Aqueous adsorption of bisphenol A over a porphyrinic porous organic polymer.

A new porphyrinic porous organic polymer (PPOP) with high stability and excellent textural properties (929 m2/g surface area with 0.73 cm3/g pore volume) was made via the Friedel-Crafts reaction and applied for bisphenol A (BPA) adsorption in water. The material was examined by X-ray diffraction, N2 adsorption-desorption isotherms, scanning electron microscopy, infrared spectroscopy, X-ray photoelectron spectroscopy, and solid-state 13C CP-MAS nuclear magnetic resonance spectroscopy. PPOP was proven highly effective for capturing BPA among the many adsorbent materials investigated. The Langmuir model could closely match the adsorption isotherm data with a high adsorption amount of ca. 653 mg/g at 25 °C. Approximately 95% of BPA was adsorbed in 50 min, and the pseudo-second-order kinetic model satisfactorily described the adsorption behavior. This adsorption process was exothermic (ΔH° = -39.10 kJ/mol), and the capacity gradually decreased with increasing pH. Spectroscopic analyses indicated that the BPA adsorption on PPOP was affected by (1) π-π interaction between BPA and the aromatic constituents of PPOP, (2) hydrogen bonding between the N sites of porphyrin units in PPOP and the hydroxyl group of BPA and, and (3) hydrophobic interactions. PPOP was easily regenerated after acetone washing, and >98% efficiency was observed throughout the five repeated adsorption-desorption cycles.

Valorization of fly ash as a harmless flame retardant via carbonation treatment for enhanced fire-proofing performance and mechanical properties of silicone composites.

Owing to the environmental and economic problems arising from fly ash (FA), there have been various ongoing efforts over the past decades to find a use for it. Among the various applications of FA, its use as a filler in polymer composites has gained much attention. However, most studies have applied FA as a semi-reinforcing filler, which only marginally improves mechanical properties arising from the poor surface wettability of FA with polymer matrices. To solve this problem and to explore new applications, FA was carbonated by bubbling CO2 in water in this study. The carbonated FA was adopted as a fire-proofing filler in silicone rubber (SR). The surface properties and compositional changes of FA by carbonation were thoroughly examined. Mechanical and thermal properties of carbonated FA-filled SR were evaluated. In particular, the gas torch test confirmed that the carbonation of FA increased the penetration time of SR composites by 11%. In addition, the penetration time of the carbonated FA-filled SR composite was 2-3 times greater than that of the composites filled with commercially available fillers.

Highly efficient adsorptive removal of sulfamethoxazole from aqueous solutions by porphyrinic MOF-525 and MOF-545.

The metal-organic frameworks MOF-525 and MOF-545 comprised of Zr-oxide clusters and porphyrin moieties in different geometries were synthesized solvothermally and applied for the adsorptive removal of the broadly used organic contaminant sulfamethoxazole (SMX) from water. Both MOFs were found highly efficient for the adsorption of SMX with the maximum adsorption capacities of 585 and 690 mg/g for MOF-525 and MOF-545, respectively. The latter value is the highest adsorption capacity reported so far for the adsorption of SMX molecules on any adsorbent. The adsorption equilibrium could be modeled successfully by the Langmuir model, which showed close to matching with the experimental data. Their adsorption equilibriums were attained within 120 and 30 min for MOF-525 and MOF-545, respectively. MOF-545 with mesopores demonstrated superior adsorption kinetics to MOF-525 with micropores, and the simulation by the pseudo-second-order kinetic model indicated ca. 20 times faster adsorption by MOF-545 than MOF-525. Both showed pH-dependent adsorption of SMX with a gradual reduction at high pH due to the repulsion between negatively charged adsorbent and SMX. The adsorption of SMX conducted over a group of representative MOFs with different physicochemical properties and detailed characterization confirmed that the high adsorption capacity of the porphyrin MOFs is achieved by H-bonding between the SMX molecule and the N-sites of the porphyrin units in the MOFs, π-π interaction, and the high surface area. The adsorbents were easily regenerated by simple washing with acetone and reusable with >95% efficiency during 4 repeated adsorption-desorption cycles.

Porous Covalent Organic Polymers Comprising a Phosphite Skeleton for Aqueous Nd(III) Capture.

In order to meet the ever-increasing industrial demand for rare-earth elements (REEs), it is desirable to separate and recycle them at low concentrations from various sources including industrial and urban wastes. Here, we introduced phosphorus binding sites on the hydrophobic surface of a robust and high-surface area porous polymer backbone for environmentally benign and selective recovery of REEs via adsorption. For this purpose, two porous covalent organic polymer (COP) materials incorporated with in-built phosphite functionality (P-COP-1 and P-COP-2) were synthesized and applied for the adsorptive separation of Nd(III) ions from aqueous solution. A strategy to develop a series of P-COPs via a simple Friedel-Crafts reaction was introduced, and their application to the selective adsorption of REEs was explored for the first time. The newly synthesized P-COPs were amorphous and/or weakly crystalline and showed excellent chemical stability and large specific surface area with sufficient mesoporosity for enhanced diffusion of REE ions. P-COP-1 exhibited an exceptionally high Nd(III) adsorption capacity of 321.0 mg/g, corresponding to the stoichiometric ratio of P/Nd(III) = 1:0.7 and high selectivity of >86% over other competing transition and alkaline earth metal ions, whereas P-COP-2 gave a Nd(III) adsorption capacity of 175.6 mg/g at 25 °C and pH 5. Moreover, P-COP-1 showed a distribution coefficient value of 5.45 × 105 mL/g, which is superior to other benchmark adsorbent materials reported so far. Finally, the P-COPs were reusable for a minimum of 10 cycles without deterioration in adsorption capacities.

Selective Adsorption of Rare Earth Elements over Functionalized Cr-MIL-101.

Efficient rare earth elements (REEs) separation and recovery are crucial to meet the ever-increasing demand for REEs extensively used in various high technology devices. Herein, we synthesized a highly stable chromium-based metal-organic framework (MOF) structure, Cr-MIL-101, and its derivatives with different organic functional groups (MIL-101-NH2, MIL-101-ED (ED: ethylenediamine), MIL-101-DETA (DETA: diethylenetriamine), and MIL-101-PMIDA (PMIDA: N-(phosphonomethyl)iminodiacetic acid)) and explored their effectiveness in the separation and recovery of La3+, Ce3+, Nd3+, Sm3+, and Gd3+ in aqueous solutions. The prepared materials were characterized using various analytical instrumentation. These MOFs showed increasing REE adsorption capacities in the sequence MIL-101 < MIL-101-NH2 < MIL-101-ED < MIL-101-DETA < MIL-101-PMIDA. MIL-101-PMIDA showed superior REE adsorption capacities compared to other MOFs, with Gd3+ being the element most efficiently adsorbed by the material. The adsorption of Gd3+ onto MIL-101-PMIDA was examined in detail as a function of the solution pH, initial REE concentration, and contact time. The obtained adsorption equilibrium data were well represented by the Langmuir model, and the kinetics were treated with a pseudo-second-order model. A plausible mechanism for the adsorption of Gd3+ on MIL-101-PMIDA was proposed by considering the surface complexation and electrostatic interaction between the functional groups and Gd3+ ions under different pH conditions. Finally, recycling tests were carried out and demonstrated the higher structural stability of MIL-101-PMIDA during the five adsorption-regeneration runs.