OH-mediated Degradation Research Articles

Epitaxial-grafting strategy to boost inert hydroxide photocatalytic performance: A case study of SnOx-MgSn(OH)6

To utilize -OH on the inert hydroxides, a layer of photoactive SnOx was epitaxially grafted on MgSn(OH)6 (MgHS) by controlling the hydrothermal solution at ca. pH 4. SnOx shows a strong interaction with MgHS and acts as photoactive sites to provide photoinduced electrons (e−) and holes (h+), while the host provides a hydroxyl-rich surface to strengthen and sustain ∙OH-mediated degradation process. Furthermore, both the transferring of photoinduced h+ from SnOx to MgHS and the adsorption of benzene (C6H6) on MgHS were promoted by SnOx. The synergistic effect between SnOx and MgHS is responsible for the high and stable performance for abating bisphenol A solution and gaseous C6H6 exhaust. ∙OH and protonated O2− are the main active species. This work demonstrated that the epitaxial-grafting of photoactive metal oxides on a host hydroxide photocatalyst is a promising strategy to boost the photocatalytic performance of inert hydroxide photocatalysts for environmental remediation.

Atmospheric chemistry of 2-nitrobenzaldehyde: Initiated by photo-excitation, OH-oxidation, and small TiO2 clusters adsorption catalysis

The fate of 2-nitrobenzaldehyde (2-NBA) is of interest in atmospheric chemistry as it is a semi-volatile organic compound with high photosensitivity. This study presents a quantum chemical study of the gas-phase reactions of 2-NBA photo-excitation and OH-oxidation in the absence and presence of small TiO2 clusters. To further understand the unknown photolysis mechanism, the photo-reaction pathways of ground singlet state and the lying excited triplet state of 2-NBA were investigated including the initial and subsequent reactions of proton transfer, direct CO, NO2, and HCO elimination routes in the presence of O2 and NO. Meanwhile, the OH-mediated degradation of 2-NBA proceeded via five H-extraction and six OH-addition channels by indirect mechanism, which follows a succession of reaction steps initiated by the formation of weakly stable intermediate complexes. The H-extraction from the –CHO group was the dominant pathway with a negative activation energy of -1.22 kcal/mol. The calculated rate coefficients at 200–600 K were close to the experimental data in literature within 308–352 K, and the kinetic negative temperature independence was found in both experimental literature and computational results. Interestingly, 2-NBA was favored to be captured onto small TiO2 clusters via six adsorption configurations formed via various combination of three types of bonds of Ti···O, Ti···C, and O···H between the molecularly adsorbed 2-NBA and TiO2 clusters. Comparison indicted that the chemisorptions of aldehyde oxygen have largest energies. The results suggested adsorption conformations have a respectable impact on the catalysis barrier. This study is significant for understanding the atmospheric chemistry of 2-nitrobenzaldehyde.

Unravelling the effects of complexation of transition metal ions on the hydroxylation of catechol over the whole pH region

Catechol pollutants (CATPs) serving as chelating agents could coordinate with many metal ions to form various CATPs-metal complexes. Little information is available on the effects of complexation of metal ions on CATPs degradation. This work presents a systematical study of •OH-mediated degradation of catechol and catechol-metal complexes over the whole pH range in advanced oxidation processes (AOPs). Results show that the pH-dependent complexation of metal ions (Zn2+, Cu2+, Ti4+ and Fe3+) promotes the deprotonation of catechol under neutral and even acidic conditions. The radical adduct formation (RAF) reactions are both thermodynamically and kinetically favorable for all dissociation and complexation species, and OH/O− group-containing C positions are more vulnerable to •OH attack. The kinetic results show that the complexation of the four metal ions offers a wide pH range of effectiveness for catechol degradation. At pH 7, the apparent rate constant (kapp) values for different systems follow the order of catechol+Ti4+ ≈ catechol+Zn2+ > catechol+Cu2+ > catechol+Fe3+ > catechol. The mechanistic and kinetic results would greatly improve our understanding of the degradation of CATPs-metal and other organics-metal complexes in AOPs. The toxicity assessment indicates that the •OH-based AOPs have the ability for decreasing the toxicity and increasing the biodegradability during the processes of catechol degradation.

Kinetics and mechanism of OH-mediated degradation of three pentanols in the atmosphere

Pentanols as potential biofuels have attracted considerable interest, and thus it is of great importance to gain insights into their combustion and atmospheric chemistry.

Nano-zerovalent manganese/biochar composite for the adsorptive and oxidative removal of Congo-red dye from aqueous solutions

Congo-red (CR), a precursor of textile products and a contaminant of great concern, has contaminated aquatic environments. Here, we explored the synthesis of mesoporous nano-zerovalent manganese (nZVMn) and Phoenix dactylifera leaves biochar (PBC) composite for the removal of CR from water. The nZVMn/PBC adsorbed 117.647 mg/g of CR versus 25.316 mg/g by PBC at [CR]0 = 20 mg/L and [PBC]0 = [nZVMn/PBC]0 = 500 mg/L. Variation of [nZVMn/PBC]0, [CR]0 and pH influenced the adsorption of CR. Freundlich adsorption isotherm and pseudo-first-order kinetic models best fitted CR adsorption. The H2O2 coupling with nZVMn/PBC promoted removal of CR possibly due to the formation of hydroxyl radical (●OH) and caused 95 % removal of CR versus 77 % by nZVMn/PBC alone. The ●OH scavengers inhibited the removal of CR. The nZVMn/PBC showed a good reusability and efficient removal of CR up to the seventh cycle of treatment. Results reveal that nZVMn improved performance, thermal stability and reusability of biochar. Degradation products from ●OH-mediated degradation of CR were studied by ultraperformance liquid chromatography with mass spectrometric detector to establish degradation pathways. The ion-chromatographic analysis showed the formation of non-toxic inorganic acetate product, which suggests high potential of the newly fabricated adsorbent in the removal of CR.

Rapid transformation of H1-antihistamines cetirizine (CET) and diphenhydramine (DPH) by direct peroxymonosulfate (PMS) oxidation

With growing interest in advanced oxidation processes (AOPs), the number of research studies on peroxymonosulfate (PMS) mediated pollutant degradation has increased significantly due to its high radical generation potential upon activation. However, rare studies have focused on the non-radical based PMS reactions. In this study, degradation of model H1-antihistamines cetirizine (CET) and diphenhydramine (DPH) by unactivated PMS was investigated. Addition of scavengers to the reaction mixture ruled out the involvement of hydroxyl radical (OH), sulfate radical (SO4–), singlet oxygen (1O2) and superoxide anion radical (O2–), indicating direct PMS oxidation as the predominant reaction path. Such a mechanism was further supported by the N-oxide products identified by mass spectrometry and nuclear magnetic resonance (NMR) analyses. Solution pH had a pronounced influence on the degradation kinetics regardless the presence or absence of transition metal Fe(II). The highest species dependent second order rate constants were kHSO5-/DPH0 of 175 ± 15.9 M–1 s–1 and kHSO5-/CET- of 36.6 ± 0.16 M–1 s–1. The addition of 100 μM Fe(II) promoted OH mediated degradation of H1-antihistamines and their N-oxide products. This study demonstrated selective transformation with the potential for extensive degradation employing both the direct and catalytic PMS oxidative processes.

Photoformation of reactive oxygen species and their potential to degrade highly toxic carbaryl and methomyl in river water.

Reactive oxygen species (ROS) including singlet oxygen (1O2) and hydroxylradicals (OH) photogenerated in natural waters play important roles in indirect photolysis of man-made pollutants. This study was conducted to investigate how the generation of these two ROS influences the degradation of two highly toxic insecticides (methomyl and carbaryl) in river water. To accomplish this, the reaction rate constants of 1O2 and OH with carbaryl and methomyl were determined; the degradation rate constants of the tested insecticides in ultrapure water (direct photolysis) and in river water in the presence and absence of 1O2 and OH scavengers were also measured. The rate constants for the reaction of OH with carbaryl and methomyl were found to be (14.8 ± 0.64) × 109 and (4.68 ± 0.52) × 109 M-1 s-1, respectively. The reaction rate constant of 1O2 with carbaryl (2.98 ± 0.10) × 105 M-1 s-1, was much higher than that of methomyl (<104 M-1 s-1). Indirect photolysis by OH accounted for 63% and 62%, while 1O2 accounted for 26% and 30% and direct photolysis accounted for 1.4% and 7% of methomyl and carbaryl degradation, respectively. The high degradation rate in river water demonstrated by both insecticides suggests that indirect photolysis mediated by OH is an important means of their degradation in river water. In addition, kinetic calculations of OH-mediated degradation rate constants of the compounds agrees with their experimentally-determined values thereby confirming the importance of OH towards their degradation.

Theoretical and experimental insights into the ·OH-mediated mineralization mechanism of flutriafol

Flutriafol is one of the widely used triazole fungicides in global pesticides market, and its degradation mechanisms are important to develop powerful technologies to remove it. Insight into the kinetics and mechanisms of ·OH-mediated mineralization of flutriafol have been obtained using quantum chemical calculation and electrochemical experiment methods. The complete ·OH-mediated degradation pathway of flutriafol was proposed by density functional theory (DFT) simulation and the potential energy surface was mapped out for possible reactions. On the basis of DFT calculations, the optimal ·OH-mediated mineralization mechanism of flutriafol was revealed, and a series of intermediates were observed accumulated in the degradation process, most significance among which were (2-fluorophenyl) (4-fluorophenyl)-Methanone, phenol, dihydroxybenzenes, benzoquinones, muconic acids, maleic acids, oxalic acids and formic acid. To give deeper insight into the ·OH-mediated reaction mechanism, the electrostatic potential (ESP) and average local ionization energy (ALIE) analysis were conducted for o-benzoquinone and p-benzoquinone. The proposed mechanism was further validated by electrochemical experiments at TiO2-NTs/SnO2-Sb/PbO2 anode. The main intermediates were identified and quantified by experimental method, indicating that the proposed ·OH-mediated degradation mechanism derived from DFT calculations was feasible. These detailed findings could be instrumental for a comprehensive understanding of the ·OH-mediated mineralization mechanism of flutriafol and the similar contaminants.

Kinetics and Mechanism of •OH Mediated Degradation of Dimethyl Phthalate in Aqueous Solution: Experimental and Theoretical Studies

The hydroxyl radical ((•)OH) is one of the main oxidative species in aqueous phase advanced oxidation processes, and its initial reactions with organic pollutants are important to understand the transformation and fate of organics in water environments. Insights into the kinetics and mechanism of (•)OH mediated degradation of the model environmental endocrine disruptor, dimethyl phthalate (DMP), have been obtained using radiolysis experiments and computational methods. The bimolecular rate constant for the (•)OH reaction with DMP was determined to be (3.2 ± 0.1) × 10(9) M(-1)s(-1). The possible reaction mechanisms of radical adduct formation (RAF), hydrogen atom transfer (HAT), and single electron transfer (SET) were considered. By comparing the experimental absorption spectra with the computational results, it was concluded that the RAF and HAT were the dominant reaction pathways, and OH-adducts ((•)DMPOH1, (•)DMPOH2) and methyl type radicals (•)DMP(-H)α were identified as dominated intermediates. Computational results confirmed the identification of transient species with maximum absorption around 260 nm as (•)DMPOH1 and (•)DMP(-H)α, and these radical intermediates then converted to monohydroxylated dimethyl phthalates and monomethyl phthalates. Experimental and computational analyses which elucidated the mechanism of (•)OH-mediated degradation of DMP are discussed in detail.

Electrochemical degradation of the antibiotic sulfachloropyridazine by hydroxyl radicals generated at a BDD anode

The treatment of aqueous solutions of the antibiotic sulfachloropyridazine (SCP) was carried out at the natural pH of the solution (pH 4.5) with hydroxyl radicals (OH) generated at a BDD anode surface by electro-oxidation using an undivided electrochemical cell equipped with a three-dimensional carbon-felt cathode. Hydroxyl radicals are powerful oxidants and react with the antibiotic leading to its overall mineralization. The kinetic study showed that oxidative degradation of SCP follows pseudo first-order reaction kinetics, with a relatively short degradation time. The degree of mineralization of SCP solutions increased with the applied current, being higher than 95% after 8h of electrolysis at 350mA or higher current. To determine the degradation pathway upon the action of hydroxyl radicals, the cyclic and aliphatic by-products, as well as the released inorganic ions, were identified and quantified over electrolysis time. The values of the rate constants of reactions between OH and the SCP and its intermediates were determined by the competition kinetics method using p-hydroxybenzoic acid. The absolute rate constant for the OH-mediated degradation of SCP was found to be 1.92×109M−1s−1. Toxicity assessment by the Microtox® method during the electro-oxidation of SCP solutions revealed the formation of compounds that can be more toxic than the parent molecule, but the overall results confirm the effectiveness of this electrochemical process for the removal of the antibiotic SCP and its by-products from aqueous media.

Nitrate-Induced Photolysis in Natural Waters: Controls on Concentrations of Hydroxyl Radical Photo-Intermediates by Natural Scavenging Agents

The importance of the principal natural scavenging agents for hydroxyl radicals (•OH) was evaluated, and a general framework was developed to predict the significance of nitrate-induced, •OH-mediated degradation of aquatic contaminants. Rate constants for •OH scavenging by dissolved organic matter (DOM) from five surface water sources were in a narrow range (2.3 ± 0.77 × 104 (mg of C/L)-1 s-1), which is similar to previously reported values and suggests that the importance of DOM as a •OH sink can be estimated simply from the dissolved organic carbon (DOC) concentration of a water. Scavenging of •OH by carbonate and bicarbonate is generally less important, but these ions can be the major cause of •OH scavenging in low DOC, high alkalinity waters. Use of the framework is illustrated by predicting levels of •OH and half-lives of the corn herbicide acetochlor in waters ranging from pristine to highly influenced by agricultural activities.