Electrochemical water splitting is one of the most promising approaches for sustainable energy conversion and storage toward a future hydrogen society. This demands durable and affordable ...electrocatalysts for the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER). In this study, we report the preparation of uniform Ni-P-O, Ni-S-O, and Ni-S-P-O electrocatalytic films on nickel foam (NF) substrates
via
flow cell-assisted electrodeposition. Remarkably, electrodeposition onto 12 cm
2
substrates was optimized by strategically varying critical parameters. The high quality and reproducibility of the materials is attributed to the use of a 3D-printed flow cell with a tailored design. Then, the as-fabricated electrodes were tested for overall water splitting in the same flow cell under alkaline conditions. The best-performing sample, NiSP/NF, required relatively low overpotentials of 93 mV for the HER and 259 mV for the OER to produce a current density of 10 mA cm
−2
. Importantly, the electrodeposited films underwent oxidation into amorphous nickel (oxy)hydroxides and oxidized S and P species, improving both HER and OER performance. The superior electrocatalytic performance of the Ni-S-P-O films originates from the unique reconstruction process during the HER/OER. Furthermore, the overall water splitting test using the NiSP/NF couple required a low cell voltage of only 1.85 V to deliver a current density of 100 mA cm
−2
. Overall, we demonstrate that high-quality electrocatalysts can be obtained using a simple and reproducible electrodeposition method in a robust 3D-printed flow cell.
A reproducible and efficient electrodeposition method in a 3D-printed flow cell is used to synthesize high-quality Ni-S-P-O films on nickel foam for overall water splitting.
Lactose is commonly crystallized in the presence of whey proteins, forming co-crystals of lactose and proteins. This work hypothesized that flavonoids such as rutin or epigallocatechin-3-gallate ...(EGCG) could be incorporated into the lactose and protein co-crystal structure since flavonoids may interact with both lactose and proteins. The interactions between whey proteins and flavonoids were first studied. Then, lactose–protein solutions were crystallized with and without flavonoids, measuring the kinetic parameters of crystallization and characterizing the resulting crystals. The incorporation of flavonoids in lactose–protein co-crystals depended on the hydrophilic nature of flavonoids. The hydrophilic EGCG was scarcely enclosed in the crystal lattice of lactose and avoided the inclusion of whey proteins in the crystals. In contrast, the less water-soluble rutin interacted with whey proteins and lactose, leading to the formation of co-crystals containing lactose, protein, and a large concentration of rutin (3.468 ± 0.392 mg per 100 mg of crystals).
The study evaluated the spatial and seasonal variations of microplastic abundances in water, sediments, and commercial fishes of a semi-urban tourist impacted estuary in the Gulf of Mexico, Mexico. ...The prevalence of microplastics (MPs) elucidated diffuse sources namely long-range transport, domestic, agricultural, fishing, industrial and recreational activities and the local climatic conditions. Seasonally, the mean abundances of MPs in both water and sediments were high during Nortes (strong winds) followed by the dry and rainy seasons. Overall, black and blue colored MPs dominated the region and all the recovered plastics were fibers. The commercial fishes (n = 187) contained 881 MPs in their gastrointestinal tracts, suggesting that the food web of the estuary is highly prone to microplastic contamination. SEM images of extracted plastic fibers presented surface morphologies that are impacted by physical strains. Further, the elemental characterization of fibers using EDX displayed significant peaks of Al, As, Cl, Cr, Cu, Pb, and Zn that were used as additives during the production of plastics. The main types of polymers included low-density polyethylene, polyester, polypropylene, polycarbonate, rayon, polyvinyl chloride, polyacrylonitrile, polyamide, nylon and polyethylene terephthalate. MP abundances demonstrated in this study elucidate that estuaries are a major conduit for land-derived plastics to the ocean and the results will aid in implementing remedial/clean up actions of the estuary for better conservation of the ecosystem.
Display omitted
•Seasonal differences of MP accumulation were studied in a semi-urban estuary.•Strong winds are considered to be the major force on MP abundances.•Primary use of plastic materials by tourists are observed based on the type and morphological characters of MPs.•Presence of nearly 881 MPs in 187 commercial fish samples suggest potential risks to human health.
The electrochemical oxidation of sulfite ions offers encouraging advantages for large-scale hydrogen production, while sulfur dioxide emissions can be effectively used to obtain value-added ...byproducts. Herein, the performance and stability during sulfite electrolysis under alkaline conditions are evaluated. Nickel foam (NF) substrates were functionalized as the anode and cathode through electrochemical deposition of palladium and chemical oxidation to carry out the sulfite electro-oxidation and hydrogen evolution reactions, respectively. A combined analytical approach in which a robust electrochemical flow cell was coupled to different in situ and ex situ measurements was successfully implemented to monitor the activity and stability during electrolysis. Overall, satisfactory sulfite conversion and hydrogen production efficiencies (>90%) at 10 mA·cm–2 were mainly attributed to the use of NF in three-dimensional electrodes with a large surface area and enhanced mass transfer. Furthermore, stabilization processes associated with electrochemical dissolution and sulfur crossover through the membrane induced specific changes in the chemical and physical properties of the electrodes after electrolysis. This study demonstrates that NF-based electrocatalysts can be incorporated in an efficient electrochemical flow cell system for sulfite electrolysis and hydrogen production, with potential applications at a large scale.
A series of pyrene-fullerene C60 dyads bearing pyrene units (PyFC12, PyFPy, Py2FC12 and PyFN) were synthesized and characterized. Their optical properties were studied by absorption and fluorescence ...spectroscopies. Dyads were designed in this way because the pyrene moeities act as light-harvesting molecules and are able to produce "monomer" (PyFC12) or excimer emission (PyFPy, Py2FC12 and PyFN). The fluorescence spectra of the dyads exhibited a significant decrease in the amount of pyrene monomer and excimer emission, without the appearance of a new emission band due to fullerene C60. The pyrene fluorescence quenching was found to be almost quantitative, ranging between 96%-99% depending on the construct, which is an indication that energy transfer occurred from one of the excited pyrene species to the fullerene C60.
Display omitted
•Carrageenans decreased the time to reach the mutarotation equilibrium of lactose.•At mutarotation equilibrium, β-lactose isomer decreased by carrageenans presence.•The solubility of ...lactose decreased by carrageenans addition.•Carrageenans incorporation shrank the metastable zone (MZ) of lactose.
It has been reported that polysaccharides like carrageenan can change the crystallization of lactose. However, it is still unclear whether changes in lactose mutarotation, solubility, and super-solubility are involved in carrageenans' effect on lactose crystallization. It has been established that the conversion of α- to β-lactose forms (mutarotation) in an aqueous solution has a significant impact on lactose crystallization. Similarly, lactose solubility changes lead to changes in the metastable zone (MZ), a region between the solubility and super-solubility of lactose. The width of this MZ determines the temperature drop necessary to induce lactose nucleation. This work aimed to study the effect of carrageenans on lactose mutarotation and solubility. For this purpose, lactose solutions were added with ι and κ- carrageenan at two concentrations: 50 and 100 mg L−1. Optical rotation measurements estimated the proportion of β/α isomers in lactose solutions. Besides, solubility and super- solubility was determined to build the MZ. The presence of carrageenans changed both the time to reach the mutarotation balance and the proportion of β/α isomers at mutarotation equilibrium. Carrageenans decreased the solubility of lactose in a range of temperatures between 10 and 60 °C and reduced the metastable zone width (MZW).
Lactose is recovered by crystallization from cheese whey that is a by-product of cheesemaking. The whey used for the recovery of lactose usually has a residual content of protein that alters the ...crystallization of lactose. In addition, the pH of whey may fluctuate depending on the cheese variety. However, there is little information on how the pH modifies the effect that whey proteins have on lactose crystallization. Accordingly, this work aimed to evaluate the individual and combined effect of whey proteins and pH on the kinetics of crystallization, the crystal size distribution and the crystallinity of lactose. The addition of whey proteins in lactose solutions (25% v/v) modified the process of lactose crystallization. However, the effect that whey proteins had on lactose crystallization heavily depended on the pH. The number of crystals per milliliter as well as the growth and size distribution of crystals was the most affected with the changes in pH (pHs of 7, 5.5 and 4) and the addition of whey proteins (0 and 0.63%). All the treatment produced mostly α-lactose monohydrated but some treatments also generated crystals of β-lactose (pH 5.5, 0% of proteins). Amorphous lactose was observed mainly in lactose solutions adjusted at pH 7 and added with whey proteins. This particular treatment also incorporated the highest amount of protein into the lattice of lactose crystals. The results of this work highlight the importance of controlling the pH of lactose crystallization, especially if there is a presence of whey proteins.
Display omitted
•The pH modifies the effect that whey proteins have on lactose crystallization.•Whey proteins act as nuclei promoting the primary heterogeneous nucleation of lactose.•The size distribution of lactose crystals is narrowed by whey proteins mainly at pH 7.•Whey proteins contribute to the formation of amorphous lactose at pHs of 5.5 and 7.•At pH 5.5 in the absence of proteins is enhanced the formation of β-lactose.
Ketoprofen is a commercially available drug sold as a racemic mixture that belongs to the family of non-steroidal anti-inflammatory drugs known as profens. It has been demonstrated (in vitro) that ...(S)-ketoprofen is around 160 times more potent than its enantiomer (R)-ketoprofen, while accumulation of (R)-ketoprofen can cause serious side effects, such as dyspepsia, gastrointestinal ulceration/bleeding, pain, salt and fluid retention, and hypertension. In this work, four commercially available lipases were systematically assessed. Parameters such as conversion, enantiomeric excess, and enantioselectivity were considered. Among them, and by evaluating lipase load, temperature, solvent, and alcohol, Candida rugosa lipase exhibited the best results in terms of enantioselectivity E = 185 ((S)-enantiopreference) with esterification conversions of c = 47% (out of 50%) and enantiomeric excess of 99%. The unreacted (R)-enantiomer was recovered by liquid-liquid extraction and racemized under basic media, which was recycled as starting material. Finally, the (S)-alkyl ketoprofen ester was successfully enzymatically hydrolyzed to the desired (S)-ketoprofen with c = 98.5% and 99% ee. This work demonstrated the benefit and efficiency of using Candida rugosa lipase to kinetically resolve racemic ketoprofen by an environmentally friendly protocol and with the recycling of the undesired (R)-ketoprofen.
Palladium-based electrocatalysts are widely used in alkaline direct alcohol fuel cells. The synthesis and characterization of carbon-supported bimetallic nanoparticles (NP) of AuPd and AgPd is ...described using pecan nutshell extract (Carya illinoinensis) which serves as both, reducing and the stabilizing agent. This environmentally friendly route generates bimetallic NP for a wide range of applications, including electrocatalysis; since particularly AuPd NP proved to be a potentially suitable electrode material for alkaline direct methanol fuel cells. The electrocatalytic activity of these nanomaterials was comparable to commercially available Pd/C 1% in the electro-oxidation of methanol in alkaline media.
•Pd-based nanoparticles using pecan nutshell extract (Carya illinoinensis) as reducing and stabilizing agent were synthesized.•Green AuPd/C exhibited electrocatalytic activity to promote methanol oxidation in alkaline media.•Direct assessment of electrocatalytic activity in sols of nanoparticles using screen-printed electrodes was demonstrated.
Bimetallic carbon-supported nanoparticles, AuPd/C and AgPd/C, are synthesized using aqueous extract of pecan nutshell waste and their electrocatalytic performance compared to commercial Pd/C for electro-oxidation of methanol in alkaline direct fuel cells. Display omitted
Flow devices fabricated by means of 3D-printing offer an economic and effective approach for testing different electrochemical systems at the laboratory scale. Here, the fabrication and optimization ...of a novel filter-press electrochemical reactor is described. 3D-printing is used to obtain critical components of the device as a sustainable and efficient manufacturing approach. Hydrodynamics and mass transfer of different flow distributors, turbulence promoters, and nickel foam, as a three-dimensional (3D) electrode, were evaluated by a convenient set of well-known techniques for filter-press reactor characterization. Furthermore, the chemical stability of 3D-printed materials was assessed in several electrolytes used for common electrochemical applications. Designed configurations and geometries exhibited enhanced turbulence and large mass transfer coefficients, which make them adequate for processes such as electrosynthesis, electrodeposition, and electrochemical water splitting. Ultimately, superior performance was validated for nickel foam, demonstrating robustness of the reactor for realistic evaluation of electrocatalytic materials. Therefore, the proposed electrochemical reactor provides a low-cost and versatile alternative for testing electrochemical systems in a wide range of applications.
PDF
