甲醇在聚苯胺修饰铂钼共沉积电极上的催化氧化

用恒电位法和循环伏安法在铂电极上分别制备了聚苯胺修饰的分散氢钼青铜电极和分散铂电极,以及聚苯胺修饰的不同铂钼比例的铂与氢钼青铜共沉积电极。用循环伏安法研究了制备电极在c(H2SO4)=0.5mol/L水溶液中的电化学行为,以及对c(CH3OH)=0.1 mol/L的催化氧化行为。其中,分散氢钼青铜电极对甲醇无催化氧化的作用,铂与氢钼青铜共沉积电极对甲醇的催化氧化效果优于分散铂电极。铂-氢钼青铜共沉积电极对甲醇氧化的催化能力与共沉积铂钼的比例有关,当制备电极所用的溶液中n(氯铂酸)∶n(钼酸钠)=2∶1时,共沉积电极对甲醇的催化氧化活性最高,此时甲醇在共沉积电极上的氧化峰电流是单纯铂电极的2.632倍。     

甲醇在碳载纳米Pt电极上的电化学研究

应用循环伏安法制备了nano-Pt/GC修饰电极,优化了铂微粒在电极表面的沉积条件,并用扫描电子显微镜(SEM)和在硫酸中的循环伏安曲线对其进行了表征。结果表明铂微粒较为均匀地分散在玻碳电极表面,粒径约为140nm,电极具有很大的比表面积。循环伏安实验结果表明nano-Pt/GC电极对甲醇电氧化的催化活性明显高于铂片电极,在该修饰电极上甲醇正向扫描和反向扫描时的氧化峰电位分别是0.67V和0.49V,峰电流为61.00mA/cm2和50.50mA/cm2,分别是铂片电极上的3.13倍和3.10倍,有效地提高了金属铂的利用率,铂微粒在电极表面的最佳沉积条件是循环次数为100次和沉积速度为5mV/s。     

甲醛在nano-Pt/GC电极上的电催化氧化研究

应用循环伏安法制备了nano-Pt/GC电极,并用SEM和电极在H2SO4中的循环伏安曲线对其进行了表征。结果表明,该方法制备的电极表面铂粒子分布较为均匀,粒径大小约为140nm,电极具有较大比表面积。电化学实验表明,该电极对甲醛电氧化的催化活性明显好于铂片电极。修饰电极的催化活性与铂粒子的沉积条件有关,铂微粒在电极表面的最佳沉积条件为循环次数100次和沉积速度5mV/s。     

乙二醛在纳米TiO2-Pt电极上的电催化氧化

通过电沉积修饰铂微粒制备Ti基纳米TiO₂-Pt（Ti/nano-TiO₂-Pt）修饰电极,采用循环伏安法研究了乙二醛在Ti/nano-TiO₂-Pt上的电催化氧化。结果表明：Ti/nano-TiO₂-Pt修饰电极对乙二醛的氧化呈现较高的电催化活性,可作为乙二醛电氧化合成乙醛酸的高活性催化电极。     

钯复合材料电极催化甲醇氧化机理

在NaY/Teflon修饰玻碳电极上电化学辅助沉积钯微粒,制备钯复合材料电极,研究催化反应机理。采用循环伏安法(CV)、计时电流法和扫描电镜进行表征,结果表明,钯复合材料电极对甲醇的催化是单电子过程,改变甲醇氧化途径,降低活化能。该电极具有优越的放电特性,提高甲醇和电极利用率,对甲醇氧化具有良好的电催化活性。     

甲醇在铂微粒修饰碳纳米管/纳米TiO2-聚苯胺膜电极上的电催化氧化

在0.5mol·L-1硫酸介质中,采用循环伏安的电化学聚合方法,以50mv·s-1的扫描速度,在-0.1～0.9V范围内以碳纳米管/纳米TiO2(CNT/nanoTiO2)电极为基体聚合得到了聚苯胺(PAn)复合膜电极,用循环伏安法研究了CNT/nanoTiO2-PAn-Pt电极在0.5mol·L-1H2SO4溶液中的电化学行为以及对甲醇氧化的电催化行为。结果表明,CNT/nanoTiO2-PAn-Pt电极对甲醇的氧化具有很高的电催化活性,并同时存在PAn的协同催化作用。在Pt载量为0.56mg/cm2时,甲醇氧化峰电流达到152mA/cm2,随着Pt载量的增加,甲醇的氧化峰电流最高可达410mA/cm2。     

用磷钼酸修饰甲醇燃料电池的铂电极

近年来以杂多化合物为基础的催化体系受到广泛的关注.为了研究杂多酸与铂电极对甲醇电催化氧化的协同效应,通过循环伏安扫描法制备了磷钼酸（H3PMo12O40）修饰铂电极.通过循环伏安和计时电流法研究了该修饰电极对甲醇氧化的电催化活性和抗中间产物的毒化作用,并比较了该修饰电极与其单酸盐（Na2MoO4）修饰铂电极的性能,测试结果表明：磷钼酸修饰铂电极能够提高对甲醇氧化反应的催化活性,基本上同其单酸盐Na2MoO4修饰铂电极的催化活性相当,并且这种促进作用主要是由Mo原子价态变化引起的.同时计时电流曲线测试结果表明,该修饰电极具有一定的抗毒化作用,但不如钼酸钠好.     

铂微粒修饰聚苯胺膜电极对甲酸电催化氧化的研究

采用循环伏安法研究Pt盘电极 (Pt)、铂微粒修饰Pt盘电极 [Pt(Pt) ]和Pt微粒修饰聚苯胺膜电极 [PAN(Pt) ]对甲酸电催化氧化行为的影响 ,比较了它们对甲酸电催化氧化的活性 ,发现PAN(Pt)电极对甲酸电催化氧化的表观电流密度为 3 79× 10 2 mA·cm-2 ,分别比Pt、Pt(Pt)和Pt-PDMA/Pt电极约高 2 35、2 5和 6 3倍。峰电位比Pt PDMA/Pt电极约低 0 16V。     

纳米TiO_2-Pt复合膜电极间接电催化氧化甘油为甘油醛的研究

运用电沉积法在纳米TiO2膜上电沉积分散的Pt微粒制成钛基纳米TiO2-Pt复合膜(nano TiO2-Pt)修饰电极,采用循环伏安法和电解氧化法,研究了复合膜电极的电催化活性以及氧化甘油为甘油醛的过程。结果表明,纳米TiO2为锐钛矿型,Pt纳米粒子均匀分散在TiO2多孔膜的表面和内部。复合膜电极在常温常压下对甘油的电化学氧化具有高催化活性和稳定性,在25~30℃下,电流密度为25 m A/cm2时,电流效率达84%,电解产率达89.6%。     

甲醇在聚苯胺载铂电极上的电催化氧化

用循环伏安法在玻碳电极上电聚合导电高分子聚苯胺用于附载Pt，提高了Pt的分散度。发现甲醇在Pt／PAN／GC电极和Pt／GC电极上均能自发解离出强吸附中间体CO，证实聚苯胺膜的存在有利于提高电极对甲醇的电催化氧化活性，CO在Pt／PAN／GC电极上的氧化峰电流明显高于Pt／GC电极。通过比较甲醇的电催化氧化活性可知，Pt/PAN／GC电极催化氧化甲醇的峰电流为58．68mA/cm^2和50．00mA／cm^2，是Pt／GC电极氧化峰电流的1．6倍和1．7倍。     

The electrocatalytic oxidation of ascorbic acid on polyaniline film synthesized in the presence of β-naphthalenesulfonic acid

Polyaniline-β-naphthalenesulfonic acid composite film on platinum electrode surface has been synthesized via the electrochemical polymerization of aniline in the presence of β-naphthalenesulfonic acid (NSA). FT-IR, UV-vis and electrochemical characterization indicate the formation of the doped polyaniline. Further investigations found that the polyaniline (PAN) doped with NSA extended the electroactivity of PAN in neutral and even in alkaline media. The PAN-NSA composite film coated platinum electrodes are shown to be good electrocatalytic surfaces for the oxidation of ascorbic acid (AA) in phosphate buffer solution (PBS) of pH 7.0. The anode peak potential of AA shifts from 0.62 V at bare platinum electrode to 0.34 V at the PAN-NSA composite modified platinum electrode with greatly enhanced current response. A linear calibration graph is obtained over the AA concentration range of 5-60 mM using cyclic voltammetry. The kinetics of the catalytic reaction is investigated using rotating disk electrode (RDE) voltammetry, cyclic voltammetry and chronoamperometry. The results are explained using the theory of electrocatalytic reactions at chemically modified electrodes. The PAN-NSA composite film on the electrode surface shows good reproducibility and stability.     

Graphite Electrodes Modified with Platinum‐Nickel Nano‐Particles for Methanol Oxidation

Methanol electro‐oxidation is investigated at graphite electrodes modified with various platinum and nickel nano‐particle deposits using cyclic voltammetry. The modified electrodes are prepared by the simultaneous electrodeposition of metals from their salt solutions using potentiostatic and galvanostatic techniques. They show enhanced catalytic activity towards methanol oxidation in KOH solution. The catalytic activity of platinum nano‐particles is found to be significantly affected by the presence of relatively small amounts of nickel deposits. A comparison is made between the electrocatalytic activity of Pt/C and (Pt‐Ni)/C electrodes. The results show that the methanol electro‐oxidation current increases with an increase in the nickel content. In particular, the highest catalytic activity is achieved for platinum to nickel deposits of 95%:5% (wt.‐%), in other cases the catalytic activity decreases. It is found that Ni enhances the catalytic activity of Pt by increasing the number of active sites, as well as through an electron donation process from Ni to Pt. This process takes place once the nickel hydroxide (Ni(OH)₂)/nickel oxy‐hydroxide (NiOOH) transformation begins. The effect of the methanol concentration on the methanol oxidation reaction is investigated. The order of reaction, with respect to methanol, at the modified (Pt‐Ni)/C electrode is found to be 0.5.     

Novel conjugated polymer/graphene/platinum composite for enhancing electrocatalytic oxidation of methanol

A novel conjugated polymer containing electron transport groups with high electron affinity, denoted POXD was synthesized upon polycondensation. The polymer was characterized by Fourier transform infrared (FTIR) spectra and ¹H nuclear magnetic resonance (¹H NMR) spectroscopy. Furthermore, the conjugated polymer/graphene (POXD/RGO) composite film was prepared, which was subsequently used as the support for the electrodeposition of platinum. The microstructure and morphology of the prepared samples were characterized by X‐ray photoelectron spectroscopy (XPS) and field emission scanning electron microscopy (FE‐SEM). The electrocatalytic activity for the oxidation of methanol was investigated through cyclic voltammogram method. The POXD/RGO composite film can facilitate the electrodeposition of Pt nanoparticles compared with graphene (RGO) support. The POXD/RGO/Pt composite exhibits more excellent electrocatalytic property for the oxidation of methanol, such as lower oxidation potential and higher current intensity, which might be attributed to the high electron affinity of the polymer and the interaction of the Pt nanoparticles with polymer. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Electrocatalytic oxidation of methanol and C1 molecules on highly dispersed electrodes Part 1: Platinum in polyaniline

The oxidation of methanol and C1 molecules was investigated on platinum-modified polyaniline electrodes. It was found that such electrodes are conducting even at 0.0 V vs RHE. They were found to have a higher electrocatalytic activity than bulk platinum electrodes. Moreover, the poisoning effect is drastically decreased as proved by in situ EMIRS studies which show no significant CO_ads signal. Finally, kinetic results show that the methanol electrooxidation is first order with respect to methanol and that the main oxidation product is formaldehyde.     

Preparation and electroactivity of polyaniline/poly(acrylic acid) film electrodes modified by platinum microparticles

The preparation and properties of poly(acrylic acid) (PAA)-doped polyaniline (PANI) film electrodes further modified by electrodeposition of platinum particles were investigated by cyclic voltammetry and in situ conductivity measurement. The PANI/PAA film exhibits a better electroactivity and higher stability, even in solutions of lower acidity, although its polymerization rate is decreased three-fold compared to that of PANI. The conductivity of the PANI/PAA film increases by a factor of two compared to that of PANI. The effects of the carboxylic acid groups of PAA in the PANI matrix on the performance of the film are discussed. The electrocatalytic activity of PANI/PAA/Pt for reduction of hydrogen and oxidation of MeOH is higher than that of PANI modified with Pt particles alone. Characterization of the electrodes by SEM shows the platinum modification procedure yields roughly spherical catalyst particles 0.51mum in diameter dispersed throughout the polyaniline.     

Preparation and electroactivity of polyaniline/poly(acrylic acid) film electrodes modified by platinum microparticles

The preparation and properties of poly(acrylic acid) (PAA)-doped polyaniline (PANI) film electrodes further modified by electrodeposition of platinum particles were investigated by cyclic voltammetry and in situ conductivity measurement. The PANI/PAA film exhibits a better electroactivity and higher stability, even in solutions of lower acidity, although its polymerization rate is decreased three-fold compared to that of PANI. The conductivity of the PANI/PAA film increases by a factor of two compared to that of PANI. The effects of the carboxylic acid groups of PAA in the PANI matrix on the performance of the film are discussed. The electrocatalytic activity of PANI/PAA/Pt for reduction of hydrogen and oxidation of MeOH is higher than that of PANI modified with Pt particles alone. Characterization of the electrodes by SEM shows the platinum modification procedure yields roughly spherical catalyst particles 0.51mum in diameter dispersed throughout the polyaniline.     

Electrocatalytic Activity of Platinum modified Polypyrrole Films for the Methanol Oxidation reaction

The catalytic activity of platinum modified polypyrrole films prepared in different ways was studied for the methanol oxidation reaction. Surprisingly, no catalytic activity was observed for films modified with colloidal platinum particles incorporated into the film during its synthesis or for the film synthesised with tetrachloroplatinate complex as a nucleophilic counter-ion, which was subsequently cathodically reduced. On the other hand, high catalytic activity was observed for platinum deposited onto pre-synthesised polypyrrole film. The platinum load, film thickness and potential of platinum deposition were found to be important parameters. High electrocatalytic activity was also observed for platinum layers deposited directly onto the glassy carbon (GC) support. However, in the latter case the stability of the electrocatalytic activity was lower when compared with the polypyrrole film modified by cathodically deposited Pt.     

Polyaniline‐supported platinum‐hydrous ruthenium oxide nanocomposite as electrocatalyst for methanol oxidation

A novel composite electrode is fabricated through the electrodeposition of hydrous ruthenium oxide (RuO₂·xH₂O) and platinum (Pt) particles into the matrix of polyaniline (PANI). Scanning electron microscopy reveals that RuO₂·xH₂O and Pt particles are homogeneously distributed into the matrix of PANI. A comparison of the sizes of Pt and RuO₂·xH₂O particles incorporated into the PANI film reveals that Pt particles are smaller in sizes as compared with the sizes of RuO₂·xH₂O particles. The catalytic activity of composite electrodes was evaluated for the oxidation of methanol by using cyclic voltammetry and chronoamperometry. A relatively high catalytic current was noticed for the oxidation of methanol (2.37 mA/cm²) at PANI‐Pt‐RuO₂·xH₂O electrode (+0.6 V (V vs. Ag/AgCl) in comparison to oxidation current at PAN‐Pt (1.27 mA/cm²) electrode. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

3D Electrodes from aluminium foams prepared by replication process

Aluminium foams with pores displaying both regular size and distribution have been prepared by replication methods. Their volumetric density and electrical conductivity were 0.65 g cm^?3 and 2.44 MS m^?1, respectively. This method represents a simple way to produce 3D metal macroporous electrodes. In addition, the aluminium foam has been employed as support to produce 3D platinum electrodes (Pt/Al foam) by electrodeposition. The conditions for platinum electrodeposition have been established, and the electrodes were characterized by scanning electron microscopy and cyclic voltammetry. The electrocatalytic behaviour of the Pt/Al foam electrodes to methanol oxidation has been tested in 1 M CH₃OH + 0.5 M H₂SO₄ solutions.