Sub-solidus phase equilibria in CeO2–SrO system

In this communication, we report on the synthesis and characterization of a series of compounds with the general composition Ce_1−xSr_xO_2−x (0.0≤x≤1.0), to establish a detailed phase relation in the CeO₂–SrO system. The X-ray diffraction (XRD) pattern of the each product was refined to determine the solid solubility and the homogeneity range. The solid solubility limit of SrO in CeO₂ lattice, under the slow cooled conditions, is represented as Ce_0.91Sr_0.09O_1.91 (i.e. 9 mol% of SrO). A careful delineation of the phase boundary revealed that the stoichiometric SrCeO₃, in fact, contains a little amount of CeO₂ also. The mono-phasic compound could be obtained at the nominal composition Sr_0.55Ce_0.45O_1.45. The nominal composition Sr₂CeO₄, under the heat treatment used in the present investigation, was a bi-phasic mixture of SrCeO₃ and SrO. No new ordered phases were obtained in this system.     

Synthesis and low temperature fluorination of the alkaline-earth palladates Ba2−xSrxPdO3 (x = 0–2)

Since the discovery of superconductivity in Sr₂CuO₂F_2+δ there has been an increased interest in ternary oxide-fluorides. Sr₂CuO₂F_2+δ is prepared via low temperature (T = 220 °C) reaction routes. Low temperature fluorination induces an interesting structural rearrangement in the parent compound Sr₂CuO₃, which is a one-dimensional material containing linear chains of vertex sharing CuO₄ squares along the crystallographic b axis. Upon fluorination, one oxide is substituted by two fluorides and Cu²⁺ becomes octahedrally coordinated by four oxides and two fluorides. The fluorinated compound Sr₂CuO₂F_2+δ displays the T-type structure (La₂CuO₄). Insertion of excess fluorine, δ, also takes place and this fluorine occupies interstitial sites in the T structure. Although the starting material Ca₂CuO₃ is isostructural to Sr₂CuO₃, Ca₂CuO₂F_2+δ displays the T′ (Nd₂CuO₄) structure due to the smaller radius of Ca²⁺ compared to that of Sr²⁺.

The alkaline-earth palladates with the general formula A₂PdO₃ (A = Ba, Sr) are isostructural with the A₂CuO₃(A = Ca, Sr) materials. We prepared the Ba_2−xSr_xPdO₃ (x = 0–2) series and performed low temperature fluorination, which led to the synthesis of the series Ba_2−xSr_xPdO₂F_2+δ (0 ≤ x ≤ 1.5). All the compounds in the Ba_2−xSr_xPdO₂F_2+δ series show T′ structure (Ca₂CuO₂F_2+δ). Similarities and differences with Sr₂CuO₂F_2+δ and Ca₂CuO₂F_2+δ will be discussed.     

Catalytic decomposition of H2O2 on Co3O4 doped with MgO and V2O5

The effects of doping of Co₃O₄with MgO (0.4–6 mol%) and V₂O₅ (0.20–0.75 mol%) on its surface and catalytic properties were investigated using nitrogen adsorption at −196°C and decomposition of H₂O₂ at 30–50°C. Pure and doped samples were prepared by thermal decomposition in air at 500–900°C, of pure basic cobalt carbonate and basic carbonate treated with different proportions of magnesium nitrate and ammonium vanadate. The results revealed that, V₂O₅ doping followed by precalcination at 500–900°C did not much modify the specific surface area of the treated Co₃O₄ solid. Treatment of Co₃O₄ with MgO at 500–900°C resulted in a significant increase in the specific surface area of cobaltic oxide. The catalytic activity in H₂O₂ decomposition, of Co₃O₄ was found to suffer a considerable increase by treatment with MgO. The maximum increase in the catalytic reaction rate constant (k) measured at 40°C on Co₃O₄ due to doping with 3 mol% MgO attained 218, 590 and 275% for the catalysts precalcined at 500, 700 and 900°C, respectively. V₂O₅-doping of Co₃O₄ brought about a significant progressive decrease in its catalytic activity. The maximum decrease in the reaction rate constant measured at 40°C over the 0.75 mol% V₂O₅-doped Co₃O₄ solid attained 68 and 93% for the catalyst samples precalcined at 500 and 900°C, respectively. The doping process did not modify the activation energy of the catalyzed reaction but much modified the concentration of catalytically active constituents without changing their energetic nature. MgO-doping increased the concentration of CO³⁺–CO²⁺ ion pairs and created Mg²⁺–CO³⁺ ion pairs increasing thus the number of active constituents involved in the catalytic decomposition of H₂O₂. V₂O₅-doping exerted an opposite effect via decreasing the number of CO³⁺–CO²⁺ ion pairs besides the possible formation of cobalt vanadate.     

Pt/Au/Fe3O4的制备及其电化学性能

以制得的纳米Fe₃O₄颗粒作为载体,用还原法将还原出的Au与Pt分别负载到Fe₃O₄颗粒表面,制得纳米Pt/Au/Fe₃O₄复合材料。对Pt/Au/Fe₃O₄进行紫外可见光吸收光谱、透射电子显微镜、X射线衍射及光电子能谱等物理表征,结果表明,Au与Pt均匀地沉积到了Fe₃O₄纳米颗粒表面。对纳米Pt/Au/Fe₃O₄复合材料进行循环伏安扫描,当H₂PtCl₆的加入量达到8 mL时,Pt/Au/Fe₃O₄催化性能最佳;正扫电流峰i_p与扫描速率的平方根v^1/2线性相关,Pt/Au/Fe₃O₄催化氧化甲醇的过程受扩散控制;对催化剂进行201次循环伏安扫描,催化剂仍然能保持较好的催化性能且稳定性良好。因此,所合成催化剂Pt/Au/Fe₃O₄是一种具有良好化学稳定性的阳极催化剂材料。     

Photothermal performance of MFe2O4 nanoparticles

In this paper, we synthesized three kinds of ferrites and investigated their photothermal property. The result indicated that the photothermal effect of Fe₃O₄ and MnFe₂O₄ nanoparticles declined while that of ZnFe₂O₄ nanoparticles maintained relatively stable after preservation for 70 days, and then ZnFe₂O₄ nanoparticles could effectively kill cancer cells under NIR laser.     

Fe2O3/Al2O3氧载体用于甲烷化学链燃烧：负载量与制备方法的影响

以不同方法制备了系列Fe₂O₃/Al₂O₃氧载体,采用XRD、H₂-TPR、CH₄-TPR、O₂-TPD和BET等分析技术对氧载体进行了表征。研究了不同Fe₂O₃负载量氧载体的甲烷化学链燃烧性能,考察了不同制备方法对Fe₂O₃/Al₂O₃氧载体结构、反应性和产物选择性的影响。结果表明,Fe₂O₃负载量对氧载体活性及产物中CO₂选择性的影响较大,负载量较低时氧载体活性较低且引起甲烷部分氧化产物CO含量增加。制备方法亦对氧载体与甲烷的反应活性有所影响,整体上共沉淀法制备的质量分数60％Fe₂O₃/Al₂O₃氧载体具有较高的氧化活性和化学链循环稳定性。其在反应温度850℃、反应时间15 min、30次循环后甲烷转化率及产物中CO₂选择性均未见明显降低。     

碱性介质中制备纳米四氧化三锰及其超级电容特性

比较了不同碱溶液中纳米Mn₃O₄的制备及其超级电容性能。用X射线粉末衍射仪、扫描电子显微镜和原子力显微镜等技术手段分别测试了晶体结构和表面形貌。用循环伏安、恒流充放电和交流阻抗测试了材料的电化学性能。结果表明,在氢氧化钠、氨水中Mn²⁺沉淀氧化可以直接制备纳米Mn₃O₄;碳酸钠中先生成MnCO₃,加氢氧化钠可转化为纳米Mn₃O₄。NaOH、NH₃和Na₂CO₃ 3种介质中制备的Mn₃O₄晶粒尺寸分别为29.5、20.2和36.3 nm。纳米Mn₃O₄经连续充放电循环后可活化为Birnessite-type MnO₂。氨水中制备的Mn₃O₄活化后比容量最大,达到239 F/g,是一种具有应用前景的超级电容器材料。     

The story of Sr2RuO4

This article reports on the experiments performed in the Sr–Ru–O system, the motivation behind them and their impact on basic research and device applications. It refers to the time from 1987 to 2003, with emphasis on the occurrences before the discovery of superconductivity in Sr₂RuO₄ in 1994. Apart from the title compound Sr₂RuO₄ itself and related ruthenates, it touches on many different topics like titanates, ferrates, high-T_c superconducting cuprates, crystal growth by floating zone melting and thin films as well as fundamental and applied research.     

煤灰/K_2CO_3/Fe_2O_3对脱矿无烟煤燃点与燃烧速率的影响(英文)

考察了煤灰/K2CO3/Fe2O3及其之间的相互作用对酸洗无烟煤燃点和燃烧速率的影响。不同温度下制备的煤灰显示了不一样的性质(如化学组成、颜色和形貌)。脱矿无烟煤(负载和非负载催化剂)的燃烧反应性测试在热重分析仪(TGDTG)中完成,结果表明,煤灰本身对酸洗无烟煤的燃点几乎没有影响,而高温下制备的煤灰能够明显提高酸洗无烟煤的燃烧速率。当煤灰和K2CO3或者Fe2O3的混合物加入酸洗无烟煤中作为燃烧催化剂时,可以看出与单独使用K2CO3或Fe2O3相比,煤灰的加入明显导致酸洗煤的燃烧速率下降,而对其燃点影响不大。同样,K2CO3和Fe2O3之间的相互作用也能够对酸洗无烟煤的燃烧速率产生负面影响。     

化学链制氢中Fe2O3/LaFeO3载氧体的性能研究

采用柠檬酸络合法制备Fe₂O₃/LaFeO₃复合氧化物,将该氧化物作为化学链制氢过程的载氧体,在反应温度为900 ℃、常压下,对Fe₂O₃/CH₄（剂烷比）、进水量、金属负载量进行了考察。结果表明,剂烷比为2：1、进水量为0.1 mL、质量分数15%Fe时载氧体性能最好,甲烷转化率达到60%,单次循环氢气产量为45 mL。将该评价结果与XRD和H₂-TPR表征结果进行关联发现,反应过程的活性位不是金属氧化物,而是吸附氧,而且吸附氧越容易还原,甲烷转化率和氢气产量越高。通过连续60次还原-氧化循环发现,该载氧体上甲烷转化率和氢气产量比较稳定,循环后仍然保持钙钛矿结构。     

Ce3+、Tb3+离子及Ce3+-Tb3+离子对在Sr4Si3O8Cl4基质中发光的研究

研究了Ce³⁺、Tb³⁺、离子及Ce³⁺-Tb³⁺离子对在Sr₄Si₃O₈Cl₄基质中的发射光谱和激发光谱。初步讨论了Ce³⁺、Tb³⁺离子之间发光敏化的机理。     

碱土Sr对Co/Al2O3催化剂甲烷部分氧化反应的影响

以γ-Al₂O₃为载体,采用共浸渍法制备了Sr-Co/Al₂O₃系列催化剂,研究了助剂Sr对Co/Al₂O₃催化剂上甲烷部分氧化(POM)制合成气反应的影响,并利用N₂物理吸附、X射线衍射、H₂-程序升温还原和热重等技术对催化剂的理化性质进行了表征。结果表明,未添加助剂的Co/Al₂O₃和800℃焙烧的Sr-Co/Al₂O₃催化剂在POM反应初期催化活性很低,然而,当添加Sr的质量分数高于2%时,催化剂表现出很好的催化活性和稳定性。焙烧后的新鲜催化剂上主要存在两类Co物种,一类是与载体相互作用较弱、易被H₂还原为单质的Co₃O₄;另一类是与载体相互作用较强、难还原、无催化活性的CoAl₂O₄尖晶石。在焙烧过程中,Sr易形成Sr₄Al₁₄O₂₅,从而削弱Co与Al₂O₃之间的相互作用,能在一定程度上抑制CoAl₂O₄物种的形成,提高催化剂的稳定性和活性。未添加Sr的Co/Al₂O₃在反应时易发生物相改变生成尖晶石,导致催化剂迅速失活;但当焙烧温度达到800℃时,添加有限量的Sr还是无法阻止CoAl₂O₄的产生。     

Combined investigation of experimental characterization and theoretic calculation on the structure of dextran-Fe3O4 clusters

Dextran-Fe₃O₄ hybrid clusters were fabricated by coprecipitating ferric and ferrous ions in the presence of dextran, and after characterization of these clusters combined with calculation based on classical nucleation theory, a structure model of these hybrid clusters was proposed. The hybrid cluster was believed including small Fe₃O₄ nanoparticles and dextran which acted as both nucleating agent and stabilizer, so that exist in both the inside of magnetite nanoparticles and the periphery of the hybrid clusters. Besides, the effects of W_CD (weight_{iron cation}:weight_dextran) and molecular weight of dextran on the size, morphology and magnetic property of clusters were also investigated in this paper. It was found that the variation of W_CD and molecular weight of dextran have great effect on the size of the hybrid clusters, but have almost no effect on the size of the Fe₃O₄ nanoparticles. The characterization of magnetic property demonstrated that the Fe₃O₄ nanoparticles are of a single domain and the saturation magnetization was affected by the size of dextran-Fe₃O₄ hybrid clusters.     

Mg改性对Co/γ-Al2O3-TiO2催化燃烧丙烷性能影响

采用分步浸渍法制备了系列Mg改性的Co/γ-Al_2O_3-TiO_2催化剂,通过X射线衍射(XRD)、紫外可见漫反射光谱(DR-UV-vis)、N_2吸附-脱附(BET)、X射线光电子能谱(XPS)和H_2程序升温还原(H_2-TPR)等技术对催化剂进行表征,并考察了其对丙烷燃烧的催化性能。结果表明,Co在原始γ-Al_2O_3-TiO_2载体和Mg改性MgO/γ-Al_2O_3-TiO_2载体上均以Co_3O_4的形式存在;Mg掺入后与Al_2O_3作用形成MgAl_2O_4尖晶石,改善了载体的织构性质,提升了Co_3O_4在催化剂载体表面的暴露数量和分散程度。此外,MgAl_2O_4与Co_3O_4相互作用提升了Co_3O_4颗粒表面Co~(3+)/Co~(2+)和O_(ads)/O_(latt)的比例,并削弱了Co-O键键能,从而提升了其对丙烷的催化燃烧活性。当Mg负载量为15%(质量分数)时,在Co/MgO(15%)/γ-Al_2O_3-TiO_2催化剂上进行丙烷燃烧,丙烷90%转化率的温度比无Mg掺杂的Co/γ-Al_2O_3-TiO_2催化剂的降低了45℃,并且连续反应40 h其活性保持稳定。     

Fast synthesis of dopamine-coated Fe3O4 nanoparticles through ligand-exchange method

A fast approach was described for the synthesis of water-dispersible monodisperse dopamine-coated Fe₃O₄ nanoparticles（DA-Fe₃O₄） with uniform size and shape via ligand-exchange of oleic acid on Fe₃O₄ using only 2 min.The prepared DA-Fe₃O₄ nanoparticles were characterized by transmission electron microscopy,Fourier transform infrared spectrometry,and vibrating sample magnetometer.The results indicated that the resulting DA-Fe₃O₄ nanoparticles had an average diameter of about 19.2 nm. The magnetic saturation value of the prepared DA-Fe₃O₄ nanoparticles was determined to be 72.87 emu/g,which indicating a well-established superparamagnetic property.     

基于Fe_3O_4/乙二胺四乙酸磁性粒子的集成化蛋白质组学方法

建立了基于Fe_3O_4/乙二胺四乙酸(EDTA)磁性粒子的集成化蛋白质组学研究方法。首先用共沉淀法合成EDTA负载的Fe_3O_4/EDTA磁性粒子。在优化的溶液条件下(95%乙腈-1%三氟乙酸,体积分数),100μg Fe_3O_4/EDTA磁性粒子可吸附12.4μg牛血清白蛋白(BSA),吸附容量是商品化磁珠的10倍左右。以BSA作为标准蛋白质,对所合成的Fe_3O_4/EDTA磁性粒子作为蛋白质组学反应器的酶解时间进行了优化,发现Fe_3O_4/EDTA磁性粒子处理BSA酶解1、8和16 h的肽段序列覆盖率和特征肽段结果相当。因此,可以将复杂的蛋白质样品前处理时间缩短至2 h内。最后,将所合成的Fe_3O_4/EDTA磁性粒子应用于血清的蛋白质组学研究,成功地鉴定出218种蛋白质,其中包含了41种美国食品药品管理局(FDA)认证的生物标志物。所发展的基于Fe_3O_4/EDTA磁性粒子的蛋白质组学样品前处理方法将蛋白质样品预富集、还原、烷基化、酶解、多肽除盐和洗脱等步骤集成到一起,减少了样品转移和处理所造成的损失。这种技术具有快速、灵敏和易于操作的特点,可用于临床蛋白质组学研究。     

Fe3O4@PI催化剂的制备及其费托合成性能

分别采用水热、水热-包覆、球磨法制备了Fe_3O_4、聚酰亚胺(PI)改性的Fe_3O_4@PI和Fe_3O_4-PI催化剂用于费托合成反应,对比研究了PI改性及其含量变化对Fe基催化剂催化CO加氢产物分布的影响规律。结合XRD、SEM、TEM、H_2-TPR、COTPD、FT-IR、XPS、TG和接触角实验等手段对催化剂样品进行了表征。结果表明,Fe_3O_4、Fe_3O_4@PI和Fe_3O_4-PI样品均为球形颗粒; PI改性促进了Fe_3O_4的还原,亲水性增强。Fe_3O_4@PI样品中,PI均匀包覆于Fe_3O_4表面,具有较好的热稳定性;与Fe_3O_4、Fe_3O_4-PI相比,Fe_3O_4@PI样品CO吸附增强。在CO加氢反应中,与Fe_3O_4相比,PI改性的Fe_3O_4@PI和Fe_3O_4-PI样品催化活性下降,二次加氢能力受到抑制,烯烃选择性提高; Fe_3O_4@PI样品烯烃选择性增加明显,烯烷比(O/P)由改性前的0.50提高至2.15;适宜含量的PI改性促进C5+烃生成。     

Lotus-stalk Bi4Ge3O12 as binder-free anode for lithium and sodium ion batteries

The synthesized lotus-stalk Bi₄Ge₃O₁₂ utilized as binder-free anode for LIBs demonstrates excellent cycling performance. The synthesized lotus-stalk Bi₄Ge₃O₁₂ is composed of nanosheets, which is contribute to outstanding lithium storage performance.     

SO_4~(2-)功能化处理对Fe_2O_3催化剂上氨选择性催化还原NO_x性能的促进机理研究

采用沉淀法制备了Fe(OH)_3和Fe_2O_3。通过硫酸化处理得到SO_4~(2-)/Fe(OH)_3和SO_4~(2-)/Fe_2O_3两种催化剂,并将其应用于氨选择性催化还原NO_x(NH_3-SCR)反应,研究了SO_4~(2-)功能化处理对Fe_2O_3催化剂上NH_3-SCR脱硝性能的促进机理。结果表明,与纯的Fe_2O_3相比,硫酸化处理得到的催化剂上SCR活性得到显著提升;其中,SO_4~(2-)/Fe(OH)_3表现出更加优异的催化性能,在250-450℃时NO_x转化率高于80%,且具有优异的稳定性和抗H_2O+SO_2性能。XRD、Raman、TG、FT-IR、H_2-TPR、NH_3-TPD和in situ DRIFTS等表征结果显示,硫酸功能化处理能抑制Fe_2O_3的晶粒生长,同时SO_4~(2-)与Fe~(3+)结合形成硫酸盐复合物,提高了催化剂表面酸性位点的数量和酸强度,抑制了Fe_2O_3上的氨氧化反应,从而提高了其脱硝催化性能。     

Fe_3O_4/RGO复合材料的制备及其电化学性能研究

以改进Hummers法合成的氧化石墨烯(GO)为前驱体,通过水热法结合烧结工艺制备了四氧化三铁/还原氧化石墨烯(Fe_3O_4/RGO)复合材料。利用X射线衍射(XRD)、拉曼光谱(Raman)、扫描电镜(SEM)、透射电镜(TEM)等手段对复合材料的理化性能进行表征;通过充放电测试、循环伏安(CV)和电化学阻抗谱(EIS)等技术,综合考察了材料的储锂性能及电化学性能增强机制。结果表明,在200和600 m A/g电流密度下,Fe_3O_4/RGO复合负极循环60次后的放电比容量分别保持在709和479 mAh/g,表现出良好的倍率性能;相较于纯Fe_3O_4负极,复合负极呈现出更优异的锂电性能,其电化学性能的改善得益于RGO能增强材料的电导性和结构稳定性。