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The development of catalysts for the treatment of volatile organic compounds (VOCs) by photocatalytic oxidation is very important for treating industrial flue gases. Although defect engineering has been developed into an effective method to improve the photocatalytic activity of TiO2 semiconductor materials, few holistic studies have been performed on the structure and properties of TiO2. Herein, a one-step hydrothermal method was used to synthesize three types of nanoscale TiO2 (p-TiO2 with only Ti vacancies, n-TiO2 with only O vacancies, and pn-TiO2 with dual Ti/O vacancies) for the photocatalytic removal of gaseous toluene to determine the relationship between the redox capacity of the electron–hole pairs and the type of conductive semiconductors. It was found that pn-TiO2 exhibited a higher gaseous toluene conversion (99.6%) within 2 h, with 2.8-fold faster photocatalytic kinetics than p-TiO2 and 1.26-fold faster than n-TiO2. Based on the results of an experimental study and theoretical calculations, it was verified that the dual vacancies in pn-TiO2 enabled the valence and conduction bands to be fully exploited to generate ·OH and ·O2–, respectively, for the synergistic degradation of gaseous toluene. Because of the characteristics of the p-n homojunction, charge transfer and separation were efficiently increased in pn-TiO2, resulting in the effective treatment of gaseous toluene. In addition, after five cycles of photocatalytic degradation of toluene, the degradation rate by pn-TiO2 remained over 80%, indicating potential applications for pn-TiO2. In this study, a rational pathway is demonstrated for photocatalysts containing dual vacancies to degrade toluene based on the synergistic effect of free radicals, providing an inspiration for designing materials with vacancies or homojunctions and providing means of eliminating VOCs in practical applications. [ABSTRACT FROM AUTHOR]

Reduction of carcinogenic hexavalent chromium (Cr(VI)) by ferrous iron (Fe(II)) to essentially nontoxic trivalent chromium (Cr(III)) is a simple and effective method for Cr(VI) decontamination. In this study, the photoreduction efficacy of Cr(VI) in acidic Fe(III)/Fe(II) solutions was examined in the presence of dicarboxylic acids (DCA) (i.e. oxalic acid (Oxal), malonic acid (Mal), succinic acid (Suc), and glutaric acid (Glu)). Rates of Cr(VI) reduction under UV irradiation depend on the photochemistry of Fe(III)/Fe(II) complexes with DCA, following the order of Oxal > Suc ≈ Glu > Mal. Fe(III)-oxalato complexes are favorable for transforming Cr(VI) due to the formation of relative abundance of Fe(II) and reductive radicals such as,after photoreaction, whereas Fe(III)-Mal complexes upon UV irradiation generate the lowest amount of Fe(II) among all the Fe-DCA complexes, and thus have poor capacity for Cr(VI) reduction. The effects of Suc and Glu on the Cr(VI) reduction are insignificant since the Fe(III)-OH complexes are still the main Fe(III) species due to their weak chelating abilities with Fe(III). This work has important implications for selecting the favorable ligands of Fe(III) for light-induced Cr(VI) transformation and designing the methods for treating wastewater with low-molecular-weight acids and Cr(VI). [ABSTRACT FROM AUTHOR]

Graphene oxide (GO) contains not only aromatic carbon lattice but also carboxyl groups which enhanced the aqueous solubility of GO. To study the transformation of GO nanosheets in natural environments, GO aqueous dispersion was mixed with Fe3+ ions to form photoactive complex. Under visible light irradiation, Fe(III) of the complex would be reduced to Fe(II) which could subsequently reduce highly toxic Cr(VI) to Cr3+. The electron of the reduction was contributed by the decarboxylation of carboxyl groups on GO and iron was acting as a catalyst during the photoreduction. On the other hand, the consumption of carboxyl groups may convert GO to rGO which are tend to aggregate since the decreased electrostatic repulsion and the increased π-π attraction. The formed Cr3+ may be electrostatically adsorbed by the rGO sheets and simultaneously precipitated with the aggregated rGO sheets, resulting the effective removal of chromium and GO nanosheets from the aqueous environment. This study may shed a light on understanding the environmental transformation of GO and guide the treatment of Cr(VI). [ABSTRACT FROM AUTHOR]

The excellent photocatalytic performance was attributed to upshift of d-band center, and highly energetic electrons induced by the CB flexibility alleviated the photoinduced electron recombination in defective MIL-125. [Display omitted] Solar energy is becoming the most promising option to mitigate the energy crisis in the future and can be applied in renewable and economical technologies such as water splitting and pollutants degradation. The promotion of the electronic energetic level is considered an efficient method to enhance the photocatalytic performance of semiconductor materials for solar energy conversion. The highly energetic electrons exhibit a remarkable reduction ability by virtue of the electronic spin polarization, which is associated with the conduction band (CB) position. Thus, the regulation of the CB position due to the redistribution of electrons by means of defect engineering presents potential. Here, a series of titanium-based metal–organic frameworks (Ti-based MOFs) named MIL-125-m% containing different extents of defects are reported to enable photocatalytic activity under simulated sunlight and visible light illumination for remarkably enhanced photocatalytic hydrogen evolution and pollutant degradation. The experimental results illustrated that MIL-125–5 % exhibited a superior photocatalytic hydrogen evolution rate (16507.27 μmol·g−1·h−1), much higher than that of MIL-125-0 % (1.444 μmol·g−1·h−1). The excellent photocatalytic performance was attributed to upshift of d-band center, which strengthened the adsorption of H*, facilitating the H 2 evolution reaction. In addition, the degradation rate of MIL-125-5 % was up to twice the original rate, for the highly energetic electrons induced by the CB flexibility alleviated the photoinduced electron recombination in defective MIL-125. The strategy of defect engineering provides a new path to control the flexibility of the CB position by electronic spin polarization on adjustable metal–organic frameworks (MOFs), and the photocatalytic effect is changed accordingly. [ABSTRACT FROM AUTHOR]

Construction of metal monovacancies in ZnO reduced e g occupation and induced electron spin polarization near the Fermi level. Moreover, spin-polarized orbital coupling and internal polarization electric field promoted surface redox reactions and accelerated carrier interfacial transfer, which released the restrictions of reaction condition in simultaneously photocatalytic hydrogen generation and pollutant degradation. [Display omitted] • Metal monovacancies are successfully developed in lamellar Zn-V-20. • Low eg occupancy optimizes electron configuration and spin structure. • Simultaneous hydrogen generation and pollutants degradation are enhanced. • Spin polarization proved by DFT and XAS is the reason of photocatalytic enhancement. Simultaneous hydrogen generation and pollutants removal is considered as the potential solution to the energy and environmental crisis, which can cut the consumption of expensive sacrificial electron donors and reduce the ecotoxicity of wastewater containing pollutants. However, the integration of two redox half-reactions in one system is still a challenge, limited by irreconcilable reaction conditions and low kinetics. In this study, ZnO with abundant metal monovacancies (Zn-V-m) was fabricated to manipulate the spin state by tailoring the electron occupancy of e g -orbitals, which simultaneously endowed the material with both outstanding photocatalytic oxidation and reduction performance. Compared with pristine ZnO, the prepared Zn-V-20 increases the H 2 production rate by 56.4-fold and enhances the pollutants removal efficiency by 27.5-fold. It is impressive that simultaneous hydrogen generation and pollutants degradation in one system is accomplished and accelerated. Furthermore, Zn L -edge X-ray absorption spectra (XAS) and density functional theory (DFT) calculations suggest that low electron occupancy of e g -orbitals optimizes the spin structure and leads to spin polarization, which provides the critical motivation for enhancing photocatalytic performance. This work accelerates the reaction rates of pollutants degradation and hydrogen generation at the surface interface by manipulating electron spin polarization, guiding the rational design of TMO-based catalysts for simultaneous energy recovery and wastewater purification. [ABSTRACT FROM AUTHOR]

The overall maximization of photocatalytic H 2 O 2 production efficiency urgently requires the comprehensive optimization of each step in multiplex photocatalysis. Despite numerous endeavors, isolated researches focusing on single efficiencies hinder further advancements in overall catalytic activity. In this work, a series of imine-linked COFs (TT-COF-X), incorporating electronically tunable functional groups (X = ─H, ─OMe, ─OH, ─Br), are rationally fabricated for visible-light-driven H 2 O 2 production via a dual-channel pathway involving 2e - water oxidation and 2e - oxygen reduction. Combined simulations and characterizations reveal that the synergistic modification of functional groups for electronic conjugation and locally intramolecular polarity collectively enhanced light absorption, charge separation and transfer, and interface water-oxygen affinity efficiency. Notably, femtosecond time-resolved transient absorption (fs-TA) reveals that the polarity-induced built-in electric field play a crucial role in facilitating exciton dissociation by reacting BIEF-mediated shallow trapping state. The simultaneously optimal tri-efficiency ultimately results in the highest H 2 O 2 production rate of 3406.25 µmol h -1  g -1 and apparent quantum yields of 8.1% of TT-COF-OH. This study offers an emerging strategy to rational design of photocatalysts from the comprehensive tri-efficiency-oriented perspective., (© 2024 Wiley‐VCH GmbH.)

Perfluoroalkyl and polyfluoroalkyl substances (PFASs) are persistent in the environment and have been detected in a variety of plants such as vegetables, cereals, and fruits. Increasing evidence shows that plants are at a risk of being adversely affected by PFASs. This review concludes that PFASs are predominantly absorbed by roots from sources in the soil; besides, the review also discusses several factors such as soil properties and the species of PFASs and plants. In addition, following uptake by root, long-chain PFASs (C ≥ 7 for PFCA and C ≥ 6 for PFSA) were preferentially retained within the root, whereas the short-chain PFASs were distributed across tissues above the ground - according to the studies. The bioaccumulation potential of PFASs within various plant structures are further expressed by calculating bioaccumulation factor (BAF) across various plant species. The results show that PFASs have a wide range of BAF values within root tissue, followed by straw, and then grain. Furthermore, owing to its high water solubility than other PFASs, PFOA is the predominant compound accumulated in both the soil itself and within the plant tissues. Among different plant groups, the potential BAF values rank from highest to lowest as follows: leaf vegetables > root vegetables > flower vegetables > shoot vegetables. Several PFAS groups such as PFOA, PFBA, and PFOS, may have an increased public health risk based on the daily intake rate (ID). Finally, future research is suggested on the possible PFASs degradation occurring in plant tissues and the explanations at genetic-level for the metabolite changes that occur under PFASs stress., Competing Interests: The authors declare no competing interests., (© 2022 The Author(s).)