Nematic-Fluctuation-Mediated Superconductivity Revealed by Anisotropic Strain in Ba(Fe_{1-x}Co_{x})_{2}As_{2}.

Anisotropic strain is an external field capable of selectively addressing the role of nematic fluctuations in promoting superconductivity. We demonstrate this using polarization-resolved elasto-Raman scattering by probing the evolution of nematic fluctuations under strain in the normal and superconducting state of the paradigmatic iron-based superconductor Ba(Fe_{1-x}Co_{x})_{2}As_{2}. In the parent compound BaFe_{2}As_{2} we observe a strain-induced suppression of the nematic susceptibility which follows the expected behavior of an Ising order parameter under a symmetry breaking field. For the superconducting compound, the suppression of the nematic susceptibility correlates with the decrease of the critical temperature T_{c}, indicating a significant contribution of nematic fluctuations to electron pairing. Our results validate theoretical scenarios of enhanced T_{c} near a nematic quantum critical point.

Synthesis of α,ß- and ß-Unsaturated Acids and Hydroxy Acids by Tandem Oxidation, Epoxidation, and Hydrolysis/Hydrogenation of Bioethanol Derivatives.

We report a reaction platform for the synthesis of three different high-value specialty chemical building blocks starting from bio-ethanol, which might have an important impact in the implementation of biorefineries. First, oxidative dehydrogenation of ethanol to acetaldehyde generates an aldehyde-containing stream active for the production of C4 aldehydes via base-catalyzed aldol-condensation. Then, the resulting C4 adduct is selectively converted into crotonic acid via catalytic aerobic oxidation (62 % yield). Using a sequential epoxidation and hydrogenation of crotonic acid leads to 29 % yield of ß-hydroxy acid (3-hydroxybutanoic acid). By controlling the pH of the reaction media, it is possible to hydrolyze the oxirane moiety leading to 21 % yield of α,ß-dihydroxy acid (2,3-dihydroxybutanoic acid). Crotonic acid, 3-hydroxybutanoic acid, and 2,3-dihydroxybutanoic acid are archetypal specialty chemicals used in the synthesis of polyvinyl-co-unsaturated acids resins, pharmaceutics, and bio-degradable/ -compatible polymers, respectively.

Leveraging Green Ammonia for Resilient and Cost-Competitive Islanded Electricity Generation from Hybrid Solar Photovoltaic-Wind Farms: A Case Study in South Africa.

Hybrid solar photovoltaic (PV) and wind generation in combination with green ammonia as a seasonal energy storage vector offers an excellent opportunity to decrease the levelized cost of electricity (LCOE). In this work, an analysis is performed to find the most cost-effective configuration of power-to-ammonia-to-power (P2A2P). In P2A2P, wind and solar resources are combined with energy storage to design a resilient electricity grid. For daily generation, batteries are utilized for energy storage, whereas ammonia is employed to cope with seasonal fluctuations. The costs of energy storage capacity have a significant influence on the LCOE. Therefore, this work studies the effect of solar/wind hybrid generation systems and energy storage capacity on the LCOE. A base case of the region of De Aar in South Africa was selected because this inland location has excellent wind and solar resources. The optimized battolyzer and Haber-Bosch design capacity led to an overall load factor of 20-30%. At a 30% load factor, a hybrid system with 37% wind-based and 63% solar-based energy generation capacity was the most cost-effective configuration, resulting in a LCOE of 0.15 USD/kWh at a 5% annual discount rate. In an optimistic scenario for PV costs, the LCOE achieved is essentially unaltered (0.14 USD/kWh), while the contribution of wind and PV changes to 25 and 75%, respectively. This analysis indicates that appropriate designing of hybrid energy solutions will play a key role in determining the final energy storage capacities needed to reduce the LCOE. While these costs for LCOE are above those reported for coal-powered electricity in South Africa (e.g., 0.072 USD/kWh for businesses and 0.151 USD/kWh for households), a carbon tax of 50 USD/ton of CO2 can increase these costs to 0.102 and 0.191 USD/kWh, rendering a more promising outlook for the P2A2P concept.

Hydrophobic zeolites for biofuel upgrading reactions at the liquid-liquid interface in water/oil emulsions.

HY zeolites hydrophobized by functionalization with organosilanes are much more stable in hot liquid water than the corresponding untreated zeolites. Silylation of the zeolite increases hydrophobicity without significantly reducing the density of acid sites. This hydrophobization with organosilanes makes the zeolites able to stabilize water/oil emulsions and catalyze reactions of importance in biofuel upgrading, i.e., alcohol dehydration and alkylation of m-cresol and 2-propanol in the liquid phase, at high temperatures. While at 200 °C the crystalline structure of an untreated HY zeolite collapses in a few hours in contact with a liquid medium, the functionalized hydrophobic zeolites keep their structure practically unaltered. Detailed XRD, SEM, HRTEM, and BET analyses indicate that even after reaction under severe conditions, the hydrophobic zeolites retain their crystallinity, surface area, microporosity, and acid density. It is proposed that by preferentially anchoring hydrophobic functionalities on the external surface, the direct contact of bulk liquid water and the zeolite is hindered, thus preventing the collapse of the framework during the reaction in liquid hot water.

Cavitation intensifying bags improve ultrasonic advanced oxidation with Pd/Al2O3 catalyst.

Advanced oxidation processes can potentially eliminate organic contaminants from industrial waste streams as well as persistent pharmaceutical components in drinking water. We explore for the first time the utilization of Cavitation Intensifying Bags (CIB) in combination with Pd/Al2O3 catalyst as possible advanced oxidation technology for wastewater streams, oxidizing terephthalic acid (TA) to 2-hydroxyterephthalic acid (HTA). The detailed characterization of this novel reaction system reveals that, during sonication, the presence of surface pits of the CIB improves the reproducibility and thus the control of the sonication process, when compared to oxidation in non-pitted bags. Detailed reaction kinetics shows that in the CIB reactor the reaction order to TA is zero, which is attributed to the large excess of TA in the system. The rate of HTA formation increased ten-fold from ~0.01 µM*min-1 during sonication in the CIB, to ~0.10 µM*min-1 for CIB in the presence of the Pd/Al2O3 catalyst. This enhancement was ascribed to a combination of improved mass transport, the creation of thermal gradients, and Pd/Al2O3 catalyst near the cavitating bubbles. Further analysis of the kinetics of HTA formation on Pd/Al2O3 indicated that initially the reaction underwent through an induction period of 20 min, where the HTA concentration was ~0.3 µM. After this, the reaction rate increased reaching HTA concentrations ~6 µM after 40 min. This behavior resembled that observed during oxidation of hydrocarbons on metal catalysts, where the slow rate formation of hydroperoxides on the metal surface is followed by rapid product formation upon reaching a critical concentration. Finally, a global analysis using the Intensification Factor (IF) reveals that CIB in combination with the Pd/Al2O3 catalyst is a desirable option for the oxidation of TA when considering increased oxidation rates and costs.

Catalytic Performance of Ni/CeO2/X-ZrO2 (X = Ca, Y) Catalysts in the Aqueous-Phase Reforming of Methanol.

In this study, we reported on the effect of promoting Ni/ZrO2 catalysts with Ce, Ca (two different loadings), and Y for the aqueous-phase reforming (APR) of methanol. We mainly focused on the effect of the redox properties of ceria and the basicity provided by calcium or yttrium on the activity and selectivity of Ni in this reaction. A systematic characterization of the catalysts was performed using complementary methods such as XRD, XPS, TPR, CO2-TPD, H2 chemisorption, HAADF-STEM, and EDS-STEM. Our results reveal that the improvement in reducibility derived from the incorporation of Ce did not have a positive impact on catalytic behaviour thus contrasting with the results reported in the literature for other Ce-based catalytic compositions. On the contrary, the available Ni-metallic surface and the presence of weak basic sites derived from Ca incorporation seem to play a major role on the catalytic performance for APR of methanol. The best performance was found for a Ce-free catalyst with a molar Ca content of 4%.

Interplay of Support Chemistry and Reaction Conditions on Copper Catalyzed Methanol Steam Reforming.

A series of Cu catalysts supported on SiO2, Al2O3-SiO2, TiO2 rutile, and Cu/TiO2 anatase metal oxides has been studied for methanol reforming in the vapor phase. The highest activity was obtained on Cu/SiO2 catalysts (5493 µmol H2 min-1·gcat -1) followed by Cu/TiO2 rutile, Cu/Al2O3-SiO2, and anatase. XRD and HRTEM characterization after reaction revealed that on Cu/SiO2 significant sintering occurred during reaction. In contrast, the particle size growth on Cu/TiO2 rutile and anatase was less pronounced, which could be associated with the interaction between Cu clusters and TiO2. Characterization by TGA showed that on Cu/Al2O3-SiO2 the main cause of deactivation was coke deposition.

Synthesis of C4 and C8 Chemicals from Ethanol on MgO-Incorporated Faujasite Catalysts with Balanced Confinement Effects and Basicity.

A new type of catalyst has been designed to adjust the basicity and level of molecular confinement of KNaX faujasites by controlled incorporation of Mg through ion exchange and precipitation of extraframework MgO clusters at varying loadings. The catalytic performance of these catalysts was compared in the conversion of C2 and C4 aldehydes to value-added products. The product distribution depends on both the level of acetaldehyde conversion and the fraction of magnesium as extraframework species. These species form rather uniform and highly dispersed nanostructures that resemble nanopetals. Specifically, the sample containing Mg only in the form of exchangeable Mg(2+) ions has much lower activity than those in which a significant fraction of Mg exists as extraframework MgO. Both the (C6+C8)/C4 and C8/C6 ratios increase with additional extraframework Mg at high acetaldehyde conversion levels. These differences in product distribution can be attributed to 1) higher basicity density on the samples with extraframework species, and 2) enhanced confinement inside the zeolite cages in the presence of these species. Additionally, the formation of linear or aromatic C8 aldehyde compounds depends on the position on the crotonaldehyde molecule from which abstraction of a proton occurs. In addition, catalysts with different confinement effects result in different C8 products.

Nanostructured carbon-metal oxide hybrids as amphiphilic emulsion catalysts.

Nanohybrids composed of "onion-like" carbon, single-walled (SWCNTs) or multi-walled carbon nanotubes (MWCNTs) fused to silica or alumina particles have been compared as stabilizers of water/oil emulsions and interfacial catalysts. The amphiphilic character of these nanohybrids makes them effective in stabilizing emulsions (up to 85 % of total volume) comprising of small droplets (less than 40 µm). Furthermore, these nanohybrids have been used as supports for transition metal particles (palladium and copper) to catalyze reactions at the water/oil interface. Three different reaction systems have been conducted in the emulsions to demonstrate the principle: 1) hydrogenation of phenanthrene; 2) hydrogenation of glutaraldehyde and benzaldehyde; 3) oxidation of tetralin. Comparison of the maximum conversions achieved in emulsions as opposed to the single phase, together with much better control of selectivity in the two-phase system shows the benefits of using these nanohybrid catalysts.

Solid nanoparticles that catalyze biofuel upgrade reactions at the water/oil interface.

A recoverable catalyst that simultaneously stabilizes emulsions would be highly advantageous in streamlining processes such as biomass refining, in which the immiscibility and thermal instability of crude products greatly complicates purification procedures. Here, we report a family of solid catalysts that can stabilize water-oil emulsions and catalyze reactions at the liquid/liquid interface. By depositing palladium onto carbon nanotube-inorganic oxide hybrid nanoparticles, we demonstrate biphasic hydrodeoxygenation and condensation catalysis in three substrate classes of interest in biomass refining. Microscopic characterization of the emulsions supports localization of the hybrid particles at the interface.