Recyclable Biomimetic Sunflower Pollen-based Photocatalyst for Enhanced Degradation of Pharmaceuticals.

Recent trends in addressing the impending water crisis focus on the development of innovative water treatment methods. This work utilizes pollen as a core template to synthesize highly efficient onion-like photocatalysts for pollutant mineralization. The study showcases a novel electrochemical synthesis method that maintains the structural integrity of pollen, resulting in increased surface area and enhanced photocatalytic activity. After 90-min of visible light irradiation, over 99% mineralization is achieved. These hybrid photocatalysts demonstrate exceptional stability and efficacy in degrading pollutants. The used photocatalysts can be recycled into biopellets with an ash content of less than 7% (weight), moisture content of less than 8% (weight), and a calorific value of ≈22.1 ± 0.3 MJ kg-1. Additionally, the resulting ashes serve as effective peroxymonosulphate activators for pollutant mineralization. This process offers sustainable waste management while minimizing waste production, providing a practical solution for water purification. The efficacy of this approach in pollutant removal is underscored by mineralization rates exceeding 99%.

Validation of a 3D Local-Scale Adaptive Solar Radiation Model by Using Pyranometer Measurements and a High-Resolution Digital Elevation Model.

The result of the multidisciplinary collaboration of researchers from different areas of knowledge to validate a solar radiation model is presented. The MAPsol is a 3D local-scale adaptive solar radiation model that allows us to estimate direct, diffuse, and reflected irradiance for clear sky conditions. The model includes the adaptation of the mesh to complex orography and albedo, and considers the shadows cast by the terrain and buildings. The surface mesh generation is based on surface refinement, smoothing and parameterization techniques and allows the generation of high-quality adapted meshes with a reasonable number of elements. Another key aspect of the paper is the generation of a high-resolution digital elevation model (DEM). This high-resolution DEM is constructed from LiDAR data, and its resolution is two times more accurate than the publicly available DEMs. The validation process uses direct and global solar irradiance data obtained from pyranometers at the University of Salamanca located in an urban area affected by systematic shading from nearby buildings. This work provides an efficient protocol for studying solar resources, with particular emphasis on areas of complex orography and dense buildings where shadows can potentially make solar energy production facilities less efficient.

Electrodeposited Ni-Rich Ni-Pt Mesoporous Nanowires for Selective and Efficient Formic Acid-Assisted Hydrogenation of Levulinic Acid to γ-Valerolactone.

In pursuit of friendlier conditions for the preparation of high-value biochemicals, we developed catalytic synthesis of γ-valerolactone by levulinic acid hydrogenation with formic acid as the hydrogen source. Both levulinic and formic acid are intermediate products in the biomass transformation processes. The objective of the work is twofold: the development of a novel approach for milder synthesis conditions to produce γ-valerolactone and the reduction of the economic cost of the catalyst. Ni-rich Ni-Pt mesoporous nanowires were synthesized in an aqueous medium using a combined hard-soft-template-assisted electrodeposition method, in which porous polycarbonate membranes controlled the shape and the Pluronic P-123 copolymer served as the porogen agent. The electrodeposition conditions selected favored nickel deposition and generated nanowires with nickel percentages above 75 atom %. The increase in deposition potential favored nickel deposition. However, it was detrimental for the porous diameter because the mesoporous structure is promoted by the presence of the platinum-rich micelles near the substrate, which is not favored at more negative potentials. The prepared catalysts promoted the complete transformation to γ-valerolactone in a yield of around 99% and proceeded with the absence of byproducts. The coupling temperature and reaction time were optimized considering the energy cost. The threshold operational temperature was established at 140 °C, at which, 120 min was sufficient for attaining the complete transformation. Working temperatures below 140 °C rendered the reaction completion difficult. The Ni78Pt22 nanowires exhibited excellent reusability, with minimal nickel leaching into the reaction mixture, whereas those with higher nickel contents showed corrosion.

Assessing the Chemical Stability and Cytotoxicity of Electrodeposited Magnetic Mesoporous Fe-Pt Films for Biomedical Applications.

The development of feasible micro/nanoplatforms for various biomedical applications requires holistic research that explores scalable synthesis and design pathways and imposes an interdisciplinary integration of materials science, physical, medical, chemical, and biological knowledge. Thanks to their unique characteristics (i.e., structure, large specific surface areas, tuneability, versatility, and integrity), mesoporous materials have emerged as potential candidates for being part of micro/nanoplatforms for therapeutic, monitoring, and diagnostic applications. In this context, Fe-Pt mesoporous materials are excellent candidates to be part of biomedical micro/nanoplatforms, thanks to their chemical nature, structure, and magnetic properties, which endow them with magnetic locomotion, high cargo capability of therapeutic agents inside the mesoporous cavity, and large surface area for surface functionalization. However, the chemical stability in biological media and cytotoxicity of the Fe-Pt mesoporous material (without considering the effects of architecture and shape) are pivotal elements that determine the suitability of these materials for biomedical applications. This work demonstrates the following: (i) the potential of electrochemical deposition, based on the use of block copolymer micellar solutions as electrochemical media, as an easy, inexpensive, and scalable strategy to synthesize mesoporous Fe-Pt components with tunable chemical composition, porosity, magnetism, and shape (in this case films, but other architectures like nanowires can be easily fabricated using simultaneously hard templates); (ii) the excellent corrosion stability, which is comparable to bulk Au, and minimal chemical dissolution in biological media after 160 h of immersion (∼0.88% of Fe and ∼0.0019% of Pt), which confirms the robustness of Fe-Pt; and (iii) negligible cytotoxicity on HaCaT cells (human immortalized keratinocytes), which reinforces the biocompatibility of Fe-Pt mesoporous structures. Also, the presence of Fe-Pt mesoporous films seems to induce a slight increase in cell viability. These results confirm the biocompatibility of Fe-Pt mesoporous films, making them suitable for biomedical applications.

Cyclobutane-Containing Scaffolds as Useful Intermediates in the Stereoselective Synthesis of Suitable Candidates for Biomedical Purposes: Surfactants, Gelators and Metal Cation Ligands.

Efficient and versatile synthetic methodologies are reported for the preparation of products that are suitable candidates to be used as surfactants, gelators for hydroxylic solvents or metal cation ligands, with potential use in several fields including biomedical applications. The common structural feature of all the synthesized products is the presence of a cis or trans-1,2- or cis-1,3-difunctionalized cyclobutane ring. In the two first cases, the key intermediates including enantiomerically pure 1,3-diamines and 1,3-amino alcohols have been prepared from ß-amino acid derivatives obtained, in turn, from a chiral half-ester. This compound is also precursor of γ-amino esters. Furthermore, two kind of polydentate ligands have also been synthesized from a symmetric 1,5-diamine obtained from norpinic acid, which was easily prepared from commercial verbenone.

Bismuth oxyiodide-based composites for advanced visible-light activation of peroxymonosulfate in pharmaceutical mineralization.

The presence of pharmaceutical pollutants in water bodies represents a significant environmental and public health concern, largely due to their inherent persistence and potential to induce antibiotic resistance. Advanced oxidation processes (AOPs) that employ peroxymonosulfate (PMS) activation have emerged as an effective means of degrading these contaminants. Bismuth oxyiodides (BiOI), which are known for their visible-light photocatalytic properties, demonstrate considerable potential for removal of pharmaceutical pollutants. This study examines the synthesis and performance of BiOI-based composites with barium ferrite (BFO) nanoparticles for enhanced PMS activation under visible light. BiOI and Bi5O7I were synthesized via solvothermal and electrodeposition methods, respectively, and their morphologies and crystalline structures were observed to exhibit distinctive characteristics following annealing. The formation of the composite with BFO resulted in an improvement in the catalytic properties, which in turn enhanced the surface area and availability of active sites. The objective of the photocatalytic studies was to evaluate the degradation and mineralization of tetracycline (TC) under visible light, PMS, and combined conditions. The Bi5O7I(ED)-BFO catalyst was identified as the optimal candidate, achieving up to 99.8% TC degradation and 99.4% mineralization within 90 min at room temperature. The synergistic effect of BFO in BiOI-based composites significantly enhanced performance across all conditions, indicating their potential for efficient remediation of pharmaceutical pollutant. The material's performance was further evaluated in tap water, where the degradation efficiency decreased to 56.4% and mineralization to 38.2%. These results reflect the challenges posed by complex water matrices. However, doubling the PMS concentration to 5 mM led to improved outcomes, with 93.8% degradation and 81.4% mineralization achieved. These findings demonstrate the material's robust potential for treating pharmaceutical pollutants in real-world conditions, advancing sustainable water treatment technologies.

Attuning doped ZnO-based composites for an effective light-driven mineralization of pharmaceuticals via PMS activation.

Water treatment technologies need to go beyond the current control of organic contaminants and ensure access to potable water. However, existing methods are still costly and often inadequate. In this context, novel catalysts that improve the mineralization degree of a wider range of pharmaceuticals through more benign and less consuming methodologies are highly sought after. ZnO, especially when doped, is a well-known semiconductor that also excels in the photocatalytic removal of persistent organic pollutants. In this study, we investigated the effect of doping ZnO nanoparticles with either copper, gallium or indium on the structure, morphology, photophysical properties and photocatalytic mineralization of pharmaceuticals. Their architecture was further improved through the fabrication of composites, pairing the best performing doped ZnO with either BaFe12O19 or nickel nanoparticles. Their suitability was tested on a complex 60-ppm multi-pollutant solution (tetracycline, levofloxacin and lansoprazole). The activation strategy combined photocatalysis with peroxymonosulfate (PMS) as an environmentally friendly source of highly oxidative sulfate radicals. The alliance of doped ZnO and BaFe12O19 was particularly successful, resulting in magnetic microcroquette-shaped composites with excellent inter-component synergy. In fact, indium outperformed the other proposed metal dopants, exceeding 97% mineralization after 1 h and achieving complete elimination after 3 h. All composites excelled in terms of reusability, with no catalytic loss after 10 consecutive cycles and minimal leakage of metal ions, highlighting their applicability in water remediation.

Advanced degradation of organic pollutants using sonophotocatalytic peroxymonosulfate activation with CoFe2O4/Cu- and Ce-doped SnO2 composites.

The rampant upsurge of organic pollutants in aqueous media has become one of the major concerns nowadays. Finding non-specific catalysts that can target a wide range of organic pollutants is a key challenge. Eco-friendly oxidative radicals, such as promoted by peroxymonosulfate (PMS), are necessary for efficient water decontamination. We propose a multicomponent composite catalyst for activating PMS using a dual strategy of sonophotocatalysis. The composite integrates cobalt ferrite and Cu- or Ce-doped SnO2, with the at. % of doping metal and the mixture ratio carefully balanced. The top-performing architectures were able to decompose rhodamine B (20 ppm), a representative pollutant, in under 3 min and achieve over 70% mineralization in just 5 min. The synthesized nanocomposites demonstrated exceptional sonophotocatalytic performance, even when treating complex and diverse multipollutant solutions (80 ppm), achieving over 75% mineralization after 150 min. Considering their high stability and reusability, the proposed CoFe2O4/Cu- and Ce-doped SnO2 materials are among the state-of-the-art heterogeneous catalysts for mineralizing organic pollutants through PMS activation.

Fe/Au galvanic nanocells to generate self-sustained Fenton reactions without additives at neutral pH.

The generation of reactive oxygen species (ROS) via the Fenton reaction has received significant attention for widespread applications. This reaction can be triggered by zero-valent metal nanoparticles by converting externally added H2O2 into hydroxyl radicals (˙OH) in acidic media. To avoid the addition of external additives or energy supply, developing self-sustained catalytic systems enabling onsite production of H2O2 at a neutral pH is crucial. Here, we present novel galvanic nanocells (GNCs) based on metallic Fe/Au bilayers on arrays of nanoporous silica nanostructures for the generation of self-sustained Fenton reactions. These GNCs exploit the large electrochemical potential difference between the Fe and Au layers to enable direct H2O2 production and efficient release of Fe2+ in water at neutral pH, thereby triggering the Fenton reaction. Additionally, the GNCs promote Fe2+/Fe3+ circulation and minimize side reactions that passivate the iron surface to enhance their reactivity. The capability to directly trigger the Fenton reaction in water at pH 7 is demonstrated by the fast degradation and mineralization of organic pollutants, by using tiny amounts of catalyst. The self-generated H2O2 and its transformation into ˙OH in a neutral environment provide a promising route not only in environmental remediation but also to produce therapeutic ROS and address the limitations of Fenton catalytic nanostructures.

Study of Electrical and Dielectric Behaviors of Copper-Doped Zinc Oxide Ceramic Prepared by Spark Plasma Sintering for Electronic Device Applications.

In this study, Cu-doped ZnO aerogel nanoparticles with a 4% copper concentration (Cu4ZO) were synthesized using a sol-gel method, followed by supercritical drying and heat treatment. The subsequent fabrication of Cu4ZO ceramics through Spark Plasma Sintering (SPS) was characterized by X-ray diffraction (XRD), field-emission gun scanning electron microscopy (FE-SEM) equipped with EDS, and impedance spectroscopy (IS) across a frequency range of 100 Hz to 1 MHz and temperatures from 270 K to 370 K. The SPS-Cu4ZO sample exhibited a hexagonal wurtzite structure with an average crystallite size of approximately 229 ± 10 nm, showcasing a compact structure with discernible pores. The EDS spectrum indicates the presence of the base elements zinc and oxygen with copper like the dopant element. Remarkably, the material displayed distinct electrical properties, featuring high activation energy values of about 0.269 ± 0.021 eV. Complex impedance spectroscopy revealed the impact of temperature on electrical relaxation phenomena, with the Nyquist plot indicating semicircular arc patterns associated with grain boundaries. As temperature increased, a noticeable reduction in the radius of these arcs occurred, coupled with a shift in their center points toward the axis center, suggesting a non-Debye-type relaxation mechanism. Dielectric analyses revealed a temperature-driven evolution of losses, emphasizing the material's conductivity impact. Non-Debye-type behavior, linked to ion diffusion, sheds light on charge storage dynamics. These insights advance potential applications in electronic devices and energy storage.

Conductive microemulsions for template CoNi electrodeposition.

Microemulsions have been revealed as feasible templates to grow magnetic nanostructures using an electrodeposition method. Reducing agents are not required and the applied potential has been used as driving force of the nanostructure growth. A systematic study of conductive microemulsion systems to allow the CoNi electrodeposition process has been performed. Different surfactants and organic components have been tested to form microemulsions with a CoNi electrolytic bath as an aqueous component in order to define the microemulsions showing enough conductivity to perform an electrodeposition process from the aqueous component. By using microemulsions of the aqueous electrolyte solution-Triton X-100-diisopropyl adipate system, CoNi electrodeposition has been achieved, the structure of the deposits being dependent on the composition and structure of the microemulsion, which can act as a soft-template to obtain different discontinuous deposits. The magnetic properties of the CoNi deposits vary with their structure.

Enhanced Activation of Peroxymonosulfate for Tetracycline Degradation Using CoNi-Based Electrodeposited Films.

Synthesizing efficient heterogeneous catalysts with multiple active sites able to activate peroxymonosulfate (PMS) for the degradation of persistent organic pollutants continues to be a challenge for societies worldwide. In response, cost-effective, eco-friendly oxidized Ni-rich and Co-rich CoNi micro-nanostructured films were fabricated following a two-step process based on simple electrodeposition using green deep eutectic solvent as an electrochemical media and thermal annealing. The CoNi-based catalysts demonstrated exceptional efficiency in the heterogeneous catalyzed activation of PMS for tetracycline degradation and mineralization. The effects of the catalysts' chemical nature and morphology, the pH, the concentration of PMS, irradiation with visible light, and the duration of contact with the catalysts on the degradation and mineralization of tetracycline were also studied. In dark conditions, oxidized Co-rich CoNi degraded more than 99% of tetracyclines in only 30 min and mineralized more than 99% of them in only 60 min. Moreover, the degradation kinetics doubled from 0.173 min-1 in dark conditions to 0.388 min-1 under visible light irradiation. In addition, the material demonstrated excellent reusability and can be easily recovered with simple heat treatment. Given those findings, our work provides new strategies for constructing high-efficiency and cost-effective PMS catalysts and elucidating the effects of operational parameters and primary reactive species formed by the catalyst-PMS system on water treatment technologies.

Scalable Microfabrication of Multi-Emitter Arrays in Silicon for a Compact Microfluidic Electrospray Propulsion System.

The recent proliferation of SmallSats and their use in increasingly demanding applications require the development of onboard electric propulsion compatible with the power, mass, and volume constraints of these spacecraft. Electrospray propulsion is a promising technology for SmallSats due to its unique high efficiency and scalability across the wide power range of these platforms, for example, from a few watts available in a CubeSat to a few hundred watts in a MiniSat. The implementation of electrospray propulsion requires the use of microfabrication techniques to create compact arrays of thousands of electrospray emitters. This article demonstrates the microfabrication of multi-emitter electrospray sources of a scalable size for electrospray propulsion. In particular, a microfabrication and assembly process is developed and demonstrated by fabricating sources with arrays of 1, 64, and 256 emitters. The electrospray sources are tested in a relevant environment for space propulsion (inside a vacuum chamber), exhibiting excellent propulsive performance (e.g., absence of beam impingement in the extractor electrode, absence of hysteresis in the beam current versus propellant flow rate characteristic, proper operation in the cone-jet electrospraying mode, etc.) and nearly coincident output per emitter. Several design elements contribute to this performance: the even distribution of the propellant among all emitters made possible by the implementation of a network of microfluidic channels in the backside of the emitter array; the small dead volume of the network of microfluidic channels; the accurate alignment between the emitters and extractor orifices; and the use of a pipe-flow configuration to drive the propellant through closed conduits, which protects the propellant.

Utilization of lignocellulosic biomass: A practical journey towards the development of emulsifying agent.

With each passing year, the agriculture and wood processing industries generate increasingly high tonnages of biomass waste, which instead of being burned or left to accumulate should be utilized more sustainably. In parallel, advances in green technology have encouraged large companies and nations to begin using eco-friendly materials, including eco-friendly emulsifiers, which are used in various industries and in bio-based materials. The emulsion-conducive properties of lignocellulosic materials such as cellulose, hemicellulose, and lignin, the building blocks of plant and wood structures, have demonstrated a particular ability to alter the landscape of emulsion technology. Beyond that, the further modification of their structure may improve emulsion stability, which often determines the performance of emulsions. Considering those trends, this review examines the performance of lignocellulosic materials after modification according to their stability, droplet size, and distribution by size, all of which suggest their outstanding potential as materials for emulsifying agents.

Utilizing Biomass-Based Graphene Oxide-Polyaniline-Ag Electrodes in Microbial Fuel Cells to Boost Energy Generation and Heavy Metal Removal.

Although regarded as environmentally stable, bioelectrochemical fuel cells or, microbial fuel cells (MFCs) continue to face challenges with sustaining electron transport. In response, we examined the performance of two graphene composite-based anode electrodes-graphene oxide (GO) and GO-polymer-metal oxide (GO-PANI-Ag)-prepared from biomass and used in MFCs. Over 7 days of operation, GO energy efficiency peaked at 1.022 mW/m2 and GO-PANI-Ag at 2.09 mW/m2. We also tested how well the MFCs could remove heavy metal ions from synthetic wastewater, a secondary application of MFCs that offers considerable benefits. Overall, GO-PANI-Ag had a higher removal rate than GO, with 78.10% removal of Pb(II) and 80.25% removal of Cd(II). Material characterizations, electrochemical testing, and microbial testing conducted to validate the anodes performance confirmed that using new materials as electrodes in MFCs can be an attractive approach to improve the electron transportation. When used with a natural organic substrate (e.g., sugar cane juice), they also present fewer challenges. We also optimized different parameters to confirm the efficiency of the MFCs under various operating conditions. Considering those results, we discuss some lingering challenges and potential possibilities for MFCs.

Enhanced Photocatalytic Removal of Cyanotoxins by Al-Doped ZnO Nanoparticles with Visible-LED Irradiation.

The ZnO-based visible-LED photocatalytic degradation and mineralization of two typical cyanotoxins, microcystin-LR (MC-LR), and anatoxin-A were examined. Al-doped ZnO nanoparticle photocatalysts, in Al:Zn ratios between 0 and 5 at.%, were prepared via sol-gel method and exhaustively characterized by X-ray diffraction, transmission electron microscopy, UV-vis diffuse reflectance spectroscopy, photoluminescence spectroscopy, and nitrogen adsorption-desorption isotherms. With both cyanotoxins, increasing the Al content enhances the degradation kinetics, hence the use of nanoparticles with 5 at.% Al content (A5ZO). The dosage affected both cyanotoxins similarly, and the photocatalytic degradation kinetics improved with photocatalyst concentrations between 0.5 and 1.0 g L-1. Nevertheless, the pH study revealed that the chemical state of a species decisively facilitates the mutual interaction of cyanotoxin and photocatalysts. A5ZO nanoparticles achieved better outcomes than other photocatalysts to date, and after 180 min, the mineralization of anatoxin-A was virtually complete in weak alkaline medium, whereas only 45% of MC-LR was in neutral conditions. Moreover, photocatalyst reusability is clear for anatoxin-A, but it is adversely affected for MC-LR.

Removal of Cyanobacteria and Cyanotoxins in Waters.

Harmful cyanobacterial algal blooms and cyanotoxins currently pose a major threat to global society, one that exceeds local and national interests due to their extremely destructive effects on the environment and human health [...].

Photocatalytic treatment of natural waters. Reality or hype? The case of cyanotoxins remediation.

This review compiles recent advances and challenges in the photocatalytic treatment of natural water by analyzing the remediation of cyanotoxins. The review frames the treatment need based on the occurrence, geographical distribution, and legislation of cyanotoxins in drinking water while highlighting the underestimated global risk of cyanotoxins. Next, the fundamental principles of photocatalytic treatment for remediating cyanotoxins and the complex degradation pathway for the most widespread cyanotoxins are presented. The state-of-the-art and recent advances on photocatalytic treatment processes are critically discussed, especially the modification strategies involving TiO2 and the primary operational conditions that determine the scalability and integration of photocatalytic reactors. The relevance of light sources and light delivery strategies are shown, with emphasis on novel biomimicry materials design. Thereafter, the seldomly-addressed role of water-matrix components is thoroughly and critically explored by including natural organic matter and inorganic species to provide future directions in designing highly efficient strategies and scalable reactors.

Exploring the Potential of Cotton Industry Byproducts in the Plastic Composite Sector: Macro and Micromechanics Study of the Flexural Modulus.

The textile sector produces yearly great quantities of cotton byproducts, and the major part is either incinerated or landfilled, resulting in serious environmental risks. The use of such byproducts in the composite sector presents an attractive opportunity to valorize the residue, reduce its environmental impact, and decrease the pressure on natural and synthetic resources. In this work, composite materials based on polypropylene and dyed cotton byproducts from the textile industry were manufactured. The competitiveness of the resulting composites was evaluated from the analyses, at macro and micro scales, of the flexural modulus. It was observed that the presence of dyes in cotton fibers, also a byproduct from the production of denim items, notably favored the dispersion of the phases in comparison with other cellulose-rich fibers. Further, the presence of a coupling agent, in this case, maleic anhydride grafted polypropylene, enhanced the interfacial adhesion of the composite. As a result, the flexural modulus of the composite at 50 wt.% of cotton fibers enhanced by 272% the modulus of the matrix. From the micromechanics analysis, using the Hirsch model, the intrinsic flexural modulus of cotton fibers was set at 20.9 GPa. Other relevant micromechanics factors were studied to evaluate the contribution and efficiency of the fibers to the flexural modulus of the composite. Overall, the work sheds light on the potential of cotton industry byproducts to contribute to a circular economy.

Xyloglucan coating for enhanced strength and toughness in wood fibre networks.

In recent times, cellulosic materials are witnessing strong interest from both industry and academia for their ability to progress in high-value products with green stamp. Besides the renewability and biodegradability appeal, exceptional properties such as mechanical strength together with toughness are pursued. In the present work, wood fibre networks from eucalyptus Kraft pulp fibres and cellulose nanofibres are combined to produce nanostructured composite networks with outstanding mechanical behaviour. For this purpose, xyloglucan (XG) polymer is adsorbed on cellulose nanofibres (CNF) forming core-shell CNF fibrils in hydrocolloidal suspension which is used to dramatically strengthen wood fibre networks. TEMPO-CNF at two different oxidation levels were coated with XG. The exceptional Young's modulus and tensile strength found for fibre networks with only 10 wt% CNF was attributed to the fibre-fibre bond strength with better homogeneous stress distribution at the micro/nano scale. The production, mechanical characterization and structure analysis of such bionanocomposites is here presented.