Hydrogenation of unsaturated hydrocarbons occurs efficiently on noble-metal catalysts, such as platinum, rhodium, and palladium.[1] The reaction mechanism first proposed by Horiuti and Polanyi [2] in 1934 proceeds by a) hydrogen dissociation on the metal surface, b) alkene adsorption, c) subsequent hydrogen addition to alkene and, finally, d) desorption of the product (alkane). Real hydrogenation catalysts represent very complex systems for studying reaction mechanisms at the molecular level. Therefore, model systems with a reduced complexity have been invoked ranging from single crystals to metal particles deposited on oxide films. [3][4][5][6][7][8] The conclusions regarding reaction mechanism and structural sensitivity are often based upon experiments on single metal crystals.[3] In particular, hydrogenation of alkenes has been shown to be structure insensitive.Herein, we report results showing that alkene hydrogenation reaction under low-pressure conditions, which does not occur on Pd(111) single crystal, proceeds efficiently on palladium nanoparticles. We show that the formation of weakly bound "subsurface" hydrogen is a key factor for hydrogenation to occur efficiently. The subsurface hydrogen exists in both Pd systems. However, the nanoparticle dimensions are such that this hydrogen is accessible to the adsorbed alkene, and hydrogenation occurs. In contrast, for crystals, the hydrogen atoms diffuse so deep into the bulk that they are not accessible to an adsorbed alkene, and therefore hydrogenation does not occur.We have studied the surface chemistry of ethene and different pentene isomers on both Pd(111) single crystal and Pd particles deposited on a thin alumina film (Figure 1). The particles studied are approximately 5 nm in diameter and consist primarily (% 90 %) of (111) facets [8] (% 10 % are (100) facets). The experiments were performed in ultrahigh vacuum on clean and well-defined systems. Using the temperatureprogrammed desorption (TPD) technique, we have observed that a number of hydrocarbon transformations, such as dehydrogenation and H-D exchange, occur on both palla-

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Catalytic depolymerisation of lignins with different β-O-4 linkage percentages affected both the yield and the nature of aromatic monomeric products.

The Haber mechanism describing the process of hydrogenating nitrobenzene to aniline is shown to be incorrect and a new mechanism is proposed.

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A set of 7 different lignin preparations was generated from a range of organosolv (acidic, alkaline, ammonia-treated and dioxane-based), ionic liquid, autohydrolysis and Kraft pretreatments of lignocelluloses. Each lignin was characterised by 2D HSQC NMR spectroscopy, showing significant variability in the -O-4 content of the different lignin samples. Each lignin was then valorised using three biocatalytic methods (microbial biotransformation with Rhodococcus jostii RHA045, treatment with Pseudomonas fluorescens Dyp1B or Sphingobacterium sp. T2 manganese superoxide dismutase) and two chemocatalytic methods (catalytic hydrogenation using Pt/alumina catalyst, DDQ benzylic oxidation/Zn reduction). Highest product yields for DDQ/Zn valorisation were observed from poplar ammonia percolation-organosolv lignin, which had the highest -O-4 content of the investigated lignins and also gave the highest yield of syringaldehyde (243 mg/L)

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