Methanol photo-reforming with water on pure titania for hydrogen production.

The behaviour of titania for the photo-reforming of methanol with water at ambient temperature has been examined. It is shown that the reactivity is very poor, compared with metal-loaded catalysts at low methanol levels in solution, but the rate becomes much higher at high methanol levels, such that the difference from metal-loaded samples is much less. The optimum yield is with approximately a 1 : 1 methanol/water solution. The reaction also proceeds well in the gas phase. During all such catalysis, the titania becomes blue, due to light absorption increasing across the range 400-800 nm. However, this does not result in visible range activity for the photo-reforming and is due to the reduction of the material in the presence of light and the formation of anion vacancies and Ti3+ centres. These anion vacancies are only very slowly re-oxidized in air on P25 titania, taking days to recover the original whiteness of the oxide. The performance of anatase, rutile and the mixed phase is compared. This article is part of a discussion meeting issue 'Science to enable the circular economy'.

PdZn catalysts for CO2 hydrogenation to methanol using chemical vapour impregnation (CVI).

The formation of PdZn bimetallic alloys on ZnO, TiO2 and Al2O3 supports was investigated, together with the effect of alloy formation on the CO2 hydrogenation reaction. The chemical vapour impregnation (CVI) method produced PdZn nanoparticles with diameters of 3-6 nm. X-ray photoelectron spectroscopy and X-ray diffraction revealed the changes in the structure of the PdZn alloy that help stabilise formate intermediates during methanol synthesis. PdZn supported on TiO2 exhibits high methanol productivity of 1730 mmol kgcat-1 h-1 that is associated with the high dispersion of the supported PdZn alloy.

H2 production by the photocatalytic reforming of cellulose and raw biomass using Ni, Pd, Pt and Au on titania.

Here, we report a method for sustainable hydrogen production using sunlight and biomass. It is shown that cellulose can be photoreformed to produce hydrogen, even in solid form, by use of metal-loaded titania photocatalysts. The experiments performed verified that the process is enabled by initial hydrolysis via glucose, which itself is shown to be efficiently converted to produce hydrogen by photocatalysis. Importantly, it is shown that not only precious metals such as Pt, Pd and Au can be used as the metal component, but also much more economic and less environmentally damaging Ni is effective. Even more importantly, we show for the first time, to the best our knowledge, that fescue grass as raw biomass can be effective for hydrogen production without significant pre-treatment. This provides additional benefits for the efficiency of biomass hydrogen production, because fewer processing steps for the raw material are required than in the production of purer forms of cellulose, for example.

Methanol oxidation on Fe2O3 catalysts and the effects of surface Mo.

The adsorption of methanol on haematite has been investigated using temperature programmed methods, combined with in situ DRIFTS. Model catalysts based on this material have then been made with a shell-core configuration of molybdenum oxide monolayers on top of the haematite core. These are used as models of industrial iron molybdate catalysts, used to selectively oxidise methanol to formaldehyde, one of the major chemical outlets for methanol. Haematite itself is completely ineffective in this respect since it oxidises it to CO2 and the DRIFTS shows that this occurs by oxidation of methoxy to formate at around 200 °C. The decomposition behaviour is affected by the absence or presence of oxygen in the gas phase; oxygen destabilises the methoxy and enhances formate production. In contrast, when a monolayer of molybdena is placed onto the surface by incipient wetness, and it remains there after calcination, the pathway to formate production is blocked and formaldehyde is the main gas phase product in TPD after methanol dosing.

Encapsulation of Au Nanoparticles on a Silicon Wafer During Thermal Oxidation.

We report the behavior of Au nanoparticles anchored onto a Si(111) substrate and the evolution of the combined structure with annealing and oxidation. Au nanoparticles, formed by annealing a Au film, appear to "float" upon a growing layer of SiO2 during oxidation at high temperature, yet they also tend to become partially encapsulated by the growing silica layers. It is proposed that this occurs largely because of the differential growth rates of the silica layer on the silicon substrate between the particles and below the particles due to limited access of oxygen to the latter. This in turn is due to a combination of blockage of oxygen adsorption by the Au and limited oxygen diffusion under the gold. We think that such behavior is likely to be seen for other metal-semiconductor systems.

Evolution of active catalysts for the selective oxidative dehydrogenation of methanol on Fe2O3 surface doped with Mo oxide.

Iron molybdate catalysts are used for the selective oxidation of methanol to formaldehyde. In this paper we have attempted to understand what determines high selectivity in this reaction system by doping haematite with surface layers of Mo by incipient wetness impregnation. This works well and the Mo appears to form finely dispersed layers. Even very low loadings of Mo have a marked effect on improving the selectivity to formaldehyde. Haematite itself is a very poor catalyst with high selectivity to combustion products, whereas, when only 0.25 monolayers of Mo are deposited on the surface, formaldehyde and CO selectivities are greatly enhanced and CO2 production is greatly diminished. However, even with as much as seven monolayers of Mo dosed on to the surface, these materials achieve much less selectivity to formaldehyde at high conversion than do the industrial catalysts. The reason for this is that the Mo forms a 'skin' of ferric molybdate on a core of iron oxide, but does not produce a pure Mo oxide monolayer on the surface, a situation which is essential for very high yields of formaldehyde.

The structure and reactivity of anchored nanoparticles on a reducible support.

We have used scanning tunnelling microscopy (STM) to study the structure and reactivity of metal nanoparticles on a TiO2(110) surface. We have deposited two metals (Pt and Ru) using different techniques, metal vapour deposition (MVD) for Pt and metal organic chemical vapour deposition (MOCVD) for Ru. Pt was deposited onto a (1 x 3) reconstructed surface and is found to sinter at temperatures above 873 K, where the onset of nanoparticle mobility is expected. The effect that Pt has on the rate of re-oxidation of a more reduced titania sample with a (1 x 1) terminated surface was studied. At 673 K no preferential re-growth around the particles is observed and this has been attributed to the desorption characteristics of oxygen from Pt surfaces. The results are compared to those obtained from Pd covered TiO2 where such preferential growth has previously been observed. Ru was deposited using a carbonyl precursor, Ru3(CO)12, and is found to adsorb preferentially on the (1 x 2) rows of a surface consisting of both (1 x 1) and (1 x 2) added row structures. Upon annealing the compound is initially de-carbonylated to leave Ru nanoparticles on the surface, which can then sinter with increasing temperature. These particles have been alloyed with Pt and their re-oxidation characteristics studied. The alloy particles alter the oxygen desorption characteristics from that of the constituent elements (Pt and Ru) and consequently an enhancement in the rate of re-oxidation of a TiO2(110) surface at 673 K is observed.

Temporal variation in community composition, pigmentation, and F(v)/F(m) of desert cyanobacterial soil crusts.

Summers on the Colorado Plateau (USA) are typified by harsh conditions such as high temperatures, brief soil hydration periods, and high UV and visible radiation. We investigated whether community composition, physiological status, and pigmentation might vary in biological soil crusts as a result of such conditions. Representative surface cores were sampled at the ENE, WSW, and top microaspects of 20 individual soil crust pedicels at a single site in Canyonlands National Park, Utah, in spring and fall of 1999. Frequency of cyanobacterial taxa, pigment concentrations, and dark adapted quantum yield [F(v)/F(m)] were measured for each core. The frequency of major cyanobacterial taxa was lower in the fall compared to spring. The less-pigmented cyanobacterium Microcoleus vaginatus showed significant mortality when not in the presence of Nostoc spp. and Scytonema myochrous (Dillw.) Agardh. (both synthesizers of UV radiation-linked pigments) but had little or no mortality when these species were abundant. We hypothesize that the sunscreen pigments produced by Nostoc and Scytonema in the surface of crusts protect other, less-pigmented taxa. When fall and spring samples were compared, overall cyanobacterial frequency was lower in fall, while sunscreen pigment concentrations, chlorophyll a concentration, and F(v)/F(m) were higher in fall. The ratio of cyanobacterial frequency/chlorophyll a concentrations was 2-3 times lower in fall than spring. Because chlorophyll a is commonly used as a surrogate measure of soil cyanobacterial biomass, these results indicate that seasonality needs to be taken into consideration. In the fall sample, most pigments associated with UV radiation protection or repair were at their highest concentrations on pedicel tops and WSW microaspects, and at their lowest concentrations on ENE microaspects. We suggest that differential pigment concentrations between microaspects are induced by varying UV radiation dosage at the soil surface on these different microaspects.

Sex expression, skewed sex ratios, and microhabitat distribution in the dioecious desert moss Syntrichia caninervis (Pottiaceae).

The moss Syntrichia caninervis is the dominant soil bryophyte in a blackbrush (Coleogyne ramosissima) community in the southern Nevada Mojave Desert, with a mean cover of 6.3%. A survey of the 10-ha study site revealed an expressed ramet sex ratio of 14♀ : 1♂ (N = 890), with 85% of ramets not expressing sex over their life span, and an expressed population sex ratio of 40♀ : 2♂ : 1♀♂ (female : male : mixed-sex, N = 89), with 52% of populations not expressing sex. A greater incidence of sex expression was associated with shaded microsites, higher soil moisture content, and taller ramets. Shaded microsites had higher surface soil moisture levels than exposed microsites. In the exposed microhabitat, surface soil moisture was positively correlated with ramet height but not with sex expression. Male ramets and populations were restricted to shaded microhabitats, whereas female ramets and populations were found in both shaded and exposed microhabitats, suggesting gender specialization. The rarity of mature sporophytes, found in 0% of the ramets sampled and in only 3% of the populations, is probably due to the rarity of mixed-sex populations. We hypothesize that mixed-sex populations are rare because of factors relating to male rarity and that the differential cost of sex expression reduces the clonal growth capacity of male individuals.

Gestational diabetes mellitus and gene mutations which affect insulin secretion.

We investigated whether genetic mutations known to impair insulin secretion and glucose tolerance are operative in a group of American women with gestational diabetes mellitus. Study groups were comprised of elderly non-diabetic controls (n = 55) with normal glucose tolerance and patients with gestational diabetes (n = 50), together with one family with maturity-onset diabetes of the young (three controls and three affected). No mutations were detected in any exon of the human glucokinase gene or the mitochondrial tRNA[Leu](UUR) gene by single strand conformational analysis and direct exon sequencing. Also, chi2 analysis showed no significant association with gestational diabetes for a polymorphism at position -30 (G --> A) of the beta-cell-specific glucokinase gene promoter. We have determined that glucokinase and mitochondrial tRNA[Leu](UUR) gene mutations, which are known to impair insulin secretion are relatively uncommon and do not constitute a large component of genetic risk for gestational diabetes in the study population.