Modelling Sorption and Transport of Gases in Polymeric Membranes across Different Scales: A Review

Professor Giulio C. Sarti has provided outstanding contributions to the modelling of fluid sorption and transport in polymeric materials, with a special eye on industrial applications such as membrane separation, due to his Chemical Engineering background. He was the co-creator of innovative theories such as the Non-Equilibrium Theory for Glassy Polymers (NET-GP), a flexible tool to estimate the solubility of pure and mixed fluids in a wide range of polymers, and of the Standard Transport Model (STM) for estimating membrane permeability and selectivity. In this review, inspired by his rigorous and original approach to representing membrane fundamentals, we provide an overview of the most significant and up-to-date modeling tools available to estimate the main properties governing polymeric membranes in fluid separation, namely solubility and diffusivity. The paper is not meant to be comprehensive, but it focuses on those contributions that are most relevant or that show the potential to be relevant in the future. We do not restrict our view to the field of macroscopic modelling, which was the main playground of professor Sarti, but also devote our attention to Molecular and Multiscale Hierarchical Modeling. This work proposes a critical evaluation of the different approaches considered, along with their limitations and potentiality

CO2 sorption modelling in humidified Polyvinyl amine (PVAm) with PC-SAFT

Carbon dioxide emissions represent one of the main environmental issue of our time. The greenhouse gases atmospheric loading, due to anthropogenic activities, are causing a continue rise of global temperature. In the field of CO2 capture from gas streams, membrane technologies are promising alternative to the more common operations. Among these, Facilitated Transport Membranes show high performances in terms of CO2 permeabilities and selectivities even at low pressures by coupling a simple solution diffusion transport mechanism and a reversible chemical reaction with a carrier agent. Polyvinyl amine (PVAm) binds one primary amino group for each monomer along the chain, showing high hydrophilicity and affinity to CO2. In this work we use the PC-SAFT [1] Equation of State to model the H2O uptake and the solubility of CO2 in the ternary system of PVAm / H2O / CO2

Modelling water sorption in Facilitated Transport Membranes with PC-SAFT Equation of State: the case of Polyvinyl amine

Facilitated transport membranes have great potential for carbon dioxide removal. By coupling the solution diffusion mechanism and the facilitation effect of the chemical reaction, CO2 transport in such systems is substantially higher compared to other gases, like nitrogen and methane. The presence of water is needed in the membrane to activate the reaction mechanism, and affects the sorption and diffusion of all the gases in the membrane. The present work focuses on the modelling of water sorption in purified Lupamin\uae (polyvinylamine (PVAm)), with the PC-SAFT Equation of State (EoS) (Gross and Sadowski, 2001). The work is aimed at finding the best parameters and association schemes to model the water sorption in PVAm with the PC-SAFT model, in order to use it to model more complex situations such as the multicomponent sorption in the system

Quaterpyridine Ligands for Panchromatic Ru(II) Dye Sensitizers

A new general synthetic access to carboxylated quaterpyridines (qpy), of interest as ligands for panchromatic dyesensitized solar cell organometallic sensitizers, is presented. The strategic step is a Suzuki−Miyaura cross-coupling reaction, which has allowed the preparation of a number of representative unsubstituted and alkyl and (hetero)aromatic substituted qpys. To bypass the poor inherent stability of 2-pyridylboronic acid derivatives, we successfully applied N-methyliminodiacetic acid (MIDA) boronates as key reagents, obtaining the qpy ligands in good yields up to (quasi)gram quantities. The structural, spectroscopic (NMR and UV−vis), electrochemical, and electronic characteristics of the qpy have been experimentally and computationally (DFT) investigated. The easy access to the bis-thiocyanato Ru(II) complex of the parent species of the qpy series, through an efficient route which bypasses the use of Sephadex column chromatography, is shown. The bis-thiocyanato Ru(II) complex has been spectroscopically (NMR and UV−vis), electrochemically, and computationally investigated, relating its properties to those of previously reported Ru(II)−qpy complexes.“This document is the Accepted Manuscript version of a Published Work that appeared in final form in [The Journal of Organic Chemistry], copyright © American Chemical Society after peer review and technical editing by the publisher

Mixed Matrix Membranes based on PPO and graphene for gas separation

Novel composite Mixed Matrix Membranes (MMM) were fabricated by dispersion of different loadings of graphene nanoparticles (from 0.3 to 15 % weight percentage) in a dense permeable glassy polymer, poly (2,6-dimethyl-1,4-phenylene oxide), PPO, by solvent casting procedure. The permeability, selectivity and diffusivity of helium, nitrogen and carbon dioxide have been measured at two different temperatures, 35° and 65°C and the effect of graphene loading was studied. (R. Rea et al. 2018)

Making the Communication of CCS more "human"

CCS communication has proven a tough challenge, particularly for the difficulty in raising interest for the technology, which is still unknown to the majority of the population, and for the complexity of conveying information about its potential for reducing emissions. In this paper we present a research based effort for bringing CCS nearer to people, through visual material developed taking into account emotional needs related to the technology. The production of a short introductory film on CCS is illustrated and its testing with a sample of 700 high school students

Permeability and Selectivity of PPO/Graphene Composites as Mixed Matrix Membranes for CO2 Capture and Gas Separation

We fabricated novel composite (mixed matrix) membranes based on a permeable glassy polymer, Poly(2,6-dimethyl-1,4-phenylene oxide) (PPO), and variable loadings of few-layer graphene, to test their potential in gas separation and CO2 capture applications. The permeability, selectivity and diffusivity of different gases as a function of graphene loading, from 0.3 to 15 wt %, was measured at 35 and 65 \u25e6C. Samples with small loadings of graphene show a higher permeability and He/CO2 selectivity than pure PPO, due to a favorable effect of the nanofillers on the polymer morphology. Higher amounts of graphene lower the permeability of the polymer, due to the prevailing effect of increased tortuosity of the gas molecules in the membrane. Graphene also allows dramatically reducing the increase of permeability with temperature, acting as a \u201cstabilizer\u201d for the polymer matrix. Such effect reduces the temperature-induced loss of size-selectivity for He/N2 and CO2/N2, and enhances the temperature-induced increase of selectivity for He/CO2. The study confirms that, as observed in the case of other graphene-based mixed matrix glassy membranes, the optimal concentration of graphene in the polymer is below 1 wt %. Below such threshold, the morphology of the nanoscopic filler added in solution affects positively the glassy chains packing, enhancing permeability and selectivity, and improving the selectivity of the membrane at increasing temperatures. These results suggest that small additions of graphene to polymers can enhance their permselectivity and stabilize their propertie