Catalytic transformation of renewables (Olefin, bio‐sourced, et al.)

The objective of this Special Issue is to provide new diverse contributions that can demonstrate recent applications in biomass transformation using heterogeneous catalysts. In recent decades, a wide variety of biomass-derived chemicals have emerged as key platform chemicals for the production of fine chemicals and liquid fuels using heterogeneous catalysts as the preferred option for most of the developed and proposed catalytic processes. A range of heterogeneous catalysts have been evaluated for effective biomass conversion, such as supported metal nanoparticles, mixed metal oxides and zeolites, where the control of particle size, porosity, acid-basic and redox properties is crucial for providing active, stable and selective heterogeneous catalysts. Moreover, the crucial role of the solvent, choice of reactor design and final chemical processes for controlling activity, selectivity and deactivation phenomena has been demonstrate

Ti/Zr/O Mixed Oxides for the Catalytic Transfer Hydrogenation of Furfural to GVL in a Liquid-Phase Continuous-Flow Reactor

This work aims to develop an efficient catalyst for the cascade reaction from furfural to y-valerolactone in a liquid-phase continuous reactor. This process requires both Lewis and Brønsted acidity; hence, a bifunctional catalyst is necessary to complete the one-pot reaction. Ti/Zr/O mixed oxide-based catalysts were chosen to this end as balancing metal oxide composition allows the acidity characteristics of the overall material to be modulated. Oxides with different compositions were then synthesized using the co-precipitation method. After characterization via porosimetry and NH3-TPD, the catalyst with equimolar quantities of the two components was demonstrated to be the best one in terms of superficial area (279 m2/g) and acid site density (0.67 mmol/g). The synthesized materials were then tested using a plug flow reactor at 180 C, with a 10 min contact time. Ti/Zr/O (1:1) was demonstrated to be the most promising catalyst during the recycling tests as it allowed obtaining the highest selectivities in the desired products (about 45% in furfuryl isopropyl ether and 20% in y-valerolactone) contemporaneously with 100% furfural conversion

Effect of dietary antioxidant supplementation on rabbit performance, meat quality and oxidative stability of muscles

[EN] The aim of this study was to cast light on the effects of EconomasE™ (EcoE), a patented pre-mixture of nutritional additives consisting mainly of organic selenium (0.15 or 0.30 mg/kg feed; Se) combined with vitamin C (5 and 10 mg/kg feed; VC), compared to DL-α-tocopherol acetate (100 or 200 mg/kg feed; VE) dietary supplementation on rabbit performance and meat quality. In fact, the role of Se supplementation in the rabbit diet has not yet been elucidated in the literature and, more specifically, there are no studies on the possible synergistic action between organic Se compared with VE on lipids, fatty acids (FA) and the oxidative stability of two glycolytic muscles, longissimus lumborum (LL) and biceps femoris (BF). Two hundred and seventy New Zealand White rabbits were divided into five dietary groups of 54 rabbits each: 1) control (basal diet = BD; CTRL); 2) VE100 (BD + VE100 mg/kg); 3) VE200 (BD + VE200 mg/kg); 4) EcoE100 (BD + EcoE100 mg/kg); and 5) EcoE200 (BD + EcoE200 mg/kg). Neither of the antioxidant treatments affected growth performance, carcass traits or meat characteristics. Lipid and fatty acid contents were similar in LL and BF and not influenced by the dietary treatment. Meat oxidative stability was strongly improved by both antioxidants. These findings indicate that both EcoE and VE greatly improved the oxidative stability of LL and BF muscles at the dosage rates which, from an economic point of view, would normally be included in the formulation of feeds for rabbits.This study is part of a multidisciplinary research project funded by the Department of Veterinary Medical Science (University of Bologna, Italy). 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A fixed-time second order sliding mode observer for a class of nonlinear systems

This paper presents a second order fixed time sliding mode observer based on an extension of the super-twisting algorithm. This observer can be applied to a class of nonlinear system with a block-wise representation. The block structure provides a straightforward form to the application of the proposed second order sliding mode algorithm, yielding to finite-time convergence with a settling time independent to the system initial conditions. Finally, as numerical simulation example, the case of a linear induction motor is studied, exposing the efficiency and feasibility of the proposal

Aquivion® PFSA-based spray-freeze dried composite materials with SiO2 and TiO2 as hybrid catalysts for the gas phase dehydration of ethanol to ethylene in mild conditions

Aquivion PFSA resin, a perfluorinated ion-exchange polymer, has been used as a heterogeneous strong acid catalyst for a range of reactions; however, the activity of this material is limited due to the extremely low surface area of the polymer. In this paper we described the one-step synthesis of Aquivion® PFSA-based hybrid materials using heterocoagulation and spray-freeze-drying of sols containing the precursor of the active phases. The intimated encapsulation of different nano-oxides, such as TiO2 and SiO2 in the superacid resin matrix was easily obtained using this technique and compared with similar catalysts prepared by the impregnation conventional route. The approach led to the preparation of porous micro-granules characterised by a high homogeneity in the phase distribution and high surface area. The prepared materials were active and selective for the gas phase dehydration of ethanol to ethylene in mild conditions. The increase of the porosity improved the activity of the composites, compared to the pure Aquivion® PFSA, and allowed to reduce the amount of the superacid resin. Moreover, the type of encapsulated oxide, TiO2 or SiO2, modified the improved performance of the catalysts, having TiO2 the higher efficiency for ethanol conversion and selectivity in ethylene at very low temperature

Morphology and mechanics of star copolymer ultrathin films probed by atomic force microscopy in the air and in liquid

Star copolymer films were produced by using spin-coating, drop-casting, and casting deposition techniques, thus obtaining ultrathin and thick films, respectively. The morphology is generally flat, but it becomes substrate-dependent for ultrathin films where the planarization effect of films is not efficient. The indentation hardness of films was investigated by Force Volume Maps in both the air and liquid. In the air, ultrathin films are in the substrate-dominated zone and, thus, the elastic modulus E is overestimated, while E reaches its bulk value for drop-casted ultrathin and thick films. In liquid (water), E follows an exponential decay for all films with a minimum soaked time t0 of 0.37 and 2.65 h for ultrathin and drop-casted ultrathin and thick films, respectively. After this time, E saturates to a value on average 92% smaller than that measured in the air due to film swelling. Such results support the role of film morphology in the antimicrobial activity envisaged in the literature, suggesting also an additional role of film hardness

Superacid resin-based heterogeneous catalysts for the selective acylation of 1,2-methylenedioxybenzene

In this work, we firstly report on the use of highly active and selective Aquivion superacid resins as heterogeneous catalysts for the acylation of 1,2-methylenedioxybenzene (MDB) with propionic anhydride (AP). The reaction was investigated and optimized using solvent-free conditions to selectively produce 3,4-methylenedioxypropiophenone (MDP1P), a key intermediate for the manufacture of active ingredients used in insecticide formulations with a volume of production of roughly 3000 t/y. Interestingly, Aquivion-based catalysts allows to work in mild reaction conditions (i. e. 80 °C), obtaining MDP1P yields as high as 44 % after only 1 h of reaction (selectivity 83 %). A detailed study of the AP reactivity demonstrated its tendency to promote oligomerization reactions that, as confirmed by ex-situ and in-situ FT-ATR analyses, caused the deactivation of the catalyst forming surficial carbonaceous residues. In this context, a fast oxidation of the resin surface organic residues using a diluted HNO3 (or H2O2) solution was proven to be an efficient method to regenerate the catalyst, which can be reused for several reaction cycles. The results obtained in preliminary scale-up tests were basically unaffected by the reaction volume (up to 800 mL), paving the way for possible future applications of the process

Strategies to improve hydrogen activation on gold catalysts

Catalytic reactions involving molecular hydrogen are at the heart of many transformations in the chemical industry. Classically, hydrogenations are carried out on Pd, Pt, Ru or Ni catalysts. However, the use of supported Au catalysts has garnered attention in recent years owing to their exceptional selectivity in hydrogenation reactions. This is despite the limited understanding of the physicochemical aspects of hydrogen activation and reaction on Au surfaces. A rational design of new improved catalysts relies on making better use of the hydrogenating properties of Au. This Review analyses the strategies utilized to improve hydrogen–Au interactions, from addressing the importance of the Au particle size to exploring alternative mechanisms for H2 dissociation on Au cations and Au–ligand interfaces. These insights hold the potential to drive future applications of Au catalysis. (Figure presented.)

AgCu Bimetallic Electrocatalysts for the Reduction of Biomass-Derived Compounds

The electrochemical transformation of biomass-derived compounds (e.g., aldehyde electroreduction to alcohols) is gaining increasing interest due to the sustainability of this process that can be exploited to produce value-added products from biowastes and renewable electricity. In this framework, the electrochemical conversion of 5-hydroxymethylfurfural (HMF) to 2,5-bis(hydroxymethyl)furan (BHMF) is studied. Nanostructured Ag deposited on Cu is an active and selective electrocatalyst for the formation of BHMF in basic media. However, this catalyst deserves further research to elucidate the role of the morphology and size of the coated particles in its performance as well as the actual catalyst surface composition and its stability. Herein, Ag is coated on Cu open-cell foams by electrodeposition and galvanic displacement to generate different catalyst morphologies, deepening on the particle growth mechanism, and the samples are compared with bare Ag and Cu foams. The chemical–physical and electrochemical properties of the as-prepared and spent catalysts are correlated to the electroactivity in the HMF conversion and its selectivity toward the formation of BHMF during electroreduction. AgCu bimetallic nanoparticles or dendrites are formed on electrodeposited and displaced catalysts, respectively, whose surface is Cu-enriched along with electrochemical tests. Both types of bimetallic AgCu particles evidence a superior electroactive surface area as well as an enhanced charge and mass transfer in comparison with the bare Ag and Cu foams. These features together with a synergistic role between Ag and Cu superficial active sites could be related to the twofold enhanced selectivity of the Ag/Cu catalysts for the selective conversion of HMF to BHMF, that is, >80% selectivity and ∼ 100% conversion, and BHMF productivity values (0.206 and 0.280 mmol cm–2 h–1) ca. 1.5–3 times higher than those previously reported

Transition metal b-site substitutions in laalo3 perovskites reorient bio-ethanol conversion reactions

LaAlO3 perovskites, as such and with 25% molar Al substitution by Cu, Co, or Ga, have been prepared by sol-gel methods and tested as heterogeneous catalysts in the gas-phase conversion of ethanol. LaAlO3 presented a significant acidic character, with high formation of ethylene by ethanol dehydration. B-site substitutions increased the basicity of the catalysts, favoring the dehydrogenation of ethanol to acetaldehyde. The most reducible Cu-and Co-substituted materials, characterized by easier formation of surface oxygen vacancies, promoted the self-condensation of acetaldehyde by the Tishchenko mechanism, with formation of acetone and odd-carbon number products. Aldol coupling of acetaldehyde, favored on pure and Ga-substituted LaAlO3, led to the formation of butadiene and hexadiene. The role of Ga insertion, favoring both dehydrogenation of ethylene and dehydration of higher alcohols, corresponds to an amphoteric character. The formation of olefins and diolefins on all catalysts suggests that LaAl-based materials present the most acidic character among La-perovskites