Highly Active Nickel Nanoparticles Supported on TiO2 Nanotube Electrodes for Methanol Electrooxidation

Nickel nanoparticles/TiO₂ nanotubes/Ti electrodes were prepared by galvanic deposition of nickel nanoparticles on the TiO₂ nanotubes layer on titanium substrates. Titanium oxide nanotubes were fabricated by anodizing titanium foil in a DMSO fluoride‐containing electrolyte. The morphology and surface characteristics of titanium dioxide nanotubes and Ni/TiO₂/Ti electrodes were investigated using scanning electron microscopy and energy‐dispersive X‐ray spectroscopy, respectively. The results indicated that nickel nanoparticles were homogeneously deposited on the surface of TiO₂ nanotubes. The electrocatalytic behaviour of nickel nanoparticles/TiO₂/Ti electrodes for the methanol electrooxidation was studied by electrochemical impedance spectroscopy, cyclic voltammetry, differential pulse voltammetry and chronoamperometry methods. The results showed that Ni/TiO₂/Ti electrodes exhibit a considerably higher electrocatalytic activity toward the oxidation of methanol.     

Gold particles supported on self-organized nanotubular TiO2 matrix as highly active catalysts for electrochemical oxidation of glucose

Au/TiO₂/Ti electrode was prepared by a two-step process of anodic oxidation of titanium followed by cathodic electrodeposition of gold on resulted TiO₂. The morphology and surface analysis of Au/TiO₂/Ti electrodes was investigated using scanning electron microscopy and EDAX, respectively. The results indicated that gold particles were homogeneously deposited on the surface of TiO₂ nanotubes. The nanotubular TiO₂ layers consist of individual tubes of about 60–90 nm in diameter, and the electrode surface was covered by gold particles with a diameter of about 100–200 nm which are distributed evenly on the titanium dioxide nanotubes. This nanotubular TiO₂ support provides a high surface area and therefore enhances the electrocatalytic activity of Au/TiO₂/Ti electrode. The electrocatalytic behavior of Au/TiO₂/Ti electrodes in the glucose electro-oxidation was studied by cyclic voltammetry. The results showed that Au/TiO₂/Ti electrodes exhibit a considerably higher electrocatalytic activity toward the glucose oxidation than that of gold electrode.     

片层WC/C的原位合成及其在甲醇氧化中的应用

以片层二硫化钨(WS2)为前驱体,氯化钠(Na Cl)为介质,CO为气体碳源,采用程序升温法一步合成片层碳化钨/碳复合材料(WC/C)。通过X射线衍射(XRD),X射线近边吸收谱(XANES)和扫描电镜(SEM)等一系列手段对样品的化学组成、形貌、结构等进行表征。研究发现,在高温渗碳过程中,不仅利用WS2的片层结构和Na Cl的锚定作用合成了具有薄层孔洞的WC,而且Na Cl和WS2金属面对碳膜生长的催化作用使WC表面覆有原位生长的碳膜,为电子传输提供了有效通道。将该材料作为载体材料进行电化学性能测试,结果表明:负载少量Pt后制得的Pt/WC/C电催化剂,在甲醇氧化反应(MOR)中表现出良好的电催化活性、稳定性及优异的抗CO中毒能力。     

Small-sized and contacting Pt-WC nanostructures on graphene as highly efficient anode catalysts for direct methanol fuel cells

The synergistic effect between Pt and WC is beneficial for methanol electro-oxidation, and makes Pt-WC catalyst a promising anode candidate for the direct methanol fuel cell. This paper reports on the design and synthesis of small-sized and contacting Pt-WC nanostructures on graphene that bring the synergistic effect into full play. Firstly, DFT calculations show the existence of a strong covalent interaction between WC and graphene, which suggests great potential for anchoring WC on graphene with formation of small-sized, well-dispersed WC particles. The calculations also reveal that, when Pt attaches to the pre-existing WC/graphene hybrid, Pt particles preferentially grow on WC rather than graphene. Our experiments confirmed that highly disperse WC nanoparticles (ca. 5?nm) can indeed be anchored on graphene. Also, Pt particles 2-3?nm in size are well dispersed on WC/graphene hybrid and preferentially grow on WC grains, forming contacting Pt-WC nanostructures. These results are consistent with the theoretical findings. X-ray absorption fine structure spectroscopy further confirms the intimate contact between Pt and WC, and demonstrates that the presence of WC can facilitate the crystallinity of Pt particles. This new Pt-WC/graphene catalyst exhibits a high catalytic efficiency toward methanol oxidation, with a mass activity 1.98 and 4.52 times those of commercial PtRu/C and Pt/C catalysts, respectively.     

嵌段共聚物模板法一步制备WC/C基底电极材料

以酚醛树脂作为碳源,采用嵌段共聚物模板法一步制备新型有序介孔碳化钨/碳（WC/C）纳米颗粒. WC/C颗粒的比表面积为414 m²·g^-1,表面的平均孔径约为38 nm,处于介孔范围内（2 ~ 50 nm）. 通过调节树脂预聚时间以及碳化温度等条件制备出结构形貌较优的WC/C复合材料,并探讨了材料形成机理. 使用X射线衍射、扫描电镜、透射电镜及氮气吸脱附等方法表征了复合材料的结构. 将贵金属铂负载于WC/C表面制备得新电催化材料Pt-WC/C,使用循环伏安法和计时电流法对Pt-WC/C复合材料的电化学性能进行检测,并与商用碳载铂（Pt/C）材料进行对比. 测试结果发现,Pt-WC/C对甲醇的电催化活性以及稳定性等方面都表现出优于商用Pt/C材料的活性,这主要归功于碳化钨高度分散于碳表面.     

Nickel modified ionic liquid/carbon paste electrode for highly efficient electrocatalytic oxidation of methanol in alkaline medium

In this study, the electrocatalytic oxidation of methanol at nickel modified ionic liquid/carbon paste electrode (Ni/IL/CPE) in alkaline medium is presented. The ionic liquid, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, is incorporated into the electrode as a binder. Electrochemical impedance spectroscopy is employed to evaluate the electron transfer rate of this electrode. Ni(II) ions are incorporated into the electrode by immersion of this electrode in 1.0?M nickel sulfate solution. Cyclic voltammetry and chronoamperometry techniques are used for the electrochemical study of this modified electrode in the absence and the presence of methanol. The effect of methanol concentration on the anodic peak current shows an increase in the anodic peak current up to 1.25?M. Current density of Ni/IL/CPE for methanol oxidation in alkaline media is investigated by comparison with some of the previously reported electrodes. Results show that this electrode exhibits a high efficient electrocatalytic activity toward the oxidation of methanol with the current density of 17.6?mA?cm^?2. The rate constant for chemical reaction between methanol and redox sites of electrode is calculated. This new proposed electrode is simple and efficient enough, and it can be widely used as anode in direct methanol fuel cell.     

Cost-effective electrodeposition of platinum nanoparticles with ionic liquid droplet confined onto electrode surface as micro-media

We report here for the first time on the use of a droplet of water-immiscible ionic liquid (IL) containing metallic precursor confined onto electrode surface as new micro-media for cost-effective electrodeposition of platinum nanoparticles. 1-n-Butyl-3-methylimidazolium hexafluorophosphate (BmimPF₆), a typical water-immiscible IL, is found to be able to form a stable droplet onto electrode surface in which the metallic precursor (i.e., chloroplatinic acid hexahydrate (H₂PtCl₆)) for electrodeposition of Pt nanoparticles can be stably dissolved when the prepared electrode is used in aqueous solutions. The electrodeposition of Pt nanoparticles is carried out in the aqueous solution of 0.1 M KPF₆ with the H₂PtCl₆-containing IL droplet-confined glassy carbon electrode as working electrode at −1.5 V vs. Ag/AgCl. The Pt nanoparticles electrodeposited from the IL droplet micro-medium are characterized to have a uniform morphology and to possess an excellent electrocatalytic activity toward the oxidation of methanol. Compared with the existing methods for the electrodeposition of metals with ILs as the solvents, the method demonstrated here requires a less amount of ILs and metallic precursors and is thus anticipated to provide a new and cost-effective approach to the deposition of metallic nanoparticles onto conducting substrate.     

碳化钨/碳化二钨核壳结构纳米复合材料的制备及电化学性能

以偏钨酸铵为钨源, 铁黄(FeOOH)为载体, 将表面包覆法与原位还原碳化技术相结合, 制备出了具有核壳结构的碳化钨(WC)/碳化二钨(W₂C)纳米复合材料; 应用X射线衍射(XRD)分析、透射电子显微镜(TEM)和X射线能量散射谱(EDS)等手段对不同阶段样品的晶相、形貌、微结构和化学组成等特征进行了表征. 结果表明, 负载体经煅烧后, 载体及包裹层的物相均发生了变化, 形貌也相应地发生了改变; 经盐酸处理及还原碳化后, 样品由WC和W₂C纳米颗粒构成, 并构成了以W₂C为壳, 以WC为核的典型核壳结构; 结合表征结果对核壳结构的形成机理进行了探讨. 采用三电极体系循环伏安法测试了样品在酸性、中性和碱性溶液中对甲醇的电催化氧化活性. 结果表明, 与颗粒状碳化钨和介孔空心球状碳化钨相比, 样品的电催化活性有了明显的提高. 这说明W₂C与WC构成核壳结构纳米复合材料后, 其电化学性能有了明显的提升, 核壳结构纳米复合材料是提高碳化钨催化材料活性的有效途径之一.     

Sponge-like TiO2 layers for dye-sensitized solar cells

A titanium oxide layer used in a dye-sensitized solar cell (DSSC) has to meet two opponent properties to enable high conversion efficiency: a large surface area (for high dye loading) and good connection between TiO₂ grains (for efficient extraction of electrons toward the front contact). In order to meet a trade-off between these criteria a preparation method for TiO₂ paste formulation based on Pechini sol–gel method and commercial nanocrystalline TiO₂ powder has been developed. A series of TiO₂ pastes with different molar ratios between titanium isopropoxide, citric acid and ethylene glycol (1:X:4X) in the paste have been examined. The structure and morphology as well as cross-cut tests of deposited and sintered TiO₂ layers have been analyzed. Results reveal that the paste with X = 8 exhibits the best properties, resulting in an overall conversion efficiency of DSSC under standard test conditions (100 mW/cm², 25 °C, AM 1.5G) up to 6.6% for ionic liquid based electrolyte.     

The electrooxidation of small organic molecules on platinum nanoparticles supported on gold: influence of platinum deposition procedure

The electrocatalytic properties of small platinum nanoparticles were investigated for the oxidation of CO, methanol, and formic acid using voltammetry, chronoamperometry, and surface-enhanced Raman spectroscopy. The particles were generated by galvanostatic deposition of platinum on a polished gold surface from an H₂PtCl₆ containing electrolyte and ranged between 10 and 20 nm in diameter for low platinum surface concentrations, 10 and 120 nm for medium concentrations, and full Pt monolayers for high concentrations. CO stripping and bulk CO oxidation experiments on the particles up to 120 nm in diameter displayed pronounced structural effects. The CO oxidation current-time transients show a current decay for low platinum coverages and a current maximum for medium and high coverages. These results were also observed in the literature for particles of 2- to 5-nm size and agglomerates of these particles. The similarities between the literature and our results, despite large differences in particle size and morphology, suggest that particle structure and morphology are also very important catalytic parameters. Surface-enhanced Raman spectroscopy data obtained for the oxidation of CO on the Pt-modified Au electrodes corroborate this conclusion. A difference in the ratio between CO adsorbed in linear- and bridge-bonded positions on the Pt nanoparticles of different sizes demonstrates the influence of the surface morphology. The oxidation activity of methanol was found to decrease with the particle size, while the formic acid oxidation rate increases. Again, a structural effect is observed for particles of up to ca. 120 nm in diameter, which is much larger than the particles for which a particle size effect was reported in the literature. The particle shape effect for the methanol oxidation reaction can be explained by a reduction in available “ensemble sites” and a reduction in the mobility of CO formed by decomposition of methanol. As formic acid does not require Pt ensemble sites, decreasing the particle size, and thus, the relative number of defects, increases the reaction rate. Dedicated to Prof. Dr. Teresa Iwasita on the occasion of her 65th birthday in recognition of her numerous contributions to interfacial electrochemistry.     

Enhanced photo-electrocatalytic performance of Pt/RGO/TiO2 on carbon fiber towards methanol oxidation in alkaline media

In the present work, a novel electrode composed of TiO₂, reduced graphene oxide (RGO) and Pt nanoparticles on carbon fiber (CF), denoted as Pt/RGO/TiO₂/CF, has been fabricated successfully and employed as a photo-electrocatalyst for methanol oxidation in alkaline media. The spherical TiO₂ nanoparticles are loaded on CF surface by an in situ method and wrapped by the gauze-like RGO. Meanwhile, the RGO effectively extends the absorption edge to visible light region based on the UV–vis diffuse reflectance absorption spectra (DRS) and promotes the good dispersion of Pt nanoparticles electro-deposited on the surface of RGO-wrapped TiO₂. The as-prepared Pt/RGO/TiO₂/CF electrode shows enhanced electrocatalytic activity and stability compared with Pt/TiO₂/CF and Pt/CF electrodes both with and without light irradiation. The RGO plays an important role for the enhancement of electrocatalytic and photo-electrocatalytic performance. Moreover, Pt/RGO/TiO₂/CF presents a higher photo-electrocatalytic activity for methanol oxidation with light irradiation than that without light irradiation due to the synergistic effect among them.     

Self-organized nanotubular TiO2 matrix as support for dispersed Pt/Ru nanoparticles: Enhancement of the electrocatalytic oxidation of methanol

We explore oxidative electrocatalytic properties of a system consisting of bimetallic Pt/Ru nanoparticles dispersed over a nanotubular self-organized TiO₂ matrix. The nanotubular TiO₂ layers consist of individual tubes of 100 nm diameter, 500 nm length and 15 nm wall thickness. This nanotubular TiO₂ support provides a high surface area and it significantly enhances the electrocatalytic activity of Pt/Ru for methanol oxidation (relative to the performance of Pt/Ru at the same loading but immobilized on a conventional compact TiO₂ support). Annealed to anatase, the TiO₂ nanotubular support exhibits even higher enhancement effect during electrooxidation of methanol than when used in the “as-formed” amorphous structure. The overall electrocatalytic activity of the system can be further increased by illumination with UV-light (wavelength 325 nm).     

Synthesis and Performance of Polyvinylpyrrolidone‐Protected Pd Nanoparticles Supported on TiO2MWCNTs under Protection of PVP for in Alcohols Oxidation in Alkaline Media

This paper describes the synthesis and performance of Pd/p‐TiO₂‐MWCNTs for alcohol electrooxidation. Regulation of the steric repulsive forces of polyvinylpyrrolidone was used to achieve even dispersion of Pd nanoparticles over the TiO₂ surfaces. The order of the electroactivities of the Pd/p‐TiO₂? MWCNTs in alcohol oxidation was ethanol>ethylene glycol>methanol. The order of the stabilities of alcohol oxidation by Pd/p‐TiO₂? MWCNTs was ethylene glycol>ethanol>methanol. Electroimpedance spectroscopy showed that at a potential of ?0.1 V, the Pd/p‐TiO₂? MWCNTs had good tolerance of adsorbed CO in ethylene glycol oxidation, and at ?0.2 V, the Pd/p‐TiO₂? MWCNTs had good adsorbed CO tolerance in methanol oxidation.     

Ionic Liquid Assisted Synthesis of Au–Pd Bimetallic Particles with Enhanced Electrocatalytic Activity

Morphology‐ and composition‐controlled synthesis of Au–Pd bimetallic particles was realized by a facile ionic liquid assisted route at room temperature. The morphologies of the synthesized particles, such as nanoflake‐constructed spheres with a core–shell structure, nanoparticle‐constructed spheres, and nanoparticle‐constructed dendrites, could be well controlled by the present route. The ionic liquid was found to play a key role in the formation of these interesting particles. Moreover, the composition (Au:Pd) of the particles could be modulated by means of the molar ratio of the metal precursors in the feeding solutions. The Au–Pd bimetallic particles exhibit high electrocatalytic activity toward oxidation of ethanol and formic acid. Furthermore, cyclic voltammetric studies on the as‐prepared Au–Pd bimetallic particles revealed good electroactivity for H₂O₂, which results in an effective amperometric H₂O₂ sensor.     

Platinum catalysed nanoporous titanium dioxide electrodes in H2SO4 solutions

The preparation and electrochemistry of dispersed Pt metal on nanoporous titanium dioxide coatings is described. It is shown that photocatalytic deposition of Pt centres on a nanoporous titanium dioxide layer fabricated from TiO₂ nanoparticles leads to high surface area electrocatalysts. The reactions investigated are the evolution of hydrogen and the oxidation of carbon monoxide and methanol.     

Nano composite system based on coumarin derivative–titanium dioxide nanoparticles and ionic liquid: Determination of levodopa and carbidopa in human serum and pharmaceutical formulations

The combination of coumarin derivative (7-(1,3-dithiolan-2-yl)-9,10-dihydroxy-6H-benzofuro[3,2-c]chromen-6-on), (DC)–titanium dioxide nanoparticles (TiO₂) and ionic liquid (IL) yields nanostructured electrochemical sensor, formed a novel kind of structurally uniform and electrocatalytic activity material. This new ionic liquid–TiO₂ nanoparticles modified carbon paste electrode (IL–CTP) due to its enhanced conductivity presented very large current response from electroactive substrates. The modified electrode was characterized by different methods including a scanning electron microscope (SEM), electrochemical impedance spectroscopy (EIS) and voltammetry. A pair of well-defined quasi reversible redox peaks of coumarin derivative was obtained at the modified carbon paste electrode (DC/IL–CTP) by direct electron transfer between the coumarin derivative and the CP electrode. Dramatically enhanced electrocatalytic activity was exemplified at the DC/IL–CTP electrode, as an electrochemical sensor to study the electro oxidation of levodopa (LD) and carbidopa (CD). Based on differential pulse voltammetry (DPV), the oxidation of LD and CD exhibited the dynamic range between 0.10– 900.0 μM and 20.0–900.0 μM respectively, and the detection limit (3σ) for LD and CD were 41 nM and 0.38 μM, respectively. DPV was used for simultaneous determination of LD and CD at the DC/IL–CTP electrode, and quantitation of LD and CD in some real samples (such as tablets of Parkin-C Fort and Madopar, Sinemet, water, urine, and human blood serum) by the standard addition method.     

Au/TiO2 nanotube catalysts prepared by combining sol–gel method with hydrothermal treatment and their catalytic properties for CO oxidation

A new preparation method for Au/TiO₂ nanotubes (NTs) by combing sol–gel with hydrothermal treatment technique was developed. The TiO₂ NTs calcined at 300 °C were nearly uniform, and the gold particles were distributed homogeneously. The possible formation mechanism was suggested. The 5 % Au/TiO₂ NTs calcined at 300 °C had the best catalytic activity for CO oxidation, and their conversion of CO remained at 100 % during 60 h on stream. This preparation method could improve the thermal stability of Au/TiO₂ nanotube catalysts.     

高度有序的二氧化钛纳米管阵列的制备及其光催化活性的研究

采用电化学阳极氧化法在钛表面构筑了一种结构有序、微米级的TiO₂纳米管阵列膜层. 考察了制备电压、氧化时间、溶液搅拌等实验参数对TiO₂纳米管阵列形貌和尺寸的影响. 应用SEM和XRD对膜层的形貌和晶型进行了分析和表征, 并通过TiO₂纳米管阵列膜对甲基橙的光催化降解, 研究了TiO₂纳米管阵列膜层结构与光催化活性的关系. 结果表明: 阳极电压和溶液搅拌对制备TiO₂纳米管阵列的结构起到关键的作用. 控制20 V电压制备的TiO₂纳米管阵列膜, 管长达2.6～3.3 μm, 经500 ℃热处理后具有最高的光催化活性, 其光催化性能明显优于一般的TiO₂纳米颗粒膜.     

Photo(UV)-enhanced performance of Pt–TiO2 nanostructure electrode for methanol oxidation

We report an improved performance of Pt–TiO₂ nanostructure electrode for methanol oxidation in methanol fuel cells. The nanostructure electrode consisting of Pt nanophases and a titanium oxide matrix was fabricated by means of co-sputtering deposition method. The electrode showed a remarkably enhanced performance for methanol oxidation under UV illumination compared to that without UV illumination. Such a remarkably improved performance of the Pt–TiO₂ electrode might be due to the enhanced methanol oxidation by photo-generated holes in the TiO₂ under UV illumination.     

Effect of the microstructure of the supported catalysts CuO/TiO<Subscript>2</Subscript> and CuO/(CeO<Subscript>2</Subscript>-TiO<Subscript>2</Subscript>) on their catalytic properties in carbon monoxide oxidation

The effect of the microstructure of titanium dioxide on the structure, thermal stability, and catalytic properties of supported CuO/TiO₂ and CuO/(CeO₂-TiO₂) catalysts in CO oxidation was studied. The formation of a nanocrystalline structure was found in the CuO/TiO₂ catalysts calcined at 500°C. This nanocrystalline structure consisted of aggregated fine anatase particles about 10 nm in size and interblock boundaries between them, in which Cu²⁺ ions were stabilized. Heat treatment of this catalyst at 700°C led to a change in its microstructure with the formation of fine CuO particles 2.5–3 nm in size, which were strongly bound to the surface of TiO₂ (anatase) with a regular well-ordered crystal structure. In the CuO/(CeO₂-TiO₂) catalysts, the nanocrystalline structure of anatase was thermally more stable than in the CuO/TiO₂ catalyst, and it persisted up to 700°C. The study of the catalytic properties of the resulting catalysts showed that the CuO/(CeO₂-TiO₂) catalysts with the nanocrystalline structure of anatase were characterized by the high-est activity in CO oxidation to CO₂.