Cobalt rhenium catalysts for ammonia synthesis

Cobalt rhenium ammonia synthesis catalysts which are highly active at ambient pressure and 400°C under N2/H2 (1:3) have been prepared without an ammonolysis step. For all highly active cobalt rhenium materials the post-reaction powder XRD patterns reveal there is a shift of their Re reflections to a slightly higher 2θ angle. This shift is due to mixing of cobalt and rhenium within the material and this interaction was confirmed via XAS analysis. The XRD patterns of cobalt rhenium materials with minimum ammonia synthesis activity resemble the reference pattern for metallic rhenium and show no signs of bimetallic mixing. Cobalt rhenium materials have been benchmarked against CsNO3 doped Ru/Al2O3 materials. Pre-treatments under N2/H2 (1:3), Ar/H2 (1:3), N2 and Ar gas mixtures have been shown to influence catalytic performance, with the first resulting in an instantly active material, whereas, the others lead to a 20 minute induction period prior to the development of activity upon switching to an ammonia synthesis feedstream. Also, pre-treatment in N2/H2 (1:3) resulted in a material with higher catalytic activity. CoRe4 was studied via in situ XAS/XRD to elucidate the reducibility and local environment of the two metals during reaction conditions. The phases present in the CoRe4 catalyst during ammonia production are largely bimetallic Co-Re and also monometallic Co and Re species formed during both pre-treatments. It was found the presence of nitrogen during the pre-treatment strongly promotes the mixing of the both Co and Re. Preliminary tests were also conducted on cobalt rhenium catalysts for ammonia decomposition and the materials were found to have high activity. To the author's knowledge this is the first report of low surface area materials being particularly active for this reaction

FTIR measurement of cellulose microfibril angle in historic Scots pine wood and its use to detect fungal decay

Microfibril angle (MFA) – the orientation of cellulose fibres in the S2 layer of the secondary cell wall – is a key determinant of the stiffness and strength of timber. The microfibril angle depends on the way in which the timber was grown and its position within the tree. Microfibril angle can be measured by X-ray diffraction and other methods, but the methods in current use are slow or require advanced instrumentation. The aim of this study was to explore the use of polarised Fourier transform infrared (FTIR) microscopy as a relatively fast and inexpensive method for measuring MFA in historic Scots pine (Pinus sylvestris L.). The FTIR measurements were calibrated against X-ray measurements of MFA in modern Scots pine. We observed a wide range in MFA values and a radial pattern of MFA similar to modern Scots pine in undecayed Scots pine heartwood from sixteenth and seventeenth century beams in Scottish secular buildings. The density of the heartwood was also similar to modern plantation-grown Scots pine despite the much slower growth rate recorded in the ring widths of the historic timber. The sapwood, which had been attacked by both insect pests and fungi, showed an erratic reduction in density and a large increase in MFA compared to the modern material. The increased sapwood MFA was attributed to selective destruction of the S2 layer of the wood cell walls by fungal decay. Using MFA measurements in conjunction with density offers the possibility to estimate the mechanical properties of sound historic pine timber, to detect fungal decay more sensitively than by density alone, and to distinguish between pest and fungal attack in a way that relates directly to the remaining mechanical performance of the timber

On the mechanical properties of N-functionalised dipeptide gels

The properties of a hydrogel are controlled by the underlying network that immobilizes the solvent. For gels formed by the self-assembly of a small molecule, it is common to show the primary fibres that entangle to form the network by microscopy, but it is difficult to access information about the network. One approach to understand the network is to examine the effect of the concentration on the rheological properties, such that G cx, where G is the storage modulus and c is the concentration. A number of reports link the exponent x to a specific type of network. Here, we discuss a small library of gels formed using functionalized dipeptides, and describe the underlying networks of these gels, using microscopy, small angle scattering and rheology. We show that apparently different networks can give very similar values of x

The structural and mechanical integrity of historic wood

Little is known about historic wood as it ages naturally. Instead, most studies focus on biological decay, as it is often assumed that wood remains otherwise stable with age. This PhD project was organised by Historic Scotland and the University of Glasgow to investigate the natural chemical and physical aging of wood. The natural aging of wood was a concern for Historic Scotland as traditional timber replacement is the standard form of repair used in wooden cultural heritage; replacing rotten timber with new timber of the same species. The project was set up to look at what differences could exist both chemically and physically between old and new wood, which could put unforeseen stress on the joint between them. Through Historic Scotland it was possible to work with genuine historic wood from two species, Oak and Scots pine, both from the 1500’s, rather than relying on artificial aging. Artificial aging of wood is still a debated topic, with consideration given to whether it is truly mimicking the aging process or just damaging the wood cells. The chemical stability of wood was investigated using Fourier-transform infrared (FTIR) microscopy, as well as wet chemistry methods including a test for soluble sugars from the possible breakdown of the wood polymers. The physical properties assessed included using a tensile testing machine to uncover possible differences in mechanical properties. An environmental chamber was used to test the reaction to moisture of wood of different ages, as moisture is the most damaging aspect of the environment to wooden cultural objects. The project uncovered several differences, both physical and chemical, between the modern and historic wood which could affect the success of traditional ‘like for like’ repairs. Both oak and pine lost acetyl groups, over historic time, from their hemicellulose polymers. This chemical reaction releases acetic acid, which had no effect on the historic oak but was associated with reduced stiffness in historic pine, probably due to degradation of the hemicellulose polymers by acid hydrolysis. The stiffness of historic oak and pine was also reduced by decay. Visible pest decay led to loss of wood density but there was evidence that fungal decay, extending beyond what was visible, degraded the S2 layer of the pine cell walls, reducing the stiffness of the wood by depleting the cellulose microfibrils most aligned with the grain. Fungal decay of polysaccharides in pine wood left behind sugars that attracted increased levels of moisture. The degradation of essential polymers in the wood structure due to age had different impacts on the two species of wood, and raised questions concerning both the mechanism of aging of wood and the ways in which traditional repairs are implemented, especially in Scots pine. These repairs need to be done with more care and precision, especially in choosing new timber to match the old. Within this project a quantitative method of measuring the microfibril angle (MFA) of wood using polarised Fourier transform infrared (FTIR) microscopy has been developed, allowing the MFA of both new and historic pine to be measured. This provides some of the information needed for a more specific match when selecting replacement timbers for historic buildings

Chemical and Mechanical Differences between Historic and Modern Scots Pine Wood

Timber is one of the most common historic building materials, but relatively little is known about how it ages in situ. Here we investigate historic and modern Scots pine to determine any chemical or mechanical differences between them. Fourier-transform infrared (FTIR) microscopy was used to investigate differences in the chemical composition of Scots pine (Pinus sylvestris L.) timber, comparing small samples from historic beams about 500 years old with modern timber. The hemicellulosic acetyl content was reduced by about half in the historic samples, uniformly across the thickness of the beams. A chemical mechanism was therefore suggested for the loss of acetyl groups, as has been observed in paper. In paper, deacetylation and the resulting release of acetic acid are accompanied by loss of strength. Mechanical testing of the historic timber was difficult because the available length of the samples along the grain was only 20 mm. After developing a miniaturized compression test developed for the purpose, it was shown that the relative stiffness of the historic Scots pine samples was reduced by about half compared to modern material

Sensitivity analysis of intensity-modulated plastic optical fiber sensors for effective aging detection in rapeseed transformer oil

As the focus tilts toward online detection methodologies for transformer oil aging, bypassing challenges associated with traditional offline methods, such as sample contamination and misinterpretation, fiber optic sensors are gaining traction due to their compact nature, cost-effectiveness, and resilience to electromagnetic disturbances that are typical in high-voltage environments. This study delves into the sensitivity analysis of intensity-modulated plastic optical fiber sensors. The investigation encompasses key determinants such as the influence of optical source wavelengths, noise response dynamics, ramifications of varying sensing lengths, and repeatability assessments. Our findings highlight that elongating sensing length detrimentally affects both linearity response and repeatability, largely attributed to a diminished resistance to noise. Additionally, the choice of the optical source wavelength proved to be a critical variable in assessing sensor sensitivity

An in situ XAS study of the cobalt rhenium catalyst for ammonia synthesis

A cobalt rhenium catalyst active for ammonia synthesis at 400 °C and ambient pressure was studied using in situ XAS to elucidate the reducibility and local environment of the two metals during reaction conditions. The ammonia reactivity is greatly affected by the gas mixture used in the pre-treatment step. Following H2/Ar pre-treatment, a subsequent 20 min induction period is also observed before ammonia production occurs whereas ammonia production commences immediately following comparable H2/N2 pre-treatment. In situ XAS at the Co K-edge and Re LIII-edge show that cobalt initiates reduction, undergoing reduction between 225 and 300 °C, whereas reduction of rhenium starts at 300 °C. The reduction of rhenium is near complete below 400 °C, as also confirmed by H2-TPR measurements. A synergistic co-metal effect is observed for the cobalt rhenium system, as complete reduction of both cobalt and rhenium independently requires higher temperatures. The phases present in the cobalt rhenium catalyst during ammonia production following both pre-treatments are largely bimetallic Co–Re phases, and also monometallic Co and Re phases. The presence of nitrogen during the reduction step strongly promotes mixing of the two metals, and the bimetallic Co–Re phase is believed to be a pre-requisite for activity

Controlling And Understanding Single And Multicomponent Supramolecular Gels

Supramolecular gels can be prepared by the self-assembly of small molecules into fibrous structures. The properties of the resulting gels depend on how the gels are formed, such that gels with very different properties can be prepared from a single gelator if different gelation methods are used. We have been working to understand this, and for example can prepare gels that can or cannot be 3D-printed from the same gelator by varying gelation method. Here, we will focus on explaining the design rules. As specific examples, we will discuss how varying the chirality of our dipeptide-based gelators can be used to control the self-assembled aggregates, leading to differences in the final gels. We will also show how our understanding can be expanded to multicomponent systems, where each component gelator can form gels alone. In these mixed systems, we can control assembly such that self-sorted multicomponent gels are formed. We will show how such systems can be characterised to prove this assembly and how this approach can be used to prepare gels with controlled and specific properties

Using small-angle scattering and contrast matching to understand molecular packing in low molecular weight gels

It is difficult to determine exactly the molecular packing in the aggregates in low molecular weight gels. Attempts to understand the packing have been made using X-ray diffraction, but there are complications with drying and questions as to whether the crystal structures represent the packing in the gel phase. Here, we exploit contrast matching in small-angle neutron scattering experiments. By preparing selectively deuterated analogs of the same molecule, the scattering from that section of the molecule decreases compared with the hydrogenated molecule. We examine packing in the pre-gelled solutions at high pH and in the gels at low pH. The data from the final gels show a lack of specific order in the aggregates that form the gel matrix. The packing in these systems is not well ordered in the gel state and so implies that it is likely that current models and cartoons are not correct