Ni, Co-Embedded MOF-Derived N-Doped Bimetallic Porous Carbon for Adsorption-Photocatalytic Degradation of Organic Dyes and Antibiotics.

An efficient protocol for photocatalytic degradation of organic dyes and antibiotics has been successfully established via MOF-derived (MOF = metal-organic framework) Ni, Co-embedded N-doped bimetallic porous carbon nanocomposites (NiCo/NC). Such a NiCo/NC nanocomposite features well-distributed structures, suitable specific surface areas, and more active sites determined by various characterization analyses. The catalyst exhibits higher photocatalytic performance and stability toward the liquid-phase degradation of methylene blue (MB) under visible light irradiation for 60 min, after the adsorption-desorption equilibrium and the thorough degradation into H2O and CO2. Radical quenching experiments further confirmed the dominant effect of electron holes h+ and superoxide radical anions ·O2- for the MB photodegradation process. NiCo/NC was also appropriate for the degradation of Rhodamine B, methyl orange, tetracycline hydrochloride, and norfloxacin. Moreover, NiCo/NC is robust, and its photocatalytic activity is basically maintained after 8 cycles. This work is expected to provide additional information for the design of MOF-derived carbon material with more excellent properties and lay the foundation for further industrial applications.

Separation and Analysis of Oxygen-Containing Compounds in a Shaanxi Middle/Low-Temperature Coal Tar.

A middle/low-temperature coal tar (M/LTCT) was obtained from a low-temperature carbonization plant in Shaanxi, China. The M/LTCT was separated into light components and coal tar pitch through extraction. A series of alkanes, aromatic hydrocarbons, oxygen-containing arenes (OCAs), and nitrogen-containing arenes were fractionated from light components by medium-pressure preparative chromatography with gradient elution using petroleum ether and ethyl acetate. They were analyzed using a gas chromatography-mass spectrometer (GC-MS) and a Fourier transform infrared spectrometer. The OCAs were analyzed by a Fourier transform Orbitrap MS (quadrupole exactive Orbitrap mass spectrometer), and the molecular distribution of the O 1-O 6 species was studied. OCAs are mainly oxygen-containing aromatic compounds, including aromatic phenols, furans, alkoxy aromatic hydrocarbons, aromatic ethers, aromatic aldehydes, aromatic ketones, and aromatic acids. The position of the oxygen atom on the aromatic ring and the condensation form of the aromatic ring are studied.

Insight into the Compositional Features of Organic Matter in Xilinguole Lignite through Two Mass Spectrometers.

Ethanolysis of lignite is an effective approach for converting organic matter of lignite to liquid coal derivatives. Xilinguole lignite (XL) was reacted with ethanol at 320 °C. Then ethanol and isometric carbon disulfide/acetone mixture were used to extract the reaction mixture in a modified Soxhlet extractor to afford extractable portion 1 (EP1) and extractable portion 2 (EP2), respectively. According to analysis of EP1 with a gas chromatography/mass spectrometer, phenolic compounds made up more than 33% of the compounds detected. This could be ascribed to the ethanolysis of XL; that is, ethanol could selectively break the Calkyl-O bonds in lignite, producing more phenolic compounds. Furthermore, a quadrupole Orbitrap mass spectrometer equipped with an atmospheric pressure chemical ionization source was used for comprehensive analysis of the compositional features of EP1. The analysis indicated that O1-3, N1O0-2, and N2S1O3-6 were predominant class species in EP1. Nitrogen atoms in NO-containing organic compounds may exist in the form of pyridine or amidogen, while oxygen atoms primarily exist in furan, alkoxy, carbonyl, and ester groups. In addition, possible chemical structures of NO-containing organic compounds were speculated.

Enhanced Adsorption-Photocatalytic Degradation of Organic Pollutants via a ZIF-67-Derived Co-N Codoped Carbon Matrix Catalyst.

Stable and efficient photocatalytic degradation of organic pollutants has been achieved via a ZIF-67-derived Co-embedded N-doped nanoporous carbon material catalyst (Co-N/C). The catalyst features a well-distributed structure, suitable specific surface area, and more active sites according to the various characterization analyses. The photocatalytic activity of Co-N/C was evaluated by the degradation of the target pollutant Rhodamine B (RhB). As a result, RhB could establish an adsorption-desorption equilibrium in the dark within 30 min and was thoroughly degraded into H2O and CO2 by Co-N/C under 500 W visible light irradiation in 40 min. Moreover, radical-quenching experiments and reactive oxygen species monitoring were performed to further probe the plausible photodegradation mechanism of RhB. Co-N/C is also appropriate for other alternative dyes and antibiotics affording ideal removal efficiencies. After the reaction, Co-N/C could be facilely separated by an external magnetic field and reused for eight reaction cycles without obvious deactivation of its photocatalytic properties. This study is expected to provide an instructive guideline for the design of efficient and recyclable composite photocatalysts derived from metal-organic frameworks for a broad range of environmental remediation processes.

Mesoscopic Detection of the Influence of a Third Component on the Self-Assembly Structure of A2B Star Copolymer in Thin Films.

The most common self-assembly structure for A2B copolymer is the micellar structure with B/A segments being the core/corona, which greatly limits its application range. Following the principle of structure deciding the properties, a reformation in the molecular structure of A2B copolymer is made by appending three segments of a third component C with the same length to the three arms, resulting (AC)2CB 3-miktoarm star terpolymer. A reverse micellar structure in self-assembly is expected by regulating the C length and the pairwise repulsive strength of C to A/B, aiming to enrich its application range. Keeping both A and B lengths unchanged, when the repulsion strength of C to A is much stronger than C to B, from the results of mesoscopic simulations we found, with a progressive increase in C length, (AC)2CB terpolymer undergoes a transition in self-assembled structures, from a cylindrical structure with B component as the core, then to a deformed lamellar structure, and finally to a cylindrical structure with A component as the core. This reverse micellar structure is formed with the assistance of appended C segments, whose length is longer than half of B length, enhancing the flexibility of three arms, and further facilitating the aggregation of A component into the core. These results prove that the addition of a third component is a rational molecular design, in conjunction with some relevant parameters, enables the manufacturing of the desired self-assembly structure while avoiding excessive changes in the involved factors.

Solvent Effect on the Self-Assembly of a Thin Film Consisting of Y-Shaped Copolymer.

The self-assembly of an amphiphilic Y-shaped copolymer consisting of two hydrophilic branches and one hydrophobic branch in a thin film is investigated under different conditions by virtue of mesoscopic computer modelling, accompanied by doping with a single solvent, doping with a binary solvent, and those solvent environments together with the introduction of confinement defined by various acting distances and influencing regions. A cylindrical micellar structure is maintained, as it is in the thin film with the doping of either 10% hydrophobic solvent or 10% hydrophilic solvent, whose structure consists of the hydrophobic core and hydrophilic shell. Attributed to the hydrophobicity/hydrophilia nature of the solvents, different solvents play an obvious role on the self-assembled structure, i.e., the hydrophobic solvent presents as a swelling effect, conversely, the hydrophilic solvent presents as a shrinking effect. Further, the synergistic effect of the binary solvents on the self-assembly produces the lowest values in both the average volumetric size and free energy density when the quantity of hydrophobic solvent and hydrophilic solvent is equivalent. Interestingly, the solvent effect becomes more pronounced under the existent of a confinement. When a lateral-oriented confinement is introduced, a periodically fluctuating change in the cylindrical size occurs in two near-wall regions, but the further addition of either hydrophobic or hydrophilic solvent can effectively eliminate such resulting hierarchical-sized cylinders and generate uniform small-sized cylinders. However, with the introduction of a horizontal-orientated confinement, the copolymers self-assemble into the spherical micellar structure. Moreover, the further addition of hydrophobic solvent leads to a decrease in the average size of micelles via coalescence mechanism, in contrast, the further addition of hydrophilic solvent causes an increase in the average size of micelles via splitting mechanism. These findings enrich our knowledge of the potential for the solvent effect on the self-assembly of amphiphilic copolymer system, and then provide theoretical supports on improving and regulating the mesoscopic structure of nanomaterials.