Biomimetic Photodegradation of Glyphosate in Carborane-Functionalized Nanoconfined Spaces.

The removal of organophosphorus (OP) herbicides from water has been studied using adsorptive removal, chemical oxidation, electrooxidation, enzymatic degradation, and photodegradation. The OP herbicide glyphosate (GP) is one of the most used herbicides worldwide, leading to excess GP in wastewater and soil. GP is commonly broken down in environmental conditions to compounds such as aminomethylphosphonic acid (AMPA) or sarcosine, with AMPA having a longer half-life and similar toxicity to GP. Metal-organic frameworks (MOFs) are excellent materials for purifying OP herbicides from water due to their ability to combine adsorption and photoactivity within one material. Herein, we report the use of a robust Zr-based MOF with a meta-carborane carboxylate ligand (mCB-MOF-2) to examine the adsorption and photodegradation of GP. The maximum adsorption capacity of mCB-MOF-2 for GP was determined to be 11.4 mmol/g. Non-covalent intermolecular forces between the carborane-based ligand and GP within the micropores of mCB-MOF-2 are thought to be responsible for strong binding affinity and capture of GP. After 24 h of irradiation with ultraviolet-visible (UV-vis) light, mCB-MOF-2 selectively converts 69% of GP to sarcosine and orthophosphate, following the C-P lyase enzymatic pathway and biomimetically photodegrading GP. Circumventing the production of AMPA is desirable, as it has a longer half-life and similar toxicity to GP. The exceptional adsorption capacity of GP by mCB-MOF-2 and its biomimetic photodegradation to non-toxic sarcosine make it a promising material for removing OP herbicides from water.

Irreversible deformation of hyper-crosslinked polymers after hydrogen adsorption.

Hyper-crosslinked polymers (HCPs) have been produced by the Friedel-Crafts reaction using anthracene, benzene, carbazole or dibenzothiophene as precursors and dimethoxymethane as crosslinker, and the effect of graphene oxide (GO) addition has been studied. The resulting HCPs were highly microporous with BET areas (ABET) between 590 and 1120 m2g-1. The benzene-derived HCP (B1FeM2) and the corresponding composite with GO (B1FM2-GO) exhibited the highest ABET and were selected to study their hydrogen adsorption capacities in the pressure range of 0.1 - 14 MPa at 77 K. The maximum H2 excess uptake was 2.1 and 2.0 wt% for B1FeM2 and B1FeM2-GO, respectively, at 4 MPa and 77 K. The addition of GO reduced the specific surface area but increased the density of the resultant HCP-GO composites, which is beneficial for practical applications and proves that materials giving higher gravimetric storage capacities are not necessarily those that offer higher volumetric capacities. H2 adsorption-desorption cycles up to 14 MPa showed irreversible deformation of both HCP and HCP-GO materials, which calls into question their application for hydrogen adsorption at pressures above 4 MPa.

APTES-Based Silica Nanoparticles as a Potential Modifier for the Selective Sequestration of CO2 Gas Molecules.

In this work, we have described the characterization of hybrid silica nanoparticles of 50 nm size, showing outstanding size homogeneity, a large surface area, and remarkable CO2 sorption/desorption capabilities. A wide battery of techniques was conducted ranging from spectroscopies such as: UV-Vis and IR, to microscopies (SEM, AFM) and CO2 sorption/desorption isotherms, thus with the purpose of the full characterization of the material. The bare SiO2 (50 nm) nanoparticles modified with 3-aminopropyl (triethoxysilane), APTES@SiO2 (50 nm), show a remarkable CO2 sequestration enhancement compared to the pristine material (0.57 vs. 0.80 mmol/g respectively at 50 °C). Furthermore, when comparing them to their 200 nm size counterparts (SiO2 (200 nm) and APTES@SiO2 (200 nm)), there is a marked CO2 capture increment as a consequence of their significantly larger micropore volume (0.25 cm3/g). Additionally, ideal absorbed solution theory (IAST) was conducted to determine the CO2/N2 selectivity at 25 and 50 °C of the four materials of study, which turned out to be >70, being in the range of performance of the most efficient microporous materials reported to date, even surpassing those based on silica.

Ionic Polyureas-A Novel Subclass of Poly(Ionic Liquid)s for CO2 Capture.

The growing concern for climate change and global warming has given rise to investigations in various research fields, including one particular area dedicated to the creation of solid sorbents for efficient CO2 capture. In this work, a new family of poly(ionic liquid)s (PILs) comprising cationic polyureas (PURs) with tetrafluoroborate (BF4) anions has been synthesized. Condensation of various diisocyanates with novel ionic diamines and subsequent ion metathesis reaction resulted in high molar mass ionic PURs (Mw = 12 ÷ 173 × 103 g/mol) with high thermal stability (up to 260 °C), glass transition temperatures in the range of 153-286 °C and remarkable CO2 capture (10.5-24.8 mg/g at 0 °C and 1 bar). The CO2 sorption was found to be dependent on the nature of the cation and structure of the diisocyanate. The highest sorption was demonstrated by tetrafluoroborate PUR based on 4,4'-methylene-bis(cyclohexyl isocyanate) diisocyanate and aromatic diamine bearing quinuclidinium cation (24.8 mg/g at 0 °C and 1 bar). It is hoped that the present study will inspire novel design strategies for improving the sorption properties of PILs and the creation of novel effective CO2 sorbents.

Microporous Polymer Networks for Carbon Capture Applications.

A new generation of porous polymer networks has been obtained in quantitative yield by reacting two rigid trifunctional aromatic monomers (1,3,5-triphenylbenzene and triptycene) with two ketones having electron-withdrawing groups (trifluoroacetophenone and isatin) in superacidic media. The resulting amorphous networks are microporous materials, with moderate Brunauer-Emmett-Teller surface areas (from 580 to 790 m2 g-1), and have high thermal stability. In particular, isatin yields networks with a very high narrow microporosity contribution, 82% for triptycene and 64% for 1,3,5-triphenylbenzene. The existence of favorable interactions between lactams and CO2 molecules has been stated. The materials show excellent CO2 uptakes (up to 207 mg g-1 at 0 °C/1 bar) and can be regenerated by vacuum, without heating. Under postcombustion conditions, their CO2/N2 selectivities are comparable to those of other organic porous networks. Because of the easily scalable synthetic method and their favorable characteristics, these materials are very promising as industrial adsorbents.

Influence of porous texture and surface chemistry on the CO2 adsorption capacity of porous carbons: acidic and basic site interactions.

Doped porous carbons exhibiting highly developed porosity and rich surface chemistry have been prepared and subsequently applied to clarify the influence of both factors on carbon dioxide capture. Nanocasting was selected as synthetic route, in which a polyaramide precursor (3-aminobenzoic acid) was thermally polymerized inside the porosity of an SBA-15 template in the presence of different H3PO4 concentrations. The surface chemistry and the porous texture of the carbons could be easily modulated by varying the H3PO4 concentration and carbonization temperature. Porous texture was found to be the determinant factor on carbon dioxide adsorption at 0 °C, while surface chemistry played an important role at higher adsorption temperatures. We proved that nitrogen functionalities acted as basic sites and oxygen and phosphorus groups as acidic ones toward adsorption of CO2 molecules. Among the nitrogen functional groups, pyrrolic groups exhibited the highest influence, while the positive effect of pyridinic and quaternary functionalities was smaller. Finally, some of these N-doped carbons exhibit CO2 heats of adsorption higher than 42 kJ/mol, which make them excellent candidates for CO2 capture.

Energy storage on ultrahigh surface area activated carbon fibers derived from PMIA.

High-performance carbon materials for energy storage applications have been obtained by using poly(m-phenylene isophthalamide), PMIA, as a precursor through the chemical activation of the carbonized aramid fiber by using KOH. The yield of the process of activation was remarkably high (25-40 wt%), resulting in activated carbon fibers (ACFs) with ultrahigh surface areas, over 3000 m(2) g(-1) , and pore volumes exceeding 1.50 cm(3) g(-1) , keeping intact the fibrous morphology. The porous structure and the surface chemical properties could easily be controlled through the conditions of activation. The PMIA-derived ACFs were tested in two types of energy storage applications. At -196 °C and 1 bar, H2 uptake values of approximately 3 t% were obtained, which, in combination with the textural properties, rendered it a good candidate for H2 adsorption at high pressure and temperature. The performance of the ACFs as electrodes for electrochemical supercapacitors was also investigated. Specific capacitance values between 297 and 531 g(-1) at 50 mA g(-1) were obtained in aqueous electrolyte (1 H2 SO4 ), showing different behaviors depending on the surface chemical properties.

Activated carbon fibers with a high content of surface functional groups by phosphoric acid activation of PPTA.

Activated carbon fibers (ACFs) were prepared by chemical activation of poly(p-phenylene terephthalamide (PPTA) with phosphoric acid, with a particular focus on the effects of impregnation ratio and carbonization temperature on both surface chemistry and porous texture. Thermogravimetric studies of the pyrolysis of PPTA impregnated with different amounts of phosphoric acid indicated that this reagent has a strong influence on the thermal degradation of the polymer, lowering the decomposition temperature and increasing the carbon yield. As concerns surface chemistry, TPD and chemical analysis results indicated that the addition of phosphoric acid increases the concentration of oxygenated surface groups, with a maximum at an impregnation ratio of 100 wt.%. The resulting materials present uncommon properties, namely a large amount of oxygen- and phosphorus-containing surface groups and a high nitrogen content. Porosity development following H(3)PO(4) activation was very significant, with values close to 1700 m(2)/g and 0.80 cm(3)/g being reached for the BET surface area and total pore volume, respectively. The pore size distributions remained confined to the micropore and narrow mesopore (<10 nm) range.

Highly stable performance of supercapacitors from phosphorus-enriched carbons.

Phosphorus-rich microporous carbons (P-carbons) prepared by a simple H(3)PO(4) activation of three different carbon precursors exhibit enhanced supercapacitive performance in 1 M H(2)SO(4) when highly stable performance can be achieved at potentials larger than the theoretical decomposition potential of water. This ability of P-carbons greatly enhances the energy density of supercapacitors that are capable of delivering 16 Wh/kg compared to 5 Wh/kg for the commercial carbon. An intercept-free multiple linear regression model confirms the strongest influence of phosphorus on capacitance together with micropores 0.65-0.83 nm in width that are the most effective in forming the electric double layer.