Competitive Coordination of Chloride and Fluoride Anions Towards Trivalent Lanthanide Cations (La3+ and Nd3+) in Molten Salts

Molten salt electrolysis is a vital technique to produce high-purity lanthanide metals and alloys. However, the coordination environments of lanthanides in molten salts, which heavily affect the related redox potential and electrochemical properties, have not been well elucidated. Here, the competitive coordination of chloride and fluoride anions towards lanthanide cations (La³⁺ and Nd³⁺) is explored in molten LiCl-KCl-LiF-LnCl₃ salts using electrochemical, spectroscopic, and computational approaches. Electrochemical analyses show that significant negative shifts in the reduction potential of Ln³⁺ occur when F⁻ concentration increases, indicating that the F⁻ anions interact with Ln³⁺ via substituting the coordinated Cl⁻ anions, and confirm [LnCl_xF_y]^3−x−y (y_max=3) complexes are prevailing in molten salts. Spectroscopic and computational results on solution structures further reveal the competition between Cl⁻ and F⁻ anions, which leads to the formation of four distinct Ln(III) species: [LnCl₆]³⁻, [LnCl₅F]³⁻, [LnCl₄F₂]³⁻ and [LnCl₄F₃]⁴⁻. Among them, the seven-coordinated [LnCl₄F₃]⁴⁻ complex possesses a low-symmetry structure evidenced by the pattern change of Raman spectra. After comparing the polarizing power (Z/r) among different metal cations, it was concluded that Ln−F interaction is weaker than that between transition metal and F⁻ ions.     

Influence of synthesis methods on ettringite dehydration

Journal of Thermal Analysis and Calorimetry - Ettringite is an important cement hydration product and has a significant effect on cement performance. H-ettringite (synthesized by hydration...     

一体化电极电催化二氧化碳还原研究进展

电催化二氧化碳还原反应(E-CO₂RR)可在温和条件下将CO₂转化成高附加值燃料或化学品,近年来受到广泛关注,其在实际反应中涉及到气体扩散和多电子转移等复杂过程,构筑高效、稳定的催化电极是其发展的核心之一。然而,传统涂敷电极制备时,需要将催化剂与粘结剂混合涂覆于集流体表面,此过程会造成活性位点包埋和传质过程受限,致使催化剂活性位利用率下降,同时在反应过程中电极表面容易粉化,造成稳定性下降,难以重复利用。因此,如何调控电极反应界面,提升催化剂活性位的利用率仍面临挑战。将催化剂原位生长于集流体上得到的一体化电极可直接应用于电催化反应,不仅有利于提升活性位利用率以及电荷传输能力,还能有效调控三相界面处的微观反应环境(如pH、反应物及反应中间体的浓度等),从而实现电催化性能强化。本文综述了一体化电极用于E-CO₂RR的最新进展,分析了结构和表界面调控对E-CO₂RR性能的影响规律,并对该领域仍然存在的挑战和未来一体化E-CO₂RR电极的发展进行了评述与展望。     

关联分析理论在航空维修工程中的应用

文章利用灰色系统理论的关联度分析法较好地解决了航空维修质量评价这个问题。通过举例分析，证明了这种分析方法的可行性     

Pressure-tuning domain-wall chirality in noncentrosymmetric magnetic Weyl semimetal CeAlGe

Science China Physics, Mechanics & Astronomy - The Five-hundred-meter Aperture Spherical radio Telescope (FAST) is the largest and most sensitive single-dish radio telescope in the world and...     

矿山岩体工程的系统工程

用系统工程学的观点, 重新认识矿山岩体工程的特点。建立矿山岩体工程稳定性的系统的概念。提出地质模型、设计模型、施工模型的构思, 使工程地质、设计、施工三者密切结合, 共同解决矿山岩体工程稳定问题。通过动态监测和信息反馈, 在工程施工的动态过程中不断地获得新的认识, 以便对工程实施做出新的决策。     

岩体结构力学——岩体工程地质力学的新发展

本文从岩体工程地质力学角度, 研讨了岩体结构力学的意义, 地位与作用。作者就个人的认识, 将岩体结构力学的理论特点, 概括为五个方面, 即再变形和再破坏, 岩体结构的控制作用、岩体结构控制论、赋存环境以及关于岩体的多种力学介质和力学模型构成的力学体系。     

图的距离谱综述

设D(G)为连通图G的距离矩阵,λ₁(D)≥…≥λn(D)是D(G)的特征值.距离特征值的研究可追溯到Graham和Pollack [Bell Syst.Tech.J.,1971,50:2495-2519]的工作,其中描述了负距离特征值数目与数据通信系统寻址问题之间的关系.2014年,Aouchiche和Hansen的综述[Linear Algebra Appl.,2014,458:301-386]给出了距离特征值的各种性质.本文中综述了2014-2020年间图的距离特征值研究的新进展.     

Dielectric and elastic properties of fluorine-containing tricyclic isothiocyanate liquid crystal

The dielectric and elastic properties of liquid crystals (LCs) generally depend on the molecule structure, such as polar group and carbon chain length. For further investigation of the influence of molecular structure on the dielectric and elastic properties of fluorine-containing tricyclic isothiocyanate LC, the experimental temperature was controlled at 25°C by precision hot stage, and a precision LCR meter was used to measure the capacitance of six LC cells under the voltage from 0.1 to 20 V at 1 kHz. An LC cell capacitance model and a dual-cell model were adopted to obtain the dielectric anisotropy, and the capacitance–voltage curves of six LC materials were plotted. The threshold voltage of Fréedericksz transition was analysed, and a finite difference iterative method was used to attain specific values of three elastic constants. The influence of molecular structure on the dielectric and elastic constants was finally analysed. Experimental results showed that the introduction of meta-difluoro group would increase the dielectric anisotropy and reduce the threshold voltage of LC. As the length of the alkyl carbon chain increased, the dielectric anisotropy would have an odd–even alternation effect, which would lead to changes in the elastic constants of LC.     

Differentiating between Acidic and Basic Surface Hydroxyls on Metal Oxides by Fluoride Substitution: A Case Study on Blue TiO2 from Laser Defect Engineering

Both oxygen vacancies and surface hydroxyls play a crucial role in catalysis. Yet, their relationship is not often explored. Herein, we prepare two series of TiO₂ (rutile and P25) with increasing oxygen deficiency and Ti³⁺ concentration by pulsed laser defect engineering in liquid (PUDEL), and selectively quantify the acidic and basic surface OH by fluoride substitution. As indicated by EPR spectroscopy, the laser-generated Ti³⁺ exist near the surface of rutile, but appear to be deeper in the bulk for P25. Fluoride substitution shows that extra acidic bridging OH are selectively created on rutile, while the surface OH density remains constant for P25. These observations suggest near-surface Ti³⁺ are highly related to surface bridging OH, presumably the former increasing the electron density of the bridging oxygen to form more of the latter. We anticipate that fluoride substitution will enable better characterization of surface OH and its correlation with defects in metal oxides.