Characterizing electrocatalytic surfaces: Electrochemical and NMR studies of methanol and carbon monoxide on Pt/C

We use cyclic voltammetry (CV) on fuel cell electrodes to elucidate the important differences between adsorbates resulting from carbon monoxide adsorption and methanol adsorption onto commercial Pt/C electrocatalysts in a sulfuric acid electrolyte. Under open circuit conditions, methanol was found to adsorb preferentially onto the Pt sites associated with “strongly bound” hydrogen. The sites associated with “weakly bound” hydrogen adsorbed methanol more slowly. In the case of CO adsorption, which requires no adsorbate dehydrogenation, all adsorption sites showed similar affinity towards the adsorbate. Electrochemical oxidation of the adsorbates derived from both methanol and CO exposure exhibit slower oxidation when the adsorbate is associated with cubic-packed-like sites than from close-packed-steps and other sites. NMR of a ¹³CO-adlayer prepared by electrochemical adsorption from low concentration ¹³CH₃OH shows a lower NMR shift and smaller linewidth than the previously reported values for electrochemically adsorbed ¹³CO gas. These results are interpreted in terms of adsorbate motion on the electrocatalyst surface.     

富氢气氛中CO的选择性氧化——碱金属助剂对Pt/γ-Al2O3催化剂性能的影响

研究了碱金属助剂对Pt/γ-Al₂O₃催化剂选择性氧化富氢气氛中CO性能的影响。结果表明，碱金属助剂的引入对Pt/γ-Al₂O₃的催化性能有不同程度的改变，其中添加Na和K后，能明显提高低温下的CO转化率。     

Combined XPS and TPR study of sulfur removal from a Pt/BaO/Al2O3 NO x storage reduction catalyst

Pt/Al₂O₃ and Pt/BaO/Al₂O₃ catalysts (1 wt% Pt, 10 wt%BaO) were sulfated under conditions simulating a real NSR catalyst operation. Comparative TPR and XPS studies of sulfur removal from Pt/Al₂O₃ and Pt/BaO/Al₂O₃ catalysts indicate that the sulfur removal from Al₂O₃ surface precedes reductive decomposition of BaSO₄ (250–400 °C). Barium sulfate decomposition started with further increase in desulfation temperature at the point of surface atomic ratio Ba:S = 1 (~450^o). Simultaneously, an intensive formation of sulfide species on the catalyst surface was observed. Thermodynamic analysis of the desulfation process allows us to hypothesize that barium sulfide formation may hinder sulfur removal under reducing conditions.     

New catalytic functions of Pd–Zn, Pd–Ga, Pd–In, Pt–Zn, Pt–Ga and Pt–In alloys in the conversions of methanol

Pd and Pt supported on ZnO, Ga₂O₃ and In₂O₃ exhibit high catalytic performance for the steam reforming of methanol, CH₃OH+H₂OCO₂+3HH₂, and the dehydrogenation of methanol to HCOOCH₃, 2CH₃OHHCOOCH₃+2HH₂. Combined results with temperature-programmed reduction (TPR) and XRD method revealed that Pd–Zn, Pd–Ga, Pd–In, Pt–Zn, Pt–Ga and Pt–In alloys were produced upon reduction. Over the catalysts having the alloy phase, the reactions proceeded selectively, whereas the catalysts having metallic phase exhibited poor selectivities.     

Sintering of Pt/Al2O3 reforming catalysts: EXAFS study of the behavior of metal particles under oxidizing atmosphere

The effect of an oxidative atmosphere (300 °C) is studied on fresh and sintered unchlorinated naphtha reforming catalysts containing 0.6–1% Pt. The TPR profiles show that only one species is formed using our experimental conditions, regardless of the mean crystallite size of the metal particles. The structural information supplied by EXAFS compared with cuboctahedral particle modeling, implies that such species is a surface platinum oxide, the structure of which is close to that of PtO₂, but largely distorted. This is true whether the catalyst is sintered or not.     

Electropolymerization of chlorinated phenols on a Pt electrode in alkaline solution. Part II: An electrochemical quartz crystal microbalance study

Electropolymerization of phenol and mono-, di-, tri-, pentachlorophenols was studied using EQCM on a Pt electrode at 0.78 V (SHE) in 1 M NaOH solution containing 0.1 M of the corresponding phenol. The highest electropolymerization rate was found for ortho-substituted chlorophenols indicating a weak fouling of the electrode. Low electropolymerization rates for para-substituted chlorophenols suggest a low permeability of the polymer film, resulting in rapid electrode fouling. The EQCM data suggest that electropolymerization of chlorophenols occurs without Cl-elimination for the monomers with unsubstituted ortho and para positions. Dechlorination is most pronounced for electropolymerization of para-substituted isomers. The mechanism of electropolymerization of chlorophenols is discussed.     

Effect of temperature on activity and selectivity of carbon supported Mo sulfide in simultaneous hydrodenitrogenation of pyridine and hydrodesulfurization of thiophene

Activity and selectivity of carbon supported Mo catalyst was tested in parallel hydrodenitrogenation (HDN) of pyridine and hydrodesulfurization (HDS) of thiophene in the temperature range 260–350 °C at 2 MPa of hydrogen pressure and compared with that of commercial NiMo-alumina catalyst Shell 324. The main advantages of carbon supported Mo sulfide over commercial NiMo catalyst can be summarized as follows: the markedly higher HDN and better HDS activities normalized to moles of active metals, the lower content of piperidine in the reaction products and the distinctly better selectivity towards HDN reaction.     

Premodification of Pt/γAl2O3 with Cinchonidine for the Enantioselective Hydrogenation of Ethyl Pyruvate: Effect of Premodification Conditions on Reaction Rate and Enantioselection

The premodification of a 5 wt% Pt/-Al₂O₃ catalyst with cinchonidine (0.01 and 0.2 g g^-1 _catalyst) is described and discussed. Premodification is carried out by treating the catalyst with a solution of cinchonidine followed by solvent removal. Catalysts premodified in this way give the same ee and initial rate of reaction for the enantioselective hydrogenation of ethyl pyruvate as those using the standard in situ modification procedure. Investigations of different solvents for premodification and reaction (dichloromethane, ethanol) show that it is the solvent used for the reaction that controls the observed enantioselection. Premodified catalysts also display the initial transient behavior typically observed with in situ modified catalysts in which the ee increases with conversion in the early part of the reaction. Premodified catalysts show an enhanced rate of reaction when ethanol is used as the reaction solvent compared with in situ modified catalysts under the same conditions. Premodification using aerobic conditions gives the best results and premodified catalysts can be stored prior to use for up to a week without loss of catalytic performance.     

负载型中孔分子筛催化剂的研究进展

本文对M41S中孔分子筛作载体的负载试剂的研究进展进行了综述，主要介绍了负载酸型、负载碱型和负载氧化型催化剂的研究现状，以及对其应用和发展前景作了总结和评述。     

Chemical and microstructural investigation of Pt/CeO2 catalysts reduced at temperatures ranging from 473 to 973 K

The combined application of chemical techniques and HREM shows that platinum deactivation in Pt/CeO₂ catalysts steadily increases with the reduction temperature (T_r: 473–1173 K). Though no suppression of the H₂ adsorption was observed, the TPD-H₂ traces indicate the occurrence of significant chemical changes with T_r. As revealed by HREM, the metal decoration starts at T_r: 973 K, a temperature well above those at which the chemical effects can be observed.