Is the RWGS a viable route for CO2 conversion to added value products? A techno-economic study to understand the optimal RWGS conditions.

Understanding the viability of the RWGS from a thermodynamic and techno-economic angle opens new horizons within CO2 conversion technologies. Unfortunately, profitability studies of this technology are scarce in literature and mainly focused on overall conversion and selectivity trends with tangential remarks on energy demands and process costs. To address this research gap, herein we present a comprehensive techno-economic study of the RWGS reaction when coupling with Fischer-Tropsch synthesis is envisaged to produced fuels and chemicals using CO2 as building block. We showcase a remarkable impact of operating conditions in the final syngas product and both CAPEX and OPEX. From a capital investment perspective, optimal situations involve RWGS unit running at low temperatures and high pressures as evidenced by our results. However, from the running cost angle, operating at 4 bar is the most favorable alternative within the studied scenarios. Our findings showcase that, no matter the selected temperature the RWGS unit should be preferentially run at intermediate pressures. Ultimately, our work maps out multiple operating scenarios in terms of energy demand and process cost serving as guideline to set optimal reaction conditions to unlock the potential of the RWGS for chemical CO2 recycling.

Controlling the Adsorption and Release of Ocular Drugs in Metal-Organic Frameworks: Effect of Polar Functional Groups.

A series of UiO-66 materials with different functional groups (-H, -NH2, and -NO2) have been evaluated for the adsorption and release of a common ocular drug such as brimonidine tartrate. UiO-66 samples were synthesized under solvothermal conditions and activated by solvent exchange with ethanol. Experimental results suggest that the incorporation of surface functionalities gives rise to the development of structural defects (missing linker defects) but without altering the basic topology of the UiO-66 framework. These defects improve the adsorption performance of the parent metal-organic framework (MOF), while the bulkier functionalities infer slower release kinetics, with the associated benefits for prolonged delivery of brimonidine. Among the evaluated MOFs, defective UiO-66-NO2 can be proposed as the most promising candidate due to the combination of a larger brimonidine volumetric uptake (680 mg/cm3), a prolonged delivery (period of up to 25 days), a small particle size, and a larger instability. Contrariwise, at high concentrations UiO-66-NO2 has higher toxicity toward human retinal pigment epithelium cells (ARPE-19) compared to the pure and NH2-functionalized UiO-66.

K-Promoted Ni-Based Catalysts for Gas-Phase CO2 Conversion: Catalysts Design and Process Modelling Validation.

The exponential growth of greenhouse gas emissions and their associated climate change problems have motivated the development of strategies to reduce CO2 levels via CO2 capture and conversion. Reverse water gas shift (RWGS) reaction has been targeted as a promising pathway to convert CO2 into syngas which is the primary reactive in several reactions to obtain high-value chemicals. Among the different catalysts reported for RWGS, the nickel-based catalyst has been proposed as an alternative to the expensive noble metal catalyst. However, Ni-based catalysts tend to be less active in RWGS reaction conditions due to preference to CO2 methanation reaction and to the sintering and coke formation. Due to this, the aim of this work is to study the effect of the potassium (K) in Ni/CeO2 catalyst seeking the optimal catalyst for low-temperature RWGS reaction. We synthesised Ni-based catalyst with different amounts of K:Ni ratio (0.5:10, 1:10, and 2:10) and fully characterised using different physicochemical techniques where was observed the modification on the surface characteristics as a function of the amount of K. Furthermore, it was observed an improvement in the CO selectivity at a lower temperature as a result of the K-Ni-support interactions but also a decrease on the CO2 conversion. The 1K catalyst presented the best compromise between CO2 conversion, suppression of CO2 methanation and enhancing CO selectivity. Finally, the experimental results were contrasted with the trends obtained from the thermodynamics process modelling observing that the result follows in good agreement with the modelling trends giving evidence of the promising behaviour of the designed catalysts in CO2 high-scale units.

MOF-Based Polymeric Nanocomposite Films as Potential Materials for Drug Delivery Devices in Ocular Therapeutics.

Novel MOF-based polymer nanocomposite films were successfully prepared using Zr-based UiO-67 as a metal-organic framework (MOF) and polyurethane (PU) as a polymeric matrix. Synchrotron X-ray powder diffraction (SXRPD) analysis confirms the improved stability of the UiO-67 embedded nanocrystals, and scanning electron microscopy images confirm their homogeneous distribution (average crystal size ∼100-200 nm) within the 50 µm thick film. Accessibility to the inner porous structure of the embedded MOFs was completely suppressed for N2 at cryogenic temperatures. However, ethylene adsorption measurements at 25 °C confirm that at least 45% of the MOF crystals are fully accessible for gas-phase adsorption of nonpolar molecules. Although this partial blockage limits the adsorption performance of the embedded MOFs for ocular drugs (e.g., brimonidine tartrate) compared to the pure MOF, an almost 60-fold improvement in the adsorption capacity was observed for the PU matrix after incorporation of the UiO-67 nanocrystals. The UiO-67@PU nanocomposite exhibits a prolonged release of brimonidine (up to 14 days were quantified). Finally, the combined use of SXRPD, thermogravimetric analysis (TGA), and Fourier transform infrared (FTIR) analyses confirmed the presence of the drug in the nanocomposite film, the stability of the MOF framework and the drug upon loading, and the presence of brimonidine in an amorphous phase once adsorbed. These results open the gate toward the application of these polymeric nanocomposite films for drug delivery in ocular therapeutics, either as a component of a contact lens, in the composition of lacrimal stoppers (e.g., punctal plugs), or in subtenon inserts.

Tuning porosity in macroscopic monolithic metal-organic frameworks for exceptional natural gas storage.

Widespread access to greener energy is required in order to mitigate the effects of climate change. A significant barrier to cleaner natural gas usage lies in the safety/efficiency limitations of storage technology. Despite highly porous metal-organic frameworks (MOFs) demonstrating record-breaking gas-storage capacities, their conventionally powdered morphology renders them non-viable. Traditional powder shaping utilising high pressure or chemical binders collapses porosity or creates low-density structures with reduced volumetric adsorption capacity. Here, we report the engineering of one of the most stable MOFs, Zr-UiO-66, without applying pressure or binders. The process yields centimetre-sized monoliths, displaying high microporosity and bulk density. We report the inclusion of variable, narrow mesopore volumes to the monoliths' macrostructure and use this to optimise the pore-size distribution for gas uptake. The optimised mixed meso/microporous monoliths demonstrate Type II adsorption isotherms to achieve benchmark volumetric working capacities for methane and carbon dioxide. This represents a critical advance in the design of air-stable, conformed MOFs for commercial gas storage.

"It was an education in portion size". Experience of eating a healthy diet and barriers to long term dietary change.

The aim of the study was to explore the expectations and experience of actually eating a healthy diet and using this experience to identify barriers to healthy eating and sustainable dietary change. Fifty participants (19-63 yrs) were provided with a healthy diet (i.e. complied with dietary recommendations) for three consecutive days. Afterwards a semi-structured interview was carried out to explore expectations, experience and barriers to healthy eating. Using a thematic analysis approach eight dominant themes emerged from the interviews. Four related to expectations and experience of healthy eating; realisation of what are appropriate portion sizes, an expectation to feel hungry, surprise that healthy diets comprised normal food, the desire for sweet snacks (e.g. chocolate). This demonstrated there are some misconception about healthy eating and distorted views of portion size. Four more themes emerged relating to barriers to healthy eating; competing priorities, social, peer and time pressure, importance of value for money, a lack of desire to cook. Poor knowledge of healthy eating or a lack of cooking skills were the least common barrier, suggesting that future interventions and policy to improve dietary intakes need to focus on social, cultural and economic issues rather than on lack of knowledge or skills.

Meal and snacking patterns of school-aged children in Scotland.

BACKGROUND: Current lifestyles and the choice and availability of foods may influence the eating patterns of children. The aim of this study was to investigate the meal and snacking patterns of school-aged children in Scotland. METHODS: A sub-sample of 156 children (5-17 years) from the national Survey of Sugar Intake among Children in Scotland completed a 4-day non-weighed diet diary. Meals and snacks were defined using a food-based classification system based on 'core' and 'non-core' foods. The first eating event containing a solid food item up to and including 0900 hours (1100 hours on weekend days) was defined as breakfast. Frequency of meal and snack consumption was compared between age, sex, body mass index (BMI) and socio-economic sub-groups, between term-time and school holidays and between weekdays and weekend days. Intakes of total fat, saturated fatty acids (SFA) and non-milk extrinsic sugars (NMES) on these days were also compared. RESULTS: Children ate a median of 3.3 meals plus 2.0 snacks per day, which did not vary between age and BMI groups. In all, 83% of children ate breakfast on all 4 days. Boys ate more meals than girls but the number of snacks was similar. Children from lower socio-economic groups tended to eat more meals and fewer snacks. Snacks accounted for 21% of the total daily energy intake, 22% of total fat, 24% of SFA and 39% of NMES intake. Daily intake of energy, total fat, SFA and NMES did not differ between term-time and holidays or weekdays and weekend days. CONCLUSIONS: Children tended to follow a traditional pattern of three meals a day, which was consistent between age and BMI subgroups and between school term-time and holidays.

Seasonality and pituitary volume.

Pituitary volume in humans has been reported to change size in response to experimental manipulations of photoperiod, and to be increased during an episode of non-seasonal major depression. We wanted to determine whether pituitary volume changes either across the seasons or during an episode of winter depression. Nineteen patients with winter-seasonal affective disorder and 19 sex-, age-, height-, and weight-matched controls underwent magnetic resonance imaging of the pituitary gland in both winter and summer. Images were obtained using 0.7-mm contiguous slices and the areas of all slices were summed to compute the final volume for each gland. We found no main effects or interactions involving either diagnosis or season in our primary analysis. In a post-hoc analysis, we found a trend towards a season x gender effect (P = 0.06), such that pituitary volume increased slightly (+4.0%) across seasons in women, whereas it decreased slightly (-4.3%) across seasons in men. The results suggest that neither winter depression nor the change of seasons is associated with a significant change in pituitary size.