Efficient As(III) removal from water by ZrO2 modified covalent organic framework under visible light irradiation.

Adsorption-oxidation is a promising technique to decontaminate As(III) polluted water. In present study, ZrO2-modified covalent organic framework (ZrO2-COF) was fabricated and used to remove arsenic from water under visible light irradiation. The results showed that ZrO2-COF (0.2 g/L) could efficiently capture As(III) (5 mg/L) from water and then oxidize the adsorbed As(III) into less toxic As(V) under visible light irradiation (60 min), achieving the complete decontamination of As(III) polluted water. Based on characterization results and theoretical calculations, we found that in ZrO2-COF composite, ZrO2 served as sites for adsorption of As(III)/the latter transformed As(V), while COF worked as photocatalytic center for As(III) oxidation. Effective As(III) removal could also be achieved by ZrO2-COF under visible light irradiation in complex water chemistry conditions including wide solution pH range (3-11), broad solution ion strength range (1-100 mM), the copresence of natural organic matter (0.1-1 mg/L humic acid) and various coexisting ions in solutions, as well as in real water samples. In addition, we found that ZrO2-COF had excellent reuse performance in 4 consecutive cycles. Our results showed that under visible light irradiation, ZrO2-COF composites could be a promising technique for efficient As(III) removal from water.

Efficient Photosynthesis of Hydrogen Peroxide by Cyano-Containing Covalent Organic Frameworks from Water, Air and Sunlight.

The insufficient exciton (e- -h+ pair) separation/transfer and sluggish two-electron water oxidation are two main factors limiting the H2 O2 photosynthetic efficiency of covalent organic frameworks (COFs) photocatalysts. Herein, we present an alternative strategy to simultaneously facilitate exciton separation/transfer and reduce the energy barrier of two-electron water oxidation in COFs via a dicyano functionalization. The in situ characterization and theoretical calculations reveal that the dicyano functionalization improves the amount of charge transfer channels between donor and acceptor units from two in COF-0CN without cyano functionalization to three in COF-1CN with mono-cyano functionalization and four in COF-2CN with dicyano functionalization, leading to the highest separation/transfer efficiency in COF-2CN. More importantly, the dicyano group activates the neighbouring C atom to produce the key *OH intermediate for effectively reducing the energy barrier of rate-determining two-electron water oxidation in H2 O2 photosynthesis. The simultaneously enhanced exciton separation/transfer and two-electron water oxidation in COF-2CN result in high H2 O2 yield (1601 µmol g-1 h-1 ) from water and oxygen without using sacrificial reagent under visible-light irradiation. COF-2CN can effectively yield H2 O2 in water with wide pH range, in different real water samples, in scaled-up reactor under natural sunlight irradiation, and in continuous-flow reactor for consecutively producing H2 O2 solution for water decontamination.

Covalent organic frameworks for direct photosynthesis of hydrogen peroxide from water, air and sunlight.

Solar-driven photosynthesis is a sustainable process for the production of hydrogen peroxide, the efficiency of which is plagued by side reactions. Metal-free covalent organic frameworks (COFs) that can form suitable intermediates and inhibit side reactions show great promise to photo-synthesize H2O2. However, the insufficient formation and separation/transfer of photogenerated charges in such materials restricts the efficiency of H2O2 production. Herein, we provide a strategy for the design of donor-acceptor COFs to greatly boost H2O2 photosynthesis. We demonstrate that the optimal intramolecular polarity of COFs, achieved by using suitable amounts of phenyl groups as electron donors, can maximize the free charge generation, which leads to high H2O2 yield rates (605 µmol g-1 h-1) from water, oxygen and visible light without sacrificial agents. Combining in-situ characterization with computational calculations, we describe how the triazine N-sites with optimal N 2p states play a crucial role in H2O activation and selective oxidation into H2O2. We further experimentally demonstrate that H2O2 can be efficiently produced in tap, river or sea water with natural sunlight and air for water decontamination.

Boosting Exciton Dissociation and Charge Transfer in Triazole-Based Covalent Organic Frameworks by Increasing the Donor Unit from One to Two for the Efficient Photocatalytic Elimination of Emerging Contaminants.

As novel photocatalysts, covalent organic frameworks (COFs) have potential for water purification. Insufficient exciton dissociation and low charge mobility in COFs yet restricted their photocatalytic activity. Excitonic dissociation and charge transfer in COFs could be optimized via regulating the donor-acceptor (D-A) interactions through adjusting the number of donor units within COFs, yet relevant research is lacking. By integrating the 1,2,4-triazole or bis-1,2,4-triazole unit with quinone, we fabricated COF-DT (with a single donor unit) and COF-DBT (with double donor units) via a facile sonochemical method and used to decontaminate emerging contaminants. Due to the stronger D-A interactions than COF-DT, the exciton binding energy was lower for COF-DBT, facilitating the intermolecular charge transfer process. The degradation kinetics of tetracycline (model contaminant) by COF-DBT (k = (12.21 ± 1.29) × 10-2 min-1) was higher than that by COF-DT (k = (5.11 ± 0.59) × 10-2 min-1) under visible-light irradiation. COF-DBT could efficiently photodegrade tetracycline under complex water chemistry conditions and four real water samples. Moreover, six other emerging contaminants, both Gram-negative and Gram-positive strains, could also be effectively eliminated by COF-DBT. High tetracycline degradation performance achieved in a continuous-flow system and in five reused cycles in both laboratory and outdoor experiments with sunlight irradiation showed the stability and the potential for the practical application of COF-DBT.

Efficient peroxymonosulfate activation by magnetic MoS2@Fe3O4 for rapid degradation of free DNA bases and antibiotic resistance genes.

Antibiotic resistance genes (ARGs) have become as emerging contaminant with great concerns worldwide due to their threats to human health. It is thus urgent to develop techniques to degrade ARGs in water. In this study, MoS2@Fe3O4 (MF) particles were fabricated and used to activate peroxymonosulfate (PMS) for the degradation of four types of free DNA bases (T, A, C, and G, major components of ARGs) and ARGs. We found that MF/PMS system could effectively degrade all four DNA bases (T within 10 min, A within 30 min, C within 5 min, and G within 5 min) in very short time. During the reaction process, MF could activate PMS to form the reactive radicals such as ·OH, SO4·-, O2·-, and 1O2, contributing to the degradation of DNA bases. Due to the low adsorption energy, high charge transfer, and great capability for PMS cleavage, MF exhibited excellent PMS adsorption and activation performances. MoS2 in MF could enhance the cycle of Fe(III)/Fe(II), improving the catalytic performance. Excellent catalytic performances of MF/PMS system were achieved in complex water matrix (including different solution pH, coexisting of anions and natural organic matter) as well as in real water samples (including tap water, river water, sea water, and sewage) especially under high salinity conditions due to the generation of Cl· radicals and HClO species. MF/PMS system could also efficiently degrade ARGs (chromosomal kanR and plasmid gmrA) and DNA extracted from antibiotic resistant bacteria (ARB) in super-short time. Moreover, complete disinfection of two types of model ARB (E. coli K-12 MG 1655 and E. coli S17-1) could also be achieved in MF/PMS system. The high degradation performances of MF/PMS system achieved in the reused experiments and the 14-day continuous flow reactor experiments indicated the stability of MF particles. Due to the magnetic property, it would be convenient to separate MF particles from water after use via using magnet, facilitating their reuse of MF and avoiding potential water contamination by catalysts. Overall, this study not only provided a deep insight on Fe/Mo-triggered PMS activation process, but also provided an effective and reliable approach for the treatment of DNA bases, ARGs, DNA, and ARB in water.

Periodate activation by pyrite for the disinfection of antibiotic-resistant bacteria: Performance and mechanisms.

The propagation of antibiotic-resistant bacteria (ARB) greatly endangers the ecological safety and human health. This study employed pyrite (FeS2, naturally abundant mineral) for periodate (PI) activation to disinfect ARB. FeS2/PI system could disinfect 1 × 107 CFU mL-1 of kanamycin-resistant E.coli below the limit of detection in 20 min. Efficient ARB inactivation performance was achieved in pH from 3 to 9, ionic strength from 0 to 300 mM, with HA (0.1-10 mg L-1) in suspension, and in real water samples including tap water, river water and sewage. FeS2/PI system could also efficiently disinfect gentamycin-resistant E.coli and Gram-positive B. subtilis. The generated reactive species including Fe(IV), ·O2- and ·OH would attack cell membrane and overwhelmed intracellular defense system. The intracellular kanamycin resistance genes in cells would be released and then degraded in FeS2/PI system. PI preferred to be adsorbed on Fe site of FeS2 (with lower adsorption energy, more occupancy of bonding state and stronger bonding strength). The subsequent transfer of electron cloud from Fe site to PI would cleave IO bond to generate reactive species. Moreover, FeS2/PI system could also combine with sand filtration system to efficiently capture and disinfect ARB. Therefore, FeS2/PI system is a promising approach to inactivate ARB in different scenarios.

Thiadiazole-Based Covalent Organic Frameworks with a Donor-Acceptor Structure: Modulating Intermolecular Charge Transfer for Efficient Photocatalytic Degradation of Typical Emerging Contaminants.

As novel metal-free photocatalysts, covalent organic frameworks (COFs) have great potential to decontaminate pollutants in water. Fast charge recombination in COFs yet inhibits their photocatalytic performance. We found that the intramolecular charge transfer within COFs could be modulated via constructing a donor-acceptor (D-A) structure, leading to the improved photocatalytic performance of COFs toward pollutant degradation. By integrating electron donor units (1,3,4-thiadiazole or 1,2,4-thiadiazole ring) and electron acceptor units (quinone), two COFs (COF-TD1 and COF-TD2) with robust D-A characteristics were fabricated as visible-light-driven photocatalysts to decontaminate paracetamol. With the readily excited electrons in 1,3,4-thiadiazole rings, COF-TD1 exhibited efficient electron-hole separation through a push-pull electronic effect, resulting in superior paracetamol photodegradation performance (>98% degradation in 60 min) than COF-TD2 (∼60% degradation within 120 min). COF-TD1 could efficiently photodegrade paracetamol in complicated water matrices even in river water, lake water, and sewage wastewater. Diclofenac, bisphenol A, naproxen, and tetracycline hydrochloride were also effectively degraded by COF-TD1. Efficient photodegradation of paracetamol in a scaled-up reactor could be achieved either by COF-TD1 in a powder form or that immobilized onto a glass slide (to further ease recovery and reuse) under natural sunlight irradiation. Overall, this study provided an effective strategy for designing excellent COF-based photocatalysts to degrade emerging contaminants.

Photocatalytic degradation of paracetamol and bisphenol A by chitosan supported covalent organic framework thin film with visible light irradiation.

Covalent Organic Frameworks (COFs) have attracted extensive attention for the photocatalytic degradation of emerging organic contaminants. The difficulty in separation and recovery after use yet would hinder the practical application of COFs in powder form. In present study, COFs in film form were fabricated via using chitosan as the film-substrate to support COFs (CSCF). We found that CSCF could effectively degrade two types of emerging organic contaminants under visible light irradiation. Particularly, CSCF could effectively degrade 99.8% of paracetamol (PCT) and 94.0% of bisphenol A (BPA) within 180 min under visible light irradiation. •O2- and h+ played dominant roles during the photocatalytic degradation process. Hydroxylation and cleavage were the main degradation processes. CSCF exhibited good photocatalytic degradation performance in a broad range of ionic strengths, in the presence of common coexisting ions including Cl-, NO3- and SO42-, in a wide range of pH (5-11), and in real water samples including tap water, river water and lake water. Moreover, CSCF could be easily collected after use and exhibited excellent degradation performance in five successive cycles. CSCF has potential applications to treat water with either PCT or BPA contamination. This study provided a new insight into the practical application of COFs.

Surface polaron states on single-crystal rutile TiO2 nanorod arrays enhancing charge separation and transfer.

Polaron states on TiO2 photoanodes provide an important electron transfer pathway at the electrode-electrolyte interface. Here, we electrochemically doped single-crystal rutile TiO2 nanorod arrays with exposed (110) facets to produce surface polaron states, Ti3+-OH, which greatly contributed to charge separation and transfer. Our results experimentally clarified the previously confused understanding of the origin of improved photoelectrochemical (PEC) water splitting performance and verified that the enhanced PEC effects mainly arise from surface polaron states instead of grain boundary passivation.

One-step synthesis of IrOx-decorated ultrathin NiFe LDH nanosheets for efficient oxygen evolution reaction.

The oxygen evolution reaction (OER) is a vital proton donor for various clean energy technologies. Here, we synthesized IrOx-decorated ultrathin NiFe-LDH nanosheets (thickness 1-2 nm) by a one-step co-precipitation method. The IrOx was uniformly dispersed on the surface of ultrathin NiFe-LDH nanosheets, greatly increasing the active sites and the electric conductivity for NiFe-LDH. As a result, the IrOx/U-NiFe-LDH exhibited excellent OER performance with a low overpotential (236 mV) and a Tafel slope (74.3 mA dec-1).