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Science China-Chemistry · 2014 ·Vol. 57 ·期 5 ·662-668 · IF 1.516

The effect of cation size (H+, Li+, Na+, and K+) on McLafferty-type rearrangement of even-electron ions in mass spectrometry

Chai YunFeng,Pan YuanJiang

Protonation and alkali-metal cation adduction are the most important ionization processes in soft-ionization mass spectrometry. Studies on the fragmentation mechanism of protonated and alkali-metal-cationized compounds in tandem mass spectrometry are essential and helpful for structural analysis. In some cases, it was often observed that a compound attached by different alkali-metal cations (or proton) exhibits similar fragmentation patterns but the relative abundances of product ions are different. This difference was considered to derive from the different electrostatic interactions of alkali-metal cations (or the bonded effect of proton) with the analyte. The alkali-metal cation with a smaller ionic radius shows stronger electrostatic interaction with the molecule because of its higher charge density. In addition, the bonded effect of the proton is stronger than the electrostatic interaction of the alkali-metal cation. In the present study, which used McLafferty-type rearrangements of even-electron ions ([M + Cat] + , Cat = H, Li, Na, K) as model reactions, the effect of cation size in mass spectrometric fragmentation reactions is highlighted. These considerations were also successfully applied to interpret the similar but distinct fragmentation behavior of proton and alkali-metal cation adducts of a synthetic compound (2-(acetamido(phenyl)methyl)-3-oxobutanoate) and a drug (entecavir).

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Coatings · 2023 ·Vol. 13 ·期 3 ·626 · IF 3.4

Structure, Electrochemical, and Transport Properties of Li- and F-Modified P2-Na2/3Ni1/3Mn2/3O2 Cathode Materials for Na-Ion Batteries

Xinglong Chen,Wenyue Guo,Rui Li,Peng Du,Xiaowen Zhan,Shan Gao

The development of cobalt-free P2-Na2/3Ni1/3Mn2/3O2cathodes is hampered by poor electrochemical performance, resulting from structural instability during high-voltage cycling. Herein, Li+and F−ions are introduced simultaneously via a simple sol–gel method. The F not only enters the lattice but forms chemically stable NaF on the surface. The modified electrode delivered significantly better electrochemical performance than the pristine one, including much-enhanced capacity retention (64% vs. 36%, 100 cycles) at 0.5 C and a four-time higher capacity output at 10 C. The ex situ XRD and in situ Raman analysis revealed cyclability enhancement mechanisms in terms of inhibiting the P2–O2 phase transition and Na+/vacancy ordering. The conductivity measurements (based on AC impedance and DC polarization) and GITT analysis proved, on both bulk material and electrode levels, that Na+conduction and, thus, rate performance is notably promoted by doping. The individual contribution of Li and F to the overall performance improvement was also discussed. Furthermore, a solid-state sodium-metal battery was successfully demonstrated with the modified cathode. The above results verify that Li+/F−incorporation can enable enhancements in both cyclability and rate capability of the P2-Na2/3Ni1/3Mn2/3O2cathodes and are expected to provide a new perspective for the rational design of high-performance layered oxide cathode materials for progressive sodium-ion batteries.

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Energy Technology · 2019 ·Vol. 7 ·期 11 ·1900754 · IF 3.163

Plant Oil–Inspired 3D Flower-Like Zn3V3O8 Nanospheres Coupled with N-Doped Carbon as Anode Material for Li-/Na-Ion Batteries

Shikun Cheng,Qiang Ru,Zhenglu Shi,Yuqing Gao,Yang Liu,Xianhua Hou,Fuming Chen,Francis Chi-Chung Ling

Plant oil–inspired 3D flower-like Zn 3 V 3 O 8 nanospheres coupled with nitrogen doped (N-doped) carbon synthesized via the microemulsion/calcination strategy are used as anodes for lithium-/sodium-ion batteries (LIBs/SIBs). The synergistic interaction between the unique 3D flower-like structure and the existence of N-doped carbon can provide enough space to buffer volume expansion during the Li + /Na + intake/outlet process and enhance conductivity, respectively. Thus, the material delivers progressive electrochemical performance. Specifically, the Zn 3 V 3 O 8 nanospheres exhibit a reversible specific capacity of 1140.6 mAh g −1 after 200 cycles for LIBs and 113.0 mAh g −1 after 400 cycles for SIBs at a current density of 200 mA g −1 . Furthermore, the Zn 3 V 3 O 8 nanospheres electrode owns rate capability for LIBs such as 933.8, 847.9, 780.8, and 664.1 mAh g −1 at elevated current densities of 200, 400, 800, and 1600 mAh g −1 , respectively. In addition, it delivers reversible capacities of 207.5, 119.2, 74.1, and 42.7 mAh g −1 at 100, 200, 500, 1000, and 2000 mA g −1 for SIBs, respectively.

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Journal of Materials Chemistry A · 2016 ·Vol. 5 ·期 2 ·600-608 · IF 8.262

A long cycle-life and high safety Na+/Mg2+ hybrid-ion battery built by using a TiS2 derived titanium sulfide cathode

Xiaofei Bian,Yu Gao,Qiang Fu,Sylvio Indris,Yanming Ju,Yuan Meng,Fei Du,Natalia Bramnik,Helmut Ehrenberg,Yingjin Wei

The practical uses of magnesium-ion batteries are hindered by their poor rate capability and fast capacity decay. Moreover, traditional sodium ion batteries suffer from serious safety problems resulting from the sodium dendrites formed on the anode. In order to circumvent these problems, we designed a highly reversible Na+/Mg2+ hybrid-ion battery composed of a metallic Mg anode, a TiS2 derived titanium sulfide cathode and a 1.0 M NaBH4 + 0.1 M Mg(BH4)2/diglyme hybrid electrolyte. The battery showed remarkable electrochemical performances with a large discharge capacity (200 mA h g−1 at the 1C rate), high rate capability (75 mA h g−1 at the 20C rate) and long cycle life (90% capacity retention after 3000 cycles). Moreover, it exhibited excellent safety properties due to dendrite-free Mg deposition of the anode and the high thermal stability of the cathode. These merits demonstrate the great potential of the reported Na+/Mg2+ hybrid-ion battery for large-scale energy storage.

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Nanoscale · 2017 ·Vol. 9 ·期 40 ·15558-15565 · IF 7.367

Synthesis of long hierarchical MoS2 nanofibers assembled from nanosheets with an expanded interlayer distance for achieving superb Na-ion storage performance

Zhonggui Gao,Xiao Yu,Jiang Zhao,Wenxia Zhao,Ruimei Xu,Yong Liu,Hui Shen

MoS2 material is considered as a promising anode material candidate in Na-ion batteries (NIBs) due to its high theoretical capacity and layered structure. However, MoS2 nanosheets usually tend to restack or aggregate during the synthesis and cycling process, which makes the advantages of the separated nanosheets disappear. Here, we present a PVP-assisted synthesis for growing long hierarchical MoS2 nanofibers with a length up to 74.5 μm, which were further assembled from intercrossed curly nanosheets with expanded (002) interlayer spacings in the range of 0.62 nm to 1.14 nm. Such architectural design simultaneously combines multiple-scale structural features that are desired for Na-ion storage. On the one hand, the nanosheets can provide a large surface area which is in contact with the electrolyte, a short Na-ion diffusion pathway from the lateral side and facile Na-ion insertion and extraction through the expanded (002) interlayer; on the other hand, the hierarchical MoS2 nanofibers possess a one dimensional structure and a suitable amount of carbon, which can both serve as an electrical highway and prevent them from restacking, resulting in an enhanced electrochemical performance. When used as an anode in NIBs, they demonstrated excellent cycling performance (537 mA h g−1 at 0.1 A g−1 after 200 cycles, and 370 mA h g−1 at 2 A g−1 over 200 cycles) and outstanding rate capability (329 mA h g−1 at 10 A g−1).

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PROGRESS IN SOLID STATE CHEMISTRY · 2026 · IF 9.7

A-site cation engineering of Mn5+-activated ABaPO4 (A=Li, Na, K) phosphors for high-performance NIR-II luminescence and optical thermometry

Yutong Wang,Hang Zhao,Jiayin Niu,Anurak Weahayee,Wanwisa Limphirat,Theeranun Siritanon,Jingyi Ren,Peng Jiang,Yanfei Sun,Tingting Lu

The development of high-performance narrowband near-infrared second window (NIR-II) phosphors remains a critical challenge in the fields of advanced bioimaging and optical thermometry. Herein, a series of Mn 5+ -doped ABaPO 4 (A = Li, Na, K) phosphors are synthesized via conventional solid-state method, and the effect of A-site alkali metal cations on their crystal structure and luminescence properties is comparatively investigated. Mn K -edge X-ray absorption near-edge structure (XANES) spectroscopy unambiguously confirms that Mn ions are predominantly stabilized in the +5 oxidation state and exclusively occupy tetrahedral [PO 4 ] sites in all three hosts. All samples exhibit characteristic narrowband NIR-II emission in the 1160-1200 nm range originating from the 1 E → 3 A 2 spin-forbidden transition of Mn 5+ . The lattice distortion induced by different A-site cations significantly modulates the doping limit, crystal field strength, thermal stability and temperature sensing performance of Mn 5+ ions. All three Mn 5+ -doped hosts exhibit good thermal stability. The fluorescence decay lifetime of LiBaPO 4 : Mn 5+ reaches 772.436 μs＀ NaBaPO 4 : Mn 5+ shows unique energy level splitting and achieves a maximum relative temperature sensitivity of 2.43% K −1 based on the fluorescence intensity ratio technique. KBaPO 4 : Mn 5+ possesses a highly symmetric crystal lattice and a higher doping limit, with a thermal quenching activation energy ( ΔE ) of 0.414 eV. This work not only provides three promising NIR-II phosphors for bioimaging and optical thermometry, but also offers new insights into the research of Mn 5+ -activated phosphate systems.

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Mining Metallurgy & Exploration · 2026 · IF 2.5

Removal Mechanism of Fe-Al-Na-K-Mn Impurities in Quartz Sand by Hydrochloric Acid-Oxalic Acid-Citric Acid Ternary Mixed Acids

Wang Guangdong,Bai Ziyang,Li Maohui,Mao Xishan,Yu Jie,Su Chang,Hu Wenwen,Ma Bo,Sun Wenzhou,Lu Youjun

In response to the limitations of the traditional acid leaching process in terms of environmental impact and safety, this study developed a ternary mixed acid system (hydrochloric acid - oxalic acid - citric acid) without the use of hydrofluoric acid and nitric acid. The influence of three process parameters, namely, the concentration of the mixed acids, the liquid-solid ratio, the acid leaching temperature, and the acid leaching time, on the removal efficiency of impurities such as Fe, Mn, Al, K, and Na in quartz sand was systematically investigated. The experimental results revealed that the optimal acid leaching conditions were a hydrochloric acid concentration of 4.5 mol·L − 1 , an oxalic acid concentration of 0.03 mol·L − 1 , a citric acid concentration of 0.04 mol·L − 1 , a liquid-solid ratio (mass ratio) of 5:1, a constant temperature of 60 ℃, and a holding time of 3 h. Under these conditions, the removal rates of Fe, Mn, and Al reached 89.2%, 71.0%, and 60.1%, respectively. Moreover, K and Na were also removed to a certain extent, with removal rates of 39.6% and 25.5%, respectively. Mechanistic analysis revealed that in the ternary mixed acid system, hydrochloric acid provides an acidic environment, and the combination of oxalic acid and citric acid synergistically promotes the dissolution of impurities through complexation, reducing impurities on the surface of quartz sand, improving the cleanliness, and forming micro-porous structures. Compared with the traditional hydrogen fluoride-nitric acid leaching process, the fluorine-free ternary mixed acid system proposed in this study has a similar or even better removal efficiency for impurities such as Fe and avoids the environmental and safety risks associated with hydrogen fluoride. This system can achieve the simultaneous removal of various impurities in quartz sand under normal pressure and medium-low-temperature conditions, providing a new technical path for the development of quartz sand purification technology for safety and environmental protection.

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CARBON · 2026 · IF 12.7

Oxygen Functional Groups and Pore Regulation of Sucrose-Derived Carbon for Enhancing Electrochemical Stability in the Cathode of RT Na-S Batteries

Renlin Zhu,Xiaodong Lv,Chenghui Fu,Xianze Long,Shudong Zhang,Jiayue Xie,Yibo Lin,Qingqing Huang,Zhaohai Chen,Kangning Jiang,Run Huang

Sucrose-derived carbon spheres are promising host materials for cathode sulfur species in Room-Temperature (RT) Na-S batteries. Therefore, the morphology, micro-mesoporous structure, and oxygen-containing functional groups of sucrose-derived nanocarbon spheres were regulated to effectively accommodate sulfur species. This structural design facilitates sulfur confinement, improves charge/ion transport, and enhances the cycling stability of AC@S composites. With increasing activation temperature, the developed porous structure provides more storage sites for active sulfur species; however, excessive activation can reduce the content of oxygen- containing functional groups and weaken the chemical anchoring capability of the carbon framework. Among the prepared samples, AC@S-900 delivered the highest initial capacity of 1323.35 mAh g -1 at 1.0 C, whereas AC@S-750 exhibited superior cycling durability, delivering an initial specific capacity of 941.48 mAh g -1 and maintaining 566.04 mAh g -1 after 1500 cycles, corresponding to an ultralow capacity decay rate of 0.027% per cycle. DFT calculations further suggested that oxygen-containing functional groups can provide polar adsorption/catalytic sites, reduce the conversion energy barriers of Na 2 S x species. Specifically, the carbon framework's carbonyl (C=O) and epoxy (C-O-C) groups can enhance the sulfur redox kinetics. Download: Download high-res image (308KB) Download: Download full-size image

CAS / MDL: 57-09-0
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Journal of Materials Chemistry A · 2026 · IF 9.5

Construction of Sb2S3@NC Core-Shell Nanorod with Hollow Feature as Anode via Microstructure Regulation Strategy for High-Performance Na⁺/K⁺ Storage

Rong Jiang,Junyuan Huang,Ruixue Ma,Qian Li,Longjun Dai,Runyu Li,Xingpeng Chen,Yang Ren,Zhu Liu,Xu Chen,Xiaowei Zhou

Antimony trisulfide (Sb2S3) is a highly promising anode material for alkali-metal batteries due to its high theoretical capacity and abundant resources. However, severe volume expansion during charge-discharge and low electrical conductivity restrict its electrochemical performance. In this study, Sb2S3@NC core-shell nanorod with hollow feature (H-Sb2S3@NC) was successfully prepared via high-temperature carbonization and secondary sulfidation of the inorganic-organic Sb2S3@PDA composite precursor. It would induce the volatilization of partial Sb2S3 by controlling temperature during carbonization, concurrently forming the inorganic core-shell nanorod structure and its hollow feature. Compared to Sb2S3@NC without hollow feature, H-Sb2S3@NC exhibits superior cycling and rate performance when as anode for sodium-ion (SIBs) and potassium-ion batteries (PIBs). Specifically, as anode for SIBs, H-Sb2S3@NC retains 517.0 mAh g⁻¹ after 100 cycles at 100 mA g⁻¹ and even delivers 535.5 mAh g⁻¹ at 1000 mA g⁻¹ (Sb2S3@NC: 60.6 mAh g⁻¹ after 100 cycles at 100 mA g⁻¹, 39.7 mAh g⁻¹ at 1000 mA g⁻¹). For PIBs, H-Sb2S3@NC provides 431.1 mAh g⁻¹ after 50 cycles at 100 mA g⁻¹ (Sb2S3@NC: 208.3 mAh g⁻¹ under the same conditions). Ex situ characterizations confirm Sb2S3 undergoes a reversible conversion-alloying reaction during Na⁺/K⁺ storage. The internal voids of H-Sb2S3@NC could effectively buffer volume expansion stress, while N-doping in the NC (nitrogen-doped carbon) layer enhances ion/electron transport. These two factors synergistically ensure electrode structural stability and excellent kinetics. The temperature-controlled microstructure regulation strategy proposed in this study provides an effective approach to addressing the volume expansion problem of Sb2S3-based anodes and optimizing the electrode performance of alkali-metal ion batteries.

CAS / MDL: 62-31-7
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JOURNAL OF RARE EARTHS · 2024 ·Vol. 43 ·期 3 ·543-551 · IF 5.2

A narrow-band blue emitting phosphor by co-doping Bi3+ and alkali metal ions (Li+, Na+ and K+) with dual luminescence center

Lang Ruan,Zeyun Zhou,Yi Hu,Ruifeng Peng,Xiaoyan Chen,Ming Cheng,Zhi Zhou,Mao Xia

The technology of solid-state lighting has developed for decades in various industries. Phosphor, as an element part, determines the application domain of lighting products. For instance, blue and red-emitting phosphors are required in the process of plant supplementing light, arrow-band emitting phosphors are applied to backlight displays, etc. In this work, a Bi 3+ -activated blue phosphor was obtained in a symmetrical and compact crystal structure of Gd3SbO7 (GSO). Then, the co-doping strategy of alkali metal ions (Li + , Na + , and K + ) was used to optimize the performance. The result shows that the photoluminescence intensity is increased by 2.1 times and 1.3 times respectively by introducing Li + and K + ions. Not only that, it also achieves narrow-band emitting with the full width of half-maximum (FWHM) reaching 42 nm through Na + doping, and its excitation peak position also shifts from 322 to 375 nm, which can be well excited by near-ultraviolet (NUV) light emitting diode (LED) chips (365 nm). Meanwhile, the electroluminescence spectrum of GSO:0.6 mol%Bi 3+ ,3 wt%Na + matches up to 93.39% of the blue part of the absorption spectrum of chlorophyll a . In summary, the Bi 3+ -activated blue phosphor reported in this work can synchronously meet the requirements of plant light replenishment and field emission displays .

研究领域: 材料科学 · 光学工程 · 固体照明 · 光电子学 · 农业光生物学
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Metals · 2023 ·Vol. 13 ·期 4 ·677 · IF 2.9

Preparation of Porous Composite Phase Na Super Ionic Conductor Adsorbent by In Situ Process for Ultrafast and Efficient Strontium Adsorption from Wastewater

Yuliang Chen,Xiangbiao Yin,Hao Fu,Zheyang Lin,Guangcan Ma,Xinpeng Wang,Qingsong Wang,Fangqiang Chen

Strontium, the main component of radioactive nuclear wastewater, is characterized by a high fission yield and an extended half-life. It is easily absorbed by the human body, thus greatly threatening the environment and the human body. In this study, a mesoporous composite phase sodium superionic conductor (NVP@NMP) was synthesized by the droplet template method, and the rapid capture of Sr2+from wastewater was achieved by constructing a nano-heterogeneous interface to increase the ion diffusion rate. NVP@NMP showed efficient and rapid removal of strontium ions in adsorption kinetics, isothermal adsorption, solution pH, and interfering ions concentration tests, especially using the equilibrium time of 2 min for strontium absorption by NVP@NMP and a maximum theoretical adsorption capacity of 361.36 mg/g. The adsorption process was spontaneous, endothermic, and feasible. At higher concentrations of other competing ions (Na, K, Ca, Mg, and Cs), the adsorbent exhibited higher selectivity towards Sr2+.TEM, XPS, and XRD analyses revealed that ion exchange was the main mechanism for the NVP@NMP ultrafast adsorption of Sr2+. In this research, we investigated the feasibility of ultrafast strontium capture by sodium superionic conductor structured phosphates and explained the ultrafast strontium adsorption mechanism of NASICON materials through XPS.Keywords:NASICON;ultrafast adsorption;strontium;ion exchange;wastewater

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IONICS · 2023 · IF 2.8

Effects of the Mn/Ni ratio on the battery performance of layered Na-Ni-Mn oxide cathode materials in sodium-ion batteries

Xiao Qingmei,Guo Ziting,Huang Jinchao,Zhong Shengwen

The development of efficient sodium-ion batteries is essential to overcome the issue of limited lithium sources for preparing lithium-ion batteries. Layered Mn-based cathode materials have significant application potential because of their simple structure and high specific capacities. Serious voltage attenuation and phase transition are the prominent problems of layered manganese-sodium ion batteries. To eliminate these issues, in this study, we investigated the effects of different Mn/Ni ratios in Na-Ni-Mn cathode materials on their structural stability and electrochemical performances. Na 0. 8MnO 2 (NNM-8010), Na 0.8 Ni 0.1 Mn 0.9 O 2 (NNM-819), Na 0.8 Ni 0.2 Mn 0.8 O 2 (NNM-828), and Na 0.8 Ni 0.3 Mn 0.7 O 2 (NNM-837) were synthesized and characterized using X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy, and electrochemical analyses. The addition of Ni 2+ increased the Mn oxidation state from + 3 to + 4, thus reducing the Jahn–Teller effect of Mn 3+ and stabilizing the material structure. NNM-819 exhibited the best electrochemical performance. Its initial discharge-specific capacity was 198.5mAh g −1 at a current density of 0.2C, and the capacity retention rate after 100 cycles was 86.9% at 0.5C. Moreover, its capacity retention rate at 1.0C high-rate cycling after 100 cycles remained high 81.9%. Graphical Abstract

CAS / MDL: 1313-99-1 497-19-8
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