Building Porous Ni(Salen)-Based Catalysts from Waste Styrofoam via Autocatalytic Coupling Chemistry for Heterogeneous Oxidation with Molecular Oxygen.

The development of robust and industrially viable catalysts from plastic waste is of great significance, and the facile construction of high performance heterogeneous catalyst systems for phenol-quinone conversions remains a grand challenge. Herein, a feasible strategy is demonstrated to reclaim Styrofoam into hierarchically porous nickel-salen-loaded hypercrosslinked polystyrene (PS@Ni-salen) catalysts with high activities through an unusual autocatalytic coupling route. The salen is immobilized onto PS chain by Friedel-Crafts alkylation of benzyl chloride derivatives, and the generated hydrogen chloride coordinately promotes the simultaneous crosslinking and bridge formation between aromatic rings via a Scholl coupling route, leading to hierarchically porous networks. After the metallization with Ni, the resultant networks exhibit high catalytic activity for the oxidation of 2,3,6-trimethylphenol to 2,3,5-trimethyl-1,4-benzoquinone under mild conditions (303 K, 1 bar of O2 ). This catalyst also demonstrates attractive recycling performance without an obvious loss of catalytic efficiency over five consecutive cycles. This methodology might provide a potential sustainable alternative to construct environmentally benign and cost-effective catalysts for specific organic transformation.

A Vinylene-Bridged Conjugated Covalent Triazine Polymer as a Visible-Light-Active Photocatalyst for Degradation of Methylene Blue.

The development of new photocatalytic platforms using novel semiconductor material is an important challenge. Herein, a sp2 carbon-conjugated covalent triazine polymer (sp2 c-CTP-4), featuring a vinylene bridge and extended π-conjugation, is prepared as a highly efficient photocatalyst for degradation of methylene blue. sp2 c-CTP-4 exhibits substantial semiconducting properties such as enhanced charge transfer and prolonged lifetime of carriers compared to its counterparts with CN or CC connections, likely due to its extended π-delocalization with an unencumbered CC bridge. Moreover, benefiting from its high chemical stability, the as-made catalyst can be recycled five times with good retention of photocatalytic activity. This study provides a new pathway for constructing a robust platform for efficient photocatalysis and gives insight into the structure-property relationship of conjugated polymers.

A Luminescent Hypercrosslinked Conjugated Microporous Polymer for Efficient Removal and Detection of Mercury Ions.

A hypercrosslinked conjugated microporous polymer (HCMP-1) with a robustly efficient absorption and highly specific sensitivity to mercury ions (Hg(2+)) is synthesized in a one-step Friedel-Crafts alkylation of cost-effective 2,4,6-trichloro-1,3,5-triazine and dibenzofuran in 1,2-dichloroethane. HCMP-1 has a moderate Brunauer-Emmett-Teller specific surface (432 m(2) g(-1)), but it displays a high adsorption affinity (604 mg g(-1)) and excellent trace efficiency for Hg(2+). The π-π* electronic transition among the aromatic heterocyclic rings endows HCMP-1 a strong fluorescent property and the fluorescence is obviously weakened after Hg(2+) uptake, which makes the hypercrosslinked conjugated microporous polymer a promising fluorescent probe for Hg(2+) detection, owning a super-high sensitivity (detection limit 5 × 10(-8) mol L(-1)).

Co(III)-Salen immobilized cellulose nanocrystals for efficient catalytic CO2 fixation into cyclic carbonates under mild conditions.

Searching for green, recyclable and highly efficient catalyst for the synthesis of cyclic carbonates from CO2 is of great importance because it is profitable for reducing the greenhouse effects and meets the principles of green chemistry. Herein, a series of cellulose nanocrystals, either the pristine or modified ones (TEMPO oxidized and Co(III)salen immobilized), were explored as catalysts for cycloaddition of epoxides and carbon dioxide. The impact of surface properties on the performance of the as-made catalysts was investigated. Co(III)-salen grafted cellulose nanocrystals was proven to be the most effective catalyst in this study, which could afford excellent yield up to 99 % after 24 h even under low CO2 pressures of 0.1 MPa. They can be easily recovered and reused for at least 4 times, demonstrating their excellent stability. We found that the surface functional groups such as enriched sulfate or carboxylic groups could also account for the enhanced catalytic activity. This work highlights the applications of green and sustainable nanoparticles in a cycloaddition reaction and offers a sustainable solution in industrial catalysis related to CO2 conversions.