Evidence for the adsorption of molecules at special sites located at copper/zinc oxide interfaces. Part 2. -- A fourier-transform infrared spectroscopy study of methanol adsorption on reduced and oxidised Cu/ZnO/SiO2 catalysts

FTIR spectra are reported of methanol adsorbed at 295 K on ZnO/SiO 2, on reduced Cu/ZnO/SiO2 and on Cu/ZnO/SiO2 which had been preoxidised by exposure to nitrous oxide. Methanol on ZnO/SiO2 gave methoxy species on ZnO and SiO, in addition to both strongly and weakly physisorbed methanol on SiO2. The corresponding adsorption of methanol on reduced Cu/ZnO/SiO2 also gave methoxy species on Cu and a small amount of bridging formate. Reaction of methanol with a reoxidised Cu/ZnO/SiO2 catalyst resulted in an enhanced quantity of methoxy species on Cu. Heating adsorbed species on Cu/ZnO/SiO2 at 393 K led to the loss of methoxy groups on Cu and the concomitant formation of formate species on both ZnO and Cu. The comparable reaction on a reoxidised Cu/ZnO/SiO2 catalyst gave an increased amount of formate species on ZnO and this correlated with an increased quantity of methoxy groups lost from Cu. An explanation is given in terms of adsorption of formate and formaldehyde species at special sites located at the copper/zinc oxide interface.

A combined temperature-programmed reaction spectroscopy and Fourier-transform infrared spectroscopy study of CO2/H2 and CO/CO2/H2 interactions with model ZnO/SiO2, Cu/SiO2 and Cu/ZnO/SiO2 methanol-synthesis catalysts

The reaction of CO2 and H2 with ZnO/SiO2 catalyst at 295 K gave predominantly hydrogencarbonate on zinc oxide and a small quantity of formate was evolved after heating at 393 K. Elevation of the reaction temperature to 503 K enhanced the rate of formation of zinc formate species. Significantly these formate species decomposed at 573 K almost entirely to CO2 and H2. Even after exposure of CO2-H2 or CO-CO2-H2 mixtures to highly defected ZnO/SiO2 catalyst, the formate species produced still decomposed to give CO2 and H2. It was concluded that carboxylate species which were formed at oxygen anion vacancies on polar Zn planes were not significantly hydrogenated to formate. Consequently it was proposed that the non-polar planes on zinc oxide contained sites which were specific for the synthesis of methanol. The interaction of CO2 and H2 with reduced Cu/ZnO/SiO2 catalyst at 393 K gave copper formate species in addition to substantial quantities of formate created at interfacial sites between copper and zinc oxide. It was deduced that interfacial formate species were produced from the hydrogenation of interfacial bidentate carbonate structures. The relevance of interfacial formate species in the methanol synthesis reaction is discussed. Experiments concerning the reaction of CO2-H2 with physical mixtures of Cu/SiO2 and ZnO/SiO2 gave results which were simply characteristic of the individual components. By careful consideration of previous data a detailed proposal regarding the role of spillover hydrogen is outlined. Admission of CO to a gaseous CO2-H2 feedstock resulted in a considerably diminished amount of formate species on copper. This was ascribed to a combination of over-reduction of the surface and site-blockage.

Characterization of precursors to methanol synthesis catalysts Cu/ZnO system

The composition of a series of hydroxycarbonate precursors to copper/zinc oxide methanol synthesis catalysts prepared under conditions reported as optimum for catalytic activity has been studied. Techniques employed included thermogravimetry (TG), temperature-programmed decomposition (TPD), X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), and Raman and FTIR spectroscopies. Evidence was obtained for various structural phases including hydrozincite, copper hydrozincite, aurichalcite, zincian malachite and malachite (the concentrations of which depended upon the exact Cu/Zn ratio used). Significantly, previously reported phases such as gerhardite and rosasite were not identified when catalysts were synthesized at optimum solution pH and temperature values, and after appropriate aging periods. Calcination of the hydroxycarbonate precursors resulted in the formation of catalysts containing an intimate mixture of copper and zinc oxides. Temperature-programmed reduction (TPR) revealed that a number of discrete copper oxide species were present in the catalyst, the precise concentrations of which were determined to be related to the structure of the catalyst precursor. Copper hydrozincite decomposed to give zinc oxide particles decorated by highly dispersed, small copper oxide species. Aurichalcite appeared to result ultimately in the most intimately mixed catalyst structure whereas zincian malachite decomposed to produce larger copper oxide and zinc oxide grains. The reason for the stabilization of small copper oxide and zinc oxide clusters by aurichalcite was investigated by using carefully selected calcination temperatures. It was concluded that the unique formation of an 'anion-modified' oxide resulting from the initial decomposition stage of aurichalcite was responsible for the 'binding' of copper species to zinc moieties.

A combined environmental scanning electron microscopy and Raman microscopy study of methanol oxidation on silver(I) oxide

The techniques of environmental scanning electron microscopy (ESEM) and Raman microscopy have been used to respectively elucidate the morphological changes and nature of the adsorbed species on silver(I) oxide powder, during methanol oxidation conditions. Heating Ag2O in either water vapour or oxygen resulted firstly in the decomposition of silver(I) oxide to polycrystalline silver at 578 K followed by sintering of the particles at higher temperature. Raman spectroscopy revealed the presence of subsurface oxygen and hydroxyl species in addition to surface hydroxyl groups after interaction with water vapour. Similar species were identified following exposure to oxygen in an ambient atmosphere. This behaviour indicated that the polycrystalline silver formed from Ag2O decomposition was substantially more reactive than silver produced by electrochemical methods. The interaction of water at elevated temperatures subsequent to heating silver(I) oxide in oxygen resulted in a significantly enhanced concentration of subsurface hydroxyl species. The reaction of methanol with Ag2O at high temperatures was interesting in that an inhibition in silver grain growth was noted. Substantial structural modification of the silver(I) oxide material was induced by catalytic etching in a methanol/air mixture. In particular, "pin-hole" formation was observed to occur at temperatures in excess of 773 K, and it was also recorded that these "pin- holes" coalesced to form large-scale defects under typical industrial reaction conditions. Raman spectroscopy revealed that the working surface consisted mainly of subsurface oxygen and surface Ag=O species. The relative lack of sub-surface hydroxyl species suggested that it was the desorption of such moieties which was the cause of the "pin-hole" formation.

In situ imaging of catalytic etching on silver during methanol oxidation conditions by environmental scanning electron microscopy

Polycrystalline silver is used to catalytically oxidise methanol to formaldehyde. This paper reports the results of extensive investigations involving the use of environmental scanning electron microscopy (ESEM) to monitor structural changes in silver during simulated industrial reaction conditions. The interaction of oxygen, nitrogen, and water, either singly or in combination, with a silver catalyst at temperatures up to 973 K resulted in the appearance of a reconstructed silver surface. More spectacular was the effect an oxygen/methanol mixture had on the silver morphology. At a temperature of ca. 713 K pinholes were created in the vicinity of defects as a consequence of subsurface explosions. These holes gradually increased in size and large platelet features were created. Elevation of the catalyst temperature to 843 K facilitated the wholescale oxygen induced restructuring of the entire silver surface. Methanol reacted with subsurface oxygen to produce subsurface hydroxyl species which ultimately formed water in the subsurface layers of silver. The resultant hydrostatic pressure forced the silver surface to adopt a "hill and valley" conformation in order to minimise the surface free energy. Upon approaching typical industrial operating conditions widespread explosions occurred on the catalyst and it was also apparent that the silver surface was extremely mobile under the applied conditions. The interaction of methanol alone with silver resulted in the initial formation of pinholes primarily in the vicinity of defects, due to reaction with oxygen species incorporated in the catalyst during electrochemical synthesis. However, dramatic reduction in the hole concentration with time occurred as all the available oxygen became consumed. A remarkable correlation between formaldehyde production and hole concentration was found.

In situ Raman studies of the selective oxidation of methanol to formaldehyde and ethene to ethylene oxide on a polycrystalline silver catalyst

The combined techniques of in situ Raman microscopy and scanning electron microscopy (SEM) have been used to study the selective oxidation of methanol to formaldehyde and the ethene epoxidation reaction over polycrystalline silver catalysts. The nature of the oxygen species formed on silver was found to depend critically upon the exact morphology of the catalyst studied. Bands at 640, 780 and 960 cm-1 were identified only on silver catalysts containing a significant proportion of defects. These peaks were assigned to subsurface oxygen species situated in the vicinity of surface dislocations, AgIII=O sites formed on silver atoms modified by the presence of subsurface oxygen and O2 - species stabilized on subsurface oxygen-modified silver sites, respectively. The selective oxidation of methanol to formaldehyde was determined to occur at defect sites, where reaction of methanol with subsurface oxygen initially produced subsurface OH species (451 cm-1) and adsorbed methoxy species. Two distinct forms of adsorbed ethene were identified on oxidised silver sites. One of these was created on silver sites modified by the interaction of subsurface oxygen species, and the other on silver crystal planes containing a surface coverage of atomic oxygen species. The selective oxidation of ethene to ethylene oxide was achieved by the reaction between ethene adsorbed on modified silver sites and electrophilic AgIII=O species, whereas the combustion reaction was perceived to take place by the reaction of adsorbed ethene with nucleophilic surface atomic oxygen species. Defects were determined to play a critical role in the epoxidation reaction, as these sites allowed the rapid diffusion of oxygen into subsurface positions, and consequently facilitated the formation of the catalytically active AgIII=O sites.

The influence of fatty acid methyl ester profiles on inter-cycle variability in a heavy duty compression ignition engine

With the advent of alternative fuels, such as biodiesels and related blends, it is important to develop an understanding of their effects on inter-cycle variability which, in turn, influences engine performance as well as its emission. Using four methanol trans-esterified biomass fuels of differing carbon chain length and degree of unsaturation, this paper provides insight into the effect that alternative fuels have on inter-cycle variability. The experiments were conducted with a heavy-duty Cummins, turbo-charged, common-rail compression ignition engine. Combustion performance is reported in terms of the following key in-cylinder parameters: indicated mean effective pressure (IMEP), net heat release rate (NHRR), standard deviation of variability (StDev), coefficient of variation (CoV), peak pressure, peak pressure timing and maximum rate of pressure rise. A link is also established between the cyclic variability and oxygen ratio, which is a good indicator of stoichiometry. The results show that the fatty acid structures did not have a significant effect on injection timing, injection duration, injection pressure, StDev of IMEP, or the timing of peak motoring and combustion pressures. However, a significant effect was noted on the premixed and diffusion combustion proportions, combustion peak pressure and maximum rate of pressure rise. Additionally, the boost pressure, IMEP and combustion peak pressure were found to be directly correlated to the oxygen ratio. The emission of particles positively correlates with oxygen content in the fuel as well as in the air-fuel mixture resulting in a higher total number of particles per unit of mass.

A parametric analysis technique for design of fuel cell and hybrid-electric vehicles

This paper presents a new simplified parametric analysis technique for the design of fuel cell and hybrid-electric vehicles. The technique utilizes a comprehensive set of ∼30 parameters to fully characterize the vehicle platform, powertrain components, vehicle performance requirements and driving conditions. It is best applied to the sizing of powertrain components and prediction of energy consumption in a vehicle. This new parametric technique makes a good complement to existing vehicle simulation software packages and therefore represents a potentially valuable tool for the hybrid vehicle designer.

Migrating to a sustainable energy system : distributed generation and storage, fuel cells and hypercars

This paper examines a number of issues in sustainable energy generation and distribution, and explores avenues that are available for integration of our society’s energy supplies. In particular, the paper presents a way in which transport vehicle energy supplies could be integrated with distributed generation schemes to achieve synergistic and beneficial outcomes. The worldwide energy system contains fundamental problems that result directly from the use of unsustainable fuels and a lack of energy system integration. There is a need to adopt an integrated, sustainable energy system for our society. The adoption of distributed generation could result in beneficial restructuring of the energy trade, and a change in the role of energy providers. Inherent benefits in distributed generation schemes would directly combat barriers to installation of renewable generation facilities, which might prove distributed renewable energy sources to be more feasible. The presence of fuel cells, batteries, power electronic inverters and intelligent controls in vehicles of the future provides many opportunities for the integration of vehicle energy supplies into a distributed generation scheme. In such a system, vehicles could play a major role in power generation and storage.

Migrating to a sustainable energy system : distributed generation and storage, fuel cells and hypercars

This paper examines a number of issues in sustainable energy generation and distribution, and explores avenues that are available for integration of our society’s energy supplies. In particular, the paper presents a way in which transport vehicle energy supplies could be integrated with distributed generation schemes to achieve synergistic and beneficial outcomes. The worldwide energy system contains fundamental problems that result directly from the use of unsustainable fuels and a lack of energy system integration. There is a need to adopt an integrated, sustainable energy system for our society. The adoption of distributed generation could result in beneficial restructuring of the energy trade, and a change in the role of energy providers. Inherent benefits in distributed generation schemes would directly combat barriers to installation of renewable generation facilities, which might prove distributed renewable energy sources to be more feasible. The presence of fuel cells, batteries, power electronic inverters and intelligent controls in vehicles of the future provides many opportunities for the integration of vehicle energy supplies into a distributed generation scheme. In such a system, vehicles could play a major role in power generation and storage.

Microalgal species selection for biodiesel production based on fuel properties derived from fatty acid profiles

Physical and chemical properties of biodiesel are influenced by structural features of the fatty acids, such as chain length, degree of unsaturation and branching of the carbon chain. This study investigated if microalgal fatty acid profiles are suitable for biodiesel characterization and species selection through Preference Ranking Organisation Method for Enrichment Evaluation (PROMETHEE) and Graphical Analysis for Interactive Assistance (GAIA) analysis. Fatty acid methyl ester (FAME) profiles were used to calculate the likely key chemical and physical properties of the biodiesel [cetane number (CN), iodine value (IV), cold filter plugging point, density, kinematic viscosity, higher heating value] of nine microalgal species (this study) and twelve species from the literature, selected for their suitability for cultivation in subtropical climates. An equal-parameter weighted (PROMETHEE-GAIA) ranked Nannochloropsis oculata, Extubocellulus sp. and Biddulphia sp. highest; the only species meeting the EN14214 and ASTM D6751-02 biodiesel standards, except for the double bond limit in the EN14214. Chlorella vulgaris outranked N. oculata when the twelve microalgae were included. Culture growth phase (stationary) and, to a lesser extent, nutrient provision affected CN and IV values of N. oculata due to lower eicosapentaenoic acid (EPA) contents. Application of a polyunsaturated fatty acid (PUFA) weighting to saturation led to a lower ranking of species exceeding the double bond EN14214 thresholds. In summary, CN, IV, C18:3 and double bond limits were the strongest drivers in equal biodiesel parameter-weighted PROMETHEE analysis.

Fuel consumption and gas emissions of an automatic transmission vehicle following simple eco-driving instructions on urban roads

Following eco-driving instructions can reduce fuel consumption between 5 to 20% on urban roads with manual cars. The majority of Australian cars have an automatic transmission gear-box. It is therefore of interest to verify whether current eco-driving instructions are e cient for such vehicles. In this pilot study, participants (N=13) drove an instrumented vehicle (Toyota Camry 2007) with an automatic transmission. Fuel consumption of the participants was compared before and after they received simple eco-driving instructions. Participants drove the same vehicle on the same urban route under similar tra c conditions. We found that participants drove at similar speeds during their baseline and eco-friendly drives, and reduced the level of their accelerations and decelerations during eco-driving. Fuel consumption decreased for the complete drive by 7%, but not on the motorway and inclined sections of the study. Gas emissions were estimated with the VT-micro model, and emissions of the studied pollutants (CO2, CO, NOX and HC) were reduced, but no di erence was observed for CO2 on the motorway and inclined sections. The di erence for the complete lap is 3% for CO2. We have found evidence showing that simple eco-driving instructions are e cient in the case of automatic transmission in an urban environment, but towards the lowest values of the spectrum of fuel consumption reduction from the di erent eco-driving studies.

Fuel additive

A fuel additive comprising one or more complex oxides having a nominal compn. as set out in formula (1): AxB1-yMyOn; wherein A is selected from one or more group III elements including the lanthanide elements or one or more divalent or monovalent cations; B is selected from one or more elements with at. no. 22 to 24, 40 to 42 and 72 to 75; M is selected from one or more elements with at. no. 25 to 30; x is defined as a no. where 0 < x ≤ l; y is defined as a no. where 0 ≤ y < 0.5. [on SciFinder(R)]

Superactivation of metal electrode surfaces and its relevance to COads oxidation at fuel cell anodes

The inhibiting effect of COads on platinum-based anodes is a major problem in the development of ambient temperature, polyelectrolyte membrane-type fuel cells. One of the unusual features of the response for the oxidative removal of the species in question is that the response observed for this reaction in the positive sweep is highly dependent on the CO admission potential, for example, when the COads is formed in the Hads region it undergoes oxidation at unusually low potentials. Such behaviour is attributed here to hydrogen activation of the platinum surface, with the result that oxide mediators (and COads oxidation) occurs at an earlier stage of the positive sweep. It is also demonstrated, for both platinum and gold in acid solution, that dramatic premonolayer oxidation responses may be observed following suitable preactivation of the electrode surfaces. It is suggested that the defect state of a solid electrode surface is an important variable whose investigation may yield improved fuel cell anode performance.

H2-O2 porous fuel injection in a radical farming scramjet

This paper reports on the experimental testing of oxygen compatible ceramic matrix composite porous injectors in a nominally two-dimensional hydrogen fuelled and oxygen enriched radical farming scramjet in the T4 shock tunnel facility. All experiments were performed at a dynamic pressure of 146 kPa, an equivalent flight Mach number of 9.7, a stagnation pressure and enthalpy of 40MPa and 4.3 MJ/kg respectively and at a fuelling condition that resulted in an average equivalence ratio of 0.472. Oxygen was pre-mixed with the fuel prior to injection to achieve enrichment percentages of approximately 13%, 15% and 17%. These levels ensured that the hydrogen-oxidiser mix injected into the engine always remained too fuel rich to sustain a flame without any additional mixing with the captured air. Addition of pre-mixed oxygen with the fuel was found to significantly alter the performance of the engine; enhancing both combustion and ignition and converting a previously observed limited combustion condition into one with sustained and noticeable combustion induced pressure rise. Increases in the enrichment percentage lead to further increases in combustion levels and acted to reduce ignition lengths within the engine. Suppressed combustion runs, where a nitrogen test gas was used, confirmed that the pressure rise observed in these experiments as attributed to the oxygen enrichment and not associated with the increased mass injected.