Green Recycling Methods to Treat Lithium-Ion Batteries E-Waste: A Circular Approach to Sustainability.

E-waste generated from end-of-life spent lithium-ion batteries (LIBs) is increasing at a rapid rate owing to the increasing consumption of these batteries in portable electronics, electric vehicles, and renewable energy storage worldwide. On the one hand, landfilling and incinerating LIBs e-waste poses environmental and safety concerns owing to their constituent materials. On the other hand, scarcity of metal resources used in manufacturing LIBs and potential value creation through the recovery of these metal resources from spent LIBs has triggered increased interest in recycling spent LIBs from e-waste. State of the art recycling of spent LIBs involving pyrometallurgy and hydrometallurgy processes generates considerable unwanted environmental concerns. Hence, alternative innovative approaches toward the green recycling process of spent LIBs are essential to tackle large volumes of spent LIBs in an environmentally friendly way. Such evolving techniques for spent LIBs recycling based on green approaches, including bioleaching, waste for waste approach, and electrodeposition, are discussed here. Furthermore, the ways to regenerate strategic metals post leaching, efficiently reprocess extracted high-value materials, and reuse them in applications including electrode materials for new LIBs. The concept of "circular economy" is highlighted through closed-loop recycling of spent LIBs achieved through green-sustainable approaches.

Activated multi-walled carbon nanotubes decorated with zero valent nickel nanoparticles for arsenic, cadmium and lead adsorption from wastewater in a batch and continuous flow modes.

Nickel nanoparticles (NiNPs) supported on activated multi-walled carbon nanotubes (MWCNTs) were used as an adsorbent applied towards Pb(II), As(V) and Cd(II) remediation from industrial wastewater. The result revealed the hydrophilic surface of MWCNTs-KOH was enhanced with the incorporation of NiNPs enabling higher surface area, functional groups and pore distribution. Comparatively, the removal of Pb(II), As(V) and Cd(II) on the various adsorbents was reported as NiNPs (58.6 ± 4.1, 46.8 ± 3.7 and 40.5 ± 2.5%), MWCNTs-KOH (68.4 ± 5.0, 65.5 ± 4.2 and 50.7 ± 3.4%) and MWCNTs-KOH@NiNPs (91.2 ± 8.7, 88.5 ± 6.5 and 80.6 ± 5.8%). Using MWCNTs-KOH@NiNPs, the maximum adsorption capacities of 481.0, 440.9 and 415.8 mg/g were obtained for Pb(II), As(V) and Cd(II), respectively. The experimental data were best suited to the Langmuir isotherm and pseudo-second order kinetic model. The fitness of experimental data to the kinetic models in a fixed-bed showed better fitness to Thomas model. The mechanism of metal ion adsorption onto MWCNTs-KOH@NiNPs show a proposed electrostatic attraction, surface adsorption, ion exchange, and pore diffusion due to the incorporated NiNPs. The nanocomposite was highly efficient for 8 adsorption cycles. The results of this study indicate that the synthesized nanocomposite is highly active with capacity for extended use in wastewater treatment.

Diagnostics of skin features through 3D skin mapping based on electro-controlled deposition of conducting polymers onto metal-sebum modified surfaces and their possible applications in skin treatment.

Analytical diagnostics of skin features was developed through application of portable and fast skin mapping based on electro-controlled deposition of conducting polymers onto metal-sebum modified surfaces. In this analytical diagnostic technique, the development of skin pattern is based on electropolymerization of conducting polymers within insulating barriers in skin stamp provided by natural sebum to monitor the 3D nature of various skin features. The recorded skin maps reach a µm-level resolution and are proved to be capable of recognition, enhancement, and reproduction of surface outlines of various skin topographies, subsequently assisting dermatological diagnosis. The technique can precisely record skin surface morphology and reflect the vertical dimension information within 10 min and is aimed to assist dermatologists working with patients suffering from skin diseases via recording or monitoring the skin surface conditions. Additionally, successful trials of loading and electro-controlled release of Cu2+ into/from the developed skin patterns reveals its potential to be also utilized for treatment of pathological skin conditions. Based on the developed analytical diagnostic technique, a well-designed 3D printed portable prototype device based on electrosynthesis of the conducting polymer powered by an ordinary battery (1.5 V) was tested and was found to have excellent performance in onsite 3D skin pattern reproduction from live human skin.

Taguchi optimization design of diameter-controlled synthesis of multi walled carbon nanotubes for the adsorption of Pb(II) and Ni(II) from chemical industry wastewater.

Herein, Taguchi L9 orthogonal array was used for the first time to optimize synthesis of diameter-controlled multi walled carbon nanotubes (MWCNTs). The nanoadsorbents, MWCNTs5-15 nm and MWCNTs16-25 nm were applied for Pb(II) and Ni(II) ion removal from paint, battery and electroplating wastewater. The results indicated successful synthesis of MWCNTs with diameter distribution ranges of 5-15 nm and 16-25 nm. The synthetized smaller diameter MWCNTs5-15 nm revealed higher Brunauer-Emett-Teller (BET) surface area of 1306 ± 5 m2/g compared to larger diameter MWCNTs16-25 nmwith the surface area of 1245 ± 4 m2/g. They demonstrated excellent adsorption of Pb(II) and Ni(II) ions within the permissible concentration proposed by WHO at pH, contact time, adsorbent dosage and temperature of 5, 60 min, 30 mg/L and 50 °C, respectively. Particularly, MWCNTs5-15 nm possessed high adsorption capacity of 215.38 ± 0.03 mg/g for Pb(II) and 230.78 ± 0.01 mg/g for Ni(II). Again, the maximum adsorption capacity of 201.35 ± 0.02 and 206.40 ± 0.02 mg/g was achieved for Pb(II) and Ni(II) using MWCNTs16-25 nm. All in all, the adsorption capacity of the nanoadsorbents at the investigated diameter range showed higher efficiency compared to other materials for heavy metals elimination from chemical industrial wastewater.

Characterization of nano-layered solid-contact ion selective electrodes by simultaneous potentiometry and quartz crystal microbalance with dissipation.

Nano-layered solid-contact potassium-selective electrodes (K+-ISEs) were explored as model ion-selective electrodes for their practical use in clinical analysis. The ultra-thin ISEs ought to be manufactured in a highly reproducible manner, potentially making them suitable for mass production. Thus, their development is pivotal towards miniaturised sensors with simplified conditioning/calibration protocols for point-of-care diagnostics. To study nano-layered ISEs, the ultra-thin nature of ISEs for the first time enabled to combine potentiometry-quartz crystal microbalance with dissipation (QCM-D) to obtain value-added information on the ISE potentiometric response regarding their physical state such as mass/thickness/viscoelastic properties/structural homogeneity. Specifically, the studies were focused on real-time observations of the ISE potentiometric response in relation to changes of their physicochemical properties during the ISE preparation (conditioning) and operation (including biofouling conditions) to identify the occurring processes that may accordingly be critical for potential instability of the ISEs, impeding their practical application. The K+-ISEs were prepared on a QCM-D gold sensor by electrodepositing poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate) layer serving as an ion-to-electron transducer subsequently covered by a spin-coated poly(vinyl chloride) based K+-ion selective membrane (K+-ISM). The studies demonstrated that the performance of the nano-layered design of K+-ISEs is detrimentally affected by such processes as water layer formation accordingly causing the instability of the electrode potential. The changes in the ISE physical state such mass/viscoelastic properties associated with water layer formation and origin of the potential instability was already observed at the ISE conditioning stage. The potential instability of nano-layered ISEs limits their practical applicability, indicating the need of new solutions in designing ISEs, for instance, exploiting new water-resistant materials and modifying preparation protocols.

Impact of molecular linker size on physicochemical properties of assembled gold nanoparticle mono-/multi-layers and their applicability for functional binding of biomolecules.

In this work the impact of molecular inter-linker size on gold nanoparticle (AuNP) mono-/multilayer structural properties, density and homogeneity has been investigated. These characteristics are of great importance for functional binding of biomolecules. Positively charged high or low molecular weight inter-linkers, poly-L-lysine (PLL) or N-(6-mercapto)hexylpyridinium (MHP), were used to attach negatively charged AuNPs on a planar gold surface as well as to further interlink into a multilayer structure via layer-by-layer deposition. The inter-particle interaction within the assembled AuNP films was adjusted by the ionic strength in the AuNPs dispersions. The AuNP layer density and structural/viscoelastic properties were evaluated by the quartz crystal microbalance with dissipation (QCM-D) technique. The validity of the commercial Voigt model, specifically developed for quantitative QCM-D data analysis of homogeneous viscoelastic films, was evaluated by a model independent analysis when comparing the assembled AuNP films with a homogeneous layer of a mucin from bovine submaxillary glands. Both AuNP mono- and multilayers, attached/interlinked via long flexible PLL molecules assembled to denser and more soft/viscous structures compared to those interlinked by short MHP compounds. Thus, PLL-interlinked AuNP mono-/multilayer structures were further investigated as a platform for laccase enzyme functional adsorption via qualitative assessment of bioelectrochemical characteristics of the enzyme.

Bioelectrocatalytic reduction of oxygen at gold nanoparticles modified with laccase.

To characterise bioelectrocatalytic oxygen reduction at gold nanoparticles (AuNPs) modified with Trametes hirsuta laccase (ThLc) combined electrochemical and quartz crystal microbalance measurements have been used. The electrodes with different degrees of AuNP-monolayer coverage, θ, have been studied. In every case of θ close to theoretically possible 44 ThLc molecules adsorbed at 22nm diameter AuNP. The bioelectrocatalytic current was recalculated down to the current at a single AuNP. Unexpectedly, the current at a single AuNP was higher when θ was higher. The maximum current reached at a single AuNP was 31·10(-18)A which corresponds to the enzyme turnover (kcat) 13s(-1). This rate is lower than the homogeneous ThLc turnover (190s(-1)) suggesting partial denaturation of ThLc upon adsorption or that some ThLc are not in DET contact with the electrode surface.

1,10-Phenanthroline derivatives as mediators for glucose oxidase.

This study is focused on possible application of some 1,10-phenanthroline derivatives (PDs) in the development of biosensors and biofuel cells. Differently from some other studies, the PDs that were not involved into structures of metal complexes were investigated. Five PDs [1,10-phenanthroline monohydrate (PMH); 5-nitro-1,10-phenanthroline (5NP); 5-amino-1,10-phenanthroline (5AP), 5-amino,6-nitro-1,10-phenanthroline (5A6NP) and 5,6-diamino-1,10-phenanthroline (56DAP)] were selected for this study. Bioelectrochemical responses of PDs and glucose oxidase (GOX)-modified graphite rod electrodes (GREs) were studied amperometrically and potentiometrically. The best redox mediators for GOX were found on PDs containing amino groups: 5AP and 56DAP. Amperometrical measurements have shown that 5NP derivative was also acting as a redox mediator but activity of 5NP was approximately four times lower than 5AP and three times lower than 56DAP. This study clearly illustrates that some PDs can be applied as redox mediators for oxidases and are suitable for the development of reagent-less biosensors and biofuel cells. Since amino groups can be very easily involved in the formation of chemical bounds, the amino-PDs are interesting compounds for the development of nanobiotechnological tools by bottom-up technique.