On the role of water in heterogeneous catalysis: a tribute to Professor M. Wyn Roberts

From the earliest studies of heterogeneous catalysis, it was apparent that water plays a more important role in many systems than simply acting as a solvent. Its wide ranging effects have attracted increasing attention in recent years and was the topic of Prof. M.W. Roberts’ final paper. The present review explores some of the latest work on water in reactions ranging from CO oxidation to Fischer Tropsch catalysis, the different mechanisms proposed for its role are discussed and compared

XPS and STM studies of the oxidation of hydrogen chloride at Cu(100) surfaces

The dissociative chemisorption of HCl on clean and oxidized Cu(100) surfaces has been investigated using x-ray photoelectron spectroscopy (XPS) and scanning tunneling microscopy (STM). Whereas the dissociation of HCl at the clean surface is limited to the formation of a (√ 2 × √ 2)-R45° Cl(a) monolayer, the presence of surface oxygen removes this barrier, leading to chlorine coverages up to twice that obtained at the clean surface. Additional features in the STM images that appear at these coverages are tentatively assigned to the nucleation of CuCl islands. The rate of reaction of the HCl was slightly higher on the oxidized surface but unaffected by the initial oxygen concentration or the availability of clean copper sites. Of the two distinct domains of adsorbed oxygen identified at room temperature on the Cu(100) surfaces, the (√ 2 × √ 2)-R45° structure reacts slightly faster with HCl than the missing row (√ 2 × 2 √ 2)-R45° O(a) structure. The results address the first stages in the formation of a copper chloride and present an interesting comparison with the HCl/O(a) reaction at Cu(110) surfaces, where oxygen also increased the extent of HCl reactions. The results emphasize the importance of the exothermic reaction to form water in the HCl/O(a) reaction on copper

Photo induced Force Microscopy: chemical spectroscopy beyond the diffraction limit

Over the last decade remarkable advances have been made in creating spectroscopic tools to interrogate surface properties using electromagnetic radiation in the near field, achieving lateral resolutions in the nanometre range. We review recent work involving one of the most promising of these spectroscopic tools, photo induced force microscopy (PiFM), which uses mechanical detection of dipole-dipole interactions enabling nanometre resolved mapping of surface properties ranging from vibrational modes of adsorbates to plasmon resonances. We discuss the origin of contrast in PiFM images, its applications as a local probe of chemical species and for mapping local electric fields in areas as diverse as zeolite films and biometric recognition. In comparison with related techniques such as photo thermal infrared spectroscopy (PTIR) and tip enhanced Raman spectroscopy (TERS) PiFM has many advantages but perhaps its most successful application is in combination with other surface characterisation methods which provide information averaged over much greater surface areas. We discuss the most recent developments of PiFM technology which are leading to higher resolution images and are widening the range of environments in which the technique can be applied, and we consider how the field is likely to progress in the future

The deposition of metal nanoparticles on carbon surfaces: the role of specific functional groups

The enormous complexity of a typical heterogeneous catalyst makes understanding the development and properties of any active nanoparticles present extremely challenging. In the case of carbon based catalysts that difficulty is compounded by the variability of the carbon powders used. We have previously developed a strategy that addresses these problems by mimicking the catalyst preparation conditions very closely but using highly ordered pyrolytic graphite crystals (HOPG) as a model surface. This enables us to examine the effects of specific functional groups on nanoparticle formation. We report here an extension of our work characterising functional groups on the HOPG surface, using XPS and AFM to explore the deposition of gold from aqueous solution onto HOPG surfaces treated in a variety of ways to alter the surface functionality. The structure and oxidation state of the resulting nanoparticles depend critically on the nature of the functional groups present and offers some insight into the development of catalysts based on these materials. Hydroxyls are identified as key functional species, reducing gold ions to their metallic state whilst being oxidised themselves to carbonyls. Carbonyls meanwhile promote the nucleation of Au3+, creating a network of islands at the HOPG surface. The results have relevance not only to catalysts using activated carbons but also the new generation of materials based on graphene and carbon nanotubes

Hydrogen generation by photocatalytic reforming of potential biofuels: polyols, cyclic alcohols and saccharides

We have studied hydrogen gas production using photocatalysis from C2-C5 carbon chain polyols, cyclic alcohols and mono and di-saccharides using palladium nanoparticles supported on a TiO2 catalyst. For many of the polyols the hydrogen evolution rate is found to be dictated by the number of hydroxyl groups and available α-hydrogens in the structure. However the rule only applies to polyols and cyclic alcohols, while the sugar activity is limited by the bulky structure of those molecules. There was also evidence of ring opening in photocatalytic reforming of cyclic alcohols that involved dehydrogenation and decarbonylation of α Csingle bondC bond

A facile route to model catalysts: the synthesis of Au@Pd core-shell nanoparticles on y-Fe2O3 (0001)

A straightforward method of synthesising Au@Pd core–shell particles on a well characterised γ-Fe2O3 (0001) substrate has been developed which will enable fundamental studies into the surface chemistry of these catalytically interesting systems. Au and Pd were sequentially deposited onto a γ-Fe2O3 (0001) substrate in ultra high vacuum by metal vapour deposition and probed by LEIS and STM. Deposition of Au followed by heating at 573 K formed nanoparticles of 5 to 10 nm in diameter whereas subsequent deposition of Pd produced smaller nanoparticles of 2 to 4 nm diameter. At this stage, LEIS shows both metals to be present but heating the combined system to 573 K resulted in the loss of the Au signal in the LEIS and disappearance of the smaller particles from the STM images indicating the formation of Au@Pd core–shell structures

Enhancing surface reactivity with a noble metal

Gold, the archetypal noble metal, is usually associated with an inhibition of surface reactivity by site blocking. In this paper however, we show that on Cu(100) surfaces a gold adlayer can actually increase the extent of reaction with the substrate

The effect of acid treatment on the surface chemistry and topography of graphite

Highly oriented pyrolytic graphite (HOPG) samples were investigated as model catalyst supports. The surfaces were treated with dilute HCl and HNO3 under ambient conditions and examined with atomic force microscopy and scanning tunnelling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). Raised features were formed on the HOPG surface after acid treatment. These protrusions were typically 4–6 nm in height and between 10 and 100 nm in width, covering 5–20% of the substrate for acid concentrations between 0.01 and 0.2 M. Both width and surface density of the features increases with acid concentration but the heights are not affected. STM images show that the graphite lattice extends over the protrusions indicating that the features are “blisters” on the surface rather than deposited material, a view that is supported by the XPS which shows no other significant adsorbates except for oxygen in the case of the nitric acid. We propose that penetration of the acid at defective sites leads to a decrease in the interplanar van der Waals forces and a local delamination similar to the “bubbles” reported between exfoliated graphene sheets and a substrate. These findings are important in the context of understanding how carbon supports stabilise active components in heterogeneous catalysts

Fabrication of complex model oxide catalysts: Mo oxide supported on Fe3O4(111)

Industrial catalysts for the oxidation of methanol to formaldehyde consist of iron molybdate [Fe2(MoO4)3]. Using a variety of techniques we have previously shown that the surface of these catalysts is segregated in MoO3, and in order to understand the relationship between surface structure and reactivity for these systems we have begun a surface science study of this system using model, single crystal oxides. Model catalysts of molybdenum oxide nanoparticles and films on an Fe3O4 (111) single crystal were fabricated by the hot-filament metal oxide deposition technique (HFMOD), where molybdenum oxides were produced using a molybdenum filament heated in an oxygen atmosphere. Low energy electron diffraction (LEED), X-ray photoelectron spectroscopy (XPS), and scanning tunnelling microscopy (STM) have been used to investigate molybdenum oxide nanoparticles and films deposited on Fe3O4 (111). The molybdenum oxide film forms in the highest oxidation state, 6+, and is remarkably stable to thermal treatment, remaining on the surface to at least 973 K. However, above ~ 573 K cation mixing begins to occur, forming an iron molybdate structure, but the process is strongly Mo coverage dependent

Effect of slurry composition on the chemical mechanical polishing of thin diamond films

Nanocrystalline diamond (NCD) thin films grown by chemical vapour deposition (CVD) have an intrinsic surface roughness, which hinders the development and per- formance of the films' various applications. Traditional methods of diamond polishing are not effective on NCD thin films. Films either shatter due to the combination of wafer bow and high mechanical pressures or produce uneven surfaces, which has led to the adaptation of the chemical mechanical polishing (CMP) technique for NCD films. This process is poorly understood and in need of optimisation. To compare the effect of slurry composition and pH upon polishing rates, a series of NCD thin films have been polished for three hours using a Logitech Tribo CMP System in conjunction with a polyester/polyurethane polishing cloth and six different slurries. The reduction in surface roughness was measured hourly using an atomic force microscope. The nal surface chemistry was examined using X-ray photoelectron spectroscopy and a scanning electron microscope. It was found that of all the various properties of the slurries, including pH and composition, the particle size was the determining factor for the polishing rate. The smaller particles polishing at a greater rate than the larger ones