Solid-state 13C CPMAS Research Articles

Record-Breaking H2S Capture and ppm-Level Sensing with a Chemically Stable Porous Organic Cage.

The first experimental investigation of a porous organic cage (POC) for the challenging task of H2S capture is reported. The N-containing cage molecular material, a tertiary amine POC (6FT-RCC3), demonstrates the highest H2S (hydrogen sulfide) capture (record capacity) for a porous material at room temperature and atmospheric pressure (20.6mmol H2S g-1; 25 H2S molecules per cage) combined with excellent reversibility for at least five adsorption-desorption cycles. In situ FTIR spectroscopy, solid-state 13C, and 15N CP MAS NMR spectroscopy experiments are applied to investigate the adsorption mechanism, identifying relatively weak interactions via hydrogen bonding. In addition, the fluorescence performances of this POC material are evaluated for the detection and sensing of H2S, where a clear H2S selectivity is observed over other gases. Remarkably, the limit of detection (LOD) is calculated to be 0.13mm (≈4.43ppm) in a tetrahydrofuran (THF) solution of H2S.

A Novel Chemical Approach for the Development of Thioesterified Cellulose Derivatives

In this study, thioesterified cellulose was synthesized by grafting thiol moiety onto a-cellulose, which was first oxidized with different reactive oxygen species (ROS) such as H2O2, Fenton reagent (FR), and peroxyacetic acid in aqueous solution. The thioesterification was done by refluxing oxidized cellulose with ethanedithiol in a mixture of toluene and water (4:1) at 85°C for 6 h. The modification of cellulose was evidenced by FTIR, Raman, solid-state 13C CP MAS NMR spectroscopy, conductometric titration, thermogravimetric analysis, X-ray diffraction, zeta potential measurement, molecular weight determination, and SEM analysis. The characteristic absorption bands for −C=O and −C(=O)−S− bonds in FTIR and Raman spectra were suggestive of the modification of cellulose. 20 % FR was the most efficient in introducing the highest amount (158.93 μmol g−1) of the -COOH groups, while cleavage of cellulose backbone was found to take place as evidenced by the result of the degree of polymerization. The presence of new peaks in 13C CP MAS NMR spectra of thiol-functionalized cellulose ascertained the anchoring of thiol onto oxidized cellulose. Additionally, the significant decrease in the C6 signals for the amorphous region of thiol-modified cellulose provided information about successful modification. In addition, the degree of substitution was determined to be about 0.025. The efficacious functionalization was further supported by the measurement of zeta potential, wherein thioesterified cellulose exhibited the highest negative zeta potential due to increased hydrophobicity. This study would open up a new route for the development of important derivatives of cellulose, including cellulose dimer, containing the thioester group which is the backbone of many antibiotics and natural products.

Enhancing the Crystallinity of Keto-enamine-Linked Covalent Organic Frameworks through an in situ Protection-Deprotection Strategy.

β-Keto-enamine-linked 2D covalent organic frameworks (COFs) have emerged as highly robust materials, showing significant potential for practical applications. However, the exclusive reliance on 1,3,5-triformylphloroglucinol (Tp aldehyde) in the design of such COFs often results in the production of non-porous amorphous polymers when combined with certain amine building blocks. Attempts to adjust the crystallinity and porosity by a modulator approach are inefficient because Tp aldehyde readily forms stable β-keto-enamine-linked monomers/oligomers with various aromatic amines through an irreversible keto-enol tautomerization process. Our research employed a unique protection-deprotection strategy to enhance the crystallinity and porosity of β-keto-enamine-linked squaramide-based 2D COFs. Advanced solid-state NMR studies, including 1D 13 C CPMAS, 1 H fast MAS, 15 N CPMAS, 2D 13 C-1 H correlation, 1 H-1 H DQ-SQ, and 14 N-1 H HMQC NMR were used to establish the atomic-level connectivity within the resultant COFs. The TpOMe -Sqm COFs synthesized utilizing this strategy have a surface area of 487 m2 g-1 , significantly higher than similar COFs synthesized using Tp aldehyde. Furthermore, detailed time-dependent PXRD, solid-state 13 C CPMAS NMR, and theoretical DFT studies shed more light on the crystallization and linkage conversion processes in these 2D COFs. Ultimately, we applied this protection-deprotection method to construct novel keto-enamine-linked highly porous organic polymers with a surface area of 1018 m2 g-1 .

Highly selective recovery of Ni(II) in neutral and acidic media using a novel Ni(II)-ion imprinted polymer.

In this work, an original ion-imprinted polymer (IIP) was synthetized for the highly selective removal of Ni(II) ions in neutral and acidic media. First a novel functional monomer (AMP-MMA) was synthetized through the amidation of 2-(aminomethyl)pyridine (AMP) with methacryloylchloride. Following Ni(II)/AMP-MMA complex formation study, the Ni(II)-IIP was produced via inverse suspension polymerization (DMSO in mineral oil) and characterized with solid state 13C CPMAS NMR, FT-IR, SEM and nitrogen adsorption/desorption experiments. The Ni(II)-IIP was then used in solid-phase extraction of Ni(II) exploring a wide range of pH (from neutral to strongly acidic solution), several initial concentrations of Ni(II) (from 0.02 to 1g/L), and the presence of competitive ions (Co(II), Cu(II), Cd(II), Mn(II), and Mg(II)). The maximum Ni(II) adsorption capacity at pH 2 and pH 7 reached values of 138.9mg/g and 169.5mg/g, that are among the best reported in literature. The selectivity coefficients toward Cd(II), Mn(II), Co(II), Mg(II) and Cu(II) are also very high, with values up to 38.6, 32.9, 25.2, 23.1 and 15.0, respectively. The Ni(II)-IIP showed good reusability of up to 5 cycles both with acidic and basic Ni(II) eluents.

Ni(II)-Incorporated Porphyrin-Based Conjugated Porous Polymer Derived from 2,6-Diformyl-4-methylphenol as a Catalyst for the Urea Oxidation Reaction

The urea oxidation reaction (UOR) is an excellent alternative to the sluggish oxygen evolution reaction (OER) as an anode reaction for hydrogen generation via electrochemical water splitting. Here, a porphyrin-based conjugated porous polymer (CPP) has been developed through the polycondensation reaction of 2,6-diformyl-4-methylphenol and pyrrole (DMP-POR). The nickel(II) complex of this conjugated polymer Ni-DMP-POR shows efficient UOR in an alkaline medium. The as-synthesized materials were characterized by solid-state 13C CP-MAS, thermogravimetric analysis (TGA), Fourier transform infrared (FT-IR) spectroscopy, X-ray photoelectron spectroscopy (XPS), powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The porous property of the materials was characterized by N2 adsorption/desorption isotherms at 77 K. Both DMP-POR and Ni-DMP-POR showed excellent thermal stability. The Ni-DMP-POR exhibits very good UOR in 1 M KOH and 0.33 M urea with an overpotential of 260 mV at 10 mA cm-2 and a Tafel slope of 48 mV dec-1. The catalyst also shows excellent chronoamperometric and chronopotentiometric stability, suggesting its future scope in sustainable hydrogen production from wastewater resources.

The preparation of CaCO3-polyalkoxysilane porous nanocomposites as effective sorbent for oil spill removal.

The novel porous nanocomposite sorbent was synthesized by the condensation of the diol monomer with the alkoxysilane cross-linker at moderately high temperatures in the presence of nano-CaCO3 particles. The structural, thermal, and morphological properties of the nanocomposite sorbents were determined by using Fourier transform infrared spectroscopy (FTIR), solid-state CPMAS 13C and 29Si NMR,scanning electron microscope (SEM), and thermal gravimetric analysis (TGA). Adding nano-CaCO3 to the network structure of the polymer not only provided pores to the sorbent but also enhanced its sorption capacity towards various oils and toxic organic solvents. The nanocomposite sorbent exhibited excellent absorption capacity for different toxic organic solvents and oils and great reusability for ten cycles. Moreover, the obtained sorbent material selectively absorbed organic liquids from the surface and bottom of the water without any capacity change owing to their hydrophobicity and oleophilicity. These features of the nanocomposite make it a potential sorbent for the cleaning of oils and oil derivative organic contaminants from the environment.

Organic matter composition and thermal stability influence greenhouse gases production in subtropical peatland under different vegetation types

Peatlands are a major carbon (C) sink globally. Organic matter quality influence greenhouse gases production. However, little is known about how organic matter from different vegetation types, influences C composition and resultant greenhouse gases production in subtropical peatland. Anoxic incubation experiments were conducted using two types of peats with different botanical origin to assess C composition, CO2 and CH4 production. First peat had cypress dominance and the second knotted spikerush and water lily (spike + lily). Solid-state CPMAS 13C NMR determined C chemical stability, MESTA determined C thermal stability, stable isotopes for C source and gas chromatograph for carbon dioxide (CO2) and methane (CH4). The results indicated dominance of autochthonous C as indicated by δ13C signatures. Low thermal stable C (LTSC) dominated in litter, FL (fermentation layer) and spike + lily sediment, high thermal stable C was dominant in cypress peat. O-alkyl C strongly correlated with LTSC whereas aromatic C correlated negatively with R400 (LTSC:total C ratio). Generally, O-alkyl decreased and alkyl increased along litter-FL-peat continuum. Spike + lily peat exhibited initial stage of decomposition. Indicated by increased alkyl C, aromatic C and aromatic:O-alkyl ratio with increasing peat depth. Also, exhibited 3 times more CH4 and CO2 production compared to cypress peat that dominantly exhibited second stage of decomposition. O-alkyl C exhibited positive relationship with CH4 (P = 0.012, r2 = 0.57) and CO2 (P = 0.047, r2 = 0.41) production whereas R400 related positively with CH4 (P = 0.05, r2 = 0.40). Organic matter thermal and chemical composition varied between the peat types and thermally and chemically labile C influenced CO2 and CH4 production.

Solid-state 13C NMR study of annealing effect on the crystalline phase of poly(ethylene-co-methacrylic acid) ionomers

Annealing effect at 65 °C on the crystalline phase of Poly (ethylene-co-methacrylic acid) (EMAA) and the EMAA ionomer neutralized with Na+ cation (EMAA54Na: 54% of carboxy groups is neutralized) were mainly investigated by the solid-state 13C CP and DPMAS NMR. The 13C NMR spectra revealed the increase of Orthorhombic crystalline phase by annealing at 65 °C, while the Monoclinic crystalline phase unchanged. In addition, no appreciable changes were detected on carboxy groups. The crystallinity estimated from the 13C DPMAS NMR for EMAA did not increase (from 19% to 20%) after annealing, while that for EMAA54Na increased from 12% to 17%. The ratio of Monoclinic/Orthorhombic = 40/60 for EMAA did not change after annealing, whereas the ratio for EMAA54Na became 30/70 from 40/60. From the variable-temperature solid-state 13C CPMAS NMR measurements, it was suggested that the Monoclinic crystalline phase begins to melt beyond 55 °C, while the Orthorhombic crystal remained; the temperature was close to the Ti endothermic transition (so-called the order-disorder transition). Furthermore, the 13C spin-lattice relaxation time in the laboratory frame (T1C) of the Orthorhombic crystalline phase became significantly long after annealing, while that of the Monoclinic crystalline phase was not altered drastically. Similarly, the T1C of the amorphous phase was not affected by annealing. These observations suggested that the interaction between Na+ cations and carboxy groups in EMAA ionomers limits crystal growth of polyethylene, and the Ti is mainly caused by the melting of Monoclinic crystal.

Organic Carbon Speciation in Urban Anthrosols—The Legacy of Historical Waste Management

The impacts of waste management on various soils of agricultural and urban lands may last centuries or even millennia; however, generally, most studies tend to focus only on decadal or shorter timescales. This study investigates the characteristic properties of anthrosols in and around the urban settlement of St Andrews (Scotland), in the context of soil management and organic carbon content and speciation. Formed by the repeated application of fresh organic and pyrogenic wastes since the medieval period, these soils provide a 1000-year urban research context based on historical accounts of town waste management. We employed complementary methods of high-field solid-state 13C-CPMAS NMR, in situ magnetic susceptibility measurement, elemental micro-analysis and portable optically stimulated luminescence (OSL). A significant proportion of the soil organic carbon was present as refractory aromatic C structures, including aryl-C moieties. Portable OSL assessment revealed differences in the intensity and rate of sediment accumulation. The medieval urban areas had higher soil phosphorus concentrations, organic carbon content and magnetic susceptibility relative to the extra-urban site located outside of the medieval burgh. The study confirms that specific signatures, including carbon group functionalities, do reveal evidence of such induced long-lasting past anthropogenic soil modifications.

Silsesquioxane-based porous polymer derived from organic chromophore with AIE characteristics for selective detection of 2,4-dinitrophenol and Ru3+

A novel silsesquioxane-based polymers (PCS-DPB) was prepared by the Friedel-Crafts reaction of octavinylsilsesquioxane (OVS) with AIE-active 4-[1-cyano-2-[4-(diphenylamino)phenyl]ethenyl]-α-[[4-(diphenylamino)phenyl]methylene]benzeneea-cetonitrile (CN-DPB). FTIR, solid state 29Si MAS and 13C CP MAS NMR spectroscopy analyses are performed to confirm its chemical structure and the presence of silsesquioxane units in the cross-linked network. XRD and TEM results prove its amorphous feature of the PCS-DPB material. TGA shows a high thermal stability of PCS-DPB with 5% mass loss temperature about 438 °C due to the highly cross-linking density and the presence of the inorganic silsesquioxane cage. The CN-DPB unit endows PCS-DPB with an excellent luminescence and a large red shift of 120 nm, which makes it to act as a probe to detect 2,4-dinitrophenol (DNP) and Ru3+ with high selectivity and sensitivity.

Synthesis of a novel freestanding conjugated triazine-based microporous membrane through superacid-catalyzed polymerization for superior CO2 separation

This study aims at developing a novel freestanding conjugated triazine-based membrane (ETM-1) with permanent porosity via a low-temperature superacid-promoted polymerization reaction. In this venue, we used the bifunctional 4-ethynylbenzonitrile (4-EBN) monomer featuring ethynyl (CCH) and nitrile (CN) functionalities. At the same time, trifluoromethanesulfonic acid (CF3SO3H) served as both the catalyst and solvent. The cross-linked Polymer's physicochemical properties were systematically examined using TGA, BET, solid-state 13C CP-MAS NMR, ATR-FT-IR, and XPS spectroscopy techniques. With conjugated s-triazine (as a result of cyclotrimerization of nitrile) and CCH (as a result of cationic polymerization of ethynyl), the microporous ETM-1 membrane displayed a superior CO2 uptake capacity of up to 3.87 mmol g−1 (170.3 mg g−1) and enhanced ideal CO2/N2 and CO2/CH4 permselectivity values of 47 ± 2 and 21 ± 1 at 298 K and 1 bar, respectively. The notable selectivity of ETM-1 towards CO2 can be stated in terms of the molecular sieving (i.e., kinetic selection) characteristic of the microporous membrane, its electron-rich π-conjugated skeleton, and enhanced basicity, suitable for interacting with CO2via dipole-quadrupole and acid-base interactions. Moreover, ETM-1 exhibited the isosteric heat of CO2 adsorption ranging from 28.1 to 34.3 kJ mol−1, implying strong physisorption of CO2 upon the high-affinity adsorption sites of the membrane.

Metal/metal oxide-decorated covalent organic frameworks as electrocatalysts for electrocarboxylation and water splitting

A o-tolidine based triazine (TTP) covalent organic framework was prepared, and successful formation of the porous polymer network was confirmed by solid state 13C and 15N CP-MAS NMR spectra, XRD, and other morphological techniques. The synthesized TTP was decorated with transition metal/metal oxide nanoparticles (Cu, Ni, and Cu–Ni). The presence of CuO and NiO nanoparticles on the TTP matrix were confirmed by Raman spectroscopy and the PXRD analysis and different morphologies with modest changes in particle size and porosity were confirmed by FE-SEM and HR-TEM studies. As evidenced by onset potential and current density, the Cu-TTP sample exhibited excellent electrocatalytic activity for the electrochemical carboxylation of propylene oxide in the presence of CO2 and HER, whereas the Ni-TTP sample displayed excellent OER activity. The presence of pyridinic, pyrrolic, and quaternary nitrogen was attributed to the excellent catalytic activity of Cu-TTP for electrocarboxylation and HER activity, whereas secondary amine bonds and a combination of mechanisms were responsible for the increased OER activity of Ni-TTP the sample, as evidenced by XPS.

Ferrocene-Based Porous Organic Polymer (FPOP): Synthesis, Characterization and an Electrochemical Study

Ferrocene-based porous organic polymers (FPOPs) were prepared from phenol-formaldehyde polymer (Bakelite) and phenol as starting materials; and two possible mechanisms for polymerization were discussed. Solid-state 13C CP-MAS NMR, FTIR, powder XRD, elemental analysis and ICP (Fe, Na, B) were performed to characterize the prepared materials. The two synthetic approaches produced polymers with different pore sizes: the FPOP synthesized through Bakelite presented a higher surface area (52 m2 g−1) when compared to the one obtained by the bottom-up polymerization from phenol (only 5 m2 g−1). Thermogravimetric analysis confirmed the thermal stability of the material, which decomposed at 350 °C. Furthermore, cyclic voltammetry (CV) of the new FPOP on modified electrodes, in ACN and 0.1 M TBAP as an electrolyte, showed fully reversible electron transfer, which is similar to that observed for the ferrocene probe dissolved in the same electrolyte. As a proof-of-concept for an electrochromic device, this novel material was also tested, with a color change detected between yellow/brownish coloration (reduced form) and green/blue coloration (oxidized form). The new hybrid FPOP seems very promising for material science, energy storage and electrochromic applications, as well as for plastic degradation.

Single-pot tandem oxidative/C-H modification amidation process using ultrasmall PdNP-encapsulated porous organosilica nanotubes.

Herein, we studied a single-pot method with a dual catalysis process towards the conversion of primary aromatic alcohols to amides using ultrasmall PdNPs of controlled uniform size (1.8 nm) inside hybrid mesoporous organosilica nanotubes (MO-NTs). The catalyst exhibited excellent performance in water under mild conditions and showed high stability. The catalytic activity towards the tandem oxidation of alcohols in the presence of amine salts and H2O2 to their corresponding amides without producing byproducts was evaluated, and high yields were obtained for all products. The structure of the organosilica nanotubes containing palladium nanoparticles was investigated using various characterization techniques such as XRD, TEM, BET, solid-state 29Si NMR and solid-state 13C CP MAS NMR. Catalyst recycling tests showed that the catalytic power of PdNPs@B-SNTs was preserved after 8 cycles and a slight decrease in catalyst activity was observed.

Metal-Free Pyrene-Based Conjugated Microporous Polymer Catalyst Bearing N- and S-Sites for Photoelectrochemical Oxygen Evolution Reaction.

The development of an efficient, sustainable, and inexpensive metal-free catalyst for oxygen evolution reaction (OER) via photoelectrochemical water splitting is very demanding for energy conversion processes such as green fuel generators, fuel cells, and metal-air batteries. Herein, we have developed a metal-free pyrene-based nitrogen and sulfur containing conjugated microporous polymer having a high Brunauer-Emmett-Teller surface area (761 m2 g−1) and a low bandgap of 2.09 eV for oxygen evolution reaction (OER) in alkaline solution. The π-conjugated as-synthesized porous organic material (PBTDZ) has been characterized by Fourier transform infrared spectroscopy (FT-IR), solid-state 13C (cross-polarization magic angle spinning-nuclear magnetic resonance) CP-MAS NMR, N2 adsorption/desorption analysis, field-emission scanning electron microscope (FESEM), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS) and thermogravimetric analysis (TGA) experiments. The material acts as an efficient catalyst for photoelectrochemical OER with a current density of 80 mA/cm2 at 0.8 V vs. Ag/AgCl and delivered 104 µmol of oxygen in a 2 h run. The presence of low bandgap energy, π-conjugated conducting polymeric skeleton bearing donor heteroatoms (N and S), and higher specific surface area associated with inherent microporosity are responsible for this admirable photoelectrocatalytic activity of PBTDZ catalyst.

Silica Chemisorbed Bis(Hydrogensulphato)Benzene (SiO2-BHSB) as a New, Environmentally Benign and Recyclable Catalyst for an Efficient Synthesis of Biscoumarin Scaffolds in Water Based Solvent

The immobilization of homogeneous catalytic material over the inert heterogeneous support is a recent strategy to overcome the drawbacks and unite the merits associated with the homogeneous as well as heterogeneous catalysts. However the physisorption-induced immobilization does not serve the purpose because of its sensitive reversible nature, a tiny change in reaction parameters may revert the physisorption and so the immobilization. In this work, a new catalytic material silica chemisorbed bis(hydrogensulphato)benzene (SiO2-BHSB) was achieved through the chemisorption of bis(hydrogensulphato)benzene as an active catalytic part on the surface of porous silica. Structural features, purity, thermal stability, and acid strength of the synthesized SiO2-BHSB material were established by adequate analytical techniques, such as FT-IR, solid-state CP-MAS 13C NMR, solid-state CP-MAS 29Si NMR, EDX, DTG, TGA, and acid–base volumetric studies. An environmentally benign catalytic protocol for the synthesis of biscoumarin scaffolds through a tandem reaction between 4-Hydroxycoumarin and structurally diverse aldehydes was developed in which the synthesized material SiO2-BHSB was observed to work as an efficient and reusable catalyst. The structures of the synthesized biscoumarin derivatives were established from their physical and spectrometric data. The synthesized catalytic material was observed to show sustained catalytic activity even after five cycles of its recovery and reuse. In comparison with the earlier reported methods, a tiny amount (2.5 mol%) of catalyst is sufficient to bring out the transformation smoothly in an aqueous-based solvent, ease of recovery, and reusability of the catalyst are additional salient features of the present protocol.

Functionalization strategy influences the porosity of amino-containing porous aromatic frameworks and the hydrogenation activity of palladium catalysts synthesized on their basis

We investigated the influence of functionalization strategy (post- or pre-) on the structure of amino-modified porous aromatic frameworks (PAF-NH2). Different techniques, such as low-temperature N2 adsorption-desorption, IR spectroscopy and solid-state CP-MAS 13C NMR spectroscopy, were used to characterize the synthesized materials. Palladium catalysts were prepared based on obtained PAF-NH2 supports, characterized by TEM, XPS and elemental analysis and studied in the semihydrogenation of C8-acetylenes and dienes. The results show that the modification approach influences structure of PAF and, therefore, the morphology and distribution of palladium nanoparticles. Post-modified catalysts proved to be more active, while pre-modified ones exhibited enhanced selectivity towards desired olefins and improved stability.

Fast and Selective Aqueous-Phase Oxidation of Styrene to Acetophenone Using a Mesoporous Janus-Type Palladium Catalyst.

A heterogeneous Janus-type palladium interphase catalyst was obtained by selective surface modification of a hollow mesoporous silica material. The catalyst comprises hydrophobic octyl groups on one side of the silica nanosheets and single-site bis-imidazoline dichlorido palladium(II) complexes on the other. The structure of this composite material has been analyzed by means of elemental analysis, atomic absorption spectroscopy, BET surface analysis, TGA, SEM and solid-state CP-MAS 13C and 29Si NMR spectroscopy. The catalyst showed extraordinary activity for the aqueous-phase oxidation of styrene to acetophenone using 30% hydrogen peroxide as the oxidant. An 88% yield of acetophenone could be achieved after 60 min.

Bifunctional crystalline microporous organic polymers: Efficient heterogeneous catalysts for the synthesis of 5-hydroxymethylfurfural

Developing efficient catalysts for the synthesis of 5-hydroxymethylfurfural (HMF) from biomass resources is very demanding as it is an important renewable platform chemical for the synthesis of biofuels, polymers and fine chemicals. Here, we have designed two new crystalline microporous bi-functional porous organic polymers through the extended aromatic substitution reaction under refluxing conditions. Porous polymers containing sulfonic acid and secondary amine groups are two reactive catalytic centres for carrying out the bi-functional heterogeneously catalysed reactions. Bifunctionalized porous polymers POPDS and POPSDS are synthesized through the reaction of 2,2′-benzidinedisulfonic acid and 4,4′-diaminostilbene-2,2′-disulfonic acid with cyanuric chloride, respectively. The materials were characterized thoroughly using powder X-ray diffraction, N2 sorption, FTIR, solid state 13C CP MAS NMR spectroscopy, FE-SEM, HR-TEM, XPS and TG/DTA analysis. These two crystalline porous polymers possesses good surface acidic and basic sites, and having flower-like and spherical particle morphologies. POPDS and POPSDS exhibited superior catalytic activity for the conversion of different small carbohydrates to 5-hydroxymethylfurfural (HMF) under microwave irradiation. Moreover, the recyclability tests of these catalysts revealed good durability up to sixth consecutive reaction cycles, suggesting the future potential of these catalysts in the sustainable synthesis of HMF.

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.