 mol·kg −1 to concentration near room temperature solubility limits. For both Rb 2 SO 4 (aq) and Cs 2 SO 4 (aq) solutions, the specific heat capacity decreases with the increase of molality at constant temperature. Combining the heat capacity data determined in this study and other thermodynamic properties ( i.e. water activity, osmotic coefficient, mean ionic activity coefficient, enthalpy of dilution and solubility) reported in literature, thermodynamic and phase equilibria properties of the binary Rb 2 SO 4 + H 2 O and Cs 2 SO 4 + H 2 O systems were modelled using a comprehensive thermodynamic framework, in which a Pitzer-Simonson-Clegg model was applied to represent the non-ideality of aqueous phases. The models can represent all the properties over wide temperature and concentration ranges. This study forms a basis for solubility prediction in multi-component systems containing Rb and Cs sulfates.
研究领域:
物理化学
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热力学
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Nature Communications
·
2025
·Vol. 16
·期 1
·1-9
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IF 15.7
Wei Shilei,Hua Hang,Zhao Yuxuan,Luo Jingshan
Zero-gap membrane electrode assembly (MEA) CO 2 electrolysers offer high energy efficiency and promise for industrial application. However, the transport of carbonates within an anion exchange membrane (AEM) electrolyser leads to CO 2 loss, thereby limiting carbon utilization efficiency. Emerging acidic anolyte electrolysers using cation exchange membrane (CEM) can address this challenge but face critical stability issues, including accelerated hydrogen evolution reaction (HER) and persistent salt precipitation. Here, we propose a porous membrane (PM) as an alternative to the CEM in acidic anolyte electrolysers. The system demonstrates continuous operation at 100 mA cm −2 for 200 h without salt precipitation, while maintaining nearly 100% CO selectivity. Furthermore, large-scale device (100 cm 2 ) also shows stable performance. Mechanism analysis suggests that enhanced water permeation and bidirectional ion transfer are critical for achieving stable performance in acidic anolyte electrolysers. These findings offer a feasible approach for high-performance, stable and scalable acidic MEA CO 2 electrolysers.
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PubMed
高影响因子
CHEMISTRY OF MATERIALS
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2025
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IF 7
Luyong Zhang,Zhencheng Wu,Jingdong Yan,Shibin Wang,Zilong Chen,Zhihua Yang,Fangfang Zhang,Shilie Pan
Sulfates have remained promising candidates for deep-ultraviolet (DUV) optical crystals owing to the inherently wide bandgaps induced by the [SO4] tetrahedral groups. However, the structural rigidity of [SO4] tetrahedra imposes severe restrictions on the polarization anisotropy, fundamentally preventing sulfates from achieving sufficient birefringence required for regulating light polarization. Herein, by incorporating f0 rare earth metal cation Y3+ into alkali metal sulfates, we synthesized six compounds, AY(SO4)2 and A3Y(SO4)3 (A = K, Rb, Cs). They exhibit dramatically enhanced birefringence between 0.013–0.056 at 546 nm, with up to 25 times that of their parent alkali metal sulfates, which originate from the highly aberrant Y–O polyhedra and the dimensionality reduction of the Y–O–S network regulated by A-site cations. This study provides valuable insights into the further exploration of sulfate-based optical materials.
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CHEMICAL ENGINEERING RESEARCH & DESIGN
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2025
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IF 3.9
Chen Li,Hong Zhang,Siyao Gu,Wenlong Lu,Xinyu Chen,Liuliu Zhong,Mingjun Zheng,Hui Wan,Lei Wang,Guofeng Guan
The selective oxidation of methacrolein (MAL) to methacrylic acid (MAA) is a crucial step in the C4 process for producing methyl methacrylate (MMA). While Cs-modified polyoxometalates (POMs) are known to enhance the catalytic activity in this reaction, wherein the influence of different cesium sources on their performanc remains unexplored. This work systematically investigates the effect of varying cesium sources onthe performance of (NH 4 + ) X Cu 0.2 CsH 2.8-X PMo 11 VO 40 (BPAV) series catalysts. Characterization results show that the introduction of CsOH facilitates the formation of spherical microstructures in the catalyst, significantly increasing its specific surface area (13.74 m 2 /g) and medium acid amounts (1.46 mmol/g). XPS analysis further confirms that CsOH enhances the interaction between cesium ions and polyoxometalate anions, promoting the electron transfer from Cs ions to POM anions and the formation of abundantV 4+ species (V 4+ /V 5+ = 2.23) for enhanced redox capability. The BPAV catalyst with CsOH/POM molar ratio of 1 achieves the optimal performance, exhibiting 85.5% MAL conversion and 90.5% MAA selectivity. Furthermore, the BPAV catalyst with CsOH source also demonstrated excellent catalytic performance in the selective oxidation of propionaldehyde and isobutyraldehyde, with product selectivity surpassing 90% in both reactions. These findings offer new insights and perspectives for the design of high- efficiency aldehyde oxidation catalysts.
研究领域:
催化化学
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材料科学
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THERMOCHIMICA ACTA
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2025
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IF 3.5
Shuchang Zhang,Meiqian Chen,Bingyang Li,Yuelong Pan,Linjun Yang
The treatment of spent ion exchange resins (CERs) has become a major concern with the development of nuclear industry. The migration and transformation mechanism of Cs in CERs in both pyrolysis and gasification were evaluated based on chemical equilibrium and experimental analysis. The pyrolysis and gasification temperatures should be limited below 813.15 K and 873.15 K, respectively, but after adding the fixatives, ZrO 2 or Nb 2 O 5 , the temperatures could be extended to 873.15 K, 1233.15 K (ZrO 2 ) or 1153.15 K (Nb 2 O 5 ). The kinetic and thermodynamic characteristics of CERs with metal ion catalysts in the gasification were evaluated based on thermogravimetric analysis. In 10 % O 2 /90 % N 2 , Fe 2+ and Mn 2+ metal nuclides would urge the decomposition of functional groups and polymer matrices, since they could promote the reaction in the second stage and the advance of the third stage. This study could provide basic data for the thermal treatment of CERs.
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INORGANIC CHEMISTRY
·
2025
·
IF 4.7
Jiale Xue,Shuyao Wang,Xiande Peng,Zhengyan Lin,Xuehua Dong,Liling Cao,Ling Huang,Guohong Zou
We present two novel antimony(III)-based tellurite sulfate crystals, Sb2(TeO3)(SO4)2-P1̅ (I) and Sb2(TeO3)(SO4)2-P21/c (II), synthesized using a dual lone pair strategy that incorporates Sb3+ and Te4+ ions into a sulfate framework. This approach significantly enhances the birefringence of these compounds, with values of 0.11 and 0.10 at 546 nm, respectively, surpassing those of many previously reported mixed alkali metal/alkaline earth metal sulfates and tellurites. Both compounds also exhibit excellent UV transparency with cutoff edges at 292 and 294 nm, making them promising candidates for short-wave UV optical applications. Structural and theoretical analyses reveal that the enhanced birefringence arises from the synergistic effects of the stereochemically active lone pairs of Sb3+ and Te4+, which contribute to the optical anisotropy. This work highlights the potential of dual SCALP elements in improving the optical properties of sulfate-based crystals and provides new insights into designing high-performance optical materials with tailored properties for advanced UV technologies.
研究领域:
材料科学
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光学材料
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无机化学
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晶体工程
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光子学
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PubMed
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2025
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IF 21.1
Shaonan Zhang,Yuandong Yan,Qian Zheng,Shicheng Yan,Zhigang Zou
Carbon dioxide reduction reaction (CO 2 RR) on highly reactive frustrated Lewis pairs (FLPs) is a promising avenue for producing high-energy-density fuels from renewable energy. Exploring the effects of alkali metal ions on FLPs electrostatic field in neutral medium is a crucial knot for highly active FLP catalyst development. Here, leveraging the distinct electrochemical stability of In-OH and Bi-OH, we create stable Lewis pairs on the Bi 0.5 In 0.5 O y shell layer of Bi 0.5 In 0.5 O y @Bi 3 In 5 core-shell assembly with coordinatively unsaturated Bi-O Vs sites (Lewis acids) and In-OH (Lewis bases) to detect alkali metal ions effects. We find that K + is able to help electrochemically stable FLPs firstly capture and stabilize protons to protonate to Bi–H Lewis acid and In–OH 2 Lewis base due to their strong steric electrostatic field; then CO 2 is captured and activated by the protonated FLPs to produce formate with high selectivity. Whereas, Li + , Na + , and Cs + will inhibit CO 2 RR and promote the competing hydrogen evolution reaction due to Li + , Na + , and Cs + breaking steric electrostatic field of FLPs by inhibiting Bi-H formation. Our results verify that modulating electrostatic field of frustrated Lewis pairs by appropriate alkali cations is a promising catalyst design concept for highly selective CO 2 RR.
研究领域:
化学
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催化材料科学
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电化学
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高影响因子
HYDROMETALLURGY
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2025
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IF 5.3
Yanfei Fan,Dandan Gao,Dongdong Li,Dewen Zeng
Alum is an important intermediate for the extraction and purification of Cs or Rb chemicals, due to its excellent separation ability for Cs, Rb and K. Although the solubility sequence K-alum > Rb-alum > Cs-alum has been well known, the separation factors among Cs, Rb and K during the formation of alum have not been determined. The formation of solid solution of alum controls the Cs or Rb content and Cs/Rb/K ratio in the sequentially precipitated Cs, Rb and K alums. In this study, the thermodynamic equilibrium separation factors were determined from the solid solution-aqueous solution equilibrium data of the two mixed alum systems: (i) RbAl(SO 4 ) 2 , CsAl(SO 4 ) 2 , and H 2 O, and (ii) KAl(SO 4 ) 2 , RbAl(SO 4 ) 2 and H 2 O. The separation factor β Cs/Rb varied from 48 to 2 with the increase of the Rb/Cs ratio in system (i), and β Rb/K varied from 22 to 0.2 with the increase of the K/Rb ratio in system (ii). This suggests that the purification of Cs or Rb using alums is more efficient from raw materials containing high Cs/Rb or Rb/K ratio than that from low Cs/Rb or Rb/K ratio. In kinetic studies, the apparent separation factors β Cs/Rb and β Rb/K were highly affected by the recrystallization process of cooling or non-cooling and the initial composition of raw alum, showing asymmetric kinetic intensification. The separation factors β Cs/Rb or β Rb/K obtained in the “dissolution by heating and crystallization by cooling (DHCC)” process for the raw alum with high initial Cs/Rb or Rb/K molar ratio is several times larger than the equilibrium value expected from thermodynamics. Finally, CsAl(SO 4 ) 2 and RbAl(SO 4 ) 2 with a metal-based purity of 99.97 % and 99.94 %, respectively, were obtained by using the DHCC process 3–4 times.
研究领域:
化学工程
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材料科学
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高影响因子
JOURNAL OF POWER SOURCES
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2025
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IF 7.9
Yi Wang,Zilong Zhang,Ze Wang,Yan Zuo,Haichuan Zhou,Dongya Sun,Yuechan Li,Yujie Yan,Tong Feng,An Xie
Electrochromic devices have garnered significant interest due to their great potential in intelligent multifunctional electrochromic energy storage devices (EESDs) and smart electronics. Tungsten oxide (WO₃) exhibits both electrochromic and pseudocapacitive characteristics, and combining these two functionalities into a single device with enhanced overall performance is a popular research topic. However, synthesizing high-performance WO₃ electrochromic films with an efficient and simple method remains a challenge. Herein, a one-step fabrication strategy is developed for the in-situ growth of hexagonal WO₃ films on FTO substrates. This strategy employs a low-temperature hydrothermal method, involving xylitol as a self-seeding agent and cesium sulfate as a capping agent. The synergistic effect of the self-seeding and capping agents results in highly efficient WO₃ films with strong substrate adhesion and a large optical modulation (86.8 %). An EESD is assembled using the WO₃ film as the working electrode and a PB film as the counter electrode. The EESD demonstrates fast bleaching/coloration switching times and a high coloration efficiency of 104.8 cm 2 C⁻ 1 . Additionally, the EESD shows a distinct and reversible color transition from transparent to dark blue, accompanied by a change in optical transmittance of 74.45 %.
研究领域:
材料科学
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能源存储与转换
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纳米技术
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高影响因子
Journal of Materials Chemistry C
·
2024
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IF 5.7
Yanran Shang,Hongyuan Sha,Dongling Yang,Zhian Li,Zujian Wang,Chao He,Rongbing Su,Bin Su,Xiaoming Yang,Xifa Long
Since the non-centrosymmetric structure is a prerequisite for second-order nonlinear optical crystals, much attention should be paid to its design. Herein, a new strategy for cation modulation was proposed and implemented with the LiCsSO4 structure as a matrix and the ammonium cation as a polar structure inducer. Then, a novel alkali metal sulfate, Li2NH4Cs(SO4)2, was obtained, which exhibits a polar structure with a space group of Pna21. The introduction of ammonium cations induces symmetry breaking with the disappearance of the inversion center. Moreover, based on the synergy of multiple cations, the large distortion of sulfate groups and their uniform arrangement occur, which directly brings about a large second harmonic generation response (1.70 × KH2PO4 under a 1064 nm laser). Therefore, this work demonstrates a new design strategy with cation modulation, which will facilitate the development of nonlinear optical crystals.
研究领域:
材料科学
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晶体学
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高影响因子
CHEMISTRY OF MATERIALS
·
2026
·
IF 7.1
Luyong Zhang,Jianyi Zuo,Guangsheng Xu,Jinbin Fan,Xue Bai,Zhihua Yang,Fangfang Zhang,Shilie Pan
Deep-ultraviolet (DUV) birefringent crystals are essential for modern optical technologies, yet achieving a balance between large birefringence and a wide bandgap remains challenging. Although conventional borosulfates with alternating [BO4] and [SO4] tetrahedra connected by sharing corners possess a wide bandgap, they suffer from small birefringence due to weak optical anisotropy resulting from the presence of only tetrahedral groups. This work introduced advantageous “genes” [BO2(OH)] groups to modify the common [B(SO4)4] supertetrahedra for the first time and ultimately produced two borosulfates, Na3B3S2O11(OH)2 and K3B3S2O11(OH)2, striking the balance. Isolated fundamental building block (FBB) [B3O3(OH)2(SO4)2] was observed in the two compounds. Additionally, three conventional borosulfates featuring isolated [B(SO4)4] supertetrahedra, Na4KB(SO4)4, Na4RbB(SO4)4, and Na3Cs2B(SO4)4, were also obtained for comparison. Structural analysis and theoretical calculations reveal that the directional alignment of [BO2(OH)] groups significantly enhances the birefringence of the borosulfates. The calculated birefringence at 1064 nm increases by approximately 10-fold, specifically from 0.0035–0.0047 for the three conventional borosulfates to 0.043–0.044 for the two hydroxylated ones. This work demonstrates the effectiveness of employing [BO2(OH)] groups in optimizing the optical anisotropy of borosulfates, providing a design paradigm for exploring advanced DUV birefringent materials in borosulfates.
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