Pillararene-Based Supramolecular Polymers for Adsorption and Separation.

Supramolecular polymers have attracted increasing attention in recent years due to their perfect combination of supramolecular chemistry and traditional polymer chemistry. The design and synthesis of macrocycles have driven the rapid development of supramolecular chemistry and polymer science. Pillar[n]arenes, a new generation of macrocyclic compounds possessing unique pillar-shaped structures, nano-sized cavities, multi-functionalized groups, and excellent host-guest complexation abilities, are promising candidates to construct supramolecular polymer materials with enhanced properties and functionalities. This review summarizes recent progress in the design and synthesis of pillararene-based supramolecular polymers (PSPs) and illustrates their diverse applications as adsorption and separation materials. All performances are evaluated and analyzed in terms of efficiency, selectivity, and recyclability. Typically, PSPs can be categorized into three typical types according to their topologies, including linear, cross-linked, and hybrid structures. The advances made in the area of functional supramolecular polymeric adsorbents formed by new pillararene derivatives are also described in detail. Finally, the remaining challenges and future perspectives of PSPs for separation-based materials science are discussed. This review will inspire researchers in different fields and stimulate creative designs of supramolecular polymeric materials based on pillararenes and other macrocycles for effective adsorption and separation of a variety of targets.

Successive choline addition enhancing the methanogenesis of waste activated sludge anaerobic digestion: Insight from hydrophilicity, electrochemical performance and microbial community.

Anaerobic digestion (AD) is a promising technology to treat waste-activated sludge, previous study proved that methane production could be enhanced with the addition of choline, this work aimed to solve the problem of rapid biodegradability of choline in the AD process by changing its dosing method. With 0.75 g/L as the optimal choline dosing concentration, experimental results showed that successive choline dosing during the first 3-6 days of AD (experimental groups, EGs) performed better than the single dosing. The accumulative biogas production in EGs was increased by 35.55-36.73%, which could be caused by the simultaneous promotion of hydrolysis-acidification and methanogenesis processes. Especially, the electron exchange capacity of digested sludge in EGs was increased by 16.71-34.58%. In addition, the surface Gibbs free energy (△GSL) of sludge in EGs was 105.51-172.21% higher (corresponding to stronger hydrophilicity and repulsion), which might help disperse sludge flocs and improve mass transfer efficiency, and the △GSL values were positively correlated with the accumulative methane production (R2 = 0.7029). Microbiological analysis showed that microbial communities in EGs were richer and Methanosaeta was regarded as the dominant species with 15.93-30.08% higher relative abundance with choline addition. According to Kyoto Encyclopedia of Genes and Genomes (KEGG) pathway analysis, EGs were found to be more active in metabolism clusters. Collectively, these findings demonstrated that successive choline dosing during the first 3-6 days is an effective and novel method to enhance methane production in AD process.

Medium-Low Temperature Conditions Induce the Formation of Environmentally Persistent Free Radicals in Microplastics with Conjugated Aromatic-Ring Structures during Sewage Sludge Pyrolysis.

Medium-low temperature pyrolysis is an effective method of retaining active components in sludge char. However, we found that incomplete cracking reactions resulted in residues of microplastics (MPs) remaining in the char; moreover, high levels of environmentally persistent free radicals (EPFRs) were detected in these MPs. Here, we investigated the temperature-dependent variations in the char-volatile products derived from sludge and MPs under different pyrolysis scenarios using multiple in situ probe coupling techniques and electron paramagnetic resonance spectroscopy, thereby identifying the sources of EPFRs and elucidating the corresponding formation-conversion mechanisms. The temperature was the key factor in the formation of EPFRs; in particular, in the 350-450 °C range, the abundance of EPFRs increased exponentially. Reactive EPFR readily formed in MPs with conjugated aromatic-ring structures (polyethylene terephthalate and polystyrene) at a temperature above 350 °C; EPFR concentrations were 5-17 times higher than those found in other types of polymers, and these radicals exhibited half-lives of more than 90 days. The EPFR formation mechanism could be summarized as solid-solid/solid-gas interfacial interactions between the polymers and the intermediate products from sludge pyrolysis (at 160-350 °C) and the homolytic cleavage-proton transfer occurring in the polymers themselves under the dual action of thermal induction and acid sites (at 350-450 °C). Based on the understanding of the evolution of EPFRs, temperature regulation and sludge components conditioning may be effective approaches to inhibit the formation of EPFRs in MPs, constituting reliable strategies to diminish the environmental risk associated with the byproducts of sludge pyrolysis.