Activation of peroxydisulfate by V-Fe concentrate ore for enhanced degradation of carbamazepine: Surface ≡V(III) and ≡V(IV) as electron donors promoted the regeneration of ≡Fe(II)

Dai

et al. 2021

Angewandte Chemie

The atomically dispersed metal is expected as one of the most promising Fenton‐like catalysts for the degradation of recalcitrant organic pollutants (ROPs) by the strong “electronic metal–support interactions” (EMSIs). Here, we develop an atomically dispersed metal–atom alloy made by guest Au atoms substitute host V atoms in the two‐dimensional VO2(B) nanobelt support (Au/VO2) to activate Fenton‐like oxidation for elimination of ROPs. The 2D nanobelt structure enlarges the exposure of atomically Au thus increasing the number of active sites to absorb more S2O82− ions. And the EMSIs regulate the charge density in Au atoms to present positive charge Au+, lowering the energy barrier of S2O82− decomposition to produce SO4.−. The Au/VO2 catalyst possesses excellent durable and reliable characteristics and exhibits record‐breaking efficiency with TOF as high as 21.42 min−1, 16.19 min−1, and 80.89 min−1 for rhodamine, phenol, and bisphenol A degradation, respectively.

Section: Figurementioning

confidence: 78%

Tailoring the Electronic Metal–Support Interactions in Supported Atomically Dispersed Gold Catalysts for Efficient Fenton‐like Reaction

Dai

et al. 2021

Angewandte Chemie

Section: Resultsmentioning

confidence: 99%

“…The result indicates that during the reaction of the material, vanadium transfers electrons to iron through internal electron transfer, so that when the iron is in a high valence state, it can return to the state of Fe(III) to proceed to the next round of reaction. [39] It is still unknown what Fe(III) became after losing electrons. Due to the short lifetime of intermediates, the products of methyl phenyl sulfoxide (PMSO) oxidized by different oxidation intermediates are generally used to determine whether HVFe existed.…”

Section: •−mentioning

confidence: 99%

Electronic Metal‐Support Interaction Directing the Design of Fe(III)‐Based Catalysts for Efficient Advanced Oxidation Processes by Dual Reaction Paths

Dai

Wang

et al. 2022

Small

Persistent organic pollutants (POPs) have a huge impact on human health due to their high toxicity and non‐degradability. It is still of great difficulty to develop highly efficient catalysts toward the degradation of POPs. Herein, it is reported that regulating electronic structure of quasi‐single atomic ferric iron (Fe(III)) in the VO2 support through the electronic metal‐support interaction (EMSI) is a versatile strategy to enhance the catalytic activity. Activated Fe(III) can react with peroxydisulfate (PDS) to produce both radicals and high‐valent iron (HVFe) simultaneously for the efficient and fast degradation of POPs. Density functional theory (DFT) calculations prove that the influence of EMSI promotes the electrons on Fe(III) 3d‐bond center moving close to the Fermi level, facilitating the charge transfer from Fe(III) to the adsorbate. Through the control experiments, both the radical path by PDS and the HVFe path aroused by the EMSI are confirmed in the POP degradation process. Consequently, the Fe/VO2 catalyst exhibits record‐breaking catalytic activity with the k‐value as high as 56.7, 43.3 µmol s−1 g−1 for p‐chlorophenol and 2,4‐dichlorophenol degradation, respectively.

“…Specifically, the dominant ROS would possess the highest inhibitory degree. , Furthermore, DFT has been extensively used to evaluate the physicochemical characteristics of compounds in SR-AOPs. The energies of the highest occupied molecular orbital ( E HOMO ) and the lowest unoccupied molecular orbital ( E LUMO ), their energy gap (Δ E = E LUMO – E HOMO ), and vertical ionization potential (VIP) are important descriptors to describe the reactivity of compounds. , Additionally, the Fukui function index can indicate the reactive sites on molecules, , with the principle that a higher Fukui index indicates a higher reactivity of the corresponding reactive sites.…”

Section: Introductionmentioning

confidence: 99%

Effects of Molecular Structure on Organic Contaminants’ Degradation Efficiency and Dominant ROS in the Advanced Oxidation Process with Multiple ROS

Zhou

et al. 2022

Environ. Sci. Technol.

Self Cite

271

In this study, the previously overlooked effects of contaminants’ molecular structure on their degradation efficiencies and dominant reactive oxygen species (ROS) in advanced oxidation processes (AOPs) are investigated with a peroxymonosulfate (PMS) activation system selected as the typical AOP system. Averagely, degradation efficiencies of 19 contaminants are discrepant in the CoCaAl-LDO/PMS system with production of SO4 •–, •OH, and 1O2. Density functional theory calculations indicated that compounds with high E HOMO, low-energy gap (ΔE = E LUMO – E HOMO), and low vertical ionization potential are more vulnerable to be attacked. Further analysis disclosed that the dominant ROS was the same one when treating similar types of contaminants, namely SO4 •–, 1O2, 1O2, and •OH for the degradation of CBZ-like compounds, SAs, bisphenol, and triazine compounds, respectively. This phenomenon may be caused by the contaminants’ structures especially the commonly shared or basic parent structures which can affect their effective reaction time and second-order rate constants with ROS, thus influencing the contribution of each ROS during its degradation. Overall, the new insights gained in this study provide a basis for designing more effective AOPs to improve their practical application in wastewater treatment.