Chemoselective catalytic hydrogenation of acrolein on Ag(111): effect of molecular orientation on reaction selectivity.

The adsorption and hydrogenation of acrolein on the Ag(111) surface has been investigated by high resolution synchrotron XPS, NEXAFS, and temperature programmed reaction. The molecule adsorbs intact at all coverages and its adsorption geometry is critically important in determining chemoselectivity toward the formation of allyl alcohol, the desired but thermodynamically disfavored product. In the absence of hydrogen adatoms (H(a)), acrolein lies almost parallel to the metal surface; high coverages force the C=C bond to tilt markedly, likely rendering it less vulnerable toward reaction with hydrogen adatoms. Reaction with coadsorbed H(a) yields allyl alcohol, propionaldehyde, and propanol, consistent with the behavior of practical dispersed Ag catalysts operated at atmospheric pressure: formation of all three hydrogenation products is surface reaction rate limited. Overall chemoselectivity is strongly influenced by secondary reactions of allyl alcohol. At low H(a) coverages, the C=C bond in the newly formed allyl alcohol molecule is strongly tilted with respect to the surface, rendering it immune to attack by H(a) and leading to desorption of the unsaturated alcohol. In contrast with this, at high H(a) coverages, the C=C bond in allyl alcohol lies almost parallel to the surface, undergoes hydrogenation by H(a), and the saturated alcohol (propanol) desorbs.

Selective oxidation with dioxygen by gold nanoparticle catalysts derived from 55-atom clusters.

Supported gold nanoparticles have excited much interest owing to their unusual and somewhat unexpected catalytic properties, but the origin of the catalytic activity is still not fully understood. Experimental work on gold particles supported on a titanium dioxide (110) single-crystal surface has established a striking size threshold effect associated with a metal-to-insulator transition, with gold particles catalytically active only if their diameters fall below approximately 3.5 nm. However, the remarkable catalytic behaviour might also in part arise from strong electronic interaction between the gold and the titanium dioxide support. In the case of industrially important selective oxidation reactions, explanation of the effectiveness of gold nanoparticle catalysts is complicated by the need for additives to drive the reaction, and/or the presence of strong support interactions and incomplete understanding of their possible catalytic role. Here we show that very small gold entities ( approximately 1.4 nm) derived from 55-atom gold clusters and supported on inert materials are efficient and robust catalysts for the selective oxidation of styrene by dioxygen. We find a sharp size threshold in catalytic activity, in that particles with diameters of approximately 2 nm and above are completely inactive. Our observations suggest that catalytic activity arises from the altered electronic structure intrinsic to small gold nanoparticles, and that the use of 55-atom gold clusters may prove a viable route to the synthesis of robust gold catalysts suited to practical application.

A novel, sensitive potentiometric hydrocarbon sensor for high-vacuum applications.

A potentiometric device based on interfacing a solid electrolyte oxygen ion conductor with a thin platinum film acts as a robust, reproducible sensor for the detection of hydrocarbons in high- or ultrahigh-vacuum environments. Sensitivities in the order of approximately 5 x 10(-10) mbar are achievable under open circuit conditions, with good selectivity for discrimination between n-butane on one hand and toluene, n-octane, n-hexane, and 1-butene on the other hand. The sensor's sensitivity may be tuned by operating under constant current (closed circuit) conditions; injection of anodic current is also a very effective means of restoring a clean sensing surface at any desired point. XPS data and potentiometric measurements confirm the proposed mode of sensing action: the steady-state coverage of Oa, which sets the potential of the Pt sensing electrode, is determined by the partial pressure and dissociative sticking probability of the impinging hydrocarbon. The principles established here provide the basis for a viable, inherently flexible, and promising means for the sensitive and selective detection of hydrocarbons under demanding conditions.

Sulfur, normally a poison, strongly promotes chemoselective catalytic hydrogenation: stereochemistry and reactivity of crotonaldehyde on clean and S-modified Cu(111).

Sulfur adatoms strongly activate the otherwise inert Cu(111) surface towards chemoselective hydrogenation of crotonaldehyde by electronically perturbing and strongly tilting the reactant.

Critical influence of adsorption geometry in the heterogeneous epoxidation of "allylic" alkenes: structure and reactivity of three phenylpropene isomers on Cu(111).

It has long been conjectured that the difficulty of heterogeneously epoxidizing higher alkenes such as propene is due to the presence in the molecule of "allylic" H atoms that are readily stripped off by the oxygenated surface of the metal catalyst resulting in combustion. Here, taking advantage of the intrinsically higher epoxidation selectivity of Cu over Ag under vacuum conditions, we have used three phenylpropene structural isomers to examine the correlation between adsorption geometry and oxidation chemistry. It is found that under comparable conditions alpha-methylstyrene, trans-methylstyrene, and allylbenzene behave very differently on the oxygenated Cu(111) surface: the first undergoes extensive epoxidation accompanied by relatively little decomposition of the alkene; the second leads to some epoxide formation and extensive alkene decomposition; and the third is almost inert with respect to both reaction pathways. This reactive behavior is understandable in terms of the corresponding molecular conformations determined by near-edge X-ray absorption fine structure spectroscopy and density functional theory calculations. The proximity to the surface of the C=C function and of the allylic H atoms is critically important in determining reaction selectivity. This demonstrates the importance of adsorption geometry and confirms that allylic H stripping is indeed a key process that limits epoxidation selectivity in such cases.

Efficient epoxidation of a terminal alkene containing allylic hydrogen atoms: trans-methylstyrene on Cu{111}.

The selective oxidation of trans-methylstyrene, a phenyl-substituted propene that contains labile allylic hydrogen atoms, has been studied on Cu{111}. Mass spectrometry and synchrotron fast XPS were used to detect, respectively, desorbing gaseous products and the evolution of surface species as a function of temperature and time. Efficient partial oxidation occurs yielding principally the epoxide, and the behavior of the system is sensitive to the order in which reactants are adsorbed. The latter is understandable in terms of differences in the spatial distribution of oxygen adatoms; isolated adatoms lead to epoxidation, while islands of "oxidic" oxygen do not. NEXAFS data taken over a range of coverages and in the presence and absence of coadsorbed oxygen indicate that the adsorbed alkene lies essentially flat with the allylic hydrogen atoms close to the surface. The photoemission results and comparison with the corresponding behavior of styrene on Cu{111} strongly suggest that allylic hydrogen abstraction is indeed a critical factor that limits epoxidation selectivity. An overall mechanism consistent with the structural and reactive properties is proposed.

Acetylene coupling on Cu(111): formation of butadiene, benzene, and cyclooctatetraene.

Acetylene trimerizes to benzene on the (111) face of copper, as it does on the (100) and (110) planes. However, Cu(111) also yields butadiene and cyclooctatetraene, the latter never previously found with Cu or any other material. No coverage threshold is observed for the onset of these coupling reactions, implying high adsorbate mobility: gaseous benzene is formed by a surface reaction rate-limited process, whereas butadiene and cyclooctatetraene are formed by desorption rate-limited processes. H/D isotope tracing shows that benzene formation proceeds via a statistically random associative mechanism, whereas butadiene formation is associated with strong kinetic isotope effects, probably associated with C-H cleavage. A pericyclic mechanism involving dimerization of C4H4 metallocycles is proposed to account for the formation of cyclooctatetraene. We also found that approximately 45 nm alpha-alumina supported copper particles operated under catalytic conditions at atmospheric pressure yield the same principal reaction products as those found with Cu(111) under vacuum conditions. It therefore seems likely that the elementary reaction steps that describe the surface chemistry of the model system are also important under practical conditions. Comparison of the structure, bonding, and reactivity of acetylene on Cu(111) and Pd(111) indicates that the effectiveness of copper in promoting C-H cleavage in adsorbed acetylene is associated with greater rehybridization of the C-C bond with concomitant weakening of the C-H bond.

Halogen-induced selectivity in heterogeneous epoxidation is an electronic effect--fluorine, chlorine, bromine and iodine in the Ag-catalysed selective oxidation of ethene.

Selectivity promotion in the Ag-catalysed heterogeneous epoxidation of ethene correlates with halogen electron affinity showing that it is an electronic phenomenon rather than a steric or geometrical effect.