Search

A series of MoOx-modified Fe2O3 catalysts have been prepared in an attempt to make core-shell oxidic materials of the type MoOx/Fe2O3. It is conclusively shown that for three monolayers of Mo dosed, the Mo stays in the surface region, even after annealing to high temperature. It is only when the material is annealed above 400 C that it reacts with the iron oxide. We show by a combination of methods, and especially by XAFS, that at temperatures above 400 C, most of the Mo converts to Fe2(MoO4)3, with Mo in a tetrahedral structure, whereas below that temperature, nanocrystalline MoO 3 is present in the sample; however, the active catalysts have an octahedral MoOx layer at the surface even after calcination to 600 C. This surface layer appears to be present at all temperatures between 300 and 600 C, and it is the nanoparticles of MoO3 that are present at the lower temperature that react to form ferric molybdate, which underlies this surface layer. It is the MoOx layer on the Fe2(MoO 4)3 underlayer that makes the surface active and selective for formaldehyde synthesis, whereas the iron oxide surface itself is a combustor. The material is both activated and improved in selectivity due to the dominance of the methoxy species on the Mo-doped material, as opposed to the much more stable formate, which is the main intermediate on Fe2O 3. © 2013 American Chemical Society.

This paper explores the relationship between diversity, locality, scale and sustainability in human systems. Using examples from brewing, steel production, and printing it suggests mass production economies of scale has peaked, creating new opportunities and challenges for sustainability science. It is concluded that there is a potential research agenda in seeking to understand where, how, why, at what cost and under what conditions smaller scale may yield sustainability advantages.

A combined operando XAFS/DRIFTS study on CeOx/Pt/Al2O3 catalysts has been performed during CO oxidation and provides insights into the changes in nanoparticle structure and adsorbed species during the reaction profile. The onset of CO2 formation is shown to be concurrent with a rapid re-oxidation of the Pt nanoparticles, evidenced by XAFS spectroscopy, and the loss of bridge bonded CO adsorbed on Pt, as shown by simultaneous DRIFTS acquisition. The continued appearance of linear bound CO on the catalyst surface is shown to remain long after catalytic light off. The interaction of Pt and CeOx is evidenced by the improved performance towards CO oxidation, compared to the non-CeOx modified Pt/Al2O3, and changes in the CO adsorption properties on Pt previously linked to Pt-CeO2 interfaces.

This paper analyses the issue of whether governmental regulation results in higher producer costs that are then passed on as higher prices to the consumer, with a longitudinal study of the European automotive market. Using a large data set for the period 1995–2010 the hedonic price analysis study concludes that the claims that regulation would result in higher per unit costs for new cars are not supported, at least as far as the pass-through into retail or list prices are concerned. Consequently, regulators need a better understanding of what the ‘cost of regulation’ claims entail over the longer term – with the implication that additional costs even where they arise are more easily absorbed than has hitherto been expected.

Large scale research facilities such as the Diamond Light Source and ISIS neutron source exist to offer access to techniques that are impractical in other settings. The time available is restricted and it is therefore imperative that experiments are well planned and executed. This work aims to help by discussing the techniques and equipment available for in situ and operando measurements with X-ray and neutron probes to encourage greater use of these facilities. The benefits of each technique for in situ measurement will be briefly discussed and the constraints they demand on reactor design will be mentioned in detail. Examples illustrating existing cell design and their use to elucidate catalytic reactions will be explored with reference to the literature. A description of progress in linking X-ray and neutron probes with secondary techniques will be included and trends and future directions will be identified.

The performance of Mo-enriched, bulk ferric molybdate, employed commercially for the industrially important reaction of the selective oxidation of methanol to formaldehyde, is limited by a low surface area, typically 5–8 m2g−1. Recent advances in the understanding of the iron molybdate catalyst have focused on the study of MoOx@Fe2O3(MoOxshell, Fe2O3core) systems, where only a few overlayers of Mo are present on the surface. This method of preparing MoOx@Fe2O3catalysts was shown to support an iron molybdate surface of higher surface area than the industrially-favoured bulk phase. In this research, a MoOx@Fe2O3catalyst of even higher surface area was stabilised by modifying a haematite support containing 5 wt% Al dopant. The addition of Al was an important factor for stabilising the haematite surface area and resulted in an iron molybdate surface area of ∼35 m2g−1, around a 5 fold increase on the bulk catalyst. XPS confirmed Mo surface-enrichment, whilst Mo XANES resolved an amorphous MoOxsurface monolayer supported on a sublayer of Fe2(MoO4)3that became increasingly extensive with initial Mo surface loading. The high surface area MoOx@Fe2O3catalyst proved amenable to bulk characterisation techniques; contributions from Fe2(MoO4)3were detectable by Raman, XAFS, ATR-IR and XRD spectroscopies. The temperature-programmed pulsed flow reaction of methanol showed that this novel, high surface area catalyst (3ML-HSA) outperformed the undoped analogue (3ML-ISA), and a peak yield of 94% formaldehyde was obtained at ∼40 °C below that for the bulk Fe2(MoO4)3phase. This work demonstrates how core–shell, multi-component oxides offer new routes for improving catalytic performance and understanding catalytic activity.

The oxidation of methanol to formaldehyde is a major chemical process carried out catalytically and iron molybdate is one of the major catalysts for this process. In this paper we explore the nature of the active and selective surfaces of iron molybdate catalysts and show that the effective catalysts comprise molybdenum rich surfaces. We conclude that it is therefore important to maximise the surface area of these active catalysts and to this end we have studied catalysts made using a new physical grinding method with oxalic acid. For super-stoichiometric materials (Fe:Mo = 1:2.2) the reaction data show that physical mixing produces effective catalysts, possibly offering an improvement over the conventional co-precipitation method.

Monometallic and bimetallic tin-containing framework architectures have been prepared by hydrothermal methods. Structural and spectroscopic techniques were used to probe the nature of the solid-acid sites, at the molecular level, using a combination of XRD, DR UV-Vis, solid state MAS NMR (119Sn, 27Al and 31P) and XAFS. The nature and strength of the solid-acid sites were experimentally probed by FT-IR spectroscopy using CD3CN as a probe molecule. To elucidate further the local-structure, the structural characteristics of the Sn sites were probed using DFT calculations, with a view to rationalising the experimental findings. These detailed structural and spectroscopic studies revealed the presence of multiple Sn environments, with the monometallic SnAlPO-5 catalyst displaying a greater number of tetrahedral Sn(IV) active centres. These framework Sn(IV) centres generated strong Lewis acid sites, when compared with their bimetallic Co–Sn analogue, thereby affording attractive possibilities for modulating catalytic reactivity.

In the present work, a combination of imaging, spectroscopic and computational methods shows that 1 dodecanethiol undergoes S-deprotonation to form 1 dodecanethiolate on the surface of palladium nanoparticles, which then self-assembles into a structure that shows a high degree of order. The alkyl chain is largely in the all-trans conformation, which occurs despite the small size of the nanoparticle, (mean diameter = 3.9 nm). Inelastic neutron scattering spectroscopy is readily able to characterise organic surface layers on nanoparticles; the nature of the material is irrelevant: whether the nanoparticle core is an oxide, a metal or a semiconductor makes no difference. Comparison to DFT calculations allows insights into the nature and conformation of the adsorbed layer.

The activation of [MoX3(L)] (with X = Cl, Br; L = tridentate ligands with S3 and SNS donor sets) by AlMe3, analogous to the industrially important [CrCl3(L)] catalysts for selective oligomerisation of alkenes, has been investigated by Mo K-edge X-ray absorption (XAS) and UV–visible spectroscopies. Time-resolved stopped-flow XAS, in combination with a newly developed anaerobic freeze-quench approach, have established the complete alkylation of the Mo centres and a slower, stepwise sequence for [MoBr3(L)]. No evidence for directly bonded or bridged Mo–Mo dimers was observed at the high Mo:AlMe3 ratios used in this study. Decomposition of the complexes is in competition with the activation and resulted in precipitation of particulate Mo over time and explains the deactivation as observed in catalytic tests. The novel freeze-quench approach, which can trap reaction solutions within 1 s of mixing, opens up a large field of homogeneous catalysis and liquid chemistry to be studied, being able to quench this rapidly, whilst characterisation techniques with long data acquisition can be performed.

The cathode electrocatalysts for proton exchange membrane (PEM) fuel cells are commonly platinum and platinum based alloy nanoparticles dispersed on a carbon support. Control over the particle size and composition has, historically, been attained empirically, making systematic studies of the effects of various structural parameters difficult. The controlled surface modification methodology used in this work has enabled the controlled modification of carbon supported Pt nanoparticles by Cr so as to yield nanoalloy particles with defined compositions. Subsequent heat treatment in 5% H2 in N2 resulted in the formation of a distinct Pt3Cr alloy phase which was either restricted to the surface of the particles or present throughout the bulk of the particle structure. Measurement of the oxygen reduction activity of the catalysts was accomplished using the rotating thin film electrode method and the activities obtained were related to the structure of the nanoalloy catalyst particles, largely determined using Cr K edge and Pt L3 edge XAS.

Multicomponent oxide shell@core catalysts have been prepared, affording overlayers of MoOx on Fe2O3. This design approach allows bulk characterization techniques, such as X-ray Absorption Fine Structure (XAFS), to provide surface sensitive information. Coupling this approach with in situ methodologies provides insights during crucial catalytic processes. Calcination studies were followed by a combination of XAFS and Raman, and demonstrate that amorphous multi-layers of MoOx are first converted to MoO3 before formation of Fe2(MoO4)3. However, a single overlayer of Oh Mo units remains at the surface at all times. In situ catalysis studies during formaldehyde production identified that Mo6+ was present throughout, confirming that gas phase oxygen transfer to molybdenum is rapid under reaction conditions. Reduction studies in the presence of MeOH resulted in the formation of reduced Mo–Mo clusters with a bonding distance of 2.6 A. It is proposed that the presence of the clusters indicates that the selective conversion of MeOH to formaldehyde requires multiple Mo sites.

Metal co-catalysts are essential for enhancing photocatalytic performance, especially in reduction reactions using semiconductor photocatalyst materials as a consequence of the reduced recombination kinetics of charge carriers by spatial charge separation. Generally Au, Pd, Pt, and their alloys are more promising candidates than Ag for photocatalytic H2 evolution experiments, although Ag can trap more electrons having more negative reduction potential than that of Au, Pd, and Pt. Here we have synthesized and examined well-defined Au, Ag, and core-shell structured Au–Ag nanoparticles as co-catalysts for TiO2 in photocatalytic H2 evolution. By varying the dissolved oxygen in the reaction suspension, we found that selective photocatalytic reduction can be achieved by fine tuning the co-catalyst materials. Whilst Au NPs are superior for proton reduction, Ag NPs exhibits excellent performance for oxygen reduction. All core-shell structured Au–Ag NPs show non-selectivity in photocatalytic reduction of proton and oxygen.

Philip Davies opened the discussion of the introductory lecture by Avelino Corma: Themetal nanoparticles inside the zeolites are in a different environment from those outside. Is there any difference in their chemistry and their catalytic behaviour? Avelino Corma answered: We were not able to determine the differences in reactivity, other than the accessibility of reactants with different sizes. It should be said that we did not use molecules specifically suited for showing potential electronic–entropic differences. I agree that this is an important point to be considered. What we clearly observed is that the clusters inside the channels were stable towards sintering. Cynthia Friend asked: Have you considered the possible effect of ligands bound to your clusters? Have van der Waals’ interactions been explicitly included? Avelino Corma replied: The theoretical calculation of the interactions of nitrobenzene with the nanoparticles includes the interactions with the support and van der Waals’ interactions. In the case of clusters, H2 dissociation has been carried out on isolated Pt, Au and Au-Pt clusters and van der Waals’ interactions were not considered. Graham Hutchings continued: You rightly point out in your design strategy that the adsorption of the reactant is the key factor, and that adsorption occurs.

Ruthenium modified carbon supported platinum catalysts have been shown to have a similar activity towards carbon monoxide oxidation as conventionally prepared bimetallic PtRu alloy catalysts. In this study the effect of the applied electrode potential and potential cycles on the location and oxidation state of the Ru species in such Ru modified Pt/C catalysts was investigated using in situ EXAFS collected at both the Ru K and Pt L3 absorption edges. The as prepared catalyst was found to consist of a Pt core with a Ru oxy/hydroxide shell. The potential dependent data indicated alloying to form a PtRu phase at 0.05 V versus RHE and subsequent dealloying to return to the Ru oxy/hydroxide decorated Pt surface at potentials greater than 0.7 V. The Ru–O distances obtained indicate that both Ru3+ and Ru4+ species are present on the surface of the Pt particles at oxidising potentials; the former is characteristic of the as prepared Ru modified Pt/C catalyst and following extensive periods at potentials above 0.7 V and the latter of the Ru oxide species on the PtRu alloy.

Copper and zinc form an important group of hydroxycarbonate minerals that include zincian malachite, aurichalcite, rosasite and the exceptionally rare and unstable—and hence little known and largely ignored1—georgeite. The first three of these minerals are widely used as catalyst precursors2, 3, 4 for the industrially important methanol-synthesis and low-temperature water–gas shift (LTS) reactions5, 6, 7, with the choice of precursor phase strongly influencing the activity of the final catalyst. The preferred phase2, 3, 8, 9, 10 is usually zincian malachite. This is prepared by a co-precipitation method that involves the transient formation of georgeite11; with few exceptions12 it uses sodium carbonate as the carbonate source, but this also introduces sodium ions—a potential catalyst poison. Here we show that supercritical antisolvent (SAS) precipitation using carbon dioxide (refs 13, 14), a process that exploits the high diffusion rates and solvation power of supercritical carbon dioxide to rapidly expand and supersaturate solutions, can be used to prepare copper/zinc hydroxycarbonate precursors with low sodium content. These include stable georgeite, which we find to be a precursor to highly active methanol-synthesis and superior LTS catalysts. Our findings highlight the value of advanced synthesis methods in accessing unusual mineral phases, and show that there is room for exploring improvements to established industrial catalysts.

A novel synthetic strategy for the design of metal nanoparticles by extrusion of anionic chloride precursors from a porous copper chlorophosphate framework has been devised for the sustainable aerobic oxidation of vanillyl alcohol (4-hydroxy-3-methoxybenzyl alcohol) to vanillin (4-hydroxy-3-methoxybenzaldehyde) using a one-step, base-free method. The precise nature of the Au, Pt, and Pd species has been elucidated for the as-synthesized and thermally activated analogues, which exhibit fascinating catalytic properties when subjected to diverse activation environments. By employing a combination of structural and spectroscopic characterization tools, it has been shown that analogous heat treatments have differing effects on extrusion of a particular metal species. The most active catalysts in this series of materials were the extruded Pt nanoparticles that were generated by reduction in H2, which exhibit enhanced catalytic behavior, when compared to its Au or Pd counterparts, for industrially significant, aerobic oxidation reactions.

By using platinum nanoparticle catalysts that are generated in situ by extrusion from a porous copper chlorophosphate framework, the role of oxidants in the selective oxidation of benzyl alcohol to benzaldehyde was evaluated, with a view to establishing structure-property relationships. With a detailed study of the kinetic properties of the oxidation reaction, it has been determined that the aerobic oxidation pathways progress with lower levels of product selectivity and higher activation energies (72.4 kJmol(-1)) than the peroxide-based ones (23.6 kJmol(-1)); affording valuable insights in the design of solid catalysts for selective oxidation reactions. Furthermore, through the use of X-ray absorption spectroscopy, the effect of calcination temperature on the degree of extrusion and its influence on nanoparticle formation have been evaluated, leading to the establishment of structure-activity correlations between the observed activation energies and the proportion of nanoparticle species generated.

A miniature proton exchange membrane (PEM) fuel cell has been designed to enable in situ XAS investigations of the anode catalyst using fluorescence detection. The development of the cell is described, in particular the modifications required for elevated temperature operation and humidification of the feed gasses. The impact of the operating conditions is observed as an increase in the catalyst utilisation, which is evident in the EXAFS collected at the Pt L-III and Ru K edges for a PtRu/C catalyst. The Pt component of the catalyst was found to be readily reduced by hydrogen in the fuel, while the Ru was only fully reduced under conditions of good gas flow and electrochemical contact. Under such conditions no evidence of O neighbours were found at the Ru edge. The results are interpreted in relation to the lack of surface sensitivity of the EXAFS method and indicate that the equilibrium coverage of O species on the Ru surface sites is too low to be observed using EXAFS.

An unambiguous inverse solution from Fraunhofer diffraction data has been achieved for an amorphous sample of low-molecular weight. The complex scattering amplitude has been reconstructed with submicron spatial resolution using the phase retrieval x-ray diffractometry technique. The technique relies on a logarithmic dispersion relation to determine the x-ray wave phase from the scattered intensity profile. Successful experimental localization of the zeros of the complex scattering amplitude was achieved by utilizing two data sets taken at different incident x-ray energies, permitting a unique solution.

We have investigated polyvinylalcohol stabilized Au and Ag based nanoparticles supported on titania prepared via sol immobilisation for the anaerobic, ambient temperature reforming of methanol with water for the photocatalytic production of hydrogen. The catalytic activity of the Au/TiO2 catalysts was strongly affected by the metal loading and calcination temperature. Here, we report the preparation and use of supported Au–Ag nanoparticles, based on either the co-reduction or the consecutive reduction of the two metals. Au–Ag supported catalysts were more active than monometallic Au and Ag catalysts and the preparation methodology had a pronounced effect in terms of catalytic activity of the Au–Ag catalysts. In fact, using a consecutive reduction where Au was firstly reduced followed by reduction of Ag gave materials which exhibited the highest catalytic performance.

Evolution of the IRAS spectrum with temperature after adsorbing methanol at room temperature. The bands at 2930 and 2820 cm− 1 are due to the methoxy species C–H stretches, while that at 2870 is due to the formate.\ud \ud Here, we report a simple, quantitative model to describe the behaviour of bi-cationic oxide catalysts, in terms of selectivity variation as a function of increased loading of one cation into a sample of the other. We consider its application to a particular catalytic system, namely the selective oxidation of methanol, which proceeds with three main C1 products, namely CO2, CO, and H2CO. The product selectivity varies in this order as Mo is added in increasing amounts to an iron oxide catalyst, and the product selectivity is determined by the distribution of dual sites and single sites of each species.

We have prepared a variety of Au, Pd and Au-Pd catalysts loaded onto P25 titania to determine how effective these materials are for the anaerobic, ambient temperature reforming of alcohols with water to produce hydrogen, and to examine the effect of the preparation method on their performance. Catalysts produced by both incipient wetness (IW) methods and by colloidal methods are successful materials for producing hydrogen, with the IW catalysts proving to be the best for the same metal loading. It is shown that, although gold catalysts generally have lower hydrogen yield than for Pd, alloying Au with Pd gives more active materials than either alone at the same weight loading, due to a synergistic effect. The catalysts are active for reforming a range of alcohols, generally producing CO2, H2 and an alkane. However, it is essential for good activity to have an H at the a-position to the oxygenate function, and so, carboxylic acids and ketones do not work. These catalysts generally show a maximum in activity at low loadings of metal (∼0.5 wt%) due to a requirement for maximising the active interface between the metal nanoparticles and the photo-active titania. © 2013 Elsevier Inc. All rights reserved.

Fe/ZSM-5(30) catalysts have been prepared by chemical vapour impregnation (CVI) using iron(iii) acetylacetonate as the precursor. These materials have been used for the oxidation of methane and ethane using aqueous hydrogen peroxide as oxidant. Heating in air leads to materials that exhibit high catalytic activity and give formic and acetic acid with high selectivity from methane and ethane respectively. Heat treatment of the uncalcined materials under a reducing atmosphere results in partial reduction of iron from the FeIII to FeII oxidation state with the majority of the iron being present as isolated octahedral extra-framework species having oxygen neighbours and showing no evidence of a coordination shell containing Al or Fe, as evidenced from studies using X-ray absorption and UV-Vis spectroscopies. These hydrogen treated catalysts show the same catalytic activity as their analogues formed by heating in air, but in contrast exhibit higher alcohol selectivities for both methane and ethane conversion to oxygenates and are reusable. Our findings for both the oxidation of methane and ethane indicate that the selectivity to the oxidation products, i.e. acids or alcohols, can be controlled by tuning the active site structure and/or oxidation state of the Fe species in Fe/ZSM-5. © 2014 the Partner Organisations.

Photocatalytic hydrogen evolution may provide one of the solutions to the shift to a sustainable energy society, but the quantum efficiency of the process still needs to be improved. Precise control of the composition and structure of the metal nanoparticle cocatalysts is essential, and we show that fine-tuning the Au-Pd nanoparticle structure modifies the electronic properties of the cocatalyst significantly. Specifically, Pdshell-Aucore nanoparticles immobilized on TiO2 exhibit extremely high quantum efficiencies for H2 production using a wide range of alcohols, implying that chemical byproducts from the biorefinery industry can be used as feedstocks. In addition, the excellent recyclability of our photocatalyst material indicates a high potential in industrial applications. We demonstrate that this particular elemental segregation provides optimal positioning of the unoccupied d-orbital states, which results in an enhanced utilization of the photoexcited electrons in redox reactions. We consider that the enhanced activity observed on TiO2 is generic in nature and can be transferred to other narrow band gap semiconductor supports for visible light photocatalysis. © 2014 American Chemical Society.

The application of socio-technical transitions analysis into realms such as sustainable mobility requires understanding the efficacy of policy measures ex ante. Electrification of the vehicle drivetrain is one possible solution to achieve carbon emission targets. National governments are developing policy measures to encourage electric vehicle (EV) technologies. To evaluate policy measures, a framework based on "adaptive neuro-fuzzy inference system" (ANFIS) was developed. For data generation, EV innovation policies of EU, USA, Japan, Germany, France and UK were analysed and compared with the patent filings in those regions. The training and validation of the framework shows that the model is able to predict the development of EV technologies. The model is subsequently applied to Austria to evaluate three proposed policy scenarios. This paper concludes that the developed framework might play a significant role for assisting EV innovation policy-making by enabling ex-ante assessment of the effects of different policy-mixes on the technical change.

This Critical Review provides an overview of the recent developments in the synthesis and characterization of bimetallic nanoparticles. Initially the review follows a materials science perspective on preparing bimetallic nanoparticles with designer morphologies, after which the emphasis shifts towards recent developments in using these bimetallic particles for catalysing either oxidation or reduction. In the final part of this review we present an overview of the utilization of bimetallic catalyst systems for the transformation of bio-renewable substrates and reactions related to the realization of a bio-refinery. Because of the sheer number of examples of transformations in this area, a few key examples, namely selective oxidation, hydrogenation/hydrogenolysis and reforming of biomass derived molecules, have been chosen for this review. Reports of bimetallic catalysts being used for the aforementioned transformations are critically analysed and the potential for exploiting such bimetallic catalysts have also been highlighted. A specific objective of this review article is to motivate researchers to synthesize some of the “designer” bimetallic catalysts with specific nanostructures, inspired from recent advances in the area of materials chemistry, and to utilize them for the transformation of biomass derived materials that are very complex and pose different challenges compared to those of simple organic molecules. We consider that supported bimetallic nanoparticles have an important role to play as catalysts in our quest for a more green and sustainable society.

In the early 2000s, the UK automotive industry was in a state of decline. Factory closures were commonplace, innovation levels modest, the supply chain shrinking, and environmental regulations seen as a threat. However, the industry has undergone a renaissance in the past decade, with UK low-carbon automotive investments of around £40 billion, increasing sector turnover, rising vehicle production volumes, and major OEM capacity expansions. This article sought to identify and understand the causal relationships between the UK's low-carbon policies and automotive industry investments via a triangulated methodology comprising an industry-wide survey, interviews of senior industry executives, extensive secondary research, construction of an investment database, and detailed policy analyses. It is concluded from the research that the strong co-operation between government and industry has proved vital to weathering the economic crisis and maintaining growth. Also, introduction of strong, cumulative industrial policies, and environmental regulations, together with funding programmes emerged as powerful driving forces for continued investment. Nevertheless, challenges remain and there is no room for complacency. Continued dialogue, support, and action are required to ensure that UK industry can deliver on low-carbon targets and build a sustainable industry and vehicle fleet.

A series of carbon supported PtRu bimetallic catalysts with varying Pt:Ru ratio were prepared and characterised using ex situ and in situ XRD, in situ EXAFS at 0 V vs. RHE, ex situ XPS and monolayer CO stripping voltammetry. Although the catalysts were found to be well mixed/alloyed, with no evidence of unalloyed Ru (oxides) present, the surfaces of the electrocatalyst nanoparticles were found to be enriched with Pt compared to the nominal bulk composition. The methanol oxidation activities of the catalysts were determined in 1.0 mol dm(-3) H2SO4. In agreement with published studies of polycrystalline bulk PtRu alloys the catalyst with a 0.6 surface fraction of Pt was found to give the best methanol oxidation activity at 30 degrees C. However, at 80 degrees C a greater surface fraction of Ru could be tolerated, with some activity at low current densities found for a Pt surface fraction as low as 0.2. The results support the conclusion that a limited amount of methanol dehydrogenation occurs at Ru sites or Ru dominated surface ensembles at 80 degrees C.

Highly active and selective aerobic oxidation of KA-oil to cyclohexanone (precursor for adipic acid and -caprolactam) has been achieved in high yields using continuous-flow chemistry by utilizing uncapped noble-metal (Au, Pt & Pd) nanoparticle catalysts. These are prepared using a one-step insitu methodology, within three-dimensional porous molecular architectures, to afford robust heterogeneous catalysts. Detailed spectroscopic characterization of the nature of the active sites at the molecular level, coupled with aberration-corrected scanning transmission electron microscopy, reveals that the synthetic methodology and associated activation procedures play a vital role in regulating the morphology, shape and size of the metal nanoparticles. These active centers have a profound influence on the activation of molecular oxygen for selective catalytic oxidations.

Anodically bonded etched silicon microfluidic devices that allow infrared spectroscopic measurement of solutions are reported. These extend spatially well-resolved in situ infrared measurement to higher temperatures and pressures than previously reported, making them useful for effectively time-resolved measurement of realistic catalytic processes. A data processing technique necessary for the mitigation of interference fringes caused by multiple reflections of the probe beam is also described.

Few can be unaware of the rising tide of Japanese foreign direct investment (FDI) into Europe, where the automotive sector has had a prominent role. Indeed, for some this is part of a wider process of ‘Japanisation’ (Oliver and Wilkenson, 1989). This process has overlain an indigenous industry already undergoing profound competitive changes, which has prompted economic and spatial restructuring, including the widespread adoption of elements of the lean production model outlined in Chapter 2. Foreign direct investment, notably within Europe, has become an important feature of restructuring. Indeed, as Wells (1992) shows, European FDI grew from 20 per cent of total UK inward FDI in 1980 to 46 per cent by 1988, with the automobile industry playing a prominent role. This chapter seeks to identify some of the main dimensions of growth and decline in the European automobile industry, because it is changes occuring among the assemblers which dominate much of the subsequent change in the components industry. We start with an historical overview of production and markets in Europe before moving on to consider investments, closures and other structural changes in the sector in the late 1980s and early 1990s. Particular attention is given to Japanese FDI and the economic integration of Eastern Europe. A flexible definition of Europe is used, because in the longer term the countries of Eastern Europe and Scandanavia may well be integrated into a wider European Community alongside other peripheral countries such as Turkey, and in any case for some firms, integration across current EC boundaries is a reality at the present time.

Steel remains the most important material input for automobile manufacture and assembly. Although the European steel industry provides inputs to a wide range of industries outside the automotive sector, the fortunes of the two sectors (especially with respect to wide strip or coil steel) have been closely linked for many years. The typical modern automobile uses a wide range of types of steel in the form of castings, forgings, turned parts and pressings. In this chapter and Chapter 6 we shall be concerned with wide coil mild steel (also known as strip steel, and sometimes sold as cut sheets) which is used in the presswork industry. In this chapter we outline the scale of steel usage in the European automotive presswork sector; the structure of the steel production and supply sector; technological change in steels; and the nature of procurement regimes in the sector. The steel and presswork supply chain is detailed in Chapter 6.

The motor industry has long been the subject of state regulation and intervention in almost all aspects of the business, and as such the state at national and international level is a key element in the context within which structural change in the industry occurs. Historically, the state has played a key, and direct, role in automobile production, notably since 1945. Not only do state laws on vehicle and petrol taxation have an impact, so too has direct ownership in the form of nationalised companies or strategic holdings in companies. The state fundamentally shapes production via laws on wages, working conditions, union and worker rights and so on. Moreover, the state fundamentally shapes car consumption through its investment policies regarding roads and other forms of transportation network, as well as through its fiscal measures. Through regional policies, national states have sought to influence the location of the automobile industry, both successfully (Volkswagen at Wolfsburg) and unsuccessfully (Chrysler at Linwood). Thus, while customer-supplier relations are a very important force for industrial spatial restructuring, the impact of state intervention in mediating those forces should not be neglected. The purpose of this chapter is to provide an account of one aspect of state intervention as it pertains to the automotive components industry in general, and to the case study sub-sectors in particular, that is, the attraction and support of foreign direct investment.

Clutches and brakes are both basic components of most vehicles, and are related in that both use friction materials in the physical operations they perform. Both are also mainly supplied to vehicle assemblers by external, independent firms. Unlike the presswork sector, the clutches and brakes markets for volume original equipment, as well as the friction materials markets, are dominated by a few multinational firms — although the aftermarket segment is much more fragmented. This chapter examines the supply chain in clutches and brakes, with the emphasis on the structure of the industry and the mechanisms by which change is transmitted through that structure. As we shall show later, product innovation by components firms has been a key facet of the sector; indeed, firms in this sector exhibit many more of the characteristics of the Lamming (1989a) post-Japanese model than do those in the presswork sector.

Here, we are simply concerned to provide a general background, both theoretical and empirical, to the more detailed discussions in the later empirical chapters. The automotive components industry is a substantial one in both employment and turnover terms, but there is also a widespread perception that it is a sector under threat for a number of reasons (BCG, 1991), leading to rationalisation, concentration and internationalisation (Carr, 1988, 1993). The following section describes the sector from the available literature and information sources. Thereafter, we move on to consider the main forces for restructuring the sector. Finally, we outline a key determinant of change in the sector — the extent to which new buyer-supplier relations are being established (Cole, 1988). Here we compare the theoretical and idealised model with the evidence for actual practice by the various vehicle assemblers and the components sector. In what emerges, it is clear that great diversity is shown in supplier policies by the vehicle assemblers, and that, for each assembler, diversity also exists according to the component under consideration.

A controlled surface reaction technique has been successfully employed to prepare a series of Pt modified Pd/C (Pt/Pd/C) and Pd modified Pt/C (Pd/Pt/C) catalysts. The resulting catalyst materials were characterised by TEM, XRD, electrochemistry, and EXAFS techniques. In the case of the Pd/Pt/C carbon catalysts, core-shell structural arrangements were found, with a 0.04 A contraction of the Pd-Pd bond distance for the 1 Pd/Pt/C being observed. A greater degree of alloying was found for the Pt/Pd/C catalysts where the surface had a mixed composition with a large proportion of the Pt in the interior of the nanoparticle. However, strong Pt characteristics were exhibited in the voltammetry of Pt/Pd/C catalysts, most notably a large increase in the stability with respect to the electrochemical environment compared to Pd alone.

The lean production model does not say much about the shop‐floor implications for working practices and labour management relations — the assumption is that workers would prefer to be under a lean regime — or indeed how firms might begin to introduce new working practices (Womak et al 1990). On the other hand, many related studies have been critical of the model, noting for example work intensification, greater management control, and questioning the notion of multi‐skilling (Rehder 1989, 1990, Dankbaar 1988, Pollert 1988) and its applicability (Wood 1991). Using four European case studies in automotive presswork, this paper examines the introduction of new working practices on the shop‐floor, and the links between those practices and the introductions of new presswork technologies. Finally, we draw conclusions from the case studies with respect to our understanding of skill and the relationship between organisational and technological changes on the shop‐floor.