Green synthesis of graphene for targeted recovery of silver from photovoltaic waste.

Atmospheric pressure microwave plasma can synthesize freestanding graphene in a few seconds at ambient conditions. Recent research has explored this method for the synthesis of graphene yet constrained by the utilization of toxic or non-renewable resources. This study aimed to substitute environmentally benign and sustainable precursors, synthesizing graphene from expired tangerine peel oil, an abundant natural source globally. The Raman spectrum of synthesized material showed a characteristic graphene-related 2D peak at microwave powers varied between 200 and 1000 W. The images of transmission electron microscopy revealed interstitial spacing of 0.34, which matched the value of X-ray diffraction calculated through Bragg's law. However, marginal variations in lattice spacing owing to the presence of oxygen functional groups were also observed. Additionally, the as-synthesized graphene deposited on a screen-printed electrode was used to selectively recover silver from spent photovoltaics. Our approach of creating a graphene-silver composite directly from waste material offers environmental benefits, resource utilization, waste reduction, and versatile applications in electrochemistry.

Green synthesized Cu-doped CeO2nanoparticles for Congo red dye adsorption and antibacterial action.

The removal of pollutants from water bodies is crucial for the well-being of humanity and is a topic of global research. Researchers have turned their attention to green synthesized nanoparticles for wastewater treatment due to their eco-friendly nature, biocompatibility, and cost-effectiveness. This work demonstrates the efficient removal of organic dye and both gram-positive and gram-negative bacteria from water bodies using copper-doped cerium oxide nanoparticles synthesized withMurraya Koenigiiextract. Characterized via various methods, the 15% copper doped cerium oxide nanoparticles (Cu 15% NPs) exhibited maximum Congo red dye adsorption (98% degradation in 35 min). Kinetic analysis favoured a pseudo-second-order model, indicating the chemical nature of adsorption. Equilibrium adsorption isotherms aligned with the Langmuir model, indicating homogenous monolayer dye adsorption on the doped adsorbent. The maximum uptake of adsorbate,Qmobtained from Langmuir model for Cu 15% NPs was 193 mg g-1. The study also showed enhanced antibacterial activity againstBacillus subtilis, Staphylococcus aureus, Escherichia coliandPseudomonas aeruginosafor Cu-doped ceria, attributed to generation of reactive oxygen species (ROS) induced by the redox cycling between Ce3+and Ce4+. This substantiated that the green synthesized copper doped cerium oxide nanoparticles are potential candidates for adsorptive removal of Congo red dye and as antibacterial agents.

Breakdown of biomass for energy applications using microwave pyrolysis: A technological review.

The agricultural industry faces a permanent increase in waste generation, which is associated with the fast-growing population. Due to the environmental hazards, there is a paramount demand for generating electricity and value-added products from renewable sources. The selection of the conversion method is crucial to develop an eco-friendly, efficient and economically viable energy application. This manuscript investigates the influencing factors that affect the quality and yield of the biochar, bio-oil and biogas during the microwave pyrolysis process, evaluating the biomass nature and diverse combinations of operating conditions. The by-product yield depends on the intrinsic physicochemical properties of biomass. Feedstock with high lignin content is favourable for biochar production, and the breakdown of cellulose and hemicellulose leads to higher syngas formation. Biomass with high volatile matter concentration promotes the generation of bio-oil and biogas. The pyrolysis system's conditions of input power, microwave heating suspector, vacuum, reaction temperature, and the processing chamber geometry were influence factors for optimising the energy recovery. Increased input power and microwave susceptor addition lead to high heating rates, which were beneficial for biogas production, but the excess pyrolysis temperature induce a reduction of bio-oil yield.

Potential of plant secondary metabolite-based polymers to enhance wound healing.

There is a global epidemic of non-healing wounds. Chronic inflammation, overexpression of pro-inflammatory cytokines, oxidative stress and bacterial infection are implicated in delayed wound healing. Natural extracts are a rich source of bioactive molecules called plant secondary metabolites (PSMs) that include terpenes and phenols. These molecules may facilitate wound healing through their antioxidant, anti-inflammatory, and antibacterial activity. After briefly outlining the process of wound healing and how it is compromised in chronic wounds, this review focuses on investigating how PSMs-based polymers may improve wound healing. Best methods for incorporating PSMs into wound dressings are reviewed and critically compared. The exiting body of literature strongly suggests that PSMs-based polymers incorporated into wound dressings could have clinical value in aiding wound healing. STATEMENT OF SIGNIFICANCE: Chronic wounds develop by the persistence of inflammation, oxidative stress and infection. Chronic wounds affect the worldwide population, by reducing quality of life of patients with significant cost to healthcare systems. To help chronic wounds to heal and overcome this burden, materials with anti-inflammatory, antioxidant and antibacterial properties are required. Plant secondary metabolites (PSMs) are volatile materials that have all these properties. PSMs-based polymers can be fabricated by polymerization techniques. The present review provides an overview of the state-of-the-art of the wound healing mechanisms of PSMs. Current developments in the field of PSMs-based polymers are reviewed and their potential use as wound dressings is also covered.

Single-Step Synthesis of Nitrogen-Doped Graphene Oxide from Aniline at Ambient Conditions.

Single-step, single-precursor synthesis of nitrogen-doped graphene oxide (N-GO) was demonstrated in this work. By choosing aniline as the sole source of carbon and nitrogen, N-GO films were fabricated using microwave plasma at a power as low as 80 W in atmospheric conditions. The aniline vapor dissociated under plasma formed islands of N-GO nanosheets on the substrates or walls of the quartz deposition chamber. The interplanar spacing in the pristine N-GO films was observed to be lower than that of GO films, which indicated a lower concentration of oxygen and other species present in the space between the N-GO layers. The as-fabricated N-GO demonstrated superior antiscaling and algicidal properties that are deemed imperative for water purification applications.

Decontamination-Induced Modification of Bioactivity in Essential Oil-Based Plasma Polymer Coatings.

Plasma polymer coatings fabricated from Melaleuca alternifolia essential oil and its derivatives have been previously shown to reduce the extent of microbial adhesion on titanium, polymers, and other implantable materials used in dentistry. Previous studies have shown these coatings to maintain their performance under standard operating conditions; however, when used in e.g., a dental implant, these coatings may inadvertently become subject to in situ cleaning treatments, such as those using an atmospheric pressure plasma jet, a promising tool for the effective in situ removal of biofilms from tissues and implant surfaces. Here, we investigated the effect of such an exposure on the antimicrobial performance of the Melaleuca alternifolia polymer coating. It was found that direct exposure of the polymer coating surface to the jet for periods less than 60 s was sufficient to induce changes in its surface chemistry and topography, affecting its ability to retard subsequent microbial attachment. The exact effect of the jet exposure depended on the chemistry of the polymer coating, the length of plasma treatment, cell type, and incubation conditions. The change in the antimicrobial activity for polymer coatings fabricated at powers of 20-30 W was not statistically significant due to their limited baseline bioactivity. Interestingly, the bioactivity of polymer coatings fabricated at 10 and 15 W against Staphylococcus aureus cells was temporarily improved after the treatment, which could be attributed to the generation of loosely attached bioactive fragments on the treated surface, resulting in an increase in the dose of the bioactive agents being eluted by the surface. Attachment and proliferation of Pseudomonas aeruginosa cells and mixed cultures were less affected by changes in the bioactivity profile of the surface. The sensitivity of the cells to the change imparted by the jet treatment was also found to be dependent on their origin culture, with mature biofilm-derived P. aeruginosa bacterial cells showing a greater ability to colonize the surface when compared to its planktonic broth-grown counterpart. The presence of plasma-generated reactive oxygen and nitrogen species in the culture media was also found to enhance the bioactivity of polymer coatings fabricated at power levels of 10 and 15 W, due to a synergistic effect arising from simultaneous exposure of cells to reactive oxygen and nitrogen species (RONS) and eluted bioactive fragments. These results suggest that it is important to consider the possible implications of inadvertent changes in the properties and performance of plasma polymer coatings as a result of exposure to in situ decontamination, to both prevent suboptimal performance and to exploit possible synergies that may arise for some polymer coating-surface treatment combinations.

Functional nanomaterials, synergisms, and biomimicry for environmentally benign marine antifouling technology.

Marine biofouling remains one of the key challenges for maritime industries, both for seafaring and stationary structures. Currently used biocide-based approaches suffer from significant drawbacks, coming at a significant cost to the environment into which the biocides are released, whereas novel environmentally friendly approaches are often difficult to translate from lab bench to commercial scale. In this article, current biocide-based strategies and their adverse environmental effects are briefly outlined, showing significant gaps that could be addressed through advanced materials engineering. Current research towards the use of natural antifouling products and strategies based on physio-chemical properties is then reviewed, focusing on the recent progress and promising novel developments in the field of environmentally benign marine antifouling technologies based on advanced nanocomposites, synergistic effects and biomimetic approaches are discussed and their benefits and potential drawbacks are compared to existing techniques.

Comparative Study of Natural Terpenoid Precursors in Reactive Plasmas for Thin Film Deposition.

If plasma polymer thin films are to be synthesised from sustainable and natural precursors of chemically heterogeneous composition, it is important to understand the extent to which this composition influences the mechanism of polymerisation. To this end, a well-studied monoterpene alcohol, terpinen-4-ol, has been targeted for a comparative study with the naturally occurring mix of terpenes (viz. Melaleuca alternifolia oil) from which it is commonly distilled. Positive ion mode mass spectra of both terpinen-4-ol and M. alternifolia oil showed a decrease in disparities between the type and abundance of cationic species formed in their respective plasma environments as applied plasma power was increased. Supplementary biological assay revealed the antibacterial action of both terpinen-4-ol and M. alternifolia derived coatings with respect to S. aureus bacteria, whilst cytocompatibility was demonstrated by comparable eukaryotic cell adhesion to both coatings. Elucidating the processes occurring within the reactive plasmas can enhance the economics of plasma polymer deposition by permitting use of the minimum power, time and precursor pre-processing required to control the extent of monomer fragmentation and fabricate a film of the desired thickness and functionality.

Highly conductive anion exchange membranes based on polymer networks containing imidazolium functionalised side chains.

Two novel types of anion exchange membranes (AEMs) having imidazolium-type functionalised nanofibrous substrates were prepared using the facile and potentially scalable method. The membranes' precursors were prepared by graft copolymerization of vinylbenzyl chloride (VBC) onto syndiotactic polypropylene (syn-PP) and polyamide-66 (PA-66) nanofibrous networks followed by crosslinking with 1,8-octanediamine, thermal treatment and subsequent functionalisation of imidazolium groups. The obtained membranes displayed an ion exchange capacity (IEC) close to 1.9 mmol g-1 and ionic (OH-) conductivity as high as 130 mS cm-1 at 80 °C. This was coupled with a reasonable alkaline stability representing more than 70% of their original conductivity under accelerated degradation test in 1 M KOH at 80 °C for 360 h. The effect of ionomer binder on the performance of the membrane electrode assembly (MEA) in AEM fuel cell was evaluated with the optimum membrane. The MEA showed a power density of as high as 440 mW cm-2 at a current density is 910 mA cm-2 with diamine crosslinked quaternized polysulfone (DAPSF) binder at 80 °C with 90% humidified H2 and O2 gases. Such performance was 2.3 folds higher than the corresponding MEA performance with quaternary ammonium polysulfone (QAPS) binder at the same operating conditions. Overall, the newly developed membrane was found to possess not only an excellent combination of physico-chemical properties and a reasonable stability but also to have a facile preparation procedure and cheap ingredients making it a promising candidate for application in AEM fuel cell.

A critical review on silver nanoparticles: From synthesis and applications to its mitigation through low-cost adsorption by biochar.

Silver nanoparticles are one of the most beneficial forms of heavy metals in nanotechnology applications. Due to its exceptional antimicrobial properties, low electrical and thermal resistance, and surface plasmon resonance, silver nanoparticles are used in a wide variety of products, including consumer goods, healthcare, catalysts, electronics, and analytical equipment. As the production and applications of silver nanoparticles containing products increase daily, the environmental pollution due to silver nanoparticles release is increasing and affecting especially the aqueous ecosystem. Silver nanoparticles can kill useful bacteria in soil and water, and bioaccumulate in living organisms even at low concentrations from 10-2 to 10 µg/mL silver can show antibacterial effect. On the other hand, the maximum silver discharge limit into freshwater is 0.1 µg/L and 3.2 µg/L for Australia and the USA, respectively. To reduce its toxic consequences and meet the regulatory guidelines, it is crucial to remove silver nanoparticles from wastewater before it is discharged into other water streams. Several technologies are available to remove silver nanoparticles, but the adsorption process using low-cost adsorbents is a promising alternative to mitigate silver nanoparticle pollution in the bulk stage. As one of the low-cost adsorbents, biochar produced from the biomass waste could be a suitable adsorbent. This review focuses on collating the latest evidence on silver nanoparticle production, applications, environmental consequences, and cost-effective technological approaches for silver removal from wastewater.

Fabrication of Nano-Onion-Structured Graphene Films from Citrus sinensis Extract and Their Wetting and Sensing Characteristics.

Graphene and its derivatives have acquired substantial research attention in recent years because of their wide range of potential applications. Implementing sustainable technologies for fabricating these functional nanomaterials is becoming increasingly apparent, and therefore, a wide spectrum of naturally derived precursors has been identified and reformed through various established techniques for the purpose. Nevertheless, most of these methods could only be considered partially sustainable because of their complexity as well as high energy, time, and resource requirements. Here, we report the fabrication of carbon nano-onion-interspersed vertically oriented multilayer graphene nanosheets through a single-step, environmentally benign radio frequency plasma-enhanced chemical vapor deposition process from a low-cost carbon feedstock, the oil from the peel of Citrus sinensis orange fruits. C. sinensis essential oil is a volatile aroma liquid principally composed of nonsynthetic hydrocarbon limonene. Transmission electron microscopy studies on the structure unveiled the presence of hollow quasi-spherical carbon nano-onion-like structures incorporated within graphene layers. The as-fabricated nano-onion-incorporated graphene films exhibited a highly hydrophobic nature showing a water contact angle of up to 1290. The surface energies of these films were in the range of 41 to 35 mJ·m-2. Moreover, a chemiresistive sensor directly fabricated using C. sinensis-derived onion-structured graphene showed a p-type semiconductor nature and a promising response to acetone at room temperature. With its unique morphology, surface properties, and electrical characteristics, this material is expected to be useful for a wide range of applications.

In-Situ Surface Modification of Terpinen-4-ol Plasma Polymers for Increased Antibacterial Activity.

Surface modification of thin films is often performed to enhance their properties. In this work, in situ modification of Terpinen-4-ol (T4) plasma polymer is carried out via simultaneous surface functionalization and nanoparticle immobilization. Terpinen-4-ol plasma polymers surface were decorated with a layer of ZnO nanoparticles in an oxygen plasma environment immediately after polymer deposition. A combination of hydrophilic modification and ZnO nanoparticle functionalization of the T4 polymer surface led to an enhancement in antibacterial properties by factor of 3 (from 0.75 to 0.25 CFU.mm-2). In addition, ZnO nanoparticle-modified coatings demonstrated improved UV absorbing characteristics in the region of 300-400 nm by 60% relative to unmodified coatings. The ZnO modified coatings were transparent in the visible region of 400-700 nm. The finding points towards the potential use of ZnO nanoparticle-modified T4 plasma polymers as optically transparent UV absorbing coatings.

Electrically Insulating Plasma Polymer/ZnO Composite Films.

In this report, the electrical properties of plasma polymer films functionalized with ZnO nanoparticles were investigated with respect to their potential applications in biomaterials and microelectronics fields. The nanocomposite films were produced using a single-step method that combines simultaneous plasma polymerization of renewable geranium essential oil with thermal decomposition of zinc acetylacetonate Zn(acac)2. The input power used for the deposition of composites were 10 W and 50 W, and the resulting composite structures were abbreviated as Zn/Ge 10 W and Zn/Ge 50 W, respectively. The electrical properties of pristine polymers and Zn/polymer composite films were studied in metal-insulator-metal structures. At a quantity of ZnO of around ~1%, it was found that ZnO had a small influence on the capacitance and dielectric constants of thus-fabricated films. The dielectric constant of films with smaller-sized nanoparticles exhibited the highest value, whereas, with the increase in ZnO particle size, the dielectric constant decreases. The conductivity of the composites was calculated to be in the in the range of 10-14-10-15 Ω-1 m-1, significantly greater than that for the pristine polymer, the latter estimated to be in the range of 10-16-10-17 Ω-1 m-1.

Eco-friendly nanocomposites derived from geranium oil and zinc oxide in one step approach.

Nanocomposites offer attractive and cost-effective thin layers with superior properties for antimicrobial, drug delivery and microelectronic applications. This work reports single-step plasma-enabled synthesis of polymer/zinc nanocomposite thin films via co-deposition of renewable geranium essential oil-derived polymer and zinc nanoparticles produced by thermal decomposition of zinc acetylacetonate. The chemical composition, surfaces characteristics and antimicrobial performance of the designed nanocomposite were systematically investigated. XPS survey proved the presence of ZnO in the matrix of formed polymers at 10 W and 50 W. SEM images verified that the average size of a ZnO nanoparticle slightly increased with an increase in the power of deposition, from approximately 60 nm at 10 W to approximately 80 nm at 50 W. Confocal scanning laser microscopy images showed that viability of S. aureus and E.coli cells significantly reduced on surfaces of ZnO/polymer composites compared to pristine polymers. SEM observations further demonstrated that bacterial cells incubated on Zn/Ge 10 W and Zn/Ge 50 W had deteriorated cell walls, compared to pristine polymers and glass control. The release of ZnO nanoparticles from the composite thin films was confirmed using ICP measurements, and can be further controlled by coating the film with a thin polymeric layer. These eco-friendly nanocomposite films could be employed as encapsulation coatings to protect relevant surfaces of medical devices from microbial adhesion and colonization.

Plant Secondary Metabolite-Derived Polymers: A Potential Approach to Develop Antimicrobial Films.

The persistent issue of bacterial and fungal colonization of artificial implantable materials and the decreasing efficacy of conventional systemic antibiotics used to treat implant-associated infections has led to the development of a wide range of antifouling and antibacterial strategies. This article reviews one such strategy where inherently biologically active renewable resources, i.e., plant secondary metabolites (PSMs) and their naturally occurring combinations (i.e., essential oils) are used for surface functionalization and synthesis of polymer thin films. With a distinct mode of antibacterial activity, broad spectrum of action, and diversity of available chemistries, plant secondary metabolites present an attractive alternative to conventional antibiotics. However, their conversion from liquid to solid phase without a significant loss of activity is not trivial. Using selected examples, this article shows how plasma techniques provide a sufficiently flexible and chemically reactive environment to enable the synthesis of biologically-active polymer coatings from volatile renewable resources.

Retention of Antibacterial Activity in Geranium Plasma Polymer Thin Films.

Bacterial colonisation of biomedical devices demands novel antibacterial coatings. Plasma-enabled treatment is an established technique for selective modification of physicochemical characteristics of the surface and deposition of polymer thin films. We investigated the retention of inherent antibacterial activity in geranium based plasma polymer thin films. Attachment and biofilm formation by Staphylococcus aureus, Pseudomonas aeruginosa, and Escherichia coli was significantly reduced on the surfaces of samples fabricated at 10 W radio frequency (RF) power, compared to that of control or films fabricated at higher input power. This was attributed to lower contact angle and retention of original chemical functionality in the polymer films fabricated under low input power conditions. The topography of all surfaces was uniform and smooth, with surface roughness of 0.18 and 0.69 nm for films fabricated at 10 W and 100 W, respectively. Hardness and elastic modules of films increased with input power. Independent of input power, films were optically transparent within the visible wavelength range, with the main absorption at ~290 nm and optical band gap of ~3.6 eV. These results suggest that geranium extract-derived polymers may potentially be used as antibacterial coatings for contact lenses.

Review on the Antimicrobial Properties of Carbon Nanostructures.

Swift developments in nanotechnology have prominently encouraged innovative discoveries across many fields. Carbon-based nanomaterials have emerged as promising platforms for a broad range of applications due to their unique mechanical, electronic, and biological properties. Carbon nanostructures (CNSs) such as fullerene, carbon nanotubes (CNTs), graphene and diamond-like carbon (DLC) have been demonstrated to have potent broad-spectrum antibacterial activities toward pathogens. In order to ensure the safe and effective integration of these structures as antibacterial agents into biomaterials, the specific mechanisms that govern the antibacterial activity of CNSs need to be understood, yet it is challenging to decouple individual and synergistic contributions of physical, chemical and electrical effects of CNSs on cells. In this article, recent progress in this area is reviewed, with a focus on the interaction between different families of carbon nanostructures and microorganisms to evaluate their bactericidal performance.

Silver removal from aqueous solution by biochar produced from biosolids via microwave pyrolysis.

The contamination of water with silver has increased due to the widespread applications of products with silver employed as antimicrobial agent. Adsorption is a cost-effective method for silver removal from aqueous solution. In this study biochar, produced from the microwave assisted pyrolysis of biosolids, was used for silver removal from an aqueous solution. The adsorption kinetics, isotherms and thermodynamics were investigated to better understand the silver removal process by biochar. X-ray diffraction results demonstrated that silver removal was a combination two consecutive mechanisms, reduction and physical adsorption. The Langmuir model fitted the experimental data well, showing that silver removal was predominantly a surface mechanism. The thermodynamic investigation demonstrated that silver removal by biochar was an exothermic process. The final nanocomposite Ag-biochar (biochar plus silver) was used for methylene blue adsorption and photodegradation. This study showed the potential of using biochar produced from biosolids for silver removal as a promising solution to mitigate water pollution and an environmentally sustainable approach for biosolids management and re-use.

Photostability of plasma polymerized γ-terpinene thin films for encapsulation of OPV.

Optically transparent, smooth, defect-free, chemically inert and with good adhesion to a variety of substrates, plasma polymers from plant-derived secondary metabolites have been identified as promising encapsulating materials for organic electronics and photovoltaics. Here, we demonstrate that an encapsulating layer of plasma polymerized γ-terpinene reduces degradation-related loss in conversion efficiency in PCPDTBT:PC70BM solar cells under ambient operating conditions. The stability of γ-terpinene films was then investigated under extreme UV irradiation conditions as a function of deposition power. When exposed to ambient air, prolonged exposure to UV-A and UV-B light led to notable ageing of the polymer. Photooxidation was identified as the main mechanism of degradation, confirmed by significantly slower ageing when oxygen was restricted through the use of a quartz cover. Under unnatural high-energy UV-C irradiation, significant photochemical degradation and oxidation occurred even in an oxygen-poor environment.

Effects of Iodine Doping on Optoelectronic and Chemical Properties of Polyterpenol Thin Films.

Owing to their amorphous, highly cross-liked nature, most plasma polymers display dielectric properties. This study investigates iodine doping as the means to tune optoelectronic properties of plasma polymer derived from a low-cost, renewable resource, i.e., Melaleuca alternifolia oil. In situ exposure of polyterpenol to vapors of electron-accepting dopant reduced the optical band gap to 1.5 eV and increased the conductivity from 5.05 × 10-8 S/cm to 1.20 × 10-6 S/cm. The increased conductivity may, in part, be attributed to the formation of charge-transfer complexes between the polymer chain and halogen, which act as a cation and anion, respectively. Higher levels of doping notably increased the refractive index, from 1.54 to 1.70 (at 500 nm), and significantly reduced the transparency of films.