固相反应法制备的Pt/C催化剂对乙醇氧化的电催化活性研究

直接甲醇燃料电池（DMFC）由于具有燃料来源丰富、价格低廉、易于携带储存等优点,近年来一直是世界上许多国家研究和开发的热点[1].但是甲醇具有一定的毒性,因此要想实现DMFC在诸如手机、笔记本电脑以及电动车等可移动电源领域的应用,必须探索寻找新的液体燃料以替代有毒性的甲醇.其中乙醇很易从农作物中大量生产,又无毒,因此很有可能用作为替代甲醇作DMFC的燃料.乙醇的电催化氧化已被众多的研究者从电催化和乙醇燃料电池的角度进行了广泛研究[2-7].其中,对乙醇电催化氧化活性较好的有pt[2-4]、pt-Ru[6-7]、Pt-Pd[5]和Pt-Mo[7]等催化剂.我们研究组报道了用固相反应法制得的Pt催化剂对甲醇氧化的电催化活性要优于用常规液

Identification of o-phenylenediamine polymerization product catalyzed by cytochrome c

The hydrogen peroxide (H2O2) and cytochrome c-dependent oxidation of o-phenylenediamine (o-PD) was investigated by spectrophotometry and electrochemistry. The results indicated that o-PD underwent facile catalytic oxidation in the presence of cytochrome c, and that the degradation of cytochrome c by hydrogen peroxide can also be partly prevented in the presence of o-PD. The hydroxyl radical scavengers (mannitol and sodium benzoate) and oxo-heme species scavenger (uric acid) do not inhibit the oxidation, which implies that the hydroxylation of o-PD may not be involved in its oxidation. Combining with the results of the mass spectrum, elemental analysis, nuclear magnetic resonance and Fourier transform infrared spectrum of the isolated product, a conceivable structure of the product was suggested. (C) 1998 Elsevier Science B.V.

Ferrocenylphosphine-imine ligands for Pd-catalyzed asymmetric allylic alkylation

Ferrocenylphosphine-imine ligands 6 derived front (R,S)-PPFNH2-R 5 and a variety of benzaldehydes were applied in the Pd-catalyzed asymmetric allylic alkylation of 1,3-diphenylprop-2-en-1-yl acetate 7a or pivalate 7b with dimethyl malonate. The substituent effects on the catalytic reaction were investigated, and 96% e.e. with 99% yield was achieved when the m-nitro substituted ligand 6k was used. (C) 2002 Elsevier Science Ltd. All rights reserved.

Direct observation of subsurface oxygen on the defects of Pd(100)

Oxygen adsorption and desorption on a Pd(100) surface with a mesoscopic defect were studied by photoemission electron microscopy (PEEM). The defect surface, with an area of approximately 200 x 60 mu m(2), behaved differently from the perfect Pd(100) surface towards the adsorption of oxygen. When saturated, both surface oxygen and subsurface oxygen coexisted on the defect surface, whereas only surface oxygen was present on the Pd(100) surface. Upon heating, subsurface oxygen diffused back to the surface and desorbed with surface oxygen at the same time. The difference in oxygen adsorption ability between the defect surface and the perfect Pd(100) surface can be attributed to different structures of these two surfaces. (C) 1999 Elsevier Science B.V. All rights reserved.

Preparation and characterization of Pd-Ag alloy composite membrane with magnetron sputtering

A Pd-Ag (24 wt%) alloy composite membrane was prepared by the magnetron sputtering. A gamma-Al2O3 membrane was synthesized by the sol-gel method and used as substrate of the Pd-Ag alloy film. The process parameters of the magnetron sputtering were optimized as a function of the compactness of the Pd-Ag alloy film. The best membrane with a thickness of 1 mu m was produced with a sputtering pressure of 2.7 Pa and a substrate temperature of 400 degrees C. The membrane had an H-2/N-2 permselectivity of 51.5-1000 and an H-2 permeation rate of 0.036-1.17 x 10(-5)cm(3)/cm(2).s. Pa, depending on operating conditions.

The effect of chromium on sulfur resistance of Pd/HY-Al2O3 catalysts for aromatic hydrogenation

Sulfur is a major poison to noble metal catalysts for deep aromatic hydrogenation in the petroleum refining industry. In order to study the sulfur resistance of Pd-based catalysts, a series of Pd, Cr, and PdCr catalysts supported on HY-Al2O3 were studied by NH3-TPD, pyridine-adsorption IR, TPR, IR spectra of adsorbed CO, and toluene hydrogenation in the presence of 3000 ppm sulfur as thiophene under the following conditions: 533-573 K, 4.2 MPa, and WHSV 4.0 h(-1). Cr has no influence on the acidity of the catalysts. TPR patterns and in situ IR spectra of adsorbed CO revealed a strong interaction between Cr and Pd, and the frequency shift of linear bonded CO on Pd indicates that the electron density of Pd decreases with the increase of the Cr/Pd atomic ratio. The catalytic performance of Pd, Cr, and PdCr catalysts shows that the sulfur resistance of Pd is strongly enhanced by Cr, and the activity reaches its maximum when the Cr/Pd atomic ratio equals 8. The active phase model "Pd particles decorated by Cr2O3" is postulated to explain the behavior of PdCr catalysts. (C) 2001 Academic Press.

Strong effect of transitional metals on the sulfur resistance of Pd/HY-Al2O3 catalysts for aromatic hydrogenation

In order to improve the sulfur resistance of noble metal catalysts in the aromatic hydrogenation of diesel fuel, the alloying effect of non-noble metals with Pd was studied. Toluene hydrogenation over Pd and Pd-M bimetallic catalysts (M = Cr, W,La, Mn, Mo, Ag) on a mixed HY-Al2O3 support was investigated in the presence of 3000 ppm sulfur as thiophene in the feedstock. The results showed that the addition of the second metals strongly affected the activity of toluene hydrogenation, which suggests that the sulfur resistibility of Pd-M bimetallic catalysts is much different from single Pd. La, Mn, Mo and Ag decreased the sulfur resistance of the palladium catalysts. For example, the toluene conversion at 553 K was observed to decrease sharply from 39.4 wt.% on Pd to 1.6 wt.% on Pd-Ag, which is by a factor of 25. One of the important findings in this article is that Cr and W increase hydrogenation activity of Pd catalysts. The reactions occurring on these catalysts include hydrogenation, isomerization and hydrocracking, The addition of the second metals has no noticeable effects on the hydrogenation and isomerization selectivity, but it slightly suppresses hydrocracking reactions. The four typical catalysts, Pd-Cr, Pd-W, Pd-Ag and Pd were characterized by infrared (IR) spectroscopy of pyridine and CO. LR spectra of CO revealed the strong interaction between Pd and the second metal as Cr, W and Ag (or their oxide), indicating that the improvement in sulfur resistance originates from electron-deficient Pd with the addition of second metals. (C) 2001 Elsevier Science B.V. All rights reserved.

Low-temperature oxidation of CO over Pd/CeO2-TiO2 catalysts with different pretreatments

A comprehensive study of the low-temperature oxidation of CO was conducted over Pd/TiO2, Pd/CeO2, and Pd/CeO2-TiO2 pretreated by a series of calcination and reduction processes. The catalysts were characterized by N-2 adsorption, XRD, H-2 chemisorption, and diffuse-reflectance infrared Fourier transform spectroscopy. The results indicated that Pd/CeO2-TiO2 has the highest activity among these catalysts, whether in the calcined state or in the reduced state. The activity of all of the catalysts can be improved significantly by the pre-reduction, and it seems that the reduction at low temperature (LTR. 150 degrees C) is more effective than that at high temperature (HTR, 500 degrees C), especially for Pd/CeO2 and Pd/TiO2. The catalysts with various supports and pretreatments are also different in the reaction mechanisms for CO oxidation at low temperature. Over Pd/TiO2, the reaction may proceed through a surface reaction between the weakly adsorbed CO and oxygen (Langmuir-Hinshelwood). For Ce-containing catalysts, however, an alteration of reaction mechanism with temperature and the involvement of the oxygen activation at different sites were observed, and the light-off profiles of the calcined Pd/CeO2 and Pd/CeOi-TiO2 show a distortion before CO conversion achieves 100%. At low temperature, CO oxidation proceeds mainly via the reaction between the adsorbed CO on Pd-0 sites and the lattice oxygen of surface CeO2 at the Pd-Ce interface, whereas at high temperature it proceeds via the reaction between the adsorbed CO and oxygen. The high activity of Pd/CeO2-TiO2 for the low-temperature CO oxidation was probably due to the enhancements of both CO activation, caused by the facilitated reduction of Pd2+ to Pd-0, and oxygen activation, through the improvement of the surface oxygen supply and the oxygen vacancies formation. The reduction pretreatment enhances metal-support interactions and oxygen vacancy formation and hence improves the activity of CO oxidation. (c) 2005 Elsevier Inc. All rights reserved.

One-step synthesis of 2-pentanone from ethanol over K-Pd/MnOx-ZrO2-ZnO catalyst

A highly active and selective K-Pd/MnOx-ZrO2-ZnO catalyst for the one-step synthesis of 2-pentanone from ethanol is described. The possible reaction pathways for ethanol reaction over K-Pd/MnOx-ZrO2-ZnO catalyst were investigated by means of TPSR, CO2- and NH3-TPD techniques. The reactions were performed in a fixed bed continuous flow reactor. Complete conversion with high selectivity for 2-pentanone, was observed under 370 similar to 390degreesC, 2 similar to 4 MPa, GHSV = 8000 similar to 10,000 h(-1) and LHSV < 1.25 h(-1) conditions. Ethanol reactions over K-Pd/MnOx-ZrO2-ZnO catalyst showed that the catalyst could catalyze dehydrogenation. aldol. dehydration and hydrogenation reactions. Both acidic and basic properties are found on the surface of K-Pd/MnOx-ZrO2-ZnO catalyst, whose multifunctionality with the combination of basic, acid and metal sites may be responsible for the efficiency of the K-PdMnOx-ZrO2-ZnO catalyst. (C) 2004 Elsevier B.V. All rights reserved.