乙二醇稳定的NaBH4还原法制备纳米Pt/C催化剂

分别采用乙二醇(EG)和H2O为溶剂,通过NaBH4还原法在酸性pH≤2和碱性pH≥12条件下制备了铂担裁量为20%(质量分数)的Pt/C催化剂,利用TEM、CV及LSV等方法对催化剂进行了表征与测试,考察了EG在NaBH4还原法中对铂纳米颗粒的稳定作用.结果表明,EG作溶剂、碱性pH≥12时,通过NaBH4还原法制备得到了平均粒径约2.5nm、粒径分布窄、在碳裁体上分散均匀的Pt/C催化荆;该催化剂的电化学比表面为74.4m2/g Pt,0.8V vs NHE时通过LSV得到的单位质量铂对甲醇电催化氧化的电流密度为229.1mA/mg Pt,分别是相同条件下H2O作溶剂时制备得到的Pt/C催化剂的5.倍和5.3倍.     

掺杂Fe元素对Pd/C催化剂性能的影响

用Fe作为掺杂元素, 以活性炭为载体, 通过浸渍还原方法制备了Pd:Fe原子比分别为1:1、2:1、1:2的Pd-Fe/C催化剂.采用TEM和XRD技术对合金催化剂的物理性质进行了测试. 结果表明, 获得的Pd-Fe/C催化剂合金粒子在载体上分布均匀, 粒径<5nm,Fe的掺杂量对Pd/C催化剂晶体结构有很大影响, 通过电化学性能测试比较, 分析了三个不同比例的Pd-Fe/C催化剂和Pd/C催化剂对氢和甲酸的电催化氧化性能. 结果得出:在相同的峰值电位下, 几种催化剂的电流密度大小顺序为: Pd-Fe/C(1:1)>Pd-Fe/C(2:1)>Pd/C>Pd-Fe/C(1:2). 结果表明, 适量掺杂Fe提高了Pd/C催化剂的催化性能, 且Pd:Fe原子比为1:1时催化性能最好.     

不同pH值对直接乙醇燃料电池Pt-SnO2/C 电催化性能的影响

采用水热法制备了高分散Pt-SnO2/C电催化剂,对制备工艺进行了最佳优化,考察了不同反应溶液pH值对电催化剂活性的影响。采用XRD、SEM、TEM、比表面积、粒度分析等手段对催化剂进行了结构表征。制备的Pt-SnO2纳米复合颗粒高度分散在活性炭载体表面,其平均粒径约4.5nm。通过循环伏安、计时电流、交流阻抗等技术测试了电极在乙醇体系中的电催化活性。结果表明,随着反应溶液pH值的增加,制备的Pt-SnO2/C催化剂可使乙醇的氧化发生在较低电位。在pH值为9、铂锡原子比为3∶1时,制备的Pt-SnO2/C复合催化剂,可以得到较高的乙醇氧化电催化活性和电化学长期稳定性,氧化峰电流密度高达104.54mA·cm-2。     

氢气还原法制备Pt/MoOx/C及其对氧还原的电催化性能

用氢气在高温下还原吸附到碳载体上的钼酸铵和氟铂酸,制备出Pt/MoOx/C金属-氧化物复合型催化剂.考察了Pt/MoOx/C催化剂的电化学性能,经旋转圆盘电极测试表明在低电位区Pt/MoOx/C对含甲醇溶液中的氧还原的催化活性高于Pt/C.     

直接甲醇燃料电池阴极催化剂Pt/MnO2(C)的制备与研究

采用液相化学沉积的方法制备了含有不同二氧化锰晶型的Pt/MnO2(C)催化剂.通过XRD对该催化剂的结构进行了初步表征,电化学循环伏安法考察了催化剂在氧饱和的0.5mol/L H2SO4溶液中的电化学性能.结果表明,Pt/MnO2(C)催化剂具有良好的氧还原催化性能,二氧化锰晶体的加入起到了一定的助催化效果.     

炭载Pt-P催化剂对甲醇氧化的电催化性能研究

通过NaH2PO2自分解方法制备了高分散性的Pt-P/C催化剂,并且使用X射线衍射(XRD)、透射电子显微镜(TEM)等表征手段对催化剂进行了表征,NaH2PO2的加入可有效降低催化剂的粒径,约为2.3nm。此外,亦用多种电化学测试手段测试了P的掺杂对甲醇的电催化氧化性能的影响,测试结果表明PtP/C催化剂不但能够增强催化剂对甲醇催化氧化的活性,而且还能够提高催化剂的稳定性。该测试结果表明Pt-P/C催化剂是一类具有潜在应用前景的直接甲醇燃料电池阳极催化剂。     

Pt/C催化剂制备及CO催化氧化性能研究

采用大气压介质阻挡放电辅助氢气热还原方法和氢气热还原方法制备Pt/C催化剂,考察了制备方法及Pt负载量对Pt/C催化性能的影响。采用X-射线衍射(XRD)、循环伏安法、CO催化氧化反应研究Pt/C催化剂的晶相结构、电催化性能和CO催化氧化活性。结果表明:大气压介质阻挡放电辅助氢气热还原所制备的样品具有更高的电化学活性和CO催化氧化活性。当Pt负载量在2%到10%之间变化时,Pt/C-PC催化活性随负载量增加而增加。XRD测试结果显示当Pt负载量为2%,5%和10%时,Pt粒径分别为:10.6 nm,9.1 nm和6.4 nm,说明采用等离子体辅助氢气热还原方法制备的Pt/C-PC催化剂,Pt负载量越大,Pt粒径越小,CO催化氧化活性更高。     

微波合成条件对催化剂Pt_2Mo/C的结构和甲醇氧化催化性能的影响

为了改善Pt/C催化剂的甲醇氧化催化性能,采用快速高效的微波加热技术合成了Mo修饰的Pt基催化剂Pt2Mo/C,并对比研究了微波反应时间和超声分散时间等条件对Pt2Mo/C的晶体结构、微观形貌和甲醇氧化催化性能的影响.结果表明:Pt2Mo/C的晶体结构主要是由微波反应时间决定的,超声分散时间对其几乎没有影响;Pt2Mo/C的微观形貌受微波反应时间和超声分散时间的共同影响.在本实验的研究范围内,微波反应时间和超声分散时间对催化剂Pt2Mo/C的甲醇氧化催化性能的影响顺序分别为10min15min20min5min和60min100min30min0min;制备高活性甲醇氧化催化剂Pt2Mo/C的最佳条件为微波反应10min和超声分散60min.     

Pd/MWCNT的合成及其对甲酸电化学氧化的催化性能

以多壁碳纳米管(MWCNT)为载体,用简单的液相还原法制备了金属载量为10%的碳载Pd催化剂(Pd/MWCNT)。X射线衍射(XRD)和透射电镜(TEM)分析结果显示Pd粒子结晶度较低,分布均匀,平均粒径为2.4nm,小于两种商业10%Pd/C催化剂。循环伏安测试结果表明Pd/MWCNT对甲酸氧化的催化活性最好,相同条件下甲酸氧化峰电流最大。极化曲线显示Pd/MWCNT电极的极化过电位和50mA/cm2下恒电流放电90分钟后的过电位都明显小于其他两种商业Pd/C催化剂,表明Pd/MWCNT催化剂对甲酸电化学氧化具有较好的催化活性和催化稳定性。     

乙二醇法制备负载型钴基-堇青石催化剂及其催化燃烧甲苯的活性

用乙二醇法和浸渍法制备两种负载在堇青石上的钴基负载催化剂,并用XRD、XPS、TPR和TPD对制备的催化剂进行表征,比较两种催化剂催化氧化(燃烧)甲苯的活性。研究结果表明,与浸渍法制备的Co/cord催化剂相比,乙二醇法制备的催化剂Co/cord-EG对甲苯催化燃烧活性明显提高。应用乙二醇法制备Co/cord-EG负载型催化剂,Co元素主要以Co2+存在于载体表面;而传统浸渍法制备的Co/cord催化剂,Co元素是以Co2+与Co3+的两种化学状态存在于载体表面。应用乙二醇法制备Co/cord-EG负载型催化剂,有助于在载体表面形成比较均匀的吸附活性位。应用乙二醇法制备的Co/cord-EG催化剂,催化活性组分能在载体表面上以更小颗粒而且更高的分散度存在,从而能明显提高其催化活性。     

Structural and optical properties of AlxOy/Pt/AlxOy multilayer absorber

We report on the microstructure and optical properties of Al_xO_y–Pt–Al_xO_y interference-type multilayer films, deposited by electron beam (e-beam) deposition onto corning 1737 glass, silicon (1 1 1) and copper substrates. The structural properties were investigated by Rutherford backscattering spectrometry, X-ray diffraction, scanning electron microscopy, energy dispersive X-ray spectroscopy and atomic force microscopy. The optical properties were extracted from specular reflection/transmission, diffuse reflectance and emissometer measurements. The stratification of the coatings consists of a semi-transparent middle Pt layer sandwiched between two layers of Al_xO_y. The top and bottom Al_xO_y layers were non-stoichiometric with no crystalline phases present. The Pt layer is in the fcc crystalline phase with a broad size distribution and spheroidal shape in and between the rims of Al_xO_y. The surface roughness of the stack was found to be comparable to the inter-particle distance. The optical calculations confirm a high solar absorptance of ∼0.94 and a low thermal emittance of ∼0.06 for the multilayer stack, which is attributed not only to the optimized nature of the multilayer interference stacks, but also to the specific surface morphology and texture of the coatings. These optical characteristics validate the spectral selectivity of the Al_xO_y–Pt–Al_xO_y interference-type multilayer stack for use in high temperature solar-thermal applications.     

Synthesis of a new perovskite Pb(Li14Nb34)O3

A high-pressure technique was adopted to obtain perovskite-type $\text{Pb(Li}{}_{\mathrm{<mtext>1</mtext><mtext>4</mtext>}}\text{Nb}{}_{\mathrm{<mtext>3</mtext><mtext>4</mtext>}}\text{)}\text{O}{}_3$. A new perovskite $\text{Pb(Li}{}_{\mathrm{<mtext>1</mtext><mtext>4</mtext>}}\text{Nb}{}_{\mathrm{<mtext>3</mtext><mtext>4</mtext>}}\text{)}\text{O}{}_3$ was characterized to have a cubic symmetry with $\text{a}{}_{\mathrm{<mtext>o</mtext>}}\text{= 4.069}\text{A}\text{?}$; Li and Nb ions in the B-site of perovskite lattice may be in a random arrangement.     

Bulk crystalline BaPb34Bi14O3: A ceramic superconductor

The preparation conditions of the high T_C ceramic superconductor Ba(Pb,Bi)O₃ is correlated with the superconducting transition. Transition onsets of all materials are similar, but transition widths and transition completeness is strongly dependent on firing temperature. Only materials prepared over a narrow temperature range, resulting in a nearly ideal weight loss, have a complete and narrow transition.     

Optimization of AlxOy/Pt/AlxOy multilayer spectrally selective coatings for solar-thermal applications

Spectrally selective Al_xO_y/Pt/Al_xO_y multilayer absorber coatings were deposited onto corning 1737 glass, Si (111) and copper substrates using electron beam (e-beam) vacuum evaporator at room temperature. The employment of ellipsometric measurements and optical simulation was proposed as an effective method to optimize and deposit multilayer solar absorber coatings. The optical constants (n and k) measured using spectroscopic ellipsometry, showed that both Al_xO_y layers, which used in the coatings, were dielectric in nature and the Pt layer was semi-transparent. The optimized multilayer coatings exhibited high solar absorptance α ∼ 0.94 ± 0.01 and low thermal emittance ? ∼ 0.06 ± 0.01 at 82 °C. The Rutherford backscattering spectroscopy (RBS) data of Al_xO_y/Pt/Al_xO_y multilayer absorber indicated the Al_xO_y layers present in the coating were nearly stoichiometry. The scanning electron microscope analysis (SEM) result indicated that the average diameter and inter-particles distance of Pt grains were statistically about 146 ± 0.17 nm and 6-10 ± 0.2 nm respectively.     

Electrostriction in Pb (Zn13Nb23)O3

The electrostriction in $\text{Pb (Zn}{}_{\mathrm{<mtext>1</mtext><mtext>3</mtext>}}\text{Nb}{}_{\mathrm{<mtext>2</mtext><mtext>3</mtext>}}\text{)}\text{O}{}_3$ crystals has been investigated using a strain gauge method. In the ferroelectric phase below 140 C, the strain vs the electric field shows a hysteresis, which is ascribed to the effect of ferroelectric domains. A quadratic relation holds between the strain x and the electric polarization P as x = QP² above about 170 C in the paraelectric phase. Values of the electrostrictive Q coefficients are determined from the measurements near 190 C, as Q₁₁ = 1.6·10^?2m⁴/C², Q₁₂ = ?0.86·10^?2m⁴/C², and Q₄₄ = 0.85·10^?2m⁴/C².     

Magnetic,electrical and thermal studies on the V1−xMox02

The monoclinic-to-tetragonal structure transition of oxides V_1?xMo_x0₂ with $\text{0≤}\text{x}\text{≤0.20}$ has been studied by means of DTA, X-ray diffraction, magnetic susceptibility (powder samples) and electrical conductivity (single crystals) measurements within the temperature region 80 K to 400 K. A linear decrease of the transition temperature of 11 K per atom % Mo was observed. The magnetic susceptibility of the low temperature phase was found to be temperature independent paramagnetic for all preparations. Electrical conductivity measurements on the same phase showed crystals with $\text{x}\text{? 0.04}$ to be semiconducting, while a metallic behavior was observed in the region $\text{0.10 ?}\text{x}\text{? 0.14}$.     

n-PbTep+−Pb1−xSnxTe heterojunctions prepared by a modified hot wall technique

$\text{n-PbTe}\text{p}{}^{\mathrm{+}}\text{?}\text{Pb}{}_{\mathrm{1?x}}\text{Sn}{}_{\mathrm{x}}\text{Te}$ heterojunctions with a long wavelength spectral cutoff (λ_c ≈ 6 μm) were prepared using the double-channel hot wall technique. The electrical and photoelectrical properties of the heterojunctions at 77, 197 and 300 K were investigated. Detectors with R_oA equal to 170 Ω cm² and a quantum efficiency of 25–40% were obtained. Reasons for the shift of the long wavelength spectral cutoff of the heterojunctions towards shorter wavelengths are given.     

Reactive plasma deposited SixCyHz films

Si_xC_yH_z films have been prepared at 200°C by reactive plasma deposition from SiH₄ and CH₄ diluted in helium in a tubular reactor. These films have a ratio s (equal to $\text{Si}\text{(}\text{Si+C}\text{))}$ ranging from 0.2 to 0.8, a refractive index ranging from 1.96 to 2.6 and an optical energy band gap in the range 2.7-2.2 eV. The total quantity of hydrogen in the film is 40% when s=0.5. Infrared analysis shows that these films have large fractions of homonuclear bonds and that this material is best described as a polymer. Mass spectrometric measurements of the gaseous products formed in the SiH₄-CH₄-He plasma have been performed and the results are related to the composition of the deposited layers.     

Core-current-enhanced domain-wall pinning in nanocrystalline Fe/sub 73.5/Cu/sub 1/Nb/sub 3/Si/sub 15.5/B/sub 7/ ribbon

We have studied the influence of surface fields H/sub p/ (generated by either direct or alternating core current) on soft magnetic properties of amorphous and nanocrystalline Fe/sub 73.5/Cu/sub 1/Nb/sub 3/Si/sub 15.5/B/sub 7/ ribbon. While in an amorphous ribbon the coercive field H/sub c/ decreases with H/sub p/, in the same optimally annealed ribbon (H/sub c/=1.3 A/m, M/sub m//spl ap/M/sub s/) H/sub c/ increases with H/sub p/ for all the explored types of H/sub p/ (static and dynamic with different phases with respect to that of the magnetizing field H). The unexpected increase of H/sub c/ in nanocrystalline ribbon is associated with the influence of H/sub p/ on the surface and main (inner) domain structure. Here, we develop a model that takes into account this influence and explains the experimental results.     

Interfacial microstructure of NiSix/HfO2/SiOx/Si gate stacks

Integration of NiSi_x based fully silicided metal gates with HfO₂ high-k gate dielectrics offers promise for further scaling of complementary metal-oxide- semiconductor devices. A combination of high resolution transmission electron microscopy and small probe electron energy loss spectroscopy (EELS) and energy dispersive X-ray analysis has been applied to study interfacial reactions in the undoped gate stack. NiSi was found to be polycrystalline with the grain size decreasing from top to bottom of NiSi_x film. Ni content varies near the NiSi/HfO_x interface whereby both Ni-rich and monosilicide phases were observed. Spatially non-uniform distribution of oxygen along NiSi_x/HfO₂ interface was observed by dark field Scanning Transmission Electron Microscopy and EELS. Interfacial roughness of NiSi_x/HfO_x was found higher than that of poly-Si/HfO₂, likely due to compositional non-uniformity of NiSi_x. No intermixing between Hf, Ni and Si beyond interfacial roughness was observed.