Activation Of Molecular Oxygen Research Articles

Biomass guided the formation of spherical catalysts for efficient photodegradation of tetracycline hydrochloride

Developing and evaluating advanced antibiotic degradation photocatalysts remains challenging owing to the lack of rational structural designs and molecular oxygen activation. In this study, a nanofluoral-biochar-modified bismuth vanadate (m-BiVO4) material with a specific structure was prepared via surface-assisted polymerization. The results show that the yeast-derived carbon material significantly broadened the capture range of n–p* visible light and improved the electron delocalization and carrier separation rates. Under visible light irradiation, m-BiVO4 exhibited a high photocatalytic degradation rate, and the degradation rate of 10 mg/L tetracycline (TC) reached 89.9 % within 180 min, almost three times that of the control group. An EPR test and free radical capture experiment showed that ·OH and ·O2– were the main active substances in the TC degradation process. Cyclic experiments also showed that the material had great stability and potential for reuse. The intermediate in the degradation pathway was identified using liquid chromatography-tandem mass spectrometry, the degradation pathway of TC in the composite system was predicted, and a corresponding degradation pathway was proposed. In this study, the synergistic effect of morphology adjustment and component cutting was realized using biomass templates, providing a new method for designing photocatalysts with specific structures.

Solar Light-Driven Molecular Oxygen Activation by BiOCl Nanosheets: Synergy of Coexposed {001}, {110} Facets and Oxygen Vacancies.

Single-crystalline BiOCl nanosheets with coexposed {001} and {110} facets, as well as oxygen vacancies, were synthesized using a simple method. These nanosheets have the ability to activate molecular oxygen, producing reactive superoxide radicals (77.8%) and singlet oxygen (22.2%) when exposed to solar light. The BiOCl demonstrated excellent photocatalytic efficiency in producing H2O2 under simulated solar light and in oxidatively hydroxylating phenylboronic acid under blue LED light. Our research highlights the significance of constructing coexposed {001} and {110} facets, as well as oxygen vacancies, in enhancing photocatalytic performance. The BiOCl nanosheets have the capability to produce H2O2 with a solar-to-chemical energy conversion efficiency of 0.11%.

Solar Light-Driven Molecular Oxygen Activation by BiOCl Nanosheets: Synergy of Coexposed {001}, {110} Facets and Oxygen Vacancies.

Single-crystalline BiOCl nanosheets with coexposed {001} and {110} facets, as well as oxygen vacancies, were synthesized using a simple method. These nanosheets have the ability to activate molecular oxygen, producing reactive superoxide radicals (77.8%) and singlet oxygen (22.2%) when exposed to solar light. The BiOCl demonstrated excellent photocatalytic efficiency in producing H2O2 under simulated solar light and in oxidatively hydroxylating phenylboronic acid under blue LED light. Our research highlights the significance of constructing coexposed {001} and {110} facets, as well as oxygen vacancies, in enhancing photocatalytic performance. The BiOCl nanosheets have the capability to produce H2O2 with a solar-to-chemical energy conversion efficiency of 0.11%.

Efficient activation of molecular oxygen across a broad pH range (2.5 to 11) utilizing an aluminum-based solid-phase Fenton reagent

Zero-valent aluminum (Al0) is an excellent electron donor with extremely low redox potential (E0(Al3+/Al0) = − 1.667 V) that could directly activate the green oxidant O2, producing reactive oxygen radicals to effectively degrade pollutants in the Al0/O2 system. However, the surface of Al0 is covered with a dense oxide film and easily re-passivated under neutral or alkaline conditions after modification. This is why it is currently mostly used at a pH of less than 4 and an induction period is required. In this study, a novel composite material, Al0-FeSO4-EDTABM, was prepared using Al0 with surface modification using FeSO4·7H2O crystals and the common ligand ethylenediaminetetraacetic acid (EDTA) through environmentally friendly one-pot mechanical ball milling (BM) to destroy the oxide film of Al0 and stimulate its activity. The properties and mechanism of the activation of molecular oxygen by Al0-FeSO4-EDTABM composites were discussed in detail. At an initial pH range of 2.5 to 11.0, the model pollutant phenol could be efficiently removed by over 92 % through the activation of molecular oxygen, without requiring an induction period. During the BM process, FeSO4·7H2O and EDTA effectively disrupted the oxide film on the surface of Al0 and prevented secondary passivation. During the degradation reaction, Al0-FeSO4-EDTABM facilitated the generation of active oxygen radicals mainly through a heterogeneous Fenton-like process. In conclusion, the innovative Al0-based composite/O2 system presents a simple and potential new method for preparing solid Fenton reagents with promising practical applications.

Tailoring local electron density and molecular oxygen activation behavior via potassium/halogen co-tuned graphitic carbon nitride for enhanced photocatalytic activity

Graphite carbon nitride (g-C3N4) is a promising photocatalyst,but its inadequate reactive sites, weak visible light responsiveness, and sluggish separation of photogenerated carriers hamperthe improvement of photodegradation efficiency. In this work, potassium (K) and halogen atoms co-modified g-C3N4 photocatalysts (CN-KX, X = F, Cl, Br, I) were constructed to adjust the electrical and band structure for enhanced generation of reactive oxygen species. Through an integration of theoretical calculation and experimental exploration, the doping sites of halogen atoms as well as the evolution of crystal, band, and electronic structures were investigated. The results show that a covalent bond is formed between the F atom and the C atom, substitution of the N atom occurs with a Cl atom, and doping of Br, I, or K atoms takes place at the interstitial site. CN-KX photocatalysts exhibits lower band gap, faster photogenerated electron migration, and enhanced photocatalytic activity. Specifically, the CN-KI photocatalyst exhibits the highest photodegradation efficiency because of its smaller interplanar spacing, formation of the midgap state, and adjustable local electron density. Equally, the doping of I atom not only provides a stable adsorption site for oxygen (O2) but also facilitates electron transfer, promoting the production of superoxide radicals (O2−) and contributing to the process of photodegradation.

Programming Tetrathiafulvalene‐Based Covalent Organic Frameworks for Promoted Photoinduced Molecular Oxygen Activation

AbstractDespite the pivotal role of molecular oxygen (O2) activation in artificial photosynthesis, the activation efficiency is often restricted by sluggish exciton dissociation and charge transfer kinetics within polymer photocatalysts. Herein, we propose two tetrathiafulvalene (TTF)‐based imine‐linked covalent organic frameworks (COFs) with tailored donor‐acceptor (D–A) structures, TTF‐PDI‐COF and TTF‐TFPP‐COF, to promote O2 activation. Because of enhanced electron push‐pull interactions that facilitated charge separation and transfer behavior, TTF‐PDI‐COF exhibited superior photocatalytic activity in electron‐induced O2 activation reactions over TTF‐TFPP‐COF under visible light irradiation, including the photosynthesis of (E)‐3‐amino‐2‐thiocyano‐α,β‐unsaturated compounds and H2O2. These findings highlight the significant potential of the rational design of COFs with D–A configurations as suitable candidates for advanced photocatalytic applications.

Visible light-driven molecular oxygen activation by lead-zinc smelting slag and tartaric acid for efficient organic pollutant degradation and Cr(VI) reduction

The remediation of heavy metal and organic-contaminated wastewater remains a significant concern in environmental science, necessitating the development of cost-effective and efficient treatment systems. This study focuses on the setup of a highly effective molecular oxygen (O2) activation system using lead–zinc smelting slag (LZSS) and tartaric acid (TA) under visible light. The LZSS-TA complex exhibited rapid photochemical reactions and demonstrated a remarkable capacity for O2 activation, resulting in the in situ generation of hydrogen peroxide (H2O2) and 99 % degradation of para-chloroaniline (p-CA). The formation of H2O2 occurred through a two-step single electron transfer pathway, whereby C-centered radicals (CHOHCHOHCOO−) generated within the system initiated the reduction of O2 to form O2−, as a crucial intermediate. The produced O2− is then reduced by Fe(II) to generate H2O2 via proton-coupled electron transfer (PCET) processes. Light-induced ligand-to-metal charge transfer (LMCT) process is the key to the production of C-centered radicals and Fe(II), which determines the production efficiency of H2O2 and OH. Additionally, this system enabled simultaneous oxidation of p-CA by 98 % and reduction of Cr(VI) by 100 % within 60 min. More importantly, O2 activation by TA-assisted LZSS under natural sunlight/solar irradiation could efficiently degrade p-CA in both ultrapure water (94 %) and reservoir water (92.5 %) within 210 min. This study significantly contributes to the understanding of light-driven O2 activation and lays the foundation for the design of cost-effective and efficient pollution remediation systems.

Engineering the defect distribution via boron doping in amorphous TiO2 for robust photocatalytic NO removal

Nitric oxide (NO) pollutant can threaten the regional environment and human health. Solar-powered photocatalytic oxidation method is desirable for NO removal (ppb level) at ambient conditions, but suffers from the unsatisfactory activity and poor selectivity due to the sluggish molecular oxygen activation. Herein, we demonstrate that efficient photocatalytic NO removal can be realized by modulating the defects distribution of amorphous TiO2 via boron doping. Theoretical calculations and experimental results reveal that H3BO3 modification can refine the structure of surface oxygen vacancies, promoting electron-rich molecular oxygen activation to •OH. Meanwhile, bulk-phase oxygen defects can be filled by free-state B atoms, accelerating the electron transfer via Ti-O-B bonding. Homogeneous boron-doped amorphous TiO2 achieves about 5 times higher NO removal efficiency (∼50%) than that of amorphous TiO2 (∼9%) without releasing remarkable NO2 (selectivity, ∼97%). This study provides a state-of-the-art approach for robust photocatalytic NO removal by engineering the defect distribution.

The role of Au and Pd in photocatalytic activation of molecular oxygen: A mechanistic study

Activation of molecular oxygen plays an important role in photocatalytic selective oxidation reactions and complete degradation of organic pollutants. Noble metal cocatalysts are often employed to modulate the activation of oxygen to reach an optimum photocatalytic performance. However, the role of the metal nanoparticles (NPs) still remains unclear and deserves investigation for the design of efficient photocatalysts. Here, Au and Pd NPs are deposited on the TiO2 photocatalyst to study the promotional mechanism of O2 dissociation with the presence of glycerol under irradiation by near-ambient-pressure photoelectron spectroscopy and in-situ spectrometry approaches. While both Au and Pd NPs can dissociate O2 into activated oxygen species, a relatively strong bonds of dissociated oxygen atom is observed on Au NPs than on the Pd NPs. This results in a moderate reduction rate of O2 and eventually favors a mild oxidation reaction process for Au, and a rapid reduction rate of O2 and eventually a deep oxidation reaction process for Pd, respectively.

MOF-derived CuO@CB@CF cathode for O2 activation to generate ROSs for efficient electro-Fenton-catalysis

The generation of reactive radicals by molecular oxygen activation has become an important advanced oxidation technique. The combination of highly active carbon materials and stable transition metal oxides can activate molecular oxygen to produce hydrogen peroxide and further produce active free radicals at the same time, which is an efficient way for the removal of organic pollutants by heterogeneous electro-Fenton (HEF) system. In this study, a novel metal organic framework (MOF) derived CuO-carbon black-carbon felt (CuO@CB@CF) composite catalytic electrode has been prepared, which can generate H2O2 efficiently by selective O2 reduction through two-electron pathway with high pollutant removal efficiency. By optimizing the calcination temperature of MOF and loading capacity, the MOF-derived CuO@CB@CF has demonstrated excellent performance as a HEF catalytic electrode. Meanwhile, the effects of applied voltage, pH value, electrode area and aeration conditions have been studied. The excellent performance of MOF-derived CuO@CB@CF provides new insights into the removal of organic pollutants through electro-Fenton processes of transition metal oxide and carbon-based catalysts.

Highly Dispersed Ni Atoms and O3 Promote Room-Temperature Catalytic Oxidation.

Transition metal oxides are promising catalysts for catalytic oxidation reactions but are hampered by low room-temperature activities. Such low activities are normally caused by sparse reactive sites and insufficient capacity for molecular oxygen (O2) activation. Here, we present a dual-stimulation strategy to tackle these two issues. Specifically, we import highly dispersed nickel (Ni) atoms onto MnO2 to enrich its oxygen vacancies (reactive sites). Then, we use molecular ozone (O3) with a lower activation energy as an oxidant instead of molecular O2. With such dual stimulations, the constructed O3-Ni/MnO2 catalytic system shows boosted room-temperature activity for toluene oxidation with a toluene conversion of up to 98%, compared with the O3-MnO2 (Ni-free) system with only 50% conversion and the inactive O2-Ni/MnO2 (O3-free) system. This leap realizes efficient room-temperature catalytic oxidation of transition metal oxides, which is constantly pursued but has always been difficult to truly achieve.

Surface-Assisted Selective Air Oxidation of Phosphines Adsorbed on Activated Carbon.

Trialkyl- and triarylphosphines readily adsorb onto the surface of porous activated carbon (AC) even in the absence of solvents through van der Waals interactions between the lone electron pair and the AC surface. This process has been proven by solid-state NMR techniques. Subsequently, it is demonstrated that the AC enables the fast and selective oxidation of adsorbed phosphines to phosphine oxides at ambient temperature in air. In solution, trialkylphosphines are oxidized to a variety of P(V) species when exposed to the atmosphere, while neat or dissolved triarylphosphines cannot be oxidized with air. When the trialkyl- and triarylphosphines PnBu3 (1), PEt3, (2), PnOct3 (3), PMetBu2 (4), PCy3 (5), and PPh3 (6) are adsorbed in a mono- or submonolayer on the surface of AC, in the absence of a solvent and at ambient temperature, they are quantitatively oxidized to the adsorbed phosphine oxides, 1ox-6ox, once air is admitted. No formation of any unwanted P(V) side products or water adducts is observed. The phosphine oxides can then be recovered in good yields by washing them off of the AC. The oxidation is likely facilitated by a radical activation of molecular oxygen due to delocalized electrons on the aromatic surface coating of AC, as proven by ESR. This easy and inexpensive oxidation method renders hydrogen peroxide or other oxidizers unnecessary and is broadly applicable to sterically hindered and even to air-stable triarylphosphines. Phosphines adsorbed at lower surface coverages on AC oxidize at a faster rate. All oxidation reactions were monitored by solution- and solid-state NMR spectroscopy.

Intensify Mass Transfer and Molecular Oxygen Activation by Defect‐Bridged Asymmetric Catalytic Sites Toward Efficient Membrane‐Based Nanoconfined Catalysis

AbstractEfficient spontaneous molecular oxygen (O2) activation is expected in advanced oxidation processes. However, it remains a great challenge to promote the reactants adsorption and accelerate the interfacial electron transfer to boost the activation kinetic of O2. Herein, defect‐rich N‐doped reduced graphene oxide/CoFe2O4 (NGCF‐OV) membrane containing asymmetric Co‐OV‐Fe sites is prepared for O2 activation. The intrinsic catalytic activity is that the asymmetric Co‐OV‐Fe sites regulate the O─O bond length, promoting more and faster electron transfer to O2 for selectively producing 1O2. Meanwhile, the adjacent graphitic N sites help confine organics to the surface and thus greatly shorten the reaction distance of 1O2 and improve its utilization efficiency. The NGCF‐OV membrane demonstrates complete degradation of bisphenol A within a retention time of 86 ms, achieving a k‐value of 0.047 ms−1, which exceeds the performance of most Fenton‐like systems. This work provides new horizons for designing an efficient and stable catalytic membrane, enriching the domain of advanced wastewater treatment strategies.

Efficient photocatalytic molecular oxygen activation by TTF-based heterojunction for water purification

Tetrathiafulvalene (TTF), one of the well-known organic photoelectric materials, was served as active sites to accelerate the activation of molecular oxygen to degrade organic pollutants. Herein, a kind of Z-scheme heterojunction photocatalysis was constructed based on g-C3N4 and TTF. According to the experimental results, the mechanism of Z-scheme heterojunction was supported, in which photogenerated electrons transferred from g-C3N4 to TTF. More importantly, TTF on the catalyst surface could serve not only as electron donor, but also as the terminal active site to transfer photoexcited electrons to adsorbed oxygen molecules, producing mass of ⋅O2–. Meanwhile, the activation rate constant of TCN-5 for RhB was 0.0624 min−1, which was 10 and 5 times of g-C3N4 and TTF, respectively. In addition, the results of EPR spectra, rotating disk electrode measurement and molecular oxygen activation measurement also demonstrated that this catalyst was energetically favorable to generate ⋅O2– through the single-electron reduction pathway of molecular oxygen. Finally, four possible photodegradation routes for RhB were proposed based on the results of HPLC-MS. This work provides a new insight on the application of organic photoelectric materials in the purification of wastewater by the molecular oxygen activation.

Programming Tetrathiafulvalene-Based Covalent Organic Frameworks for Promoted Photoinduced Molecular Oxygen Activation.

Despite the pivotal role of molecular oxygen (O2) activation in artificial photosynthesis, the activation efficiency is often restricted by sluggish exciton dissociation and charge transfer kinetics within polymer photocatalysts. Herein, we propose two tetrathiafulvalene (TTF)-based imine-linked covalent organic frameworks (COFs) with tailored donor-acceptor (D-A) structures, TTF-PDI-COF and TTF-TFPP-COF, to promote O2 activation. Because of enhanced electron push-pull interactions that facilitated charge separation and transfer behavior, TTF-PDI-COF exhibited superior photocatalytic activity in electron-induced O2 activation reactions over TTF-TFPP-COF under visible light irradiation, including the photosynthesis of (E)-3-amino-2-thiocyano-α,β-unsaturated compounds and H2O2. These findings highlight the significant potential of the rational design of COFs with D-A configurations as suitable candidates for advanced photocatalytic applications.

Amplifying chlorinated phenol decomposition via Dual-Pathway O2 Activation: The impact of zirconium loading on BiOCl

The effectiveness of photocatalytic molecular oxygen (O2) activation in pollutant removal relies on the targeted production of reactive oxygen species (ROS). Herein, we demonstrate the dual-pathway activation of O2 on BiOCl through zirconium (Zr) loading. The incorporation of Zr onto the surface of BiOCl not only leads to an increased generation of oxygen vacancies (OV) but also fosters a coupling between the d electrons of Zr and OV, forming dual-active sites known as Zr-oxygen vacancies (Zr-OV). Generally, OV adsorbs O2 and transfers one electron directly to form superoxide radicals (•O2–). Contrary to the conventional single-electron direct activation of O2 to form •O2–, Zr-OV exhibits more flexible coordination and superior electron-donating capabilities. It facilitates O2 conversion to peroxide radicals (O22–) and enables the subsequent generation of •O2– from O22–, significantly promotes the dechlorination and mineralization efficiency of chlorophenol under visible light. This study presents a straightforward strategy to precisely regulate ROS production by expanding pathways, shedding light on the critical role of managing ROS generation for effective pollutant purification.

Cyclable CuⅠ-Ov-Mn sites accelerate O2 activation to enhance photo-driven catalytic oxidation performance

Molecular oxygen activation (MOA) plays a crucial function in various oxidation reactions. Nonetheless, facile, continuous and efficient MOA remains challenging. Herein, we have successfully constructed recyclable CuⅠ-Ov-Mn sites (Ov: oxygen vacancy) for MOA by incorporating Cu single atoms in MnO2 matrix. The localized photogenerated electron at CuⅡ site drives the generation of electron-rich CuⅠ species and an adjacent photoinduced Ov, which possesses stronger O2 affinity and affords a durable O2 activation site. The CuⅡ/CuⅠ cycle accelerates the separation of charge carriers to supply adequate photogenerated electrons and assures the renewability of photoinduced Ov, thus realizing rapid and sustained O2 activation and generating abundant monatomic oxygen ions (O-). Consequently, Cu-MnO2 catalyst performed extraordinarily high activity in O2-involved reactions. For instance, in toluene oxidation, toluene conversion reached as high as 96 %, comparable to that on the state-of-the-art supported Pt catalysts. This work will bring more possibilities for modulating the O2-involved oxidative reactions.

Surface methyl/methylene regulates WO3 directional activation of molecular oxygen into singlet oxygen for the removal of organic pollutants in water

The efficient removal of organic pollutants using singlet oxygen (1O2) represents a pivotal advancement in environmental purification. Despite its potential, the controlled generation of 1O2 remains a challenging endeavor. In this study, we present a novel approach whereby methyl/methylene are utilized to modulate the production of 1O2 by tungsten trioxide (WO3), thereby enhancing the photocatalytic degradation of persistent pollutants through deep oxidation. Employing a dodecyltrimethylammonium bromide (DTAB)-assisted hydrothermal synthesis, we successfully fabricated WO3 capable of generating 1O2. This modified WO3 demonstrates superior performance in the photocatalytic degradation of chloroquine phosphate by facilitating the rapid separation of photo-generated electron-hole pairs, thereby accelerating the degradation process. Furthermore, WO3 augmented with 1O2 exhibits enhanced efficacy in decomposing other challenging organic contaminants, compared to its untreated counterpart. Our findings not only contribute to the advancement of photocatalytic design principles centered on 1O2 but also underscore the critical role of controlled 1O2 production in the effective eradication of pollutants.

Solvent-free oxidation of benzylic C(sp3)–H bond over MA3Bi2Br9 perovskite photocatalyst by efficient singlet oxygen generation

Photocatalytic selective oxidation under solvent-free conditions plays a pivotal role in green chemistry, which can diminish pollutant production and minimize resource consumption in chemical reactions. In this process, the activation of molecular oxygen (O2) plays a crucial role. Here, we demonstrate the efficient oxidation of C(sp3)–H bond in pure toluene to produce oxygenated products of benzaldehyde (BAD) and benzyl alcohol (BA) using O2 as an oxidant over lead-free MA3Bi2Br9 perovskite. Systematic spectroscopic characterizations and controlled experiments validate that MA3Bi2Br9 enables the activation of O2 to superoxide radical (•O2−) and singlet oxygen (1O2) via charged electron transfer and excitonic energy transfer, respectively. Significantly, 1O2 emerges as an important active species. The optimal photocatalytic performance delivered by MA3Bi2Br9 reaches a BAD generation rate of 10756 µmol g−1h−1, with a BAD product selectivity of 81.5 %. The performance is greater than most classical photocatalysts, representing one of the best photocatalytic activities available in the literature. The lead-free feature of MA3Bi2Br9 perovskite coupled with its impressive catalytic performance makes it promising for practical applications.

Electron Structure Tuned Oxygen Vacancy-Rich AuPd/CeO2 for Enhancing 5-Hydroxymethylfurfural Oxidation.

The design of high activity catalyst for the efficiently conversion of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) gains great interest. The rationally tailoring of electronic structure directly affects the interaction between catalysts and organic substrates, especially molecular oxygen as the oxidant. This work, the bimetallic catalysts AuPd/CeO2 were prepared by the combining method of chemical reduction and photo-deposition, effectively concerting charge between Au and Pd and forming the electron-rich state of Au. The increasing of oxygen vacancy concentration of CeO2 by acidic treatment can facilitate the adsorption of HMF for catalysts and enhance the yield of FDCA (99.0 %). Moreover, a series of experiment results combining with density functional theory calculation illustrated that the oxidation performance of catalyst in HMF conversion was strongly related to the electronic state of interfacial Au-Pd-CeO2. Furthermore, the electron-rich state sites strengthen the adsorption and activation of molecular oxygen, greatly promoting the elimination of β-hydride for the selective oxidation of 5-hydroxymethyl-2-furancarboxylic acid (HMFCA) to FDCA, accompanied with an outgoing FDCA formation rate of 13.21 mmol ⋅ g-1 ⋅ min-1 at 80 °C. The perception exhibited in this research could be benefit to understanding the effects of electronic state for interfacial sites and designing excellent catalysts for the oxidation of HMF.