High-efficiency palladium catalysts supported on ppy-modified C60 for formic acid oxidation

A facile preparation of polypyrrole-modified fullerene supported Pd nanoparticles catalyst is introduced; electrochemical measurements demonstrate that the obtained Pd/ppy-C(60) catalyst shows a good electrocatalytic activity and stability for the oxidation of formic acid.     

钯纳米晶体在电催化甲酸氧化反应中的形貌效应

本文基于课题组前期工作,选用适当的金属前驱物、还原剂、稳定剂和保护剂,通过调控氧化刻蚀和反应动力学等,成功合成了形貌和尺寸均不相同的Pd纳米晶.经过认真的纳米粒子清洗和电极修饰组装,考察了它们在电催化甲酸氧化反应中的形貌与性能的关系.研究结果表明,Pd纳米晶样品的最大电流密度以纳米八面体（nanooctahedra）、纳米线（nanowires）、纳米立方体（nanocubes）、纳米瓜子（nanotapers）、凹面纳米立方体（concave nanocubes）的顺序递增,催化甲酸氧化反应的起始氧化电位均小于0.2V.研究结果印证了Pd纳米晶催化甲酸氧化反应的催化性能在尺寸效应上主要受活性表面积的影响,扣除表面积效应后的催化性能与其尺寸没有明确关系.该系列Pd纳米晶的催化性能主要取决于其表面结构,得出Pd纳米晶催化甲酸氧化反应遵循{111}晶面〈{100}晶面〈高指数晶面的性能活性顺序.综合最大电流密度和最小操作电位因素发现,Pd凹面纳米立方体和Pd纳米瓜子具有相对较好的商用价值.     

Structural effects on the oxidation of formic acid on the high index planes of palladium

Electrochemical oxidation of formic acid has been studied on the stepped and kinked-stepped surfaces of Pd in 0.1 M HClO₄ containing 0.1 M formic acid with the use of voltammetry. The surfaces examined are Pd(S)-[n(1 0 0) × (1 1 0)], Pd(S)-[n(1 1 1) × (1 0 0)] and Pd(S)-[n(1 1 1) × (1 1 1)] series (n = 2–9). The results are compared with those of Pd(S)-[n(1 0 0) × (1 1 1)] series reported previously. All the electrodes give maximum currents of formic acid oxidation j_P between 0.5 and 0.8 V (RHE). The values of j_P plotted against the density of step (kink) atoms d_S depend on the surface structure remarkably. Pd(S)-[n(1 1 1) × (1 0 0)] surfaces provide maximum of j_P at n = 5, whereas Pd(S)-[n(1 0 0) × (1 1 0)] and Pd(S)-[n(1 1 1) × (1 1 1)] do not give maximum of j_P. The values of j_P have the following order: Pd(S)-[n(1 1 1) × (1 1 1)] < Pd(S)-[n(1 1 1) × (1 0 0)] < Pd(S)-[n(1 0 0) × (1 1 0)] < Pd(S)-[n(1 0 0) × (1 1 1)]. The anodic current at more negative potential 0.20 V (RHE) shows different activity series: Pd(1 1 1) and Pd(1 1 0) have the highest rate for formic acid oxidation at 0.20 V (RHE).     

Facile synthesis of hollow palladium/copper alloyed nanocubes for formic acid oxidation

Hollow PdCu alloyed nanocubes were successfully synthesized by a novel one-pot template-free strategy through tuning the surface energy difference of the crystal planes by alloying. Compared with the solid nanoparticles, the hollow nanocubes exhibit superior electrocatalytic activity and stability for formic acid oxidation.     

Ethylenediamine tetramethylene phosphonic acid assisted synthesis of palladium nanocubes and their electrocatalysis of formic acid oxidation

The synthesis of Pd nanocrystals of controlled size and morphology has drawn enormous interest due to their catalytic activity. We report a new and efficient strategy for the one-step synthesis of monodispersed Pd nanocubes with ethylenediamine tetramethylene phosphonate (EDTMP) as a complex-forming and capping agent. The morphology, structure, and growth mechanism of the Pd nanocubes were fully characterized via selected area electron diffraction (SAED), transmission electron microscopy (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). It was found that the morphology of the Pd nanocrystals in the proposed EDTMP–PdCl₂ system could be changed from octahedrons to nanocubes simply by adjusting the amount of iodide used during synthesis. After UV/ozone and electrochemical cleaning, the as-prepared Pd nanocubes demonstrated excellent electrocatalytic activity and stability during formic acid oxidation, owing to their abundant {100} facets and small particle size.     

Nanosized palladium on holey graphene sheets incorporating PxOy for effective formic acid oxidation

A stack of basic structural carbon units incorporating phosphorus oxides (P_xO_y) at edges and internal defects is obtained and used as a support material for Pd nanoparticles, with the aim of creating an efficient electrocatalyst for HCOOH oxidation. In contrast to the lack of activity displayed by Pd supported on lyophilized and vacuum-annealed graphene oxides, Pd on holey graphene sheets incorporating P_xO_y (Pd/HGP_xO_y) shows efficient activity and stability in HCOOH oxidation. Surface analysis of fresh and reacted catalysts reveals that HCOOH oxidation is favored by Pd/HGP_xO_y due to the decreased Pd electron density caused by electron transfer from Pd to HGP_xO_y.     

Structural effects of electrochemical oxidation of formic acid on single crystal electrodes of palladium

Structural effects on the rates of formic acid oxidation have been studied on Pd(111), Pd(100), Pd(110), and Pd(S)-[n(100) x (111)] (n = 2-9) electrodes in 0.1 M HClO4 containing 0.1 M formic acid with use of voltammetry. On the low index planes of Pd, the maximum current density of formic acid oxidation (jP) increases in the positive scan as follows: Pd(110) < Pd(111) < Pd(100). This order differs from that on the low index planes of Pt: Pt(111) < Pt(100) < Pt(110). Pd(S)-[n(100) x (111)] electrodes with terrace atomic rows n > or = 3 have almost the same jP as Pd(100), except Pd(911) n = 5. The value of jP on Pd(911) n = 5 is 20% higher than those of the other surfaces. Pd(311) n = 2, of which the first layer is composed of only step atoms, has the lowest jP in the Pd(S)-[n(100) x (111)] series. The adsorption geometry of the reaction intermediate (formate ion) is optimized by using density functional theory.     

Ethylene oxidation by lithium nitrate in the presence of palladium acetate in acetic acid

Data are reported on variations of the gas phase volume and product accumulation in ethylene oxidation by lithium nitrate in acetic acid solutions, catalyzed by palladium acetate. An assumption is made on the routes of nitrate ion reduction.

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Electrochemical fabrication of multiplicate palladium hierarchical architectures and their electrocatalysis toward oxidation of formic acid

Dendritic, cactoid, splintery flowers-like and spinous flowers-like micro/nano-Pd hierarchical architectures were successfully deposited on the conductive substrates without assistance of any templates. Distinct from other general electrodeposition at a constant potential or cyclic potential, we utilized pulse potentials as deposition and dissolution potential, which were controlled by a simple and convenient electrochemical method—differential pulse amperometry. It was found that the morphologies of these novel micro/nanoparticles could be regulated with different pulse potentials. The resulting nanostructures were characterized by scanning electron microscopy and X-ray diffractometry. The results show that series of Pd micro/nanoparticles were bounded on the different index facets. It means that the growth direction could be effectively controlled by regulating the pulse potentials. Moreover, the as-synthesized Pd micro/nanoparticles also exhibited strikingly difference in catalytic activity toward electrooxidation of formic acid.     

球状多孔Pd纳米粒子超结构的合成及其对甲酸的电催化氧化

在丙酮／水混合溶剂中,以氯代十六烷基吡啶为结构导向剂,水合肼还原PdCl42-,制得了直径范围在30～50nm之间的球状多孔Pd纳米粒子超结构．实验表明,氯代十六烷基吡啶对球状多孔Pd纳米粒子超结构的形成起着重要的作用,不加该表面活性剂时,得到的是实心Pd纳米粒子;而丙酮主要影响表面活性剂胶束的尺寸．此外,本文还研究了球状多孔Pd纳米粒子超结构对甲酸氧化的电催化活性,在0．5mol／L H2SO4＋0．5mol／L HCOOH溶液中的循环伏安结果表明,球状多孔Pd纳米粒子超结构修饰电极在酸性溶液中电催化氧化甲酸的峰电流约为180mA／mg,明显优于实心Pd纳米粒子修饰电极（峰电流为120mA／mg）,且表现出较高的稳定性．     

The oxidation of formic acid at noble metal electrodes Part 4. Platinum + palladium alloys

Formic acid oxidation has been studied on Pt + Pd alloys of known surface composition using cyclic voltammetry. The results are interpreted in terms of a strongly bound (poisoning) intermediate which adsorbs only on the Pt atoms and a direct oxidation path which involves an intermediate occupying a single site and a second intermediate occupying two sites. Steady state oxidation currents on the alloys at potentials in the range of about 0.4 to 0.9 V are larger than expected from a linear combination of the currents on the pure metals. This effect may be due to the modification of metal properties at the junction between two types of metallic atoms.     

A composite made from palladium nanoparticles and carbon nanofibers for superior electrocatalytic oxidation of formic acid

We report on a novel type of nanocomposite for use in the electrooxidation of formic acid in fuel cells. The material is composed of palladium nanoparticles (Pd-NPs) and carbon nanofibers (CNFs) and was prepared by electrospinning of the precursors Pd(acac)₂ and polyacrylonitrile, respectively, followed by thermal treatment to generate in-situ Pd-NPs that are well dispersed within the CNF framework. The nanocomposite was characterized by TEM, high-resolution TEM, SEM, XRD, Raman spectroscopy, and XPS. The size of the Pd-NPs ranges from 12 to 82 nm, depending on the temperature for carbonization (700–1,000 °C). The length and width of the CNF is in the order of tens of micrometers and 300 to 500 nm, respectively. TEM and XPS studies indicate that the Pd-NPs are firmly embedded in the CNF, resulting in a good electrochemical stability of the composite. The electrocatalytic properties of the composite with respect to the oxidation of formic acid were studied by cyclic voltammetry and chronoamperometry. They showed a distinctly improved electrocatalytic activity and stability compared to a commercial Pd-on-carbon catalyst. The Pd/CNF composite carbonized at 900 °C was found to display the best performance.

Flow injection chemiluminescence determination of naftopidil based on potassium permanganate oxidation in the presence of formaldehyde or formic acid

A flow injection method is proposed for the determination of naftopidil based upon the oxidation by potassium permanganate in a sulfuric acid medium and sensitized by formaldehyde and formic acid. The optimum chemical conditions for the chemiluminescence emission were 0.25 mM potassium permanganate and 4.0 M sulfuric acid. Two manifolds were tested and instrumental parameters such as the length of the reactor, injection volume and flow rate were compared. When using the selected manifold in the presence of 0.4 M formaldehyde, naftopidil gives a second-order calibration graph over the concentration range 0.1–40.0 mg L^–1 with a detection limit calculated (as proposed by IUPAC) of 92.5 ng mL^–1 and a standard deviation of 0.12 mg mL^–1 for ten samples of 10.0 mg L^–1 naftopidil. In the presence of 1.15 M formic acid, naftopidil gives a second-order calibration graph over the concentration range 0.05–40.0 mg L^–1 with a detection limit of 14.2 ng mL^–1 and a standard deviation of 0.37 mg mL^–1 for ten samples of 10.0 mg L^–1 naftopidil. In both cases, the determination is free from interferences from common excipients such as sucrose, glucose, lactose, starch and citric acid.     

Butylphenyl-functionalized palladium nanoparticles as effective catalysts for the electrooxidation of formic acid

Monodisperse butylphenyl-functionalized palladium (Pd-BP, dia. 2.24 nm) nanoparticles were synthesized through co-reduction of butylphenyldiazonium and H(2)PdCl(4) by NaBH(4). Because of this unique surface functionalization and a high specific electrochemical surface area (122 m(2) g(-1)), the Pd-BP nanoparticles exhibited a mass activity ～4.5 times that of commercial Pd black for HCOOH electrooxidation.     

Kinetics of the permanganate oxidation of formic acid in aqueous solution

The kinetics of the permanganate oxidation of formic acid in aqueous perchloric acid at 30°C were examined by the spectrophotometric method. The chemical reaction 2MnO + 3HCOOH + 2H⁺ → 2MnO₂ + 3CO₂ + 4H₂O, appears to proceed via several parallel reactions. The overall rate equation has been obtained by using statistical multilinear regression analysis of the 660 cases studied, and the presence in the rate equation of two new terms in relation to previous studies shows that both permanganate autocatalytic effects and acid media inhibition must be taken into account when the reaction proceeds at constant ionic strength.     

Synthesis and electrocatalytic activity of palladium nanoparticles on porous silicon

Palladium was combined with porous silicon into catalytically active functional electrode nanocomposites. Palladium nanoparticles were examined by transmission electron microscopy and atomic force microscopy; their catalytic activity was estimated using cyclic voltammetry.     

Photoactivation of alkene oxidation by molecular oxygen in the presence of palladium

A catalytic cycle which leads to α,-β ethylenic ketones and methyl ketones from terminal alkenes in the presence of palladium trifluoroacetate,oxygen and U.V. light is described.     

Catalysis of carbon monoxide oxidation with oxygen in the presence of palladium nanowires and nanoparticles

A new synthesis method based on the coagulation of metal nanoparticles, introduced by laser ablation into superfluid helium, inside of quantized vortices has been used for the fabrication of nanoweb consisting of interconnected palladium wires of a 4 nm diameter. It has been found that at temperatures above 523 K, the Pd nanoweb effectively catalyzes the oxidation of CO with molecular oxygen. Temperature cycling leads to a shift of Pd nanoweb activity to lower temperatures. The catalytic action of the Pd nanoweb has been compared to that of Pd nanoparticles with a diameter of about 2 nm prepared by laser electrodispersion.     

Synthesis and catalytic activity of platinum/porous silicon nanocomposites

Physicochemical characteristics of the functional electrode nanocomposites based on porous silicon with platinum nanoparticles were investigated with the use of electron microscopy, X-ray diffraction, and cyclic voltammetry. It is established that a decrease in the platinum nanoparticle size leads to an increase in catalytic activity of nanocomposites in the reactions of electrocatalytic oxygen reduction and hydrogen oxidation.     

Effects of anions on chemical instabilities in the oxidation of formic acid

Results are presented from experiments conducted on the electrochemical oxidation of formic acid at polycrystalline Pt under constant current conditions. Sulfuric acid and perchloric acid with and without small amounts of HCl were used as supporting electrolytes. The onset of distinctive instabilities, not observed in the HCl-free perchloric acid solution, occurred when the concentration of HCl reached 5 × 10⁶ M. For [HCl] = 1 × 10⁶ M, the observed instabilities were essentially the same as those seen in the HCl-free solution. The result indicates that instabilities might be used for the detection of fairly small anion concentrations. Instabilities observed using the sulfuric acid solution and those observed using the perchloric acid solution were drastically different. A greater extent of adsorption of a given anion cannot be the only reason for the different behaviors. It is argued that anions are directly involved in the oxidation process.