Hydrogenolysis of Hydroxymatairesinol Over Carbon-Supported Palladium Catalysts

The natural lignan hydroxymatairesinol was hydrogenolysed to a potential anticarcinogenic substance matairesinol over different carbon-supported palladium catalysts. The reaction was conducted in 2-propanol at 70 °C under hydrogen flow in a stirred glass reactor. The catalysts were characterised by N₂-physisorption, CO pulse chemisorption and pH measurement of aqueous catalyst slurries. The most active catalyst (Degussa-Hüls) gave yields of matairesinol over 90% in 4 h. It was concluded that the acidity of the catalyst had a profound influence on the reaction rate.     

Control of Polymer Composition in Pd‐Catalyzed CO/Olefin Terpolymerization Reactions

The CO/tert‐butylstyrene/ethylene terpolymerization catalyzed by Pd‐(N‐N′) complexes was studied. The results evidence that the olefin preferentially inserted in the terpolymer chain is strictly related to the nature of the nitrogen ligand, mainly to its steric constraints, and not to the kind of ligand. Indeed, slight variations in the backbone of the nitrogen ligands coordinated to palladium allow for the synthesis of terpolymers with a controlled composition.     

Control of the β-Hydride Elimination Making Palladium-Catalyzed Coupling Reactions more Diversified

Pd(II)-catalyzed coupling reactions were developed using β-heteroatom elimination and protonolysis reaction to quench the carbon–palladium bond in the presence of halide ions or nitrogen ligands (pyridine, bipyridine, phenanthroline, etc.) for regenerating the divalent palladium species. Halide ions or nitrogen ligands are necessary for the catalytic cycle and high yield of the reactions. For Pd(0)-catalyzed reactions, control of β-hydride elimination is also a challenge for making coupling reactions more diversified. Different kinds of ligands were used to make the coupling reaction suitable for aliphatic compounds. Recently, examples using chloride ion or bathophenanthroline for this purpose were also developed.     

Influence of Pt–Pd/TS-1 Catalyst Preparation on Epoxidation of Olefins with Hydrogen Peroxide

The catalytic performance of the platinum–palladium/titanium silicalite, which was a common catalyst for the direct epoxidation of olefins with hydrogen and oxygen, was tested by epoxidation of allyl chloride with hydrogen peroxide. The epoxidation capacity of the TS-1catalyst was reduced after loading palladium and platinum on it. Ti leaching and crystallinity decrease were observed by XRD and FT-IR. The decomposition of hydrogen peroxide was accelerated by the supported Pd and Pt. These contributed to the loss of epoxidation capacity of TS-1. Ti leaching and crystallinity decrease were probably main causes. We propose that the Ti leaching had the most important influence on the loss of epoxidation capacity     

Vibrationally Excited CO2 Formed in CO + NO Reaction on Pd(110) Surface in High Surface Temperature Range

The infrared chemiluminescence spectra of CO₂ formed during steady-state CO+NO reaction over Pd(110) indicated that the temperature of the bending vibrational mode was much higher than that of the antisymmetric one at higher surface temperatures such as 800–850 K. Especially, in the high temperature range, more vibrationally excited CO₂ was formed from CO+NO reaction than CO+O₂ reaction. On the basis of the result, we propose the model structure of reaction intermediates for CO₂ formation in CO+NO reaction, which is different from that in CO+O₂ reaction.     

A highly stable and efficient catalyst for direct synthesis of LPG from syngas

Liquefied petroleum gas (LPG) fuel was directly synthesized from syngas over a hybrid catalyst which contained a methanol synthesis catalyst and zeolite. The new hybrid catalyst composed of (Pd–Ca/SiO₂) and β-zeolite, showed a high activity and selectivity for LPG production. X-ray diffraction (XRD) characterization of the catalyst was used to analyze the deactivation of (Pd–Ca/SiO₂)/β-zeolite.     

在钯/耐热合金催化剂上低温催化点火的研究

研究了以耐热合金网(或薄板)为载体的钯系催化剂,用于以航空煤油—空气介质的催化点火试验。研究了催化剂制备和活化条件对催化活性的影响,以及混气温度,燃空比和线速度等因素对点火时间的影响等。实验证明这种蜂窝状钯/耐热合金属催化剂用于航空煤油—空气混气得低温催化点火是成功的。     

Pd@C3N4 nanocatalyst for highly efficient hydrogen storage system based on potassium bicarbonate/formate

Formate/bicarbonate system has several desirable properties such as noncorrosive and nonirritating nature, as well as facile handling, which make it an attractive candidate for a safe, reversible hydrogen storage material. Herein, Pd nanoparticles supported on mesoporous graphitic carbon nitride (mpg‐C₃N₄) for formate‐based reversible hydrogen storage is reported. The as‐developed Pd/mpg‐C₃N₄ material was shown to be a superior catalyst for the hydrogenation of high concentrations of bicarbonate to formate under mild conditions. The effects of reaction temperature, H₂ pressure, and bicarbonate concentration on the hydrogenation of bicarbonate to formate were investigated. The catalytic performance remained steady with high activity up to six hydrogenation cycles. The interaction between mpg‐C₃N₄ and Pd nanoparticles and the concerted effects of the nitrogen species located at mpg‐C₃N₄ and bicarbonate played a synergetic role in the enhancement of the performance of the catalyst for hydrogenation. © 2016 American Institute of Chemical Engineers AIChE J, 62: 2410–2418, 2016     

Catalysis of semihydrogenation of acetylene to ethylene: current trends,challenges, and outlook

Ethylene is an important feedstock for various industrial processes, particularly in the polymer industry. Unfortunately, during naphtha cracking to produce ethylene, there are instances of acetylene presence in the product stream, which poisons the Ziegler–Natta polymerization catalysts. Thus, appropriate process modification, optimization, and in particular, catalyst design are essential to ensure the production of highly pure ethylene that is suitable as a feedstock in polymerization reactions. Accordingly, carefully selected process parameters and the application of various catalyst systems have been optimized for this purpose. This review provides a holistic view of the recent reports on the selective hydrogenation of acetylene. Previously published reviews were limited to Pd catalysts. However, effective new metal and non-metal catalysts have been explored for selective acetylene hydrogenation. Updates on this recent progress and more comprehensive computational studies that are now available for the reaction are described herein. In addition to the favored Pd catalysts, other catalyst systems including mono, bimetallic, trimetallic, and ionic catalysts are presented. The specific role(s) that each process parameter plays to achieve high acetylene conversion and ethylene selectivity is discussed. Attempts have been made to elucidate the possible catalyst deactivation mechanisms involved in the reaction. Extensive reports suggest that acetylene adsorption occurs through an active single-site mechanism rather than via dual active sites. An increase in the reaction temperature affords high acetylene conversion and ethylene selectivity to obtain reactant streams free of ethylene. Conflicting findings to this trend have reported the presence of ethylene in the feed stream. This review will serve as a useful resource of condensed information for researchers in the field of acetylene-selective hydrogenation.     

Palladium(II) extraction from concentrated chloride media: Reactions involving thioamide derivatives

This work focuses on the detailed study of the palladium(II) extraction reactions by N-methyl-N-phenyl-octanthioamide (MPHTA) and N-methyl-N-cyclohexyl-octanthioamide (MCHTA) in toluene, since their ability to efficiently and selectively recover Pd(II) from a wide range of HCl concentrations is already known. Equilibrium data are presented and discussed, and further complemented by information depicted from UV–visible and NMR spectra. The determined apparent molar volumes show that MPHTA is monomeric, and MCHTA exhibits a slight tendency to aggregate. The Pd(II) extraction reactions by MPHTA and MCHTA are equivalent until 4.5 M HCl, passing through the formation of inner-sphere complexes with the metal ion.