Study of Innovative GO/PBI Composites as Possible Proton Conducting Membranes for Electrochemical Devices.

The appeal of combining polybenzimidazole (PBI) and graphene oxide (GO) for the manufacturing of membranes is increasingly growing, due to their versatility. Nevertheless, GO has always been used only as a filler in the PBI matrix. In such context, this work proposes the design of a simple, safe, and reproducible procedure to prepare self-assembling GO/PBI composite membranes characterized by GO-to-PBI (X:Y) mass ratios of 1:3, 1:2, 1:1, 2:1, and 3:1. SEM and XRD suggested a homogenous reciprocal dispersion of GO and PBI, which established an alternated stacked structure by mutual π-π interactions among the benzimidazole rings of PBI and the aromatic domains of GO. TGA indicated a remarkable thermal stability of the composites. From mechanical tests, improved tensile strengths but worsened maximum strains were observed with respect to pure PBI. The preliminary evaluation of the suitability of the GO/PBI X:Y composites as proton exchange membranes was executed via IEC determination and EIS. GO/PBI 2:1 (IEC: 0.42 meq g-1; proton conductivity at 100 °C: 0.0464 S cm-1) and GO/PBI 3:1 (IEC: 0.80 meq g-1; proton conductivity at 100 °C: 0.0451 S cm-1) provided equivalent or superior performances with respect to similar PBI-based state-of-the-art materials.

Reduced Graphene Oxide/Waste-Derived TiO2 Composite Membranes: Preliminary Study of a New Material for Hybrid Wastewater Treatment.

This work reports the preliminary results of the development of composite self-assembling membranes obtained by the combination of reduced graphene oxide (rGO) with commercial Degussa P25 titanium dioxide (TiO2). The purpose is to demonstrate the possibility of combining, in the same self-standing material, the capability to treat wastewater containing both inorganic and organic pollutants by exploiting the established ability of rGO to capture metal ions together with that of TiO2 to degrade organic substances. Moreover, this study also investigates the potential photocatalytic properties of tionite (TIO), to demonstrate the feasibility of replacing commercial TiO2 with such waste-derived TiO2-containing material, fulfilling a circular economy approach. Thus, rGO-TiO2 and rGO-TIO composite membranes, 1:1 by weight, were prepared and characterized by SEM-EDX, XRD, thermogravimetry, as well as by Raman and UV-Vis spectroscopies to verify the effective and homogeneous integration of the two components. Then, they were tested towards 3-mg L-1 aqueous synthetic solutions of Fe3+ and Cu2+ ions to evaluate their metal adsorption ability, with values of the order of 0.1-0.2 mmol gmembrane-1, comparable or even slightly higher than those of pristine rGO. Finally, the ability of the composites to degrade a common organic pesticide, i.e., Imidacloprid®, was assessed in preliminary photocatalysis experiments, in which maximum degradation efficiencies of 25% (after 3 h) for rGO-TiO2 and of 21% (after 1 h) for rGO-TIO were found. The result of tionite-containing membranes is particularly promising and worthy of further investigation, given that the anatase content of tionite is roughly 1/6 of the one in commercial TiO2.

Analysis of the Adsorption-Release Isotherms of Pentaethylenehexamine-Modified Sorbents for Rare Earth Elements (Y, Nd, La).

Waste from electrical and electronic equipment (WEEE) is constantly increasing in quantity and becoming more and more heterogeneous as technology is rapidly advancing. The negative impacts it has on human and environment safety, and its richness in valuable rare earth elements (REEs), are accelerating the necessity of innovative methods for recycling and recovery processes. The aim of this work is to comprehend the adsorption and release mechanisms of two different solid sorbents, activated carbon (AC) and its pentaethylenehexamine (PEHA)-modified derivative (MAC), which were deemed adequate for the treatment of REEs deriving from WEEE. Experimental data from adsorption and release tests, performed on synthetic mono-ionic solutions of yttrium, neodymium, and lanthanum, were modelled via linear regression to understand the better prediction between the Langmuir and the Freundlich isotherms for each REE-sorbent couple. The parameters extrapolated from the mathematical modelling were useful to gain an a priori knowledge of the REEs-sorbents interactions. Intraparticle diffusion was the main adsorption mechanism for AC. PEHA contributed to adsorption by means of coordination on amino groups. Release was based on protons fostering both a cation exchange mechanism and protonation. The investigated materials confirmed their potential suitability to be employed in real processes on WEEE at the industrial level.

Investigation of Sulfonated Graphene Oxide as the Base Material for Novel Proton Exchange Membranes.

This work deals with the development of graphene oxide (GO)-based self-assembling membranes as possible innovative proton conductors to be used in polymer electrolyte membrane fuel cells (PEMFCs). Nowadays, the most adopted electrolyte is Chemours' Nafion; however, it reveals significant deficiencies such as strong dehydration at high temperature and low humidity, which drastically reduces its proton conductivity. The presence of oxygenated moieties in the GO framework makes it suitable for functionalization, which is required to enhance the promising, but insufficient, proton-carrying features of GO. In this study, sulfonic acid groups (-SO3H) that should favor proton transport were introduced in the membrane structure via a reaction between GO and concentrated sulfuric acid. Six acid-to-GO molar ratios were adopted in the synthesis procedure, giving rise to final products with different sulfonation degrees. All the prepared samples were characterized by means of TGA, ATR-FTIR and Raman spectroscopy, temperature-dependent XRD, SEM and EDX, which pointed out morphological and microstructural changes resulting from the functionalization stage, confirming its effectiveness. Regarding functional features, electrochemical impedance spectroscopy (EIS) as well as measurements of ion exchange capacity (IEC) were carried out to describe the behavior of the various samples, with pristine GO and commercial Nafion® 212 used as reference. EIS tests were performed at five different temperatures (20, 40, 60, 80 and 100 °C) under high (95%) and medium (42%) relative humidity conditions. Compared to both GO and Nafion® 212, the sulfonated specimens demonstrate an increase in the number of ion-carrying groups, as proved by both IEC and EIS tests, which reveal the enhanced proton conductivity of these novel membranes. Specifically, an acid-to-GO molar ratio of 10 produces a six-fold improvement of IEC (4.23 meq g-1) with respect to pure GO (0.76 meq g-1), while a maximum eight-fold improvement (5.72 meq g-1) is achieved in SGO-15.

Capture and Release Mechanism of Ni and La Ions via Solid/Liquid Process: Use of Polymer-Modified Clay and Activated Carbons.

This study is a starting point for the development of an efficient method for rare earths (REs) and transition metals (TMs) recovery from waste electrical and electronic equipment (WEEE) via a hydrometallurgical process. The capture and release capability of mineral clays (STx) and activated carbons (AC), pristine and modified (STx-L6 and AC-L6) with a linear penta-ethylene-hexamine (L6), towards solutions representative of the process, are assessed in the lab-scale. The solids were contacted with synthetic mono- and bi-ionic solutions containing Ni(II) and La(III) in a liquid/solid adsorption process. Contacting experiments were carried out at room temperature for 90 min by fixing a La concentration at 19 mM and varying the Ni one in the range of 19-100 mM. The four solids were able to capture Ni(II) and La(III), both in single- and bi-ionic solutions; however, the presence of the polyamine always results in a large improvement in the capture capability of the pristine sorbents. For all the four solids, capture behaviour is ascribable to an adsorption or ion-sorbent interaction process, because no formation of aquo- and hydroxy-Ni or La can be formed. The polyamine, able to capture Ni ions via coordination, allowed to differentiate ion capture behaviour, thus bypassing the direct competition between Ni and La ions for the capture sites found in the pristine solids. Release values in the 30-100% range were found upon one-step treatment with concentrated HNO3 solution. However, also, in this case, different metals recovery was found depending on both the sorbent and the ions, suggesting a possible selective recovery.