钾盐沉积对VMoTi催化剂脱硝性能的影响（英文）

采用浸渍法(IM)与溶胶凝胶法(Sol-gel)制备VMoTi催化剂,并在实验室模拟选择性催化还原(SCR)催化剂的碱金属K中毒,通过X射线衍射、BET比表面积测试法、NH_3-程序升温脱附(TPD)、H_2-程序升温还原(TPR)和光电子能谱等方法对催化剂表面的理化性能进行分析,并探讨钒钛系催化剂的反应及失活机理。结果表明:与浸渍法制备的VMoTi催化剂相比,溶胶凝胶法制备的VMoTi催化剂具有较小的晶粒粒径,较大的比表面积和孔容,较多的表面酸量,较强的氧化还原能力以及较高的V~(4+)、Mo~(4+)和表面活性氧含量,因此,VMoTi (Sol-gel)催化剂表现出了较好的脱硝效率,在180～320℃的温度区间内,脱硝效率稳定在约100%。钾的加入会导致催化剂中毒,且不同方法制备的催化剂的中毒效应不同,K盐沉积对浸渍法制备的VMoTi催化剂的脱硝效率影响较大,溶胶凝胶法制备的VMoTi催化剂具有较好的抗K金属中毒的性能。通过对催化剂的表征发现,K盐削弱了活性成分与载体间的相互结合作用,增强了锐钛矿型TiO_2衍射峰的强度,降低了催化剂表面酸性及氧化还原性,同时催化剂表面的化学吸附氧及V~(4+)、Mo~(4+)等活性金属含量降低,这些因素是造成催化剂活性下降的主要原因。     

制备方法对低温NH3-SCR催化剂Mn-La结构与性能的影响

采用固相反应法、共沉淀法制备了Mn-La复合氧化物催化剂,考察了制备方法对催化剂脱硝性能及抗SO₂/H₂O性能的影响。并通过XRD、BET、H₂-TPR、NH₃-TPD、XPS等手段对催化剂的结构和物理化学特性进行了表征。结果表明,La掺杂降低了MnO_x的结晶度,增大了催化剂的比表面积和孔体积。Mn-O-La键合作用促进了锰在催化剂表面的分散,而高分散的锰更容易被还原,催化剂的还原温度向低温方向迁移,氧化还原能力得到提高。掺杂La之后,催化剂表面Br?nsted酸和总酸量增加,同时Mn⁴⁺和表面化学吸附氧的浓度也得到提高。因此,La掺杂有利于促进催化剂的脱硝活性。反应评价结果表明,共沉淀法制备的MnLa-CPM催化剂表现出最佳的脱硝效率,在80 ℃时脱硝效率接近100%。在H₂O和SO₂存在的条件下,MnLa-CPM催化剂的脱硝效率仍能达到80%,表现出了较好的抗硫水性能。     

溶胶-凝胶法辅助碳热还原氮化反应制备CeN粉末

以柠檬酸（CA）为螯合剂,即以有机物为碳源,通过溶胶-凝胶法辅助碳热还原氮化反应制备了CeN粉末。整个反应过程分为水相过程和热处理过程。水相过程主要是Ce³⁺和CA的螯合和聚酯,形成稳定的Ce³⁺-CA螯合物前驱体。通过水相过程实现Ce源与C源在分子水平上的均匀混合。热处理过程包括原位碳化和碳热还原氮化反应两部分。原位碳化过程形成的CeO₂/C粉末促进了CeO₂和C之间的紧密接触,从而减少Ce源和C源原子的扩散距离,以促进碳热还原氮化过程。     

熔盐法制备自支撑Ni掺杂Mo2C@CFP复合电极及其电催化析氢性能的研究

Mo₂C具有类似于Pt等贵金属的电子结构和催化特性,有望替代Pt等贵金属成为新型非贵金属析氢催化剂,但是纯Mo₂C导电性差且氢释放动力学慢。为提高Mo₂C的电催化析氢性能,本工作采用低温熔盐法在碳纤维纸(CFP)基底上制备了自支撑Mo₂C电催化剂,研究了Mo和MoO₃钼源、Ni和Ni(NO₃)₂镍源掺杂剂、添加炭黑等因素对合成产物物相、显微形貌和结构、电催化性能的影响。结果表明,炭黑和Ni的引入可以促使Mo₂C晶粒细化以及在表面生成褶皱状结构,能够提供更多活性位点,Ni(NO₃)₂的加入能够使采用MoO₃为钼源合成的Mo₂C的晶粒变成纳米花状结构,大大提高了其比表面积,也促进了反应生成的复合电极Ni(NO₃)₂-Mo₂C_CBO@CFP中的电子转移效率,表现出最佳的HER活性,其η₁₀为117 mV,塔菲尔斜率低至73.8 mV dec^_-1。     

298 K下离子液体BMIMPF6 中电沉积制备镧金属薄膜

以无水硝酸镧、1-丁基-3-甲基咪唑六氟磷酸（BMIMPF₆）和助溶剂丙酮为电解液,在室温（298 K）下电沉积制得镧金属薄膜。电解液BMIMPF₆的电化学窗口为-2.5~1.5 V vs. Pt,La³⁺还原为La²⁺发生于-1.7 V vs. Pt,La²⁺还原为La⁰发生于-2.1 V vs. Pt。BMIMPF₆的低吸湿性有利于在空气气氛下电沉积镧。使用扫描电子显微镜和光学显微镜观察到所制备的薄膜织构致密,经能量色散谱和X射线光电子能谱对沉积薄膜进行了表征,确定了薄膜中含有大量镧元素。通过探究电压扫描速率和硝酸镧浓度对La³⁺的电化学行为的影响,证明La³⁺的还原反应是一个受物质扩散控制的不可逆过程,La³⁺在BMIMPF₆中的扩散系数为1.47×10^-9 cm²·s^-1。本研究为获得金属镧薄膜和镧氧化物薄膜提供了一种简便的方法,并且有望用于电沉积制备其它镧系元素薄膜。     

性能优异的SrO改性Pd-Rh双金属催化剂的制备

在浸渍到Al₂O₃载体材料上之前,通过将Sr的前驱体引入到贵金属Pd和Rh的混合盐溶液中,即采用共浸渍法制备了一系列SrO改性的Pd-Rh/Al₂O₃催化剂。结果表明,由于SrO的扩散障碍效应,适量SrO（1%~2%,质量分数）的引入有利于促进Pd,Rh的分散,并且能提高催化剂的水热稳定性。水热老化之后,催化剂能保持更高的Pd,Rh分散度,并且Pd,Rh能稳定在活性更好的氧化态。因此,适量SrO改性的Pd-Rh/Al₂O₃催化剂具有更好的还原性能和三效催化活性。然而,当向催化剂中引入过量的SrO,由于SrO占据了过量的Al₂O₃的表面,而且老化后会出现新的物相SrAl₂O₄,反而会对催化剂的性能产生不利的影响。总的来说,2% SrO改性的催化剂具有最优异的三效催化活性,水热老化之后,相比于空白的Pd-Rh/Al₂O₃催化剂,2%SrO改性的催化剂使CO,HC和NO的起燃温度分别降低了23,15和27 ℃。     

MAGNETIC PROPERTIES OF Co1-xNixFe2O4/SiO2 NANOCOMPOSITES

采用溶胶--凝胶法制备了Co_1-xNi_xFe₂O₄/SiO₂(0 ≤x ≤1.0)纳米复合材料. 利用XRD, TEM, 振动样品磁强计(VSM)和Mossbauer谱测试了900℃热处理样
品的结构、晶粒尺寸和磁性. 结果表明, 样品中Co_1-xNi_xFe₂O₄铁氧体的平均晶粒尺寸在15---20 nm之间, Ni²⁺的掺杂引起CoFe₂O₄晶胞体积减小. VSM结果表明, 随Ni²⁺含量的增加, 样品的比饱和磁化强度和矫顽力变小. Mossbauer谱表明, 室温下各样品均处于磁有序状态, 样品的内磁场随Ni²⁺含量的增加而变小.     

SNDC/La2Mo2O9复合电解质材料的制备及性能表征

本文采用甘氨酸-硝酸盐法(GNP)和溶胶凝胶法分别合成了Sm_0.1Nd_0.1Ce_0.8O_1.9(SNDC) 和La₂Mo₂O₉(LAMOX)粉末,并用常压烧结的方法制备了不同比例的SNDC和LAMOX的复合材料,通过XRD和SEM等手段表征了不同复合比例样品的物相和表面形貌并测试了烧结样品的电导率。结果表明,复合样品的电导率在相变点前后随着复合量增加变化趋势相反,其中LAMOX含量为20mol%的样品在550℃时的电导率能达到0.01S/cm,高于同温度下SNDC电导率。     

溶胶-凝胶法制备La1-xSrxMnO3及其电磁性能研究

采用溶胶凝胶法,制备了La_1-xSr_xMnO₃(LSMO)纳米微粉。探究了Sr^₂₊的掺杂量对LSMO晶体结构、磁学性质、电磁特性和微波吸收性能的影响。结果表明,随Sr^₂₊含量的升高,样品的晶格常数和Mn-O-Mn键角增大,平均晶粒尺寸逐渐下降,样品出现从反铁磁性向铁磁性的转变,复介电常数呈先增大后减小的趋势。在2~18GHz内,x=0的样品在厚度为2mm时有最佳吸波效果,反射率小于-10dB对应的有效吸波频段为12.5~18GHz;Sr^₂₊的掺杂可使吸波频段有效的向低频移动,在X波段内,x=0.2的样品在厚度为2.3mm时的有效带宽达2.6GHz,证明LSMO是一种性能优异的介电损耗型吸波材料。     

溶胶凝胶法制备LaMn1-XVXO3及光催化氧化性能

以La(NO₃)₂、MnC₄H₆O₂、柠檬酸和乙二醇(EG)为主要原料,NH₄VO₃为掺杂试剂,采用溶胶凝胶法制备LaMnO₃和LaMn_1-XV_XO₃粉体。采用XRD进行晶体结构表征;采用甲基橙(MO)模拟污水,进行光催化降解实验。研究了煅烧温度、催化剂用量和掺杂量对光催化氧化降解率的影响,讨论MO降解的动力学规律。结果表明700-900 ℃煅烧温度不影响LaMnO₃晶体结构和光催化氧化降解率;掺杂量影响LaMn_1-XV_XO₃晶体结构,光催化氧化降解率随着掺杂量增加而呈下降趋势;光催化氧化实验中,LaMn_1-XV_XO₃粉体效果高于LaMnO₃,两者均符合一级动力学方程。     

掺杂Sn对V/UiO-66催化剂抗碱金属性能的影响

采用浸渍法，以UiO-66为载体，制备了V/UiO-66及改性Sn-V/UiO-66催化剂，并对催化剂的碱金属钾中毒进行了模拟，探讨了钒钛催化剂的反应机理和失活机理。结果表明，K负载后催化剂的晶型变化不大并且催化剂比表面积的变化呈现不规律波动。负载了碱金属以后，催化剂的金属氧化还原性能和表面酸量迅速降低，这是催化剂活性降低的主要原因。添加Sn能够增强VO_x与其他组分的相互作用，进而提高VO_x的可还原性及V⁵⁺的占比，使Sn-V/UiO-66催化剂表面的VO_x提供更多的酸性位点。中毒后的K-Sn-V/UiO-66催化剂仍然具有较高的总酸量和较强的氧化还原性，表明Sn-V/UiO-66催化剂具有优异的抗碱金属中毒能力。     

Preparation,characterization and electrochemical properties of mesoporous LiFe<Subscript>0.99</Subscript>Mo<Subscript>0.01</Subscript>PO<Subscript>4</Subscript>/C

A mesoporous LiFe_0.99Mo_0.01PO₄/C composite was synthesized by the sol-gel method using (NH₄)₂MoO₄ as a doping starting material. The formation of conductive carbon, metal doping and mesopores was achieved simultaneously in the prepared material. The characterizations of crystal structures and microstructures were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), extended X-ray-absorption fine-structure (EXAFS) and X-ray-absorption near-structure spectroscopy (XANES), while the surface area was determined using N₂ adsorption techniques. Cyclic voltammetry (CV) and charge-discharge cycling performance were used to characterize its electrochemical properties. The sample possessed uniformly distributed mesopores with an average pore size of 4 nm, and the specific surface area was about 69.368 m²/g. The results show that the reversible capacity of mesoporous LiFe_0.99Mo_0.01PO₄/C is about 160 mAh/g at 0.1C, 135 mAh/g at 1C and 90 mAh/g at 5C, respectively. The capacity fading is neglectable.     

Sulfidation properties of Fe-6.1 at.% Mo alloy at 973–1273 K

Sulfidation of an Fe-6.1 at% Mo alloy was investigated in H₂S-H₂ atmospheres, 10^?4 ? P_s2 ? 10²Pa, at 973-1273 K. The reaction kinetics are parabolic except at 1273 K as liquid sulfide formation leads to catastrophic corrosion. This solid-liquid transformation between Fe₂Mo₂S₄ and Mo₂S₃ occurs at 1214 ± 9 K. At 1073 K and P_s2 = 10^?4Pa, growth of a duplex Mo₂S₃/FeMo₂S₄ scale offers high resistance to sulfidation. At 973, 1073 and 1173 K, 10^?2 ? P_s2 ? 10²Pa, parabolic sulfidation kinetics of the same magnitude as for pure iron describe growth of a duplex scale composed of an inner (FeMo₂S₄ + Mo₂S₃) layer and at an outer FeS layer. Marker measurements indicated that growth of the inner two-phase layer was supported by inward migration of sulfur and that growth of the outer FeS layer resulted from outward migration of iron.     

Preparation and microstructure characterization of a nano-sized Ti<Superscript>4+</Superscript>-doped AgSnO<Subscript>2</Subscript> electrical contact material

A Ti⁴⁺-doped nano-structured AgSnO₂ material was prepared using sol-gel method and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). The results show that Ti⁴⁺ cations are successfully doped into the crystal lattice of SnO₂, and thus significantly improve the electrical conductivity of the sample. Furthermore, the coating of Ag on Ti⁴⁺-doped SnO₂ nano-sized particles enhances the surface wettability and enables the resulting AgSnO₂ material to have better mechanical properties.     

合成交换法制备Alx/HKUST-1催化CO低温还原NO

采用合成交换法成功制备双金属铜基有机金属骨架材料Al_x/HKUST-1(x=1/24,1/12,1/6,1/3),并采用X射线衍射(XRD)、扫描电子显微镜(SEM)、比表面积分析(BET)、热重分析(TG)、红外光谱(IR)、X射线光电子能谱(XPS)以及H₂程序升温还原(H₂-TPR)技术对其进行表征。研究结果表明,Al_x/HKUST-1维持前躯体(HKUST-1)的正八面体结构,掺铝(Al³⁺)后,HKUST-1的热稳性和还原性能均得到提高。Al_1/12/HKUST-1表现出最佳的催化活性,温度为210℃时,催化脱硝率达到100%,相比HKUST-1降低了50℃。催化反应后,Al_1/12/HKUST-1中Al、Cu和O的价态种类没有发生改变,但是不同价态的Al、Cu和O的含量比值发生了明显变化。Al_x/HKUST-1的催化过程遵循Langmuir-Hinshelwood反应机理。     

Room-temperature fracture toughness of MoSiBTiC alloys

Room-temperature fracture toughnesses of TiC-added Mo-Si-B alloys were evaluated for samples of three different compositions prepared using a conventional Ar arc-melting technique. The first alloy (TiCp) had a primary phase during solidification of NaCl-type TiC including an amount of Mo, with a Mo solid solution (Mo_ss) volume fraction of approximately 49% and a TiC volume fraction of approximately 19%, while the volume fraction of Mo₅SiB₂ (T₂) was approximately 31% and the remaining 1% was Mo₂C including an amount of Ti. The second alloy (T2p) had a primary phase of T₂, with volume fractions of Mo_ss, TiC, Mo₅SiB₂ (T₂), and Mo₂C of approximately 38%, 4%, 45%, and 13%, respectively. The third alloy (Mop) had a primary phase of Mo_ss, with volume fractions of Mo_ss, TiC, Mo₅SiB₂ (T₂), and Mo₂C of approximately 55%, 8%, 32%, and 6%, respectively. Room-temperature fracture toughness was evaluated by three different bending tests using Chevron-notched specimens. Fracture toughness values obtained by the three methods were relatively close with good reproducibility. Consequently, the fracture toughness values of TiCp, T2p, and Mop were evaluated to be ∼15.2 MPa(m)^1/2, ∼10.5 MPa(m)^1/2, and ∼13.6 MPa(m)^1/2, respectively. Fracture surface observations indicated that the Mo_ss phase is subject to severe plastic deformation during the fracture process. The TiC phase was also noted to leave river patterns behind through crack propagation. These fractographic results suggest that not only the ductile-phase toughening by the Mo_ss phase but also an extra-toughening mechanism by the TiC phase are responsible for the goodness of the room-temperature fracture toughness of the MoSiBTiC alloys.     

Citric based sol-gel synthesis and luminescence characteristics of CaLa2ZnO5:Euphosphors for blue LED excited white LEDs

A novel class of orange-red phosphors namely CaLa₂ZnO₅ (CLZ) doped with Eu³⁺ ions were prepared by adopting citrate based sol-gel method. Those were thoroughly characterized by means of XRD, SEM, Tg-DTA, photoluminescent (PL) spectral profiles. PL studies reveal that its emission intensity strongly depends on sintering temperature as well as the dopant ion (Eu³⁺) concentration. Eu³⁺ ion doped CaLa₂ZnO₅ phosphor has a strong excitation at 468 nm, which correspond to the popular emission line from a GaN based blue light-emitting diode (LED) chip. The influence of the preparation method on the luminescence property was studied by comparing the emission performance of phosphors prepared by sol-gel and solid-state reaction methods along with a commercial red phosphor Y₂O₂S:Eu³⁺. Thus, the intense red emission (⁵D₀ → ⁷F₂) of the Eu³⁺ doped CLZ phosphors under blue excitation suggests them to be a potential candidate for the production of white light by blue LEDs.     

Heat treatment of molybdenum under vacuum conditions

Oxide coverage of molybdenum plays an important role in several applications, for example in lighting industry. Surface conditioning procedures were simulated in an XPS instrument by in situ heat treatments while monitoring the surface composition and changes in the chemical states of molybdenum. Heat treatments have been made at different temperatures between 435 and 690 °C under vacuum conditions. It has been observed that during heating the molybdenum test samples the native MoO₃ layer on the surface dissociates, and a layer of suboxides forms on the surface. This layer hinders the further reduction of the surface, thus reaction speed decreases after the initial phase. It has been established that in the second phase of the heat treatment the activation energy of the process is 1.1 ± 0.2 eV. Reduction of MoO₃ to elemental molybdenum runs through two intermediate states: Mo⁶⁺ → Mo⁵⁺ → Mo⁴⁺ → Mo⁰.     

Surface characterization of Mo oxynitride films obtained by RF sputtering at various N2 ratios

Molybdenum oxynitride (MoN_xO_y) thin films were deposited on p-type Si(100) wafer by rf magnetron sputtering method at various nitrogen gas ratios. The surface characteristics of deposited thin films were investigated using scanning electron microscopy, atomic force microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The thickness of films decreased down to 70 from 1000 nm and the roughness was varied with increasing N₂ gas ratio. The formation of MoN_xO_y was confirmed by existence of Mo species between Mo^δ+ and Mo⁵⁺ oxidation state and ON bond in XP spectra. At 0% of N₂ gas ratio, metallic simple cubic Mo structure was observed. As the N₂ gas ratio increased, Mo nitrate and Mo silicate phases were appeared.