Polyaniline: A New Metal-Free Catalyst for Peroxymonosulfate Activation with Highly Efficient and Durable Removal of Organic Pollutants.

Metal-free heterogeneous catalysts are receiving more and more attention for wastewater remediation by activating peroxymonosulfate (PMS) due to their environmental benign. However, carbon-based materials as the most typical metal-free heterogeneous always suffer from poor durability. Inspired by the fact that a conjugated system may facilitate the electron transfer during PMS activation, we innovatively select polyaniline (PANI) as a new PMS activator and investigate its catalytic performance in detail. It is found that PANI can display better catalytic performance than traditional metal-based catalysts and popular N-doped carbocatalysts in methyl orange (MO) degradation. More importantly, PANI is not only universal for various pollutants degradation but also maintains its catalytic performance in repeated degradation experiments. The stable N sites in the conjugated chains and the oxidation-resistance benzene rings as the building units are considered to be responsible for such an excellent durability. In addition, the influences of some routine factors and actual water backgrounds are comprehensively checked and analyzed. The quenching experiments and electron paramagnetic resonance confirm that MO degradation is achieved through both radical and nonradical pathways, where SO4•- and 1O2 are primary reactive species. The reaction mechanism is also proposed with the assistance of X-ray photoelectron spectroscopy.

In Situ Growth of Nitrogen-Doped Carbon Nanotubes Based on Hierarchical Ni@C Microspheres for High Efficiency Bisphenol A Removal through Peroxymonosulfate Activation.

N-doped carbon nanotubes (NCNTs) are promising metal-free heterogeneous catalysts toward peroxymonosulfate (PMS) activation in advanced oxidation processes for wastewater remediation. However, conventional CNTs always suffer from serious agglomeration and low N content, which renders their design synthesis as an important topic in the related field. With hierarchical Ni@C microspheres as a nutritious platform, we have successfully induced in situ growth of NCNTs on their surface by feeding melamine under high-temperature inert atmospheres. These as-grown NCNTs with a small diameter (ca. 20 nm) are firmly rooted in Ni@C microspheres and present loose accumulation on their surface, and their relative content can be tailored easily by manipulating the mass ratio of melamine to Ni@C microspheres. The investigation on bisphenol A (BPA) removal reveals that the loading amount of NCNTs affects the catalytic performance greatly, and the optimum ratio of melamine to Ni@C microspheres is 5.0 because the corresponding MNC-5.0 possesses sufficient surface N sites and moderate electron transfer, resulting in powerful PMS activation and sufficient utilization of reactive oxidative species (ROS). MNC-5.0 also addresses its advantages as compared with other NCNTs from post treatment and spontaneous growth strategies. The primary ROS responsible for BPA degradation are identified as hydroxyl radical, sulfate radical, superoxide radical, and singlet oxygen through quenching experiments and electron paramagnetic resonance, and the corresponding catalytic mechanism is also put forward based on these results.

Prussian Blue Microcrystals with Morphology Evolution as a High-Performance Photo-Fenton Catalyst for Degradation of Organic Pollutants.

The morphology-dependent property of crystal materials has aroused extensive attention and raised high requirements for subtly tailoring the morphology of micro-/nanocrystals. Herein, we develop an in situ etching method for preparation of Prussian blue (PB) microcrystals with morphology evolution by progressively increasing the concentration of chloroplatinic acid in the reaction system. These PB microcrystals with controllable morphologies are employed as photo-Fenton reagents to degrade organic pollutants. PB hexapods (PB-hpds) and PB hexapod stars present superior catalytic performance to pristine PB microcubes and other PB intermediates with truncated corners or edges because of their high specific surface areas and adequate exposure of FeIII-NC coordination active sites. In the reusability test, the reused PB-hpds present more efficient catalytic performance for rhodamine B decomposition compared with the pristine catalyst. According to more investigations, the reasonable mechanism is proposed that FeIII-NC exhibits higher catalytic activity than FeII-CN in the specific coordination environment. The increased content of surface FeIII-NC coordination active sites is the key factor in accelerating the decomposition of H2O2 and enhancing the photo-Fenton performance of PB-hpds. Several operating parameters including catalyst dosage, H2O2 concentration, pH value, and reaction temperature are evaluated in detail. Classical quenching experiments and electron paramagnetic resonance measurements further reveal that HO• should be responsible for high performance of catalysts. This work will be significant for tailoring the morphology of the materials and arousing more attention to enhance the stability and reusability of catalysts.