Selective Adsorption of Ionic Species Using Macroporous Monodispersed Polyethylene Glycol Diacrylate/Acrylic Acid Microgels with Tunable Negative Charge

Monodispersed polyethylene glycol diacrylate (PEGDA)/acrylic acid (AA) microgels with a tuneable negative charge and macroporous internal structure have been produced using a Lego-inspired droplet microfluidic device. The surface charge of microgels was controlled by changing the content of AA in the monomer mixture from zero (for noncharged PEGDA beads) to 4 wt%. The macroporosity of the polymer matrix was introduced by adding 20 wt% of 600-MW polyethylene glycol (PEG) as a porogen material into the monomer mixture. The porogen was successfully leached out with acetone after UV-crosslinking, which resulted in micron-sized cylindrical pores with crater-like morphology, uniformly arranged on the microgel surface. Negatively charged PEGDA/AA beads showed improved adsorption capacity towards positively charged organic dyes (methylene blue and rhodamine B) compared to neutral PEGDA beads and high repulsion of negatively charged dye molecules (methyl orange and congo red). Macroporous microgels showed better adsorption properties than nonporous beads, with a maximum adsorption capacity towards methylene blue of 45 mg/g for macroporous PEGDA/AA microgels at pH 8.6, as compared to 23 mg/g for nonporous PEGDA/AA microgels at the same pH. More than 98% of Cu(II) ions were removed from 50 ppm solution at pH 6.7 using 2.7 mg/mL of macroporous PEGDA/AA microgel. The adsorption of cationic species was significantly improved when pH was increased from 3 to 9 due to a higher degree of ionization of AA monomeric units in the polymer network. The synthesized copolymer beads can be used in drug delivery to achieve improved loading capacity of positively charged therapeutic agents and in tissue engineering, where a negative charge of scaffolds coupled with porous structure can help to achieve improved permeability of high-molecular-weight metabolites and nutrients, and anti-fouling activity against negatively charged species

Mechanochemically improved surface properties of activated carbon cloth for the removal of As(V) from aqueous solutions

Modified activated carbon cloth is prepared by mechanochemical modification of viscose rayon carbon cloth. The effects of different milling atmospheres, in the air and inert conditions, were investigated. Changes in kind and number of acidic and basic surface groups on the surface of activated carbon cloth, upon modification, as well as before and after the sorption of arsenic were determined. Higher number of basic groups responsible for the removal of arsenic ions was achieved by modification under inert conditions. Breakage and collapse of cylindrical fibers, decrease of particle sizes, change in the shape and consistency of the particles, as well as increase of microstructural disorder i.e. the loss of turbostratic structure occurred upon milling. pHPZC values increased from 4.46 to 5.04 and 5.77 after the air and inert milling, respectively. Adsorption followed pseudo second order kinetics with chemisorption as rate-controlling step. Langmuir isotherm best fit the equilibrium data and maximum adsorption capacity is 5.5 mg g−1 at a pH value close to 7.0, typical for groundwater. The mechanism of arsenic adsorption onto activated carbon cloth milled in inert atmosphere involved electrostatic and dispersive interactions between arsenic ions and carbon particles in wide pH range (from 2 to 10)