Nanomaterials for Catalytic Remediation of Environmental Contaminants

The binary metal organic framework (MOF) is composed of two heterometallic ions bonded to an organic ligand. Compared with monometallic MOFs, bimetallic MOFs have greatly improved in terms of structure, porosity, active site, adsorption, selectivity, and stability, which has attracted wide attention. At present, many effective strategies have been designed for the synthesis of bimetallic MOF-based nanomaterials with specific morphology, structure, and function. The results show that bimetallic MOF-based nanocomposites could achieve multiple synergistic effects, which will greatly improve their research in the fields of adsorption, catalysis, energy storage, sensing, and so on. In this review, the main preparation methods of bimetallic MOFs-based materials are summarized, with emphasis on their applications in adsorption, catalysis, and detection of target pollutants in water environments, and perspectives on the future development of bimetallic MOFs-based nanomaterials in the field of water are presented. Full article

Methyl orange dye (MO) is one of the azo dyes, which is not only difficult to degrade but also hazardous to human health, therefore, it is necessary to develop an efficient photocatalyst to degrade MO. In this paper, a facile and low-cost elemental doping method was used for the surface modification of Ti₃C₂ MXene, i.e., nitrogen-doped titanium carbide was used as the nitrogen source, and the strategy of combining solvent heat treatment with non-in situ nitrogen doping was used to prepare N-Ti₃C₂ MXene two-dimensional nanomaterials with high catalytic activity. It was found that the catalytic efficiency of N-Ti₃C₂ MXene materials was enhanced and improved compared to the non-doped Ti₃C₂ MXene. In particular, N-Ti₃C₂ 1:8 MXene showed the best photo-catalytic ability, as demonstrated by the fact that the N-Ti₃C₂ 1:8 MXene material successfully degraded 98.73% of MO (20 mg/L) under UV lamp irradiation for 20 min, and its catalytic efficiency was about ten times that of Ti₃C₂ MXene, and the N-Ti₃C₂ photo-catalyst still showed good stability after four cycles. This work shows a simplified method for solvent heat-treating non-in situ nitrogen-doped Ti₃C₂ MXene, and also elaborates on the photo-catalytic mechanism of N-Ti₃C₂ MXene, showing that the high photo-catalytic effect of N-Ti₃C₂ MXene is due to the synergistic effect of its efficient charge transfer and surface-rich moieties. Therefore, N-Ti₃C₂ MXene has a good prospect as a photo-catalyst in the photocatalytic degradation of organic pollutants. Full article

Published papers highlight the roles of the catalysts in plasma catalysis systems, and it is essential to provide deep insight into the mechanism of the reaction. In this work, a coaxial dielectric barrier discharge (DBD) reactor packed with γ-MnO₂ and CeO₂ with similar nanorod morphologies and particle sizes was used for methanol oxidation at atmospheric pressure and room temperature. The experimental results showed that both γ-MnO₂ and CeO₂ exhibited good performance in methanol conversion (up to 100%), but the CO₂ selectivity of CeO₂ (up to 59.3%) was much higher than that of γ-MnO₂ (up to 28.6%). Catalyst characterization results indicated that CeO₂ contained more surface-active oxygen species, adsorbed more methanol and utilized more plasma-induced active species than γ-MnO₂. In addition, in situ Raman spectroscopy and Fourier transform infrared spectroscopy (FT-IR) were applied with a novel in situ cell to reveal the major factors affecting the catalytic performance in methanol oxidation. More reactive oxygen species (O₂²⁻, O²⁻) from ozone decomposition were produced on CeO₂ compared with γ-MnO₂, and less of the intermediate product formate accumulated on the CeO₂. The combined results showed that CeO₂ was a more effective catalyst than γ-MnO₂ for methanol oxidation in the plasma catalysis system. Full article

Photocatalytic degradation has been suggested to be a cheap and efficient way to dispose of organic pollutants, such as dyes. Therefore, our research team strives to produce nanophotocatalysts in a simple and inexpensive way. In this work, the Pechini sol–gel technique was employed for the facile synthesis of Mn_0.5Zn_0.5Fe₂O₄/Fe₂O₃ and Fe_0.5Mn_0.5Co₂O₄/Fe₂O₃ as mixed metal oxide nanoparticles for the efficient photocatalytic degradation of Rhodamine B and Congo Red dyes. XRD, FT-IR, a N₂ adsorption/desorption analyzer, EDS, FE-SEM, and an UV–Vis diffuse reflectance spectrophotometer were used to characterize the produced samples. The XRD patterns revealed that the average crystallite size of the Fe_0.5Mn_0.5Co₂O₄/Fe₂O₃ and Mn_0.5Zn_0.5Fe₂O₄/Fe₂O₃ samples is 90.25 and 80.62 nm, respectively. The FE-SEM images revealed that the Fe_0.5Mn_0.5Co₂O₄/Fe₂O₃ sample consists of cubic and irregular shapes with an average diameter of 1.71 µm. Additionally, the Mn_0.5Zn_0.5Fe₂O₄/Fe₂O₃ sample consists of spherical shapes with an average diameter of 0.26 µm. The energy gaps of the Fe_0.5Mn_0.5Co₂O₄/Fe₂O₃ and Mn_0.5Zn_0.5Fe₂O₄/Fe₂O₃ samples are 3.50 and 4.3 eV and 3.52 and 4.20 eV, respectively. In the presence of hydrogen peroxide, the complete degradation of 100 mL of 20 mg/L of Rhodamine B and Congo Red dyes occurred at pH = 8 and 3, respectively, within 50 min, using 0.1 g of the synthesized samples. Full article

Freshwater is in limited supply, and the growing population further contributes to its scarcity. The effective treatment of wastewater is essential now more than ever, because waterborne infections significantly contribute to global deaths, and millions of people are deprived of safe drinking water. Current wastewater treatment technologies include preliminary, primary, secondary, and tertiary treatments, which are effective in removing several contaminants; however, contaminants in the nanoscale range are often difficult to eliminate using these steps. Some of these include organic and inorganic pollutants, pharmaceuticals, pathogens and contaminants of emerging concern. The use of nanomaterials is a promising solution to this problem. Nanoparticles have unique properties allowing them to efficiently remove residual contaminants while being cost-effective and environmentally friendly. In this review, the need for novel developments in nanotechnology for wastewater treatment is discussed, as well as key nanomaterials and their corresponding target contaminants, which they are effective against. The nanomaterials of focus in this review are carbon nanotubes, graphene-based nanosheets, fullerenes, silver nanoparticles, copper nanoparticles and iron nanoparticles. Finally, the challenges and prospects of nanoparticle utilisation in the context of wastewater treatment are presented. Full article

Degradation of organic pollutants, especially organic dyes and antibiotics, by semiconductor photocatalysts is an efficient strategy for wastewater treatment. TiO₂ nanomaterials are considered to be promising photocatalysts due to their high chemical stability, high efficiency and availability. Anatase TiO₂ generally has superior photocatalytic activity to the rutile phase. However, the anatase phase can be irreversibly transformed to rutile phase when calcined at an elevated temperature. Methods to improve the stability of anatase are especially important for the TiO₂ gas sensors working at high temperatures. The addition of strong acids can effectively suppress this transformation process. However, these strong acids are relatively expensive, corrosive and environmentally unfriendly. Herein, oxalic acid (OA) as a natural acid was used to control the hydrolysis process of tetrabutyl titanate (TBOT), leading to controllable crystalline phase transformation and reduced crystalline size of TiO₂ on the nanoscale. What is more, the photocatalytic degradation performances were enhanced continuously when the molar ratio of OA to TBOT increased. The degradation reaction rate constants of CT650-R25 were about 10 times that of CT650-R0. The mechanism study shows that the enhanced photocatalytic activity can be attributed to the improved dispersibility, increased specific surface area and reduced recombination rates of photo-induced charge carriers and decreased energy bands as the concentration of OA increased. Thus, this work provides a simple, mild and effective method for controlling the crystalline forms of nano-TiO₂ with enhanced photocatalytic performance towards waste water treatment. Full article

Designing a novel photocatalytic composite for the efficient degradation of organic dyes remains a serious challenge. Herein, the multi-layered Co₃O₄@NP-CuO photocatalyst with unique features, i.e., the self-supporting, hierarchical porous network as well as the construction of heterojunction between Co₃O₄ and CuO, are synthesized by dealloying-electrodeposition and subsequent thermal treatment techniques. It is found that the interwoven ultrathin Co₃O₄ nanopetals evenly grow on the nanoporous CuO network (Co₃O₄@NP-CuO). The three-dimensional (3D) hierarchical porous structure for the catalyst provides more surface area to act as active sites and facilitates the absorption of visible light in the photodegradation reaction. Compared with the commercial CuO and Co₃O₄ powders, the newly designed Co₃O₄@NP-CuO composite exhibits superior photodegradation performance for RhB. The enhanced performance is mainly due to the construction of heterojunction of Co₃O₄/CuO, greatly promoting the efficient carrier separation for photocatalysis. Furthermore, the possible photocatalytic mechanism is analyzed in detail. This work provides a promising strategy for the fabrication of a new controllable heterojunction to improve photocatalytic activity. Full article