磷钼酸修饰的铂电极对二甲醚氧化的电催化作用

利用循环伏安扫描法制备了磷钼酸(H3PMo12O40)修饰的铂电极.在制备修饰电极时,随着扫描次数的增加,磷钼酸的氧化还原峰电流增大,但最终获得稳定的重现性好的磷钼酸修饰的铂电极.通过循环伏安法研究了该修饰电极对二甲醚氧化的电催化反应.结果表明,与未修饰的铂电极相比,磷钼酸修饰的铂电极电催化氧化二甲醚的起始氧化电位负移50 mV,氧化峰电位负移35 mV,氧化峰电流密度提高了1.86倍,这表明修饰电极的电催化活性有了很大的提高.同时,电位负扫时,二甲醚在425 mV(vsSCE)处出现氧化峰,表明二甲醚在修饰电极上的电氧化机理可能发生了改变.实验还发现,制备修饰电极时,降低扫速会提高还原物质杂多蓝的吸附量,但过多的修饰物质会降低铂的活性位数目,反而降低了对二甲醚氧化的电催化作用.     

甲酸在Pt-Ru/GC电极上氧化的SERS研究

采用循环伏安(CV)法、计时电流法和电化学原位表面增强拉曼散射光谱(SERS)技术研究了甲酸在Pt-Ru/GC电极上的氧化行为, 发现甲酸在Pt-Ru/GC电极上与在粗糙Pt电极上一样, 也能自发解离出强吸附中间体CO和活性中间体—COO－. 从分子水平证实钌的加入有利于提高电极对甲酸的电催化氧化活性, 当镀液中Pt：Ru的摩尔比从10∶1变化到1∶1, CO的氧化峰电位从0.41 V负移至0.35 V, 约负移了60 mV. Pt-Ru/GC(1∶1)电极与粗糙Pt电极相比, CO在电极表面氧化完毕的电位亦负移了约200 mV. 该研究结果表明, 电化学原位表面增强拉曼散射光谱技术可望成为研究电催化反应机理的普适谱学工具.     

葡萄糖在碳纳米管/纳米TiO2膜载Pt复合电极上的电催化氧化

用电化学循环伏安法和计时电位法研究了葡萄糖在碳纳米管／纳米TiO2膜载Pt(CNT／nano-TiO2／Pt)复合电极上的电催化氧化,结果表明,在碱性介质中CNT／nano-TiO2／Pt复合电极对葡萄糖的电氧化具有高催化活性,葡萄糖氧化峰电流密度高达13mA／cm^2,比铂电极上的增大一倍;复合电极性能稳定,抗中毒能力强,不易发生氧化振荡,是葡萄糖燃料电池和葡萄糖传感器的高活性催化电极。     

Ag/Au/Pt复合催化剂的制备及其对甲酸的电催化氧化

利用化学-电化学方法制备了Ag/Au/Pt复合催化剂. 该催化剂以100 nm左右的Ag颗粒为基底, 以化学方法沉积金再电沉积铂, 这降低了贵金属Au和Pt的用量. 通过SEM, EDX和XRD对样品进行表征, 并测试对甲酸的电催化氧化性能. 研究表明, 当Pt∶Au原子数比小于1∶10时, 主要表现为直接氧化, 在较低的Pt负载量(0.71 μg/cm²)情况下, Ag/Au/Pt复合催化剂对甲酸氧化的直接氧化峰电流密度达到最大. 甲酸的电催化氧化稳定性实验表明, 当Pt载量为0.05 μg时, 相对于最大峰电流密度, 循环伏安扫描第100圈时甲酸氧化的直接氧化峰电流密度仅衰减了2.29%. 同时CO氧化剥离实验表明, 当Pt∶Au＝1∶6时, Ag/Au/Pt复合催化剂对CO氧化峰电势最负, 相对于纯Pt催化剂负移了大约0.13 V, 表明该复合催化剂具有更好的抗CO毒化能力.     

Pt电极上吸附原子对仲丁醇电催化氧化性能的影响

运用电化学循环伏安和石英晶体微天平研究了HClO4溶液中仲丁醇在Pt电极及以Sb和S吸附原子修饰的Pt(Pt/Sbad和Pt/Sad)电极上的电催化氧化过程 .从电极表面质量变化可以看出 ,仲丁醇的氧化与电极表面的氧物种有着极其密切的关系 .Pt电极表面Sb吸附原子可在较低的电位下吸附氧 ,明显提高仲丁醇的氧化活性 .与Pt电极相比 ,Sb吸附原子修饰的Pt电极使仲丁醇氧化的峰电位负移约 10 0mV .相反 ,Pt电极表面S吸附原子的氧化会消耗表面氧物种 ,抑制仲丁醇的氧化 .从电极表面质量变化提供了吸附原子电催化作用的数据     

Pt电采上吸附原子对仲丁醇电催化氧化性能的影响

运用电化学循环伏安和石英晶体微天平研究了HClO4溶液仲丁醇在Pt电极及以Sb和S吸附原子修饰的Pt(Pt/Sbad和Pt/Sad）电极上的电催化氧化过程，从电极表面质量变化可以看出，仲丁醇的氧化与电极表面的氧物种表面的氧物种有着极其密切的关系，Pt电极表面Sb吸附原子可在较低的电位下吸附氧，明显提高仲丁醇的氧化活性，与Pt电极相比，Sb吸附原子修饰的Pt电极使仲丁醇氧化的峰电位负移约100mV，相反，Pt电极表面S吸附原子的氧化会消耗表面氧物种，抑制仲丁醇的氧化，从电极表面质量变化提供了吸附原子电催化作用的数据。     

树枝状纳米银颗粒的制备与电活性

在Ag(NH3)2+溶液中,在钛基体上电沉积出树枝状纳米银颗粒,研究了沉积电位对树枝状纳米银颗粒形成的影响,探讨了这种树枝状纳米银颗粒形成的机理,并研究了这种钛基树枝状纳米银电极(Ag/Ti)在碱性溶液中对甲醛氧化的电催化活性。结果表明,在30 mmol/LAg(NH3)2+以及沉积电位在-1.8～-1.2 V(vsAg)时,形成了形态为树枝状的纳米银颗粒。在沉积电位为-1.6 V(vs Ag),Ag(NH3)2+浓度为30 mmol/L的溶液中,电沉积制备的这种树枝状纳米银电极(Ag/Ti)对甲醛氧化具有强的电催化活性。循环伏安曲线表明,在0.1 mol/LNaOH溶液中以及甲醛的浓度范围在0～40 mmol/L,甲醛浓度和它的氧化峰电流密度呈现良好的线性关系,检测下限达到0.662 mmol/L,这种新型的树枝状纳米银电极有望作为甲醛检测的传感器。     

多壁碳纳米管负载铂立方体的制备及对乙醇电催化氧化性能

利用线性扫描电沉积的方法在玻碳电极或多壁碳纳米管表面制备出铂纳米立方体, 扫描电子显微镜(SEM)和透射电子显微镜(TEM)结果表明, 铂立方体的尺度约为38 nm, 由Pt(111)择优取向的小粒子围成. 运用电化学循环伏安和电位阶跃技术研究了所合成的2种催化剂和商用碳载铂对乙醇氧化的电催化活性, 发现在2种铂纳米立方体上乙醇氧化的电催化活性和稳定性均高于商用碳载铂, 其起峰电位较商业碳载铂降低168 mV. 采用电化学原位红外光谱对比研究了铂纳米立方体和商用碳载铂对乙醇氧化的电催化过程, 发现铂纳米立方体起始氧化电位提前, 催化活性增强. 乙醇在该催化剂上更易转化为乙酸, 且表现出较强的CO吸附能力.     

乙醇在不同介质中电氧化的原位表面增强拉曼光谱研究

采用常规电化学伏安技术和电化学原位表面增强拉曼光谱(in-situ SERS)技术研究了不同介质中乙醇在粗糙铂电极上的电催化氧化行为. 发现不论在酸性、中性还是碱性介质中, 乙醇均能在粗糙铂电极上自发氧化解离生成强吸附中间体CO; 碱性介质中, CO在粗糙铂电极上基本氧化完全的电位(0.20 V)比中性和酸性介质中(0.50 V)负移了约0.30 V. 而乙醇在粗糙铂电极上CV正向扫描的氧化峰电位(-0.20 V)比酸性介质中(0.65 V)负移了约0.85 V. 比较不同介质中乙醇和CO在粗糙铂电极上的氧化峰电流和峰电位可以发现, 粗糙铂电极在碱性介质中对乙醇和CO的电催化氧化活性比中性和酸性介质中更强; 可以推测, 不论在酸性、中性还是碱性介质中, 乙醇在粗糙铂电极上的氧化过程均按双途径机理进行.     

一氧化碳在硫修饰铂电极上的吸附与电氧化研究(英文)

吸附硫通常被认为是表面化学反应毒物,然而少量的硫能够增强铂的一氧化碳(CO)电氧化活性.本文利用常规电化学手段及表面增强拉曼光谱研究了CO在硫修饰的铂表面的电氧化.对于溶液中的CO,其在硫修饰铂电极上的起始氧化电位最多可以比非修饰电极负移超过300 mV,而且在硫覆盖度低于0.6的条件下电位负移量随覆盖度增加而增大.这一电催化活性的增强也受溶液pH值的影响.在低硫覆盖度(小于0.3)下,吸附态的CO电氧化峰值电位比非修饰铂电极负移约40 mV.然而,在高硫覆盖度下,其峰值电位比非修饰铂电极正移近30 mV.表面增强拉曼光谱显示共吸附硫使Pt—CO振动频率显著红移.作者认为这些结果是由于吸附硫弱化Pt—CO键及阻化CO在铂表面的移动引起的.     

Solvent extraction separation of In/III/-Tl/III/ and Hg/II/-Cd/II/-Co/II/ with sulphoxides

Solvent extraction studies have been made on some metals: In/III/-Tl/III/ and Hg/II/-Cd/II/-Co/II/, from ammonium thiocyanate solutions by dialkyl sulphoxides. Separation of these metals from one another can be achieved by suitable choice of the extracted conditions. The nature of the extractable metal species has been elucidated.     

Simultaneous propane dehydrogenation andco2hydrogenation overCrOx/SiO2catalyst

Summary Single reverse water-gas shift (RWGS) and dehydrogenation of propane with CO₂(DH-CO₂) reactions in the presence and absence of the CrO_x/SiO₂ catalyst have been studied between 673 and 873 K. It was found that the CrO_x/SiO₂ catalyst is active both in the dehydrogenation of propane and in the RWGS reactions. The obtained results suggest that the dehydrogenation of propane to propene in the presence of CO₂on CrO_x/SiO₂can be facilitated by the RWGS reaction.</o:p>     

Synthesis of chlorobis/β-diketonato/oxotechnetium/V/ and tris/β-diketonato/technetium/III/ complexes

Chlorobis/-diketonato/ oxotechnetium/V/ complexes [TcOCl/-dik/₂, -diketone=acetylacetone, benzoylacetone and dibenzoylmethane] were newly synthesized using macroamount of⁹⁹Tc. These complexes were further separated into geometrical isomers. Furthermore, an improvement of the yields for the syntheses of tris/-dike-tonato/technetium/III/ complexes [Tc/-dik/₃, -diketone=acetylacetone, benzoylacetone and 2-thenoyltrifluoroacetone] was examined using Tc/III/-thiourea complexes as a starting material.     

Direct synthesis of dimethyl carbonate ?from CH3OH AND CO2 by H3PW12O40/CexTi1-xO2 catalyst

Summary Ce_xTi_1-xO₂ and H₃PW₁₂O₄₀/Ce_xTi_1-xO₂ catalysts were prepared using a sol-gel method, and applied to the direct synthesis of dimethyl carbonate from methanol and carbon dioxide. H₃PW₁₂O₄₀/Ce_xTi_1-xO₂ showed a better catalytic performance than the corresponding Ce_xTi_1-xO₂, due to the bifunctional catalysis of Br?nsted acid sites (provided by H₃PW₁₂O₄₀) and base sites (provided by Ce_xTi_1-xO₂). H₃PW₁₂O₄₀/Ce_0.1Ti_0.9O₂ showed the highest catalytic performance among the H₃PW₁₂O₄₀/Ce_xTi_1-xO₂ catalysts.     

Crystal structure of Na3PO4 · 12H2O

The crystal structure of trisodium monophosphate hemihydrate was determined. The space group is $\text{C2}\text{c}$ and a unit cell contains eight formula units. The unit cell dimensions of $\text{Na}{}_3\text{PO}{}_4\text{·}\text{1}\text{2}\text{H}{}_2\text{O}$ are a = 9.631(3), b = 5.416(2), c = 16.938(8) Å, β = 102.60(5)°. The final R value is 0.027 for a set of 1430 independent reflections. This atomic arrangement is mainly a three-dimensional network of distorted NaO₆ octahedra. The hydrogen bonding scheme is given.     

LixNi0.8-yCo0.2ZnyOp的合成及电化学性能研究

A series of single-phase Li_xNi_0.8-yCo_0.2Zn_yO_p(0.96 ≤x≤ 1.10， 0 ≤y≤ 0.05， 2 ≤p≤ 2(1+y) ) (different in the y values) were synthesized by a two-step solid state reaction method， in which LiOH·H₂O， Zn-doped spherical Ni(OH)₂ and Co₂O₃ were used as the precursors. The ICP-AES analyses proved that the Zn-doped compounds synthesized had the nonstoichiometric form. The results of the XRD， SEM identified that the uniform particles of the as-prepared materials having a good layered structure were fine， narrowly distributed and well crystallized. The electrochemical performance test was carried out and the results showed that the as-prepared Zn-doped materials had not only a high capacity， but also a better cycling stability characterization than the un-doped one. The Li_1.06Ni_0.75Co_0.22Zn_0.03O_2.03 material has an initial reversible capacity as high as 160.5mAh·g^-1; and a first discharge efficiency 89.2%， and exhibits satisfactory cyclic stability with 90% retainable capacity after 50 cycles.     

Synthesis and characterization of Ti1−2xNbxNixO2−x/2 solid solutions

Doped-rutile has been traditionally used in ceramic pigments for its intense optical properties. In this paper, we compare the classical ceramic synthesis of Ti_1−2xNb_xNi_xO_2−x/2 system with the sol-gel methodology, which allows a reduction of the anatase-rutile transformation temperature. The composition was optimised in order to obtain a unique rutile phase with the minimum amount of pollutant Ni(II) and enhanced chromatic coordinates. Incorporation of the doping ions in the rutile structure was corroborated by XRD and Rietveld refinements. The species responsible for the colour mechanism were studied by different techniques. UV-VIS spectroscopy showed the characteristic features of Ni²⁺ ions, whose existence was corroborated by EPR and magnetic measurements. From these results, (Ni,Nb)doped-TiO₂ powder samples can be now shaped as thin films, monoliths, etc. by using sol-gel methodology without modifying their properties. This study introduces new possibilities of coloured TiO₂-based solid solutions in new combined advanced applications (colouring agent and photocatalyst, etc.).     

An investigation of the promotional effect of propylene or propane traces on the activity of sulfatedPt/g-Al2O3andPt-Sn/g-Al2O3inCH4combustion

Summary A strong promoting effect of the presence of C₃H₈or C₃H₆was determined for the combustion of CH₄in excess oxygen, over pre-sulfated 1%Pt/g-Al₂O₃and pre-sulfated 1%Pt-2%Sn/g-Al₂O₃catalysts.</o:p>     

Visible light-sensitive yellow TiO2−xNx and Fe-N co-doped Ti1−yFeyO2−xNx anatase photocatalysts

Nitrogen substituted yellow colored anatase TiO_2−xN_x and Fe-N co-doped Ti_1−yFe_yO_2−xN_x have been easily synthesized by novel hydrazine method. White anatase TiO_2−δ and N/Fe-N-doped samples are semiconducting and the presence of ESR signals at g ∼1.994-2.0025 supports the oxygen vacancy and g∼4.3 indicates Fe³⁺ in the lattice. TiO_2−xN_x has higher conductivity than TiO_2−x and Fe/Fe-N-doped anatase and the UV absorption edge of white TiO_2−x extends in the visible region in N, Fe and Fe-N co-doped TiO₂, which show, respectively, two band gaps at ∼3.25/2.63, ∼3.31/2.44 and 2.8/2.44 eV. An activation energy of ∼1.8 eV is observed in Arrhenius log resistivity vs. 1/T plots for all samples. All TiO₂ and Fe-doped TiO₂ show low 2-propanol photodegradation activity but have significant NO photodestruction capability, both in UV and visible regions, while standard Degussa P-25 is incapable in destroying NO in the visible region The mid-gap levels that these N and Fe-N-doped TiO₂ consist may cause this discrepancy in their photocatalytic activities.     

LixZryOz三元化合物的制备及表征

采用高温固相法制备了4种高纯度晶相组成的LixZryOz三元化合物,研究了焙烧温度、时间、反应物的种类和初始反应物物质的量比对产物组成的影响,进一步用XRD、SEM及BET分析方法对产物的晶相结构、表面形貌及比表面积进行了表征.实验结果表明,Li2CO3与ZrO2在适当条件下可以合成得到单斜相Li3ZrO3;以LiOH替代Li2CO3,在适当条件下可以分别合成得到四方相Li2ZrO3和三斜/单斜相Li6Zr2O7;进一步以Zr(NO3)4·5H2O代替Zr02,可将单斜相Li6Zr2O7的制备时间由96 h缩短至24 h.SEM照片显示产物硬团聚明显,粒径分布在1～10μm间,BET分析表明样品比表面积处于1.0～9.0 m2·g-1间分布,反应过程中锂的过量以及长时间高温焙烧是引起产物粒径长大和产生硬团聚的主要原因.