Hydrogen electrosorption into Pd-Pt-Au ternary alloys

Thin layers of Pd-Pt-Au alloys were prepared by metal codeposition at constant potential from chloride solutions. The process of hydrogen electrosorption into Pd-Pt-Au alloys was investigated in acidic solution (0.5 M H₂SO₄) using cyclic voltammetry and chronoamperometry, also coupled with the electrochemical quartz crystal microbalance. It was found that Pd alloying with both Pt and Au decreases the maximum hydrogen solubility, but improves the kinetics of absorbed hydrogen oxidation, which is mirrored in a negative shift of the potential of hydrogen desorption peak and shorter hydrogen desorption time. In Pd-Pt-Au alloys the effect of absorption/desorption hysteresis and the stresses connected with hydrogen absorption are reduced in comparison with pure Pd. After prior hydrogen absorption in Pd-Pt-Au alloys, surface oxides are formed and reduced at potentials even by 200 mV lower than before hydrogen treatment.     

Water-soluble poly(4-styrenesulfonic acid-co-maleic acid) stabilized ruthenium(0) and palladium(0) nanoclusters as highly active catalysts in hydrogen generation from the hydrolysis of ammonia–borane

Water-soluble poly(4-styrenesulfonic acid-co-maleic acid), PSSA-co-MA, stabilized ruthenium(0) and palladium(0) nanoclusters were for the first time prepared in situ from the reduction of ruthenium(III) chloride and potassium tetrachloropalladate(II), respectively, by ammonia–borane during its hydrolysis at room temperature. PSSA-co-MA stabilized ruthenium(0) and palladium(0) nanoclusters having average particle size of 1.9 ± 0.5 and 3.5 ± 1.6 nm, respectively, were isolated from the reaction solution and characterized by TEM and UV–visible electronic absorption spectroscopy. PSSA-co-MA stabilized ruthenium(0) and palladium(0) nanoclusters are highly active catalysts for hydrogen generation from the hydrolysis of ammonia–borane at low temperature. PSSA-co-MA stabilized ruthenium(0) and palladium(0) nanoclusters provide 51,720 and 8720 turnovers, respectively, in the hydrogen generation from the hydrolysis of ammonia–borane at 25 °C before deactivation. Catalytic hydrolysis of ammonia–borane is first order with respect to the catalyst concentration, but zero order with respect to the substrate concentration in the case of both ruthenium(0) and palladium(0) nanoclusters. Activation energies for the hydrolysis of ammonia–borane in the presence of PSSA-co-MA stabilized ruthenium(0) or palladium(0) nanoclusters (54 ± 2 kJ mol⁻¹ and 44 ± 2 kJ mol⁻¹, respectively) are smaller than most of the values reported for the same reaction in the presence of other catalyst systems.     

Nanostructured PVDF-HFP membranes loaded with catalyst obtained by supercritical CO2 assisted techniques

Polymeric catalytic membrane reactors offer a larger flexibility over conventional reactors. The most-used method to generate polymer-based catalytic membranes is the phase inversion that, however, presents some limitations; in particular, the difficulty in generating a uniform distribution of the loaded materials.In this work, we use two new processes for the formation of membranes loaded with catalyst for potential applications in catalysis: supercritical assisted phase inversion and supercritical assisted gel drying, applied to formation of poly(vinylidene fluoride-co-hexafluoropropylene) membranes loaded with palladium nanoparticles. We analyzed the effect of process parameters (polymer concentration, catalyst concentration, pressure, temperature) on the membranes morphology. The supercritical phase inversion process produced cellular asymmetric structures with cell size ranging between 3 and 6 μm and nanoporous homogeneous networks, depending on the process conditions. Palladium nanoparticles homogeneous distributions were obtained only operating at selected process conditions, i.e., pressures larger than 150 bar and temperatures lower than 45 °C.Supercritical gel drying allowed homogeneous nanoporous membranes formation at all the tested process conditions: they were characterized by very high porosity (higher than 90%) and a very uniform catalyst distribution.     

Enhanced electrocatalytic performance of cyano groups containing conducting polymer supported catalyst for oxidation of formic acid

A new palladium (Pd) based catalyst was developed using poly(diphenylamine-co-3-aminobenzonitrile) (P(DPA-co-3ABN)) as the new catalyst support. The sizes, distribution and stability of Pd nanoparticles (Pd NPs) are strongly influenced by the cyano group (–CN) present in P(DPA-co-3ABN). Field emission scanning electron microscopy image and energy dispersive x-ray analysis revealed good dispersion of Pd NP onto P(DPA-co-3ABN) matrix. The electrocatalytic activity of P(DPA-co-3ABN)/Pd catalyst electrode (CE) was investigated in terms of formic acid (FA) electro oxidation. The onset potential and catalytic current for the electro oxidation of FA are higher at P(DPA-co-3ABN)/Pd-CE as compared to PdNPs loaded pristine PDPA catalyst electrode (PDPA/Pd-CE). P(DPA-co-3ABN)/Pd-CE exhibited 18 time higher electrocatalytic current than PDPA/Pd-CE for oxidation of FA.     

X-ray diffraction and H-storage in ultra-small palladium particles

In situ X-ray diffraction (XRD) and gravimetric hydrogen uptake measurements of d ∼ 2–3 nm spherical PdH_x particles have been studied in the temperature and pressure range of 323 < T < 428 K and 0 < P < 10 bar. The Pd particles were protected from sintering with a hydrogen-permeable carbon coating. While only containing ∼300–1000 atoms, the Pd particles were found to exhibit the same fcc structure and lattice constant as the bulk. Our isothermal studies show that, with increasing x, these highly crystalline PdH_x nanoparticles also exhibit a complete transformation from the dilute α solid solution phase to the more concentrated β hydride phase. However, we observed that the character of the α–β phase transition in these nanoparticles is very different from that in the bulk. Indeed, the hydrogen uptake isotherm exhibits a noticeable positive slope in the α + β co-existence region. Furthermore, we also observed a noticeable narrowing of the α + β co-existence region (δx) in the nanoparticles. Also, a significant suppression of the critical temperature T_c for the phase boundary was observed: T_c(nano) ≈ 430 K while T_c(bulk) ≈ 570 K. These results signal a significant change in the thermodynamic behavior of very small hydride nanoparticles that may be common to many other nano-scale metal hydride systems as well.     

多功能钯树脂催化剂的研制

本文阐述了为提高汽油辛烷值而研制的多功能钯树脂催化剂(简称HEP催化剂)的制备方法及原理。同时论述了该催化剂的催化原理及工艺运转的结论。可提高汽油辛烷值1.5～3单位。又提出了废催化剂中贵金属钯回收的技术方案及其原理。钯回收率80％～90％,纯度95％～99％。     

Pd／Ag纤维覆铜触点的制备及其金相组织

用ＡＮ１／ＷＳ型卿钉机加工由挤压法和包套法制备Ｐｄ／Ａｇ５２纤维复铜触点，并进行微观结构剖析，指出挤压更适用于ＡＮ１／ＷＳ型卿钉生产复铜触点。寿命试验后微观结构剖析表明，触点在试验过程中始终保持纤维状态，不会明显形成固溶体合金。     

DMPAQ的合成及其与钯的显色反应

合成新试剂ＤＭＰＡＱ，其结构经红外光谱和元素分析证实。研究了阳离子表面活性剂溴化十四烷基吡啶（ＴＰＢ）存在下试剂与钯的显色反应。在酸性介质中，ＤＭＰＡＱ与钯形成１：１的绿色络合物，其最大吸收峰位于５９０ｎｍ，摩尔吸光系数为５．８×１０＾４Ｌ．ｍｏｌ＾－＾１．ｃｍ＾－＾１。钯量在０－１５μｇ／２５ｍｌ符合比尔定律。方法可不经分离直接用于钯催化剂和微量钯的测定。     

钯—硫醚及■叶立德配合物的合成和表征

氯化-3,3-二氟-2-丙烯基二甲基锍及溴化乙氧甲酰甲基二甲基锍分别与钯的卤化物反应,生成双(3,3-二氯-2-丙烯基二甲基锍)四氯钯(Ⅱ)和双(乙氧甲酰甲基二甲基锍)六溴二钯(Ⅱ)。进一步反应转变为配合物。二氯双(3,3-二氟-2-丙烯基甲基硫醚)合钯(Ⅱ)和二溴双(二甲基乙氧甲酰甲基■叶立德)合钯(Ⅱ)。开通过元素分析、红外光谱、核磁共振谱等测试结果确定了它们的结构。     

Cermet-type hydrogen separation membrane obtained from fine particles of high temperature proton-conductive oxide and palladium

A mixed ionic and electronic conducting hydrogen separation membrane, which consisted of proton-conductive oxide and metallic palladium, was fabricated. A porous alumina tube was employed as a support, and proton-conductive oxide particles were introduced into a microporous top layer of the support by an impregnation method. Palladium particles were deposited into the same porous layer by chemical vapor deposition. Hydrogen permeated preferentially via the membrane thus obtained with a hydrogen permeance (PH₂) of 1.2 × 10^− 9 mol·m^− 2·s^− 1·Pa^− 1 at 873 K. Selectivity for hydrogen (PH₂/PN₂) increased with the operating temperature due to an increase in proton conductivity of the membrane, and PH₂/PN₂ = 5.7 was attained at 873 K.