Fundamentals of Mechanocatalysis for Lignin Valorization

Lignin, the largest natural source of aromatics, is an appealing sustainable feedstock for many chemicals and materials. The depolymerization of lignin to mono-aromatics has remained challenging and industrial applications have remained elusive. A promising approach to biomass valorization and deconstruction has been mechanocatalysis. This approach uses mechanical energy, often supplied in ball mill reactors, to drive reaction under solvent free and ambient conditions. However, fundamental understanding of mechanocatalysis remains enigmatic, presenting its own set of challenges. The aim of this thesis is to lay fundamental groundwork to better understand mechanocatalytic systems and how these systems can be applied for depolymerizing and valorizing lignin. Characterizing the structure of lignin isolated from traditional and alternative industrial processes can be used to assess their viability as feedstock for depolymerization processes. The lignin samples are characterized by elemental analysis, nuclear magnetic resonance (NMR) spectroscopy, gel permeation chromatography (GPC), and thermogravimetric analysis (TGA). Quantification of the β O 4 ether bond content shows partial depolymerization, with all samples having less than 12 bonds per 100 aromatics. This results in a theoretical monomer yields less than 5%, strongly suggesting the alternative fractionation processes generate highly condensed lignin structures that are no more suitable for catalytic depolymerization than kraft lignin. To better understand the environments in mechanochemical reactors, a three-part modeling approach to describe the reactive conditions created during collisions is presented. The approach is focused on the creation of hot spots as the mechanism of enhanced reaction. Here, energy dissipated during a collision is converted to heat in the milling media, and the reaction proceeds thermochemically. The final result of the model is the extent of reaction over a single collision. To verify the approach, the mechanochemical decomposition of calcium carbonate is studied. The real-time CO2 production under varying milling frequencies is measured using an in-line mass spectrometer. The model describes hot spots with temperatures exceeding 1000 K that persist for tens of milliseconds. Novel behavior of catalysts under mechanocatalytic conditions is explored by introducing a new approach for ammonia production at nominally ambient conditions. As proof of concept, ammonia is synthesized mechanocatalytically by ball milling titanium in a continuous gas flow. The ammonia synthesis reaction is proposed to follow a transient Mars-van Krevelen mechanism under mechanically activated conditions, where molecular nitrogen incorporation into the titanium lattice and titanium nitride hydrogenation occur in thermodynamically distinct environments. The reactivity of nitrided titanium supports that lattice nitrogen plays a role in ammonia formation. The in situ formed titanium nitride is catalytically active, and the nitride regeneration reaction is determined to be the rate-limiting step. Finally, the mechanocatalytic hydrogenolysis of benzyl phenyl ether (BPE), a model lignin ether, is demonstrated over supported nickel catalysts at room temperature and atmospheric hydrogen pressure. The hydrogenolysis reaction network closely follows those of solution-based reactions. The mechanical energy during milling not only drives the chemical reactions, but also activates the nickel and exposes fresh metallic surfaces. Recycle experiments shows continual deactivation over three reaction cycles and the formation of polyaromatic coke species. The formation of the carbon deposits is expected to be the primary cause of deactivation. Varying support properties shows that the hydrogenolysis rate is largely independent of the support properties, but the enhanced reactivity of the oxide supports during milling contributes to the carbon loss.Ph.D

Physical and Mechanical Properties of LoVAR: A New Lightweight Particle-Reinforced Fe-36Ni Alloy

Fe-36Ni is an alloy of choice for low thermal expansion coefficient (CTE) for optical, instrument and electrical applications in particular where dimensional stability is critical. This paper outlines the development of a particle-reinforced Fe-36Ni alloy that offers reduced density and lower CTE compared to the matrix alloy. A summary of processing capability will be given relating the composition and microstructure to mechanical and physical properties

Physical and Mechanical Properties of LoVAR: A New Lightweight Particle-Reinforced Fe-36Ni Alloy

Fe-36Ni is an alloy of choice for low thermal expansion coefficient (CTE) for optical, instrument and electrical applications in particular where dimensional stability is critical. This paper outlines the development of a particle-reinforced Fe-36Ni alloy that offers reduced density and lower CTE compared to the matrix alloy. A summary of processing capability will be given relating the composition and microstructure to mechanical and physical properties

Early development of infants with neurofibromatosis type 1: a case series

Background Prospective studies of infants at familial risk for autism spectrum disorder (ASD) have yielded insights into the earliest signs of the disorder but represent heterogeneous samples of unclear aetiology. Complementing this approach by studying cohorts of infants with monogenic syndromes associated with high rates of ASD offers the opportunity to elucidate the factors that lead to ASD. Methods We present the first report from a prospective study of ten 10-month-old infants with neurofibromatosis type 1 (NF1), a monogenic disorder with high prevalence of ASD or ASD symptomatology. We compared data from infants with NF1 to a large cohort of infants at familial risk for ASD, separated by outcome at age 3 of ASD (n = 34), atypical development (n = 44), or typical development (n = 89), and low-risk controls (n = 75). Domains assessed at 10 months by parent report and examiner observation include cognitive and adaptive function, sensory processing, social engagement, and temperament. Results Infants with NF1 showed striking impairments in motor functioning relative to low-risk infants; this pattern was seen in infants with later ASD from the familial cohort (HR-ASD). Both infants with NF1 and the HR-ASD group showed communication delays relative to low-risk infants. Conclusions Ten-month-old infants with NF1 show a range of developmental difficulties that were particularly striking in motor and communication domains. As with HR-ASD infants, social skills at this age were not notably impaired. This is some of the first information on early neurodevelopment in NF1. Strong inferences are limited by the sample size, but the findings suggest implications for early comparative developmental science and highlight motor functioning as an important domain to inform the development of relevant animal models. The findings have clinical implications in indicating an important focus for early surveillance and remediation in this early diagnosed genetic disorder

International Olympic Committee consensus statement on pain management in elite athletes

Pain is a common problem among elite athletes and is frequently associated with sport injury. Both pain and injury interfere with the performance of elite athletes. There are currently no evidence-based or consensus-based guidelines for the management of pain in elite athletes. Typically, pain management consists of the provision of analgesics, rest and physical therapy. More appropriately, a treatment strategy should address all contributors to pain including underlying pathophysiology, biomechanical abnormalities and psychosocial issues, and should employ therapies providing optimal benefit and minimal harm. To advance the development of a more standardised, evidence-informed approach to pain management in elite athletes, an IOC Consensus Group critically evaluated the current state of the science and practice of pain management in sport and prepared recommendations for a more unified approach to this important topic

Genotypic variation in photosynthetic and leaf traits in cocoa

The photosynthetic characteristics of eight contrasting cocoa genotypes were studied with the aim of examining genotypic variation in maximum (light-saturated) photosynthetic rates, light-response curve parameters and water use efficiency. Photosynthetic traits were derived from single leaf gas exchange measurements using a portable infra-red gas analyser. All measurements were conducted in a common greenhouse environment. Significant variation was observed in light-saturated photosynthesis ranging from 3.4 to 5.7 µmol CO2 m-2 s-1 for the clones IMC 47 and SCA 6, respectively. Furthermore, analyses of photosynthetic light response curves indicated genotypic differences in light saturation point and quantum efficiency (i.e. the efficiency of light use). Stomatal conductance was a significant factor underlying genotypic differences in assimilation. Genotypic variation was also observed in a number of leaf traits, including specific leaf area (the ratio of leaf area to leaf weight), chlorophyll concentration and nitrogen content. There was a positive correlation between leaf nitrogen per unit area and light-saturated photosynthesis. Water use efficiency, defined as the ratio of photosynthetic rate to transpiration rate, also varied significantly between clones (ranging from 3.1 mmol mol-1 H2O for the clone IMC 47 to 4.2 mmol mol-1 H2O for the clone ICS 1). Water use efficiency was a negative function of specific leaf area, suggesting that low specific leaf area might be a useful criterion for selection for increased water use efficiency. It is concluded that both variation in water use efficiency and the photosynthetic response to light have the potential to be exploited in breeding programmes

Genotypic variation in photosynthesis in cacao is correlated with stomatal conductance and leaf nitrogen

Variation in photosynthetic parameters was observed between eight contrasting cacao (Theobroma cacao) genotypes. Net photosynthetic rate (PN) ranged from 3.4 to 5.7 μmol(CO2) m−2 s−1 for the genotypes IMC 47 and SCA 6, respectively. Furthermore, genotypic differences were detected in quantum efficiency ranging from 0.020 to 0.043 μmol(CO2) μmol−1(photon) for UF 676 and AMAZ 15/15, respectively. Differences in PN were correlated with both stomatal conductance (gs) and leaf nitrogen per unit area. Some variation in water use efficiency was observed between genotypes, both intrinsic (PN/gs) and instantaneous (PN/transpiration rate). Both measures of water use efficiency were a negative function of specific leaf area. Evidence was found for a trade-off mechanism between cacao genotypes in photosynthesis and leaf structure. High photosynthetic rate, expressed on a mass basis was associated with smaller leaves. Furthermore, thinner leaves were compensated for by a higher nitrogen content per unit mass.A. J. Daymond, P. J. Tricker, P. Hadle

Engineering Bipolar Interfaces for Water Electrolysis Using Earth-Abundant Anodes.

Developing efficient and low-cost water electrolyzers for clean hydrogen production to reduce the carbon footprint of traditional hard-to-decarbonize sectors is a grand challenge toward tackling climate change. Bipolar-based water electrolysis combines the benefits of kinetically more favorable half-reactions and relatively inexpensive cell components compared to incumbent technologies, yet it has been shown to have limited performance. Here, we develop and test a bipolar-interface water electrolyzer (BPIWE) by combining an alkaline anode porous transport electrode with an acidic catalyst-coated membrane. The role of TiO2 as a water dissociation (WD) catalyst is investigated at three representative loadings, which indicates the importance of balancing ionic conductivity and WD activity derived from the electric field for optimal TiO2 loading. The optimized BPIWE exhibits negligible performance degradation up to 500 h at 400 mA cm-2 fed with pure water using earth-abundant anode materials. Our experimental findings provide insights into designing bipolar-based electrochemical devices

Design and operating principles for high-performing anion exchange membrane water electrolyzers

Anion-exchange-membrane water electrolyzers (AEMWEs) provide a promising pathway to utilize low-carbon renewable electricity to produce clean hydrogen at high efficiency and purity, while maintaining low system costs compared to incumbent technologies. Though significant progress has been made in developing membranes and catalysts, AEMWEs still require better performance and durability to realize widespread deployment. Here, we overcome these challenges by decoupling anode and cathode polarization behavior via integration of a reference electrode in the membrane-electrode assembly. This measurement identified that the mass-transport losses dominate the cathode overpotential if feeding with electrolytes, while kinetic losses dominate the anode overpotential. These losses are mitigated by varying electrode properties and operating strategies, where a more hydrophobic, optimal loaded cathode, a high porosity anode, and operating with the cathode dry exhibited the best performance. These findings eventually enabled achieving a high-performing and durable complete PGM-free AEMWE operating at 1.5 A cm−2 for over 500 h with negligible degradation, demonstrating significant progress for AEMWEs