Inversion,chemical complexity,and interstitial transport in spinels

Spinels with the generic chemical formula AB₂O₄ have potential applications in nuclear energy and batteries. In both cases, their functionality is related to mass transport through the crystal. Here, using long-time atomistic simulations, we examine the impact of the cation structure on interstitial transport in two spinel chemistries, inverse MgGa₂O₄ and double MgAlGaO₄. We emphasize two aspects of the transport properties: the unit mechanisms that are described by individual barriers, for which we introduce pole-figure-like plots, and the aggregate behavior of those unit mechanisms. Compared to previous work on normal spinels, we find that inversion significantly reduces the rate of interstitial transport in these structures and has an impact on the stability of defects as they move through the lattice. In particular, B cation interstitials are found to be kinetically stable only in the inverse MgGa₂O₄. These results provide new insight into relationship between structure, chemistry, and transport in spinels.     

Synthesis and characterization of Co5Cr2(P2O7)4 - New pyrophosphate as a colouring substance

A new pyrophosphate(V) of the formula Co₅Cr₂(P₂O₇)₄ was obtained in the system Co₂P₂O₇–Cr₄(P₂O₇)₃ as a result of solid-state reactions taking place between different reactants. The new compound crystallizes in the orthorhombic system and belongs to the family of pyrophosphates of the general formula M₅²⁺M₂³⁺(P₂O₇)₄ and is probably isostructural with Fe₅²⁺Fe₂³⁺(P₂O₇)₄. Powder diffraction pattern, infrared spectrum and SEM image of the new compound were presented. As a new potential inorganic pigment, Co₅Cr₂(P₂O₇)₄ was tested for its thermal stability, particle size distribution and colour properties, which were studied both for powder and after introduction into organic matrix and leadless ceramic glaze. The colour of Co₅Cr₂(P₂O₇)₄ powder was defined as deep grey with the colour coordinates L*/a*/b* = 60.63/-1.42/-3.41 and according to the hue angle (h° = 247.39°) it belongs to the blue region. Co₅Cr₂(P₂O₇)₄, with its relatively high thermal stability (t _m = 1230 ± 10 °C) and appropriate colour properties, is a good candidate to be used as inorganic pigment for colouring of acrylic paints. In the case of leadless glaze, the obtained compound acts as a dye.     

Evolution of Local Structural Ordering and Chemical Distribution upon Delithiation of a Rock Salt–Structured Li1.3Ta0.3Mn0.4O2 Cathode

Lithium‐rich disordered rock‐salt oxides have attracted great interest owing to their promising performance as Li‐ion battery cathodes. While experimental and theoretical efforts are critical in advancing this class of materials, a fundamental understanding of key property changes upon Li extraction is largely missing. In the present study, single‐crystal synthesis of a new disordered rock‐salt cathode material, Li_1.3Ta_0.3Mn_0.4O₂ (LTMO), and its use as a model compound to investigate Li concentration–driven evolution of local cationic ordering, charge compensation, and chemical distribution are reported. Through the combined use of 2D and 3D X‐ray nanotomography, it is shown that Li removal accompanied by oxygen oxidation is correlated with the development of morphological defects such as particle cracking. Chemical heterogeneity, quantified by subparticle level distribution of Mn valence state, is minimal during Mn redox, which drastically increases upon the formation of cracks during oxygen redox. Density functional theory and bond valence sum mismatch calculations reveal the presence of local short‐range ordering in the pristine oxide, which gradually disappears along with the extraction of Li. The study suggests that with cycling the transformation into true cation–disordered state can be expected, which likely impacts the voltage profile and obtainable energy density of the oxide cathodes.     

苛化提纯盐湖锂矿回收含氟碳酸锂的研究

主要论述了一种提纯盐湖锂矿和回收含氟碳酸锂的方法。工艺流程：盐湖锂矿（含氟碳酸锂）通过一次水洗涤除去其中所含的大部分可溶性杂质后,按一定配比将其投入到石灰乳料浆中加热到90~95 ℃反应4 h,过滤后得到氢氧化锂溶液,将氢氧化锂溶液在100~120 ℃下进行加压浓缩4 h精制得到钙镁离子和硅含量较低的氢氧化锂溶液;向精制后的氢氧化锂溶液中通入食品级二氧化碳沉锂得到工业级碳酸锂,或继续浓缩制备氢氧化锂;用以上工艺生产得到的工业级碳酸锂通过二次碳化、阳离子交换树脂除去钙镁离子、重结晶可得到硅含量为10×10^-6以内的高纯碳酸锂,或浓缩得到钙含量为5×10^-6、镁含量为2×10^-6以内的单水氢氧化锂。     

裴沟煤矿典型断裂构造带水化学变化特征

断裂运动是错综复杂的地质作用，物质组成的变化能够通过水质中阴阳离子含量直观表现。以裴沟煤矿近20年来的突（涌）水点化验数据为依据探究各含水层水化学普遍性质，发现阳离子含量和矿化度可以作为水源判别的重要指标，以典型构造浮山寨断层为对象研究断裂构造带水化学变化特征，结果显示距离断裂构造带越近，水中Ca²⁺+Mg²⁺含量减小、Na⁺+K⁺含量增大、矿化度降低，揭示断层两盘不同含水层间水掺和程度。     

Phenyl Ethylammonium Iodide introduction into inverted triple cation perovskite solar cells for improved VOC and stability

The efficiency of more than 25% in organic-inorganic hybrid perovskite solar cells has made them very attractive in the pursuit of cheaper alternatives to Si-based devices. However, the stability of the perovskite solar cells was challenging, given their high susceptibility to moisture. Very few reports have emerged in this regard that investigated the influence of introducing large cations into a triple cation perovskite (TC-PVS), with several studies limited to single and dual cation perovskites. Further, the crystallization of TC-PVS on a polymer surface such as PEDOT is not straightforward, and their inclusion in inverted solar cell devices was limited. In this work, we investigated the impact of incorporating Phenyl ethyl ammonium cation into FAMACs triple cation composition. We demonstrated improvements in the crystallinity and more uniform coverage with little to no pinholes and smooth morphology for an optimum PEA amount of 1.67% in the precursor solution. The superior morphology, along with a passivation effect from a quasi 2D phase, led to increased photoluminescence and minority carrier lifetimes. Corresponding inverted photovoltaic devices prepared with PEA showed increased open-circuit voltage from 0.89 V for a control sample to 0.95 V for 1.67% PEA and 0.98 V for 5% PEA, doped devices in an inverted configuration. The efficiency, as a result, increased from 11.27% for a control device to 14.85% for a 1.67% PEA doped device. Further, PEA doped devices showed improved operational and thermal stability attributed to the higher moisture tolerance and light-soaking ability of the PEA doped TC-PVS compared to the undoped TC-PVS.     

基于村落宅图的分类及量化研究——以徽州传统村落群为例

本文以江西省婺源县沱川乡理坑、浙源乡虹关以及思口镇西冲的3次村落测绘作为研究的起点,逐步拓展至对12份徽州传统村落宗族图谱中的村落宅图进行分类及量化研究。通过对村落宅图的研究来还原徽州传统村落群的空间形态,探究其背后的地缘影响、血缘纽带和社会维系,归纳总结出9种村落群的基本构成要素及其所占比率,揭示村落群的空间构成和形态要素。希望在此基础上推演村落群形态的历史演变过程,还原与诠释村落群背后隐藏的内在秩序。     

用732强酸性阳离子交换树脂去除铬酸盐钝化液中的锌离子

对732强酸性阳离子交换树脂再生铬酸盐钝化液进行了探索。研究了交换处理时间、溶液初始pH、Zn(II)初始浓度及树脂用量对树脂吸附的影响,并考察了树脂的脱附和再生性能。结果表明,该树脂对Zn(II)的吸附速率快,30 min达到吸附平衡,最佳吸附pH为3~6。用树脂再生钝化液不会对Cr(VI)浓度产生影响,能达到"去锌保铬"的目的。该树脂对Zn(II)的吸附符合Langmuir吸附等温模型,为单分子层吸附,具有吸附饱和性,饱和吸附量约为85.6 mg/g。     

An Unexpected Construction of 2‐Arylquinolines from N‐Cinnamylanilines through sp3 C?H Aerobic Oxidation Induced by a Catalytic Radical Cation Salt

An unexpected reaction of cinnamylanilines was achieved through the radical cation salt‐induced aerobic oxidation of sp³ C H bonds, providing a series of 2‐arylquinolines. The mechanistic study shows that the cinnamylaniline was oxidized to an imine, which was attacked by the aniline generated through decomposition of the corresponding imine. After further intramolecular cyclization and aromatization, 2‐arylquinolines were obtained. This reaction provides a new method to construct 2‐arylquinolines from readily accessible starting materials.