Catalytic activity of nanocrystalline ZnM2O4 (M = Fe,Co) prepared via simple and facile synthesis of thermal decomposition of mixed metal complexes of Schiff bases generated from α-ketobutyric acid and diaminoguanidine

Metal complexes ([ML₂], where M = Fe, Co, or Zn; HL = 2-[(6-ethyl-5-oxo-4,5-dihydro-2H-[1,2,4]triazin-3-ylidene)-hydrazono]-butyric acid, C₉H₁₃N₅O₃) of a Schiff base derived from α-ketobutyric acid (α-KBA) and diaminoguanidine (Damgu) were synthesized and characterized using elemental, spectral, and thermal studies. The metal complexes exhibited similar decomposition behavior, with a highly exothermic final decomposition step resulting in the formation of metal oxides. Isomorphism among the complexes was revealed using a powder X-ray diffraction (PXRD) technique. Solid solution precursors ([Zn_1/3M_2/3(L)₂], where M = Fe, Co) were synthesized and characterized using various physico-chemical techniques. A thermal decomposition technique was used to prepare spinel-type zinc cobaltite (ZnCo₂O₄) and zinc ferrite (ZnFe₂O₄) nanocrystalline particles with the synthesized single source precursors. Structural studies using PXRD ascertained the predominant crystal phase to be spinel. Transmission electron microscopy (TEM) and high-resolution TEM (HRTEM) showed a mean nanoparticle size of 18 ± 2 nm. Magnetic measurements revealed a weak magnetic behavior in the synthesized spinels. In the aqueous phase, the spinels exhibited catalytic activity, reducing 4-nitrophenol (4-NP) in the presence of NaBH₄ at room temperature. Additionally, the study demonstrated that the catalyst can be recovered and reused for five cycles with a more than 85% conversion efficiency.     

CoFe2O4/CuO活化过氧乙酸高效降解磺胺甲恶唑(英文)

利用化学沉淀法和溶胶凝胶法,通过两步法成功制备出含有尖晶石钴铁氧体和氧化铜的复合催化剂CoFe₂O₄/CuO,通过扫描电子显微镜(SEM)、X射线光电子能谱(XPS)和X射线衍射(XRD)对制备出的CoFe₂O₄/CuO进行表征,探究不同高级氧化体系对磺胺甲恶唑(SMX)去除能力,考察过氧乙酸(PAA)浓度、催化剂投加量、水体中常见干扰物质(Cl^-,HCO-3,SO₄^2-,HA)和不同自由基捕获剂对SMX去除的影响。分析结果表明CoFe₂O₄/CuO同时具有CoFe₂O₄与CuO的特征,对比单独CoFe₂O₄与CuO,CoFe₂O₄/CuO对PAA展现出极高的活化性能,在最佳反应条件下(催化剂投加量=20mg·L^-1,c(PAA)=200μ...     

富含吡啶氮-钴活性位点的三维多级大/介孔石墨烯作为高效可逆氧电催化剂用于可充电锌-空气电池

随着能源危机的日益严峻,能源的储存和转换越来越受到人们的重视.目前人们加以开发和利用的清洁能源主要包括太阳能、风能、氢能、地热能以及电化学能等.其中,燃料电池和金属-空气电池等作为电化学器件为电化学能的开发及可持续利用提供了条件.特别是金属-空气电池以电极电位较负的金属如镁、铝、锌、铁等作负极,以空气中的氧或纯氧作正极,具有比能量高、性能稳定、价格便宜的特点.氧还原反应(ORR)和析氧反应(OER)是可再生电化学能量转换和储存过程中的两个关键电化学过程.贵金属(Pt/C,Ir/C,IrO₂等)虽然具有高催化活性,但价格昂贵、资源匮乏限制了其大规模的使用和发展.此外,它们的催化性能单一,难以同时实现多反应的高效催化.目前,大量研究工作集中在开发低成本、高效的ORR和OER催化剂,用来代替昂贵的铂类贵金属催化剂.在能源器件设计中,由于OER和ORR反应发生在同一个电极上,若能制备出具有ORR和OER双功能催化性能的电催化剂,将在很大程度上降低能源器件的设计难度.最近,我们的研究工作揭示了吡啶-氮-钴(pyri-N-Co)配位结构在协同作用中的重要性,协同作用大幅度提升了NiCo2O4/N掺杂石墨烯的本征催化活性.虽然金属粒子与掺氮石墨烯的结合有利于催化活性和稳定性的提高,但二维石墨烯片之间由于π-π键相互作用,容易聚集和堆叠.在实际应用中,石墨烯片之间的堆叠会导致可达表面的损失,从而使复合催化剂利用率降低,结构稳定性变差.因此,制备富含充分暴露且高效的ORR/OER活性中心的电催化剂仍然是一个巨大挑战.本文采用激光辐照法和水热法制备了具有层间大孔和片内介孔相互交联结构且负载铁酸钴纳米颗粒的三维多级孔石墨烯复合电催化剂(CoFe/3D-NLG),研究了其微观结构与ORR/OER电催化性能的关系.比表面积和X射线光电子能谱测试结果表明,CoFe/3D-NLG具有大的比表面积(322.6 m² g^-1)和孔体积(0.715 cm³ g^-1),并且富含吡啶氮-钴活性中心.电化学测试表明,对于OER电催化,CoFe/3D-NLG复合催化剂在10 mA cm_-2处的过电势为304 mV,优于商用RuO₂催化剂的322 mV;对于ORR电催化,CoFe/3D-NLG的半波电位达到872 mV,非常接近商用Pt/C催化剂(876 mV).此外,作为可充电锌空气电池的空气电极催化剂,CoFe/3D-NLG展现出了超高的开路电压(1.56 V)、高功率密度(213 mW cm_-2)以及超低充放电电压(0.63 V),并且具有良好的充放电循环稳定性.CoFe/3D-NLG优异的ORR/OER电催化性能主要归因于以下两点:1)大量的吡啶氮-钴活性位点极大地加快了缓慢的氧电催化动力学,提高了每个活性位点的ORR/OER本征催化活性;2)丰富的层间大孔和面内介孔多级孔结构促进了整个石墨烯结构中的高效传质,因而在电催化过程中吡啶氮-钴活性位点得以充分暴露于电解液中.     

二价与四价金属离子等摩尔共掺杂的锂离子电池正极材料LiMn1.9Mg0.05Ti0.05O4的制备与表征

以氢氧化锂、乙酸锰、硝酸镁和钛酸丁酯为原料, 以柠檬酸为螯合剂, 采用溶胶-凝胶法制备了二价镁离子与四价钛离子等摩尔共掺杂的尖晶石型锂离子电池正极材料LiMn_1.9Mg_0.05Ti_0.05O₄. 采用热重分析(TGA), X射线衍射(XRD), 扫描电子显微镜(SEM), 透射电子显微镜(TEM)和电化学性能测试(包括循环伏安(CV)和电化学交流阻抗谱(EIS)测试)对所得样品的结构、形貌及电化学性能进行了表征. 结果表明: 780℃下煅烧12 h 得到了颗粒均匀细小的尖晶石型结构的LiMn_1.9Mg_0.05Ti_0.05O₄材料, 该材料具有良好的电化学性能, 在室温下以0.5C倍率充放电, 在4.35-3.30 V电位范围内放电比容量达到126.8 mAh·g^-1, 循环50 次后放电比容量仍为118.5mAh·g^-1, 容量保持率为93.5%. 在55℃高温下循环30次后的放电比容量为111.9 mAh·g^-1, 容量保持率达到91.9%, 远远高于未掺杂的LiMn₂O₄的容量保存率. 二价镁离子与四价钛离子等摩尔共掺杂LiMn₂O₄, 改善了尖晶石锰酸锂的电子导电和离子导电性能, 使其倍率性能和高温性能都得到了明显的提高.     

Hydrogen and deuterium diffusion in non-stoichiometric spinel

High pressure/temperature annealing experiments are used to determine diffusivities of H⁺ and D⁺ in non-stoichiometric spinel, a low-pressure analogue for nominally anhydrous minerals in Earth’s mantle. Data are fitted to the following Arrhenius law: Diffusivity (m²/s)?=?4?±?1?×?10^?12 exp(?54?±?2 kJ?mol^?1/RT). At low temperatures, H⁺ and D⁺ diffusion in non-stoichiometric spinel is charge balanced by flux of O vacancies, with infrared data consistent with protonation of both octahedral and tetrahedral O–O edges in non-stoichiometric spinel, and additional fine structure due to Mg–Al mixing and/or coupling of structurally incorporated H⁺ with cation vacancies. Absence of changes in the fine structure of O–H absorption bands indicates that H⁺ can become locally coupled and uncoupled to other defects during bulk diffusion. As such, proton conductivity in spinel group minerals, arising from faster flux of uncoupled H⁺, can only be calculated from H⁺ mobility data if the extent of defect coupling is constrained.     

Surface-segregated, high-voltage spinel LiMn1.5Ni0.42Ga0.08O4 cathodes with superior high-temperature cyclability for lithium-ion batteries

The substitution of a small amount of Ga in the high-voltage spinel cathode LiMn_1.5Ni_0.42Ga_0.08O₄ leads to superior cyclability at room temperature and 55 °C along with higher rate capability with conventional electrolytes compared to that found with the LiMn_1.5Ni_0.5O₄ cathode. The superior performance is attributed to the segregation of the inert Ga³⁺ ions to the surface during the synthesis process, providing a robust, more stable interface with the electrolyte at the high operating voltage (~ 4.7 V), along with the stabilization of the spinel structure with a disordering of the cations in the octahedral sites.     

锂离子交换体Li1.5Ti1.625O4的研究(Ⅱ)-H1.5Ti1.625O4的交换性能研究

本文就H1.5Ti1.625O4的pH滴定、分配系数Kd、交换容量、交换等温线、交换速度等离子交换性能进行了研究.研究结果表明,H1.5Ti1.62504对锂离子表现出很好的离子交换选择性及记忆性交换功能.     

以酚醛树脂为碳源原位合成富锂层状相/尖晶石/碳核壳结构正极材料及其电化学性能

通过酚醛树酯包覆和碳热反应在富锂正极材料表面原位构建碳和尖晶石双壳保护结构, 对这种核壳结构的正极材料进行了结构和形貌表征, 并研究了其电化学性能. 研究发现, 尖晶石相为材料提供了三维锂离子迁移通道, 碳包覆层显著提高了正极材料的电子电导率, 两种效应的共同作用极大降低了材料的电化学阻抗, 提升了材料的放电比容量, 这种多壳层结构正极材料还具有优异的倍率性能, 在5C倍率下放电比容量可达到135.1 mA·h/g.     

Luminescent properties of cobalt-doped α-ZnAl2S4 spinel type single crystals

The absorption and luminescent properties of α-ZnAl₂S₄:Co spinel type crystals grown by chemical transport reactions method are investigated. The spectra are assigned to the electronic transitions of Co²⁺ ions located in tetrahedral sites. It is shown, that the revealed four radiative spectral components are caused by the ²A(²G)→⁴T₁(⁴F), ⁴T₁(⁴P)→⁴T₂(⁴F), ²E(²G)→ ⁴T₂(⁴F) and ²E(²G)→⁴T₁(⁴F) transitions.     

Spinel–rocksalt transition as a key cathode reaction toward high-energy-density magnesium rechargeable batteries

Mg-metal-anode rechargeable battery (MRB) has been a promising candidate for next-generation batteries with high energy densities and high safety. The lack of high-performance cathode materials, however, retards the development of MRBs. In recent years, it has been revealed that various spinel oxides can accommodate a large amount of Mg, exhibiting relatively high potentials (2–3 V vs. Mg²⁺/Mg) and high capacities (～150 mAh g^?1) accompanied by the coherent structural transformation into the rocksalt structure. This review summarizes the recent progress in the development of such spinel–rocksalt transition materials from the viewpoints of the reaction mechanisms, design guidelines of spinel oxides (for tailoring the redox potential, volume change, and cyclability), and challenges to construct full-cell MRBs.