加热方式及原料配比对介孔CeO2结构及其光催化性能的影响

以P123（聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物）为模板剂,Ce（NO₃）₃为反应原料,通过考察加热方式、加热温度、原料配比等因素,合成了结构性能较好、表面羟基含量较高的介孔CeO₂材料。利用XRD,N₂吸附-脱附,TEM,Raman,FT-IR等技术对合成样品的结构性能进行了表征,结果表明,当P123与Ce（NO₃）₃物质的量之比为1：10,在110℃水热下合成的CeO₂结构性能最好。以酸性橙7（AO7）为探针分子,对合成介孔CeO₂的光催化性能进行评价。光催化结果证明,由于表面羟基含量较高、介孔及氧缺位的形成,所合成结构性能较好的CeO₂,利用可见光可彻底催化降解溶液中的AO7。     

介孔NH_2-Ce-Pr-O合成及其可见光催化性能EI北大核心CSCD

以P123(聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物)为模板剂,Ce(NO_3)_3,Pr(NO_3)_3为原料,采用水热反应制备前驱物,经萃取除去P123后既得表面羟基含量较高的Ce-Pr-O介孔材料。利用氨基硅烷与表面羟基间的缩合作用,合成了氨基功能化介孔Ce-Pr-O。利用XRD,N_2吸脱附,Raman,FT-IR,XPS等技术对合成样品结构性能进行了表征。结果表明:以25%Pr(NO_3)_3掺杂所获得的Ce-Pr-O结构性能较好;该样品氨基功能化后,除孔径、表面积及孔容变小外,其他性能基本保持不变。以酸性红14(AR14)为探针分子,对合成材料的光催化性能进行评价。结果表明:由于Pr掺杂后形成氧缺位,提高了样品的可见光吸收强度;此外,通过嫁接氨基,提高AR14的吸附量。因此,所合成的氨基功能化介孔Ce-Pr-O在可见光作用下,能较彻底地催化降解溶液中的AR14。     

介孔NH_2-Ce-Pr-O合成及其可见光催化性能

以P123(聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物)为模板剂,Ce(NO_3)_3,Pr(NO_3)_3为原料,采用水热反应制备前驱物,经萃取除去P123后既得表面羟基含量较高的Ce-Pr-O介孔材料。利用氨基硅烷与表面羟基间的缩合作用,合成了氨基功能化介孔Ce-Pr-O。利用XRD,N_2吸脱附,Raman,FT-IR,XPS等技术对合成样品结构性能进行了表征。结果表明:以25%Pr(NO_3)_3掺杂所获得的Ce-Pr-O结构性能较好;该样品氨基功能化后,除孔径、表面积及孔容变小外,其他性能基本保持不变。以酸性红14(AR14)为探针分子,对合成材料的光催化性能进行评价。结果表明:由于Pr掺杂后形成氧缺位,提高了样品的可见光吸收强度;此外,通过嫁接氨基,提高AR14的吸附量。因此,所合成的氨基功能化介孔Ce-Pr-O在可见光作用下,能较彻底地催化降解溶液中的AR14。     

氨基功能化介孔Ce-Fe-O合成及其光催化性能研究

以P123(聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物)为模板剂,Ce(NO_3)_3,Fe(NO_3)_3为反应原料,通过水热反应,合成了结构性能较好的Ce-Fe-O介孔材料。利用氨基硅烷与表面羟基间的缩合作用,成功地实现了介孔Ce-Fe-O的氨基功能化。利用XRD,N_2吸脱附,Raman,FT-IR等技术对合成样品的结构性能进行了表征。结果表明:以15%Fe(NO_3)_3进行掺杂所获得的Ce-Fe-O结构性能较好;该材料氨基功能化后,除孔径、表面积及孔容变小外,其他性能基本保持不变。以酸性红14(AR14)为探针分子,对相关合成材料的光催化性能进行评价。光催化结果表明:由于氧缺位形成及氨基引入,提高了可见光吸收强度及对AR14的吸附量,所合成的氨基功能化介孔Ce-Fe-O在可见光作用下,可彻底催化降解溶液中的AR14,且降解效率高于相关光催化剂。     

铈源对甲醇水蒸气重整制氢CuO/CeO2催化剂的影响

采用沉淀法合成了CeO_2载体,再经浸渍法负载活性组分得到CuO/CeO_2催化材料,探究了铈源(Ce(NO_3)_3·6H_2O、Ce Cl_3·6H_2O、Ce(NH_4)_2(NO_3)_6、Ce(SO_4)_2·4H_2O)对CuO/CeO_2催化性能的影响。通过采用XRD、SEM、N_2O滴定、BET和H_2-TPR等表征手段对催化材料的结构和性质研究发现,四种铈源合成的CuO/CeO_2催化材料在Cu比表面积、还原性能以及活性组分和载体间的相互作用方面存在着明显差别。其中,由Ce(NO_3)_3·6H_2O合成的CuO/CeO_2催化材料的Cu比表面积较大,CuO还原温度较低,CeO_2载体与CuO之间相互作用较强,在甲醇水蒸气重整反应过程中,表现出较佳的催化活性,在反应温度为553 K,水醇比n(H_2O)/n(MeOH)为1.2,甲醇水蒸气气体空速(GHSV)为1760 h~(-1)时,甲醇的转化率为100%,重整气中CO摩尔含量为0.84%。     

阳极氧化铝模板合成介孔CeO2纳米纤维及其光致发光性能

以多孔阳极氧化铝膜(AAO)为模板,将模板的纳米孔洞作为微腔反应器,以聚环氧乙烯醚-聚环氧丙烯醚-聚环氧乙烯醚三嵌段共聚物(P123)为致孔剂、Ce(NO3)3.6H2O为铈源、无水乙醇为溶剂合成前躯体,采用压力诱导的方法将前躯体注入到AAO孔道内,经加热处理后,在模板的纳米孔洞内合成了具有介孔结构的一维CeO2纳米材料。通过SEM、TEM、XRD、EDS和N2吸附-脱附进行表征,结果表明,所合成的介孔CeO2纳米纤维具有介孔结构和较大的比表面积,并考察了其光致发光性能。     

不同表面形貌Cu2O空心球的制备及光催化性能

采用一步溶剂热法,以Cu(NO_3)_2·3H_2O为铜源,乙二醇(EG)为还原剂,聚乙烯吡咯烷酮(PVP)为表面活性剂,高温条件下制备形貌可控的Cu_2O空心球纳米材料。研究Cu(NO_3)_2·3H_2O与PVP的质量比值(w_(Cu(NO_3)_2·3H_2O)/w_(PVP))对Cu2O结构、形貌、比表面积以及光吸收特性的影响,并结合光催化机理讨论其对Cu_2O光催化性能的影响。此外,通过改变反应时间来研究Cu_2O的生长过程。结果表明,w_(Cu(NO_3)_2·3H_2O)/w_(PVP)=45时,得到的形貌为空心球表面覆盖纳米刺的Cu_2O纳米材料光催化性能最佳,在可见光辐照10 min的条件下,对甲基橙的降解率达94.3%。     

新型介孔二氧化硅囊泡结构的调变

本文采用水热合成法,利用非离子表面活性剂聚环氧乙烷-聚环氧丙烷-聚环氧乙烷(P123)对有机溶剂均三甲苯(TMB)的增容作用,合成了大孔径介孔二氧化硅囊泡材料,首次通过控制有机溶剂TMB与无机硅源正硅酸四乙酯(TEOS)的投料时间间隔t,实现对介孔二氧化硅囊泡材料结构的调变。通过小角X射线衍射和高分辨透射电镜(HTEM)检测技术对酸性P123模板体系中的材料结构转变过程进行了表征。结果表明,改变TMB与TEOS的投料时间间隔,能够实现介孔囊泡结构的调变,同时提出"协同囊泡模板"(cooperative vesicle templating,CVT)和"协同作用机制"(cooperative formation mechanism,FM)共存。通过简单合理的设计合成不同结构的介孔材料,以期开拓其在催化、分离以及医学等领域的潜在应用,也为合成其他介孔材料提供简单合理的设计思路。     

蠕虫状孔道介孔SiO2的合成及其固定化漆酶的活性

以聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物(P123)与离子型助表面活性剂{十六烷基三甲基溴化铵(CTAB)、十二烷基硫酸钠(SDS)或N-肉豆蔻酰-D-丙氨酸(C14-D-A)}为结构导向剂,合成了蠕虫状孔道的介孔SiO2,并在P123/C14-D-A/TMAPS(N-三甲氧基硅丙基-N,N,N-三甲基氯化铵)合成反应体系中,研究了扩孔剂聚乙二醇(PEG)-400的不同添加量对蠕虫状孔道的扩孔效果.合成的产物分别用X-射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)和N2吸附进行表征.此外,利用溶剂萃取法对扩孔后的蠕虫状介孔SiO2进行处理,得到不同孔径的季铵盐官能团化介孔SiO2,分别用于漆酶的固定化;并对固定化酶的稳定性、所需的最佳pH值以及降解2,4-DCP的重复利用性进行了研究.通过比较研究发现,介孔SiO2孔径与漆酶分子直径的匹配性是影响固定化漆酶比活及降解2,4-DCP效率的重要因素.     

MOFs自牺牲模板法制备ZnO及其对NO2的气敏性能

以硝酸锌和2,5-二羟基对苯二甲酸为原料,采用溶剂热法制备了Zn-MOF-74,并利用MOFs自牺牲模板法制备了ZnO纳米材料。利用热重-差示扫描量热法(TG-DSC)、X射线衍射(XRD)、红外光谱测试(FT-IR)、X射线光电子能谱测试(XPS)、氮气吸附-脱附、扫描电镜(SEM)和高倍透射电镜(HRTEM)等方法对合成的样品进行了结构表征。研究了煅烧温度对产物结构、形貌和组成的影响,以及材料的气敏传感性能。结果表明,450℃煅烧Zn-MOF-74制备的六方柱状介孔氧化锌(ZnO450)是由直径约为20 nm的粒子组成的纳米片堆叠形成的,表面残留部分有机官能团,且吸附氧含量明显高于350和550℃处理的样品。基于ZnO450的气敏传感器选择性响应NO_2气体,对100 mL·m~(-3)的NO_2气体响应值达到了77.40,是所测试的其他气体响应值的6～105倍,检出限为0.1 mL·m~(-3);并且在有SO_2等气体共存时,对NO_2的响应值基本不变,抗干扰能力强。该传感器对NO_2优异的响应能力是由于材料表面吸附氧含量高、比表面积及孔径较大,这些有利于NO_2的吸附、表面反应和扩散。     

Reactivity of Binary Mixtures of La(III) Oxide and Cu(II) Oxalate or Nitrate and Synthesis of La(III) Cuprate

Reactivity of mixtures of La(III) oxide and Cu(II) oxalate/nitrate in hydrated as well as anhydrous state was studied using TG, DTA and XRD. Cu(II) oxide formed in the endothermic decomposition of mixture containing hydrated Cu(II) nitrate and La(III) oxide could not form La₂CuO₄ while Cu(II) oxide formed in the exothermic decomposition of mixture containing hydrated/anhydrous Cu(II) oxalate and La(III) oxide reacts with La(III) oxide and develops the phases CuLaO₃ and La₂CuO₄. The maximum reactivity with respect to the formation of La₂CuO₄phase was observed in mixture containing anhydrous Cu(II) oxalate. This revised version was published online in July 2006 with corrections to the Cover Date.     

Energetics of formation of alkali and ammonium cobalt and zinc phosphate frameworks

Alkali and ammonium cobalt and zinc phosphates show extensive polymorphism. Thermal behavior, relative stabilities, and enthalpies of formation of KCoPO₄, RbCoPO₄, NH₄CoPO₄, and NH₄ZnPO₄ polymorphs are studied by differential scanning calorimetry, high-temperature oxide melt solution calorimetry, and acid solution calorimetry.α-KCoPO₄ and γ-KCoPO₄ are very similar in enthalpy. γ-KCoPO₄ slowly transforms to α-KCoPO₄ near 673 K. The high-temperature phase, β-KCoPO₄, is 5-7 kJ mol⁻¹ higher in enthalpy than α-KCoPO₄ and γ-KCoPO₄. HEX phases of NH₄CoPO₄ and NH₄ZnPO₄ are about 3 kJ mol⁻¹ lower in enthalpy than the corresponding ABW phases. There is a strong relationship between enthalpy of formation from oxides and acid-base interaction for cobalt and zinc phosphates and also for aluminosilicates with related frameworks. Cobalt and zinc phosphates exhibit similar trends in enthalpies of formation from oxides as aluminosilicates, but their enthalpies of formation from oxides are more exothermic because of their stronger acid-base interactions. Enthalpies of formation from ammonia and oxides of NH₄CoPO₄ and NH₄ZnPO₄ are similar, reflecting the similar basicity of CoO and ZnO.     

镥晶体的绝热量热法测试和热力学函数

文章合成了Lu(NO₃)₃(C₂H₅O₂N)_4.H₂O,用红外和元素分析对其进行了表征。用高精度全自动绝热量热仪,测定了该配合物80-382 K温区的热容, 利用实验热容数据, 根据热容与焓、熵的热力学关系, 求出了配合物85-350 K温区内每隔5 K相对于298.15K的标准热力学函数(HT - H298.15)m和(ST - S298.15)m.在80-350 K温度区间内,配合物的热容随温度升高而增大,没有相转移点和热力学吸收峰的出现,该配合物在此温度区间内是稳定存在的。     

Synthesis and characterization of gallium-based perovskitetype dense membrane with oxygen semipermeability

La0.15Sr0.85Ga0.3Fe0.7O3-δ(LSGFO) and La0.15Sr0.85Co0.3Fe0.7O3-δ(LSCFO) mixed oxygen-ion and electron conducting oxides were synthesized by using a combined EDTA and citrate complexing method, and the corresponding dense membranes were fabricated. The properties of the oxide powders and membranes were characterized with combined SEM, XRD, H2-TPR, O2-TPD techniques, mechanical strength and oxygen permeation measurement. The results showed that LSGFO had much higher thermochemical stability than LSCFO due to the higher valence stability of Ga3+. After the temperature-programmed reduction by 5% H2 in Ar from 20℃to 1020℃, the basic perovskite structure of LSGFO was successfully preserved. LSGFO also favors the oxygen vacancy formation better than LSCFO. Oxygen permeation measurement demonstrated that LSGFO had higher oxygen permeation flux than LSCFO, but they had similar activation energy for oxygen transportation, with a value of 110 and 117 kJ ?mol~(-1), respectively. The difference in oxygen permeation f     

Synthesis, Structure, and 31P NMR of Sulfur/Oxygen-Bridged Incomplete Cubane-Type Molybdenum and Tungsten Clusters with Triphenylphosphine Ligands

Sulfur/oxygen-bridged incomplete cubane-type triphenylphosphine molybdenum and tungsten-clusters [Mo₃S₄Cl₄(H₂O)₂(PPh₃)₃]·3THF (1A), [Mo₃S₄Cl₄(H₂O)₂(PPh₃)₃]·2THF (2A), [Mo₃OS₃Cl₄(H₂O)₂(PPh₃)₃]·2THF (1B), and [W₃S₄Cl₄(H₂O)₂(PPh₃)₃]·2THF (1C) were prepared from the corresponding aqua clusters and PPh₃ in THF/MeOH. On recrystallization from THF, procedures with and without addition of hexane to the solution gave 1A and 2A, respectively, while the procedures gave no effect on the formation of 1B and 1C. Crystallographic results obtained are as follows: 1A: monoclinic, P2₁/n, a=17.141(4) Å, b=22.579(5) Å, c=19.069(4) Å, =96.18(2)°, V=7337(3) ų, Z=4, R(R _w)=0.078(0.102); 1C: monoclinic, P2 ₁/c, a=12.635(1) Å, b=20.216(4) Å, c=27.815(3) Å, =96.16(1)°, V=7062(2) ų, Z=4, R(R _w)=0.071(0.083). If the phenyl groups are ignored, the molecule [Mo₃S₄Cl₄(H₂O)₂(PPh₃)₃] in 2A has idealized CS symmetry with the mirror plane perpendicular to the plane determined by the metal atoms, while the molecule in 1A does not have the symmetry. The tungsten compound 1C is isomorphous with the molybdenum compound 2A. ³¹P NMR spectra of 1A, 2A, and 1C were obtained and compared with similar clusters with dmpe (1,2-bis(dimethylphosphino)ethane) ligands.     

Synthesis of o-LiMnO2 by Microwave Irradiation and StudyIts Heat Treatment and Lithium Exchange

Microwave irradiation of a suspension of γ-MnOOH in a 4 mol dm⁻³ LiOH solution brought about a rapid formation of semicrystalline orthorhombic LiMnO₂ (o-LiMnO₂) within 30 min at 120°C. Cubic Li_1.6Mn_1.6O₄ was obtained by heating o-LiMnO₂ at 400°C; lithium could be topotactically extracted from Li_1.6Mn_1.6O₄ with acid to form cubic H_1.6Mn_1.6O₄.     

Solid-solid interactions in pure and Li2O-doped manganese and magnesium mixed oxides system

The solid-solid interactions between manganese and magnesium oxides in absence and in presence of small amounts of Li₂O have been investigated. The molar ratios between manganese and magnesium oxides in the form of Mn₂O₃ and MgO were varied between 0.05:1 to 0.5:1. The mixed solids were calcined in air at 400-1000°C. The techniques employed were DTA, XRD and H₂O₂ decomposition at 20-40°C.The results obtained revealed that solid-solid interactions took place between the reacting solids at 600-1000°C yielding magnesium manganates (Mg₂MnO₄, Mg₆MnO₈, MgMnO₄ besides unreacted portions of MgO, Mn₂O₃ and Mn₃O₄). Li₂O-doping (0.75-6 mol%) of the investigated system followed by calcination at 600 and 800°C decreased progressively the intensity of the diffraction lines of Mn₂O₃ (Bixbyite) with subsequent increase in the lattice parameter 'a' of MgO to an extent proportional to the amount of Li₂O added. This finding might suggest that the doping process enhanced the dissolution of Mn₂O₃ in MgO forming solid solution. This treatment led also to the formation of Li₂MnO₃. Furthermore, the doping with 3 and 6 mol% Li₂O conducted at 800°C resulted in the conversion of Mn₂O₃ into Mn₃O₄, a process that took place at 1000°C in absence of Li₂O. The produced Li₂MnO₃ phase remained stable by heating at up to 1000°C. Furthermore, Li₂O doping of the investigated system at 400-1000°C resulted in a progressive measurable increase in the particle size of MgO.The catalytic activity measurements showed that the increase in the molar ratio of Mn₂O₃ in the samples precalcined at 400-800°C was accompanied by a significant increase in the catalytic activity of the treated solids. The maximum increase in the catalytic activity expressed as reaction rate constant measured at 20°C (k _20°C) attained 3.14, 2.67 and 3.25-fold for the solids precalcined at 400, 600 and 800°C, respectively. Li₂O-doping of the samples having the formula 0.1 Mn₂O₃/MgO conducted at 400-600°C brought a progressive significant increase in its catalytic activity. The maximum increase in the value of k _20°C due to Li₂O attained 1.93 and 2.75-fold for the samples preheated at 400 and 600°C, respectively and opposite effect was found for the doped samples preheated at 800°C.This revised version was published online in November 2005 with corrections to the Cover Date.     

Preparation and study of hydrides of fullerenes C60 and C70

Fullerene hydrides were prepared by hydrogenation of fullerences C₆₀ and C₇₀ using proton transfer from 9,10-dihydroanthracene to fullerene and were studied by mass spectrometry (electron impact, field desorption), IR, UV, and¹H and¹³C NMR spectroscopy. The main product of the hydrogenation of C₆₀ is C₆₀H₃₆, which is sufficiently stable. Hydrogenation of fullerene C₇₀ gives a series of polyhydrides C₇₀H _n (n=36–46), and the main product is C₇₀H₃₆. The dehydrogenation of C₆₀H₃₆ by 2,3-dichloro-5,6-dicyano-1,4-benzoquinone is not quantitative and results in the formation of fullerene derivatives along with C₆₀. The comparison of the IR and¹H and¹³C NMR spectral data for solid C₆₀H₃₆ with the theoretical calculations suggests that the fullerene hydride has aT-symmetric structure and contains four isolated benzenoid rings located at tetrahedral positions on the surface of the closed skeleton of the molecule. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya. No. 4, pp. 671–678, April, 1997.     

Investigation of Solid-Solid Interactions between Pure and Li2O-Doped Magnesium and Ferric Oxides

The results obtained showed that the addition of small amounts of LiNO₃ to the reacting mixed solids, consisting of equimolar proportion of Fe₂O₃ and basic MgCO₃ much enhanced the thermal decomposition of magnesium carbonate. The addition of 12 mol% LiNO₃ (6 mol% Li₂O) decreased the decomposition temperature of MgCO₃ from 525.5 to362°C. MgO underwent solid–solid interaction with Fe2O3 at temperatures starting from800°C yielding MgFe₂O₄. The amount of ferrite produced increased by increasing the precalcination temperature of the mixed solids. However, the completion of this reaction required prolonged heating at elevated temperature above 1100°C. Doping with Li₂O much enhanced the solid–solid interaction between the mixed oxides leading to the formation of MgFe₂O₄ phase at temperatures starting from 700°C. The addition of 6 mol% Li₂O to the mixed solids followed by precalcination at 1050°C for 4 h resulted in complete conversion of the reacting oxides into magnesium ferrite. The heat treatment of pure and doped solids at 900–1050°C effected the disappearance of most of IR transmission bands of the free oxides with subsequent appearance of new bands characteristic for MgFe₂O₄ structure. The promotion effect of Li2O towards the ferrite formation was attributed to an effective increase in the mobility of the various reacting cations. The activation energy of formation (ΔE) of magnesium ferrite was determined for pure and variously doped solids and the values obtained were 203, 126, 95 and 61 kJ mol⁻¹ for pure mixed solids and those treated with 1.5, 3.0 and 6.0 mol% Li₂O, respectively. This revised version was published online in August 2006 with corrections to the Cover Date.     

A comparative study of CH4 and CF4 rf discharges using a consistent plasma physics and chemistry simulator

A self-consistent, one-dimensional simulator for the physics and chemistry of radio frequency (rf) plasmas was developed and applied for CH₄ and CF₄. The simulator consists of a fluid model for the discharge physics, a commercial Boltzmann equation solver for calculations of electron energy distribution fuction (EEDF), a generalized plasma chemistry code, and an interface module among the three models. The CH₄ and CF₄ discharges are compared and contrasted: CH₄ plasmas are electropositive, with negative ion densities one order of magnitude less than those of electrons, whereas CF₄ plasmas are electronegative, with ten times more negative ions than electrons. The high-energy tail of tire EEDF in CH₄, lies below both the Druyvensteyn and Maxwell distributions, whereas tire EEDF high-energy tail in CF₄ lies between the two. For CH₄, the chemistry model was applied for four species, namely, CH₄ CH₃ CH₂, and H, whereas for CF₄, five species were examined namely CF₄, CF₃, CF₂, CF, and F The predicted densities and profiles compare favorably with experimental data. Finally, the chemistry results were fedback into the physics model until convergence was obtained.