Enhanced Fenton-like catalysis via interfacial regulation of g-C3N4 for efficient aromatic organic pollutant degradation.

For the efficient degradation of organic pollutants with the goal of reducing the water environment pollution, we employed an alkaline hydrothermal treatment on primeval g-C3N4 to synthesize a hydroxyl-grafted g-C3N4 (CN-0.5) material, from which we engineered a novel Fenton-like catalyst, known as Cu-CN-0.5. The introduction of numerous hydroxyl functional groups allowed the CN-0.5 substrate to stably fix active copper oxide particles through surface complexation, resulting in a low Cu leaching rate during a Cu-CN-0.5 Fenton-like process. A sequence of characterization techniques and theoretical calculations uncovered that interfacial complexation induced charge redistribution on the Cu-CN-0.5 surface. Specifically, some of the π electrons in the tris-s-triazine units were transferred to the copper oxide particles along the newly formed chemical bonds (C(π)-O-Cu), forming a π-deficient area on the tris-s-triazine plane near the complexation site. In a typical Cu-CN-0.5 Fenton-like process, a stable π-π interaction was established due to the favorable positive-negative match of electrostatic potential between the aromatic pollutants and π-deficient areas, leading to a significant improvement in Cu-CN-0.5's adsorption capacity for aromatic pollutants. Furthermore, pollutants also delivered electrons to the Cu-CN-0.5 Fenton-like system via a "through-space" approach, which suppressed the futile oxidation of H2O2 in reducing the high-valent Cu2+ and significantly improved the generation efficiency of •OH with high oxidative capacity. As expected, Cu-CN-0.5 not only exhibited an efficient Fenton degradation for several typical aromatic organic pollutants, but also demonstrated both a low metal leaching rate (0.12 mg/L) and a H2O2 utilization rate exceeding 80%. The distinctive Fenton degradation mechanism substantiated the potential of the as-prepared material for effective wastewater treatment applications.

The CoO-doped carbon nanotubes enhance electronic performance and effectively activate persulfate for the degradation of sulfafurazole.

In recent studies, carbon nanotube (CNTs) materials and their composites have demonstrated remarkable catalytic activity in the activation of persulfate (PS), facilitating the efficient degradation of organic pollutants. In this study, a novel Co loaded carbon nanotubes (CoO@CNT) catalyst was prepared to promote PDS activation for the degradation of sulfafurazole (SIZ). Experimental results, the CNT as a carrier effectively reduces the leaching of cobalt ions and improves the electron transport capacity，whereas the introduced Co effectively activates the PDS, promoting the generation of highly reactive radicals to degrade SIZ. Under optimized conditions (a catalyst dose of 0.2 g/L, a PDS dose of 1 g/L and an initial pH = 9.0), the obtained CoO@CNT demonstrated favorable Fenton-like performance, reaching a degradation efficiency of 95.55% within 30 min. Furthermore, density functional theory (DFT) calculations demonstrate that the introduction of cobalt (Co) accelerates electron transfer, promoting the decomposition of PDS while facilitating the Co2+/Co3+ redox cycling. We further employed the environmental chemistry and risk assessment system (ECOSAR) to evaluate the ecological toxicity of intermediate products, revealing a significant reduction in ecological toxicity associated with this degradation process, thereby confirming its environmental harmlessness. Through batch experiments and studies, we gained a comprehensive understanding of the mechanism and influencing factors of CoO@CNT in the role of SIZ degradation, and provided robust support for evaluating the ecological toxicity of degradation products. This study provides a significant strategy for the development of efficient catalysts incorporating Co for the environmentally friendly degradation of organic pollutants.

Advances in two-dimensional materials for energy-efficient and molecular precise membranes for biohydrogen production.

Waste management has become an ever-increasing global issue due to population growth and rapid globalisation. For similar reasons, the greenhouse effect caused by fossil fuel combustion, is leading to chronic climate change issues. A novel approach, the waste-to-hydrogen process, is introduced to address the concern of waste generation and climate change with an additional merit of production of a renewable, higher energy density than fossil fuels and sustainable transportation fuel, hydrogen (H2) gas. In the downstream H2 purifying process, membrane separation is one of the appealing options for the waste-to-hydrogen process given its low energy consumption and low operational cost. However, commercial polymeric membranes have hindered membrane separation process due to their low separation performance. By introducing novel two-dimensional materials as substitutes, the limitation of purifying using conventional membranes can potentially be solved. Herein, this article provides a comprehensive review of two-dimensional materials as alternatives to membrane technology for the gas separation of H2 in waste-to-hydrogen downstream process. Moreover, this review article elaborates and provides some perspectives on the challenges and future potential of the waste-to-hydrogen process and the use of two-dimensional materials in membrane technology.

Removal of Chromium (VI) by a Magnetic Nanoscale Zerovalent Iron-Assisted Chicken Manure-Derived Biochar: Adsorption Behavior and Synergetic Mechanism.

Using chicken manure as raw material to prepare activated carbon as a dispersant, a novel biochar-loaded nano-zerovalent iron composite (nZVI@CMBC) was developed and applied to remove hexavalent chromium, i.e., Cr(VI), in wastewater. The dispersion of nano-zerovalent iron (nZVI) particles on the surface of chicken manure-derived biochar (CMBC) successfully inhibited the aggregation of magnetic iron particles and effectively reduced the size of nZVI particles. The results demonstrated that under acidic conditions, the removal efficiency of Cr(VI) by the nZVI@CMBC composite could reach 124.12 mg g-1. The pseudosecond-order kinetic model had a good agreement with the adsorption kinetics of the nZVI@CMBC composite, implying that the adsorption of Cr(VI) is based on the multi-layer chemical adsorption. Therefore, this study provides a new clue and strategy for removing Cr(VI) in wastewater.

Removal of aqueous pharmaceuticals by magnetically functionalized Zr-MOFs: Adsorption Kinetics, Isotherms, and regeneration.

The functionalization of metal-organic frameworks (MOFs) is imperative and challenging for the development of practical MOF-based materials. Herein, a magnetically functionalized Zr-MOF (Fe3O4@MOF-525) was synthesized via secondary-growth approach to obtain an easily-separated and recyclable adsorbent for the removal of pharmaceuticals (tetracycline (TC) and diclofenac sodium (DF)). After loading Fe3O4 nanoparticles (NPs), due to the increase of micropore volume and specific surface area caused by defects, the adsorption performance of Fe3O4@MOF-525 was improved. The kinetics could be described by the pseudo-second-order kinetic model. The different adsorption capacity and initial rate were attributed to the properties of the pharmaceuticals, including the molecular size and hydrophobicity/hydrophilicity. In isotherm experiments, the maximum adsorption capacities of DF and TC on Fe3O4@MOF-525 calculated by Sips model reached 745 and 277 mg·g-1, respectively. The thermodynamic studies indicated the adsorption was endothermic and spontaneous. The effect of pH suggested that electrostatic interaction, π-π interaction, anion-π interaction, and H-bonding were possibly involved in the adsorption process. The adsorbent was separated by magnetic and regenerated. Washed with ethanol, Fe3O4@MOF-525 remained about 80% adsorption capacity after four cycles. In-situ photo-regeneration under visible-light irradiation was another attractive method, where > 95% TC was degraded in 4 h. The reaction with scavengers revealed that 1O2 was the dominant reactive species in our system, indicating the occurrence of Type II photosensitization. The separability, excellent adsorption performance, and recyclability of Fe3O4@MOF-525 may lead to its beneficial applications in water treatment.

A novel application of In2S3 for visible-light-driven photocatalytic inactivation of bacteria: Kinetics, stability, toxicity and mechanism.

Photocatalytic bacterial inactivation under visible light emerges as a new alternative to control microbial contamination by utilizing free and renewable sunlight. However, the exploration of highly effective and safe visible-light-driven (VLD) photocatalysts remains an important step toward accessing this new technology. Herein, an eco-friendly photocatalyst, namely Indium Sulfide (In2S3), was fabricated through a facile hydrothermal method for VLD photocatalytic inactivation of bacteria. The energy band gap of the as-prepared In2S3 was measured as 2.25 eV. As expected, the obtained In2S3 photocatalyst showed remarkable inactivation efficiency toward E. coli under fluorescent tubes irradiation. The photocatalytic inactivation kinetic was perfectly fitted by a mathematical model for bacteria inactivation. In addition, In2S3 exhibited high stability and could be reused. The leakage of In3+ was not significant and showed no toxic effect to the bacteria. Based on the results of scavenger study and ESR technology, the dominant reactive species causing In2S3 VLD photocatalytic bacterial inactivation were proposed as O2-, h+, H2O2 and e-, rather than OH. The SEM study suggested that the damages to the intracellular components occurred prior to the destruction of cell wall. This study provides novel application of In2S3 for VLD photocatalytic inactivation of bacteria as well as comprehensive insight into the inactivation mechanism.

Sustainable management of landfill leachate concentrate through recovering humic substance as liquid fertilizer by loose nanofiltration.

The hybrid membrane bioreactor - nanofiltration treatment process can be an effective approach for treating the landfill leachate, but the residual leachate concentrate highly loaded with the humic substance and salts remains an environmental concern. Herein, a loose nanofiltration membrane (molecular weight cut-off of 860 Da) was used to recover the humic substance, which can act as a key component of organic fertilizer, from the leachate concentrate. The loose nanofiltration membrane showed the high permeation fluxes and high transmissions (>94.7%) for most inorganic ions (i.e., Na+, K+, Cl-, and NO3-), while retaining 95.7 ±â€¯0.3% of the humic substance, demonstrating its great potential in effective fractionation of humic substance from inorganic salts in the leachate concentrate. The operation conditions, i.e., cross-flow rates and temperatures, had more pronounced impacts on the filtration performance of the loose nanofiltration membrane. Increasing cross-flow rates from 60 to 260 L h-1 resulted in an improvement of ca. 7.3% in the humic substance rejection, mainly due to the reduced concentration polarization effect. In contrast, the solute rejection of the nanofiltration membrane was negatively dependent on the temperature. The rejection of humic substance decreased from 96.3 ±â€¯0.3% to 92.0 ±â€¯0.4% with increasing the temperature from 23 to 35 °C, likely due to the enlargement of the membrane pore size and enhancement in solute diffusivity. The humic substance was enriched from 1735 to 15,287 mg L-1, yielding a 91.2% recovery ratio with 85.7% desalination efficiency at a concentration factor of 9.6. The recovered HS had significantly stimulated the seed germination and growth of the green mungbean plants with no obvious phytotoxicity. These results demonstrate that loose nanofiltration can be an effective promising technology to recover the humic substance as a valuable fertilizer component towards sustainable management of the landfill leachate concentrate.

A Cobalt-Modified Covalent Triazine-Based Framework as an Efficient Cocatalyst for Visible-Light-Driven Photocatalytic CO2 Reduction.

Photocatalytic CO2 reduction into carbonaceous feedstock chemicals is a promising renewable energy technology to convert solar energy and greenhouse gases into chemical fuels. Here, a covalent triazine-based framework (CTF) is demonstrated as an efficient cocatalyst to reduce CO2 under visible-light irradiation. The nitrogen-rich triazine moieties in CTF contribute to CO2 adsorption, while the periodical pore structure of CTF favors the accommodation of CO2 and electron mediator. Immobilization of cobalt species onto CTF promotes the photocatalytic activity with a 44-fold enhancement over pristine CTF and the optimal CO production rate of the obtained Co/CTFs was up to 50 µmol g-1 h-1 . The results of solid-state UV-vis diffuse reflectance spectra (UV-vis DRS), CO2 adsorption and electrochemical impedance spectroscopy (EIS) illustrated that the increased activity was ascribed to the enhanced CO2 capture capacity, improved absorption of visible-light and facilitated the transfer of charge from CTF to CO2 molecules. The CTF not only serves as a substrate for active Co species, but also bridges the photosensitizer with cobalt catalytic sites for the efficient transfer of photoexcited electrons. This work highlights the capability and ease of fabricating covalent organic framework-based photocatalytic systems that are potentially useful for energy-conversion applications.

Constructing a novel family of halogen-doped covalent triazine-based frameworks as efficient metal-free photocatalysts for hydrogen production.

Halogens, as typical non-metal dopants, have attracted intensive interests for developing highly active photocatalysts. However, the essential factors and underlying mechanism of halogen modification are still unclear. Herein, we systematically report the development of halogen (F, Cl and Br)-doped covalent triazine-based frameworks (CTFs) via a facile thermal treatment of CTFs and an excess of ammonium halide. The introduction of halogen atoms endowed CTFs with multiple superior effects such as improved optical absorption, promoted charge migration, narrowed band gaps and tuned band positions. The newly developed halogen-doped CTFs showed remarkable photocatalytic activities for H2 evolution under visible-light irradiation. Notably, the most enhanced photocatalytic performance was obtained with Cl-doped CTFs, which exhibited 7.1- and 2.4-fold enhancements compared to un-doped CTFs and Cl-doped g-C3N4, respectively. The electronegativity and atomic radius of the halogen atoms affected the modification of the optical and electronic properties, leading to different photocatalytic performances of F-, Cl- and Br-doped CTFs. The conclusions presented in this work will provide some new insights into the understanding of the doping effect for the improvement of the photocatalytic activity of halogen-doped CTF photocatalysts.

Efficient Visible-Light-Driven Photocatalytic Hydrogen Evolution on Phosphorus-Doped Covalent Triazine-Based Frameworks.

Seeking efficient visible-light-driven photocatalysts for water splitting to produce H2 has attracted much attention. Chemical doping is an effective strategy to enhance photocatalytic performance. Herein, we reported phosphorus-doped covalent triazine-based frameworks (CTFs) for photocatalytic H2 evolution. Phosphorus-doped CTFs were fabricated by a facile thermal treatment using easily available red phosphorus as the external phosphorus species. The introduction of phosphorus atoms into the frameworks modified the optical and electronic property of CTFs, thus promoting the generation, separation, and migration of photoinduced electron-hole pairs. Consequently, the photocatalytic H2-production efficiency of phosphorus-doped CTFs was greatly improved, which was 4.5, 3.9, and 1.8 times as high as that of undoped CTFs and phosphorus-doped g-C3N4 calcined from melamine and urea, respectively.