Molecular understanding on ultraviolet photolytic degradation of cyano liquid crystal monomers.

Cyano liquid crystal monomers (LCMs) are proposed as emerging chemical pollutants with persistent, bioaccumulative, and toxic properties. Herein, five cyano LCMs, including 4-cyano-4'-ethylbiphenyl (2CB), 4-Butyl-4'-cyanobiphenyl (4CB), 4-cyano-4'-ethoxybiphenyl (2OCB), 4-(trans-4-Ethylcyclohexyl)benzonitrile (2CHB) and 4-(trans-4-Vinylcyclohexyl)benzonitrile (2eCHB), were selected to investigate the reaction kinetics and excited state characteristic variations with their molecular structures by ultraviolet (UV) photolysis. Theoretical calculations reveal that the benzene ring, ethoxy and double bond can deeply alter the electron distribution of cyano LCMs. This will affect the exciton separation ability, excitation properties and active sites to electrophilic attack, causing the distinction in photolysis efficiency. Due to the effective charge separation during local excitation (LE) process and the property of being most susceptible to electrophilic attack by 1O2 and O2•-, 2eCHB with double bond exhibits the largest degradation rate. Conversely, the weakest exciton separation of 2OCB with ethoxy during charge transfer (CT) process limits its subsequent sensitized photolysis process. The molecular orbital and fragment contributions to holes and electrons further deepen the understanding of the excited states charge transfer. This study confirmed that the intrinsic molecular structure, chemical nature and existing sites directly defined the excitation and decomposition activity in the UV photolysis of cyano LCMs.

Piezoelectric-channels in MoS2-embedded polyvinylidene fluoride membrane to activate peroxymonosulfate in membrane filtration for wastewater reuse.

The conjugation of membrane filtration (MF) with advanced oxidation process (AOPs) is being considered as an alternative advanced treatment process for the potable reuse of wastewater. Beyond conventional MF/AOPs conjugation, a new downstream MF process with piezoelectric-channels induced piezo-activated peroxymonosulfate (PMS) is herein constructed to deal with antiepileptic carbamazepine (CBZ) pollutants through polyvinylidene fluoride (PVDF) membrane (PVDF-M10). Through a MF process, ca. 93.8% CBZ pollutants can be removed under an ultrasonic-assisted piezo-activation PMS, whereas only 18.3% and 60.2% CBZ can be removed by using pure PVDF membrane under the same condition and PVDF-M10 membrane without ultrasonic-assisted piezo-activation. Even after 9-cycles, CBZ removal efficiency was maintained at 56.4% under this MF process. These superior performances are attributed to the piezoelectric exfoliated-MoS2 nanosheets (E-MoS2) embedded PVDF nanofibers in PVDF-M10 membrane, which lead to rich piezoelectric-channels in the membrane. These piezoelectric-channels not only produced more charges to activate PMS to boost the yield of reactive oxide species (ROS) but also provided an ideal platform for the rapid reaction between CBZ and ROS during MF process. This investigation develops a new MF technique to conjugate piezo-activation of PMS-AOPs for the efficient removal of emerging pollutants for the potable reuse of wastewater.

Molecular structure on the detoxification of fluorinated liquid crystal monomers with reactive oxidation species in the photocatalytic process.

Fluorinated liquid crystal monomers (LCMs) are begun to emerge as new persistent organic pollutants. Herein, the structure-reactivity relationships of fluorinated LCMs 1,2,3-trifluoro-5-[3-(3-propylcyclohexyl)cyclohexyl]benzene (TPrCB), 1,2-difluoro-4-[trans-4-(trans-4-propylcyclohexyl)cyclohexyl]benzene (DPrCB), 4-[(trans,trans)-4'-(3-Buten-1-yl)[1,1'-bicyclohexyl]-4-yl]-1,2-difluoro-benzene (BBDB) and 1-[4-(4-ethylcyclohexyl)cyclohexyl]-4(trifluoromethoxy)benzene (ECTB) subject to photocatalysis-generated oxidation species were investigated. The degradation rate constant of BBDB was 3.0, 2.6, and 6.8 times higher than DPrCB, TPrCB and ECTB, respectively. The results reveal that BBDB, DPrCB and TPrCB had mainly negative electrostatic potential (ESP) regions which were vulnerable to electrophilic attack by h+, •OH and •O2 -, while ECTB was composed of mainly positive ESP regions which were vulnerable to nucleophilic attack by •OH and •O2 -. The detoxification processes of BBDB, DPrCB and TPrCB included carbon bond cleavage and benzene ring opening. However, the methoxy group of ECTB reduced the nucleophilic reactivity on the benzene ring, leading to slower detoxification efficiency. These findings may help to develop LCMs treatment technologies based on structure-reactivity relationships.

Phase transition of Mg/Al-flocs to Mg/Al-layered double hydroxides during flocculation and polystyrene nanoplastics removal.

Nanoplastics, a kind of emerging pollutant in natural environments, have now drawn tremendous attention worldwide. Flocculation with Mg/Al-layered double hydroxides (LDH) precursor solutions has showed great potential for removing negatively charged nanoparticles from water. In this study, the flocculation behavior and mechanism for the removal of polystyrene nanoplastics (PSNP) with Mg/Al flocs or Mg/Al LDH were systematically analyzed and investigated. During the process of flocculation, it was observed that in situ Mg/Al LDH can be gradually formed with increasing pH, in addition, PSNP were captured or attached to the surface of LDH with a turning point around pH of 5.0. In acidic solutions with pH < 5.0, the negative surface charges of PSNP were diminished mainly due to the high concentrations of hydrogen ions and the positive charges from Mg and Al ions. In a moderately alkaline solution, Mg and Al ions gradually formed crystals capturing PSNP. Electrostatic adsorption and intermolecular force are the main mechanisms via which PSNP are captured on Mg/Al flocs. Herein, PSNP removal efficiencies from water were more than 90.0%. As the problem of plastic pollution becomes more severe, in situ LDH growth flocculation can provide an efficient way for the removal of PSNP.