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1.
Environ Sci Technol ; 58(37): 16642-16655, 2024 Sep 17.
Article in English | MEDLINE | ID: mdl-39226236

ABSTRACT

This study demonstrated that NiO and Ni(OH)2 as Ni(II) catalysts exhibited significant activity for organic oxidation in the presence of various oxyanions, such as hypochlorous acid (HOCl), peroxymonosulfate (PMS), and peroxydisulfate (PDS), which markedly contrasted with Co-based counterparts exclusively activating PMS to yield sulfate radicals. The oxidizing capacity of the Ni catalyst/oxyanion varied depending on the oxyanion type. Ni catalyst/PMS (or HOCl) degraded a broad spectrum of organics, whereas PDS enabled selective phenol oxidation. This stemmed from the differential reactivity of two high-valent Ni intermediates, Ni(III) and Ni(IV). A high similarity with Ni(III)OOH in a substrate-specific reactivity indicated the role of Ni(III) as the primary oxidant of Ni-activated PDS. With the minor progress of redox reactions with radical probes and multiple spectroscopic evidence on moderate Ni(III) accumulation, the significant elimination of non-phenolic contaminants by NiOOH/PMS (or HOCl) suggested the involvement of Ni(IV) in the substrate-insensitive treatment capability of Ni catalyst/PMS (or HOCl). Since the electron-transfer oxidation of organics by high-valent Ni species involved Ni(II) regeneration, the loss of the treatment efficiency of Ni/oxyanion was marginal over multiple catalytic cycles.


Subject(s)
Nickel , Oxidation-Reduction , Nickel/chemistry , Catalysis , Anions , Organic Chemicals/chemistry , Peroxides/chemistry , Hypochlorous Acid/chemistry
2.
Water Res ; 261: 122067, 2024 Sep 01.
Article in English | MEDLINE | ID: mdl-39003877

ABSTRACT

The abatement of micropollutants by ozonation can be accurately calculated by measuring the exposures of molecular ozone (O3) and hydroxyl radical (•OH) (i.e., ∫[O3]dt and ∫[•OH]dt). In the actual ozonation process, ∫[O3]dt values can be calculated by monitoring the O3 decay during the process. However, calculating ∫[•OH]dt is challenging in the field, which necessitates developing models to predict ∫[•OH]dt from measurable parameters. This study demonstrates the development of machine learning models to predict ∫[•OH]dt (the output variable) from five basic input variables (pH, dissolved organic carbon concentration, alkalinity, temperature, and O3 dose) and two optional ones (∫[O3]dt and instantaneous ozone demand, IOD). To develop the models, four different machine learning methods (random forest, support vector regression, artificial neural network, and Gaussian process regression) were employed using the input and output variables measured (or determined) in 130 different natural water samples. The results indicated that incorporating ∫[O3]dt as an input variable significantly improved the accuracy of prediction models, increasing overall R2 by 0.01-0.09, depending on the machine learning method. This suggests that ∫[O3]dt plays a crucial role as a key variable reflecting the •OH-yielding characteristics of dissolved organic matter. Conversely, IOD had a minimal impact on the accuracy of the prediction models. Generally, machine-learning-based prediction models outperformed those based on the response surface methodology developed as a control. Notably, models utilizing the Gaussian process regression algorithm demonstrated the highest coefficients of determination (overall R2 = 0.91-0.95) among the prediction models.


Subject(s)
Hydroxyl Radical , Machine Learning , Ozone , Ozone/chemistry , Hydroxyl Radical/chemistry , Kinetics , Water Purification/methods
3.
Adv Mater ; 36(36): e2404388, 2024 Sep.
Article in English | MEDLINE | ID: mdl-39011790

ABSTRACT

Current research on organic light emitters which utilize multiple resonance-induced thermally activated delayed fluorescence (MR-TADF) materials is gaining significant interest because of the materials' ability to efficiently generate color-pure blue emission. However, the underlying reasons for high color purity remain unclear. It is shown here that these emitters share a common electronic basis, which is deduced from resonance structure considerations following Clar's rule, and which is termed as "poly-heteroaromatic omni-delocalization" (PHOD). The simple and clear design rules derived from the PHOD concept allow extending the known chemical space by new structural motifs. Based on PHOD, a set of novel high-efficiency color-pure emitters with brilliant deep-blue hue is specifically designed.

4.
Front Med (Lausanne) ; 11: 1364357, 2024.
Article in English | MEDLINE | ID: mdl-38695029

ABSTRACT

Background: Although pharmacokinetic and pharmacodynamic models of remimazolam have been developed, their clinical application remains limited. This study aimed to administer a target-controlled infusion (TCI) of remimazolam at the effect-site concentration (Ce) in patients undergoing general anesthesia and to investigate the relationship of the remimazolam Ce with sedative effects and with recovery from general anesthesia. Methods: Fifty patients aged 20-75 years, scheduled for minimally invasive surgery under general anesthesia for less than 2 h, were enrolled. Anesthesia was induced and maintained using Schüttler's model for effect-site TCI of remimazolam. During induction, the remimazolam Ce was increased stepwise, and sedation levels were assessed using the Modified Observer's Assessment of Alertness/Sedation (MOAA/S) scale and bispectral index (BIS). Following attainment of MOAA/S scale 1, continuous infusion of remifentanil was commenced, and rocuronium (0.6 mg/kg) was administered for endotracheal intubation. The target Ce of remimazolam and the remifentanil infusion rate were adjusted to maintain a BIS between 40 and 70 and a heart rate within 20% of the baseline value. Approximately 5 min before surgery completion, the target Ce of remimazolam was reduced by 20-30%, and anesthetic infusion ceased at the end of surgery. Nonlinear mixed-effects modeling was employed to develop pharmacodynamic models for each sedation level as well as emergence from anesthesia. Results: The remimazolam Ces associated with 50% probability (Ce50) of reaching MOAA/S scale ≤4, 3, 2, and 1 were 0.302, 0.397, 0.483, and 0.654 µg/mL, respectively. The Ce50 values for recovery of responsiveness (ROR) and endotracheal extubation were 0.368 and 0.345 µg/mL, respectively. The prediction probabilities of Ce and BIS for detecting changes in sedation level were 0.797 and 0.756, respectively. The sedation scale significantly correlated with remimazolam Ce (r = -0.793, P < 0.0001) and BIS (r = 0.914, P < 0.0001). Age significantly correlated with Ce at MOAA/S1 and ROR. Conclusion: Effect-site TCI of remimazolam was successfully performed in patients undergoing general anesthesia. The remimazolam Ce significantly correlated with sedation depth. The Ce50 for MOAA/S scale ≤1 and ROR were determined to be 0.654 and 0.368 µg/mL, respectively.

5.
Sci Rep ; 14(1): 8821, 2024 Apr 17.
Article in English | MEDLINE | ID: mdl-38627454

ABSTRACT

Augmented reality (AR) applications require displays with an extended color gamut to facilitate the presentation of increasingly immersive content. The waveguide (WG) display technology, which is typical AR demonstration method, is a critical constraint on the color gamut of AR systems because of the intrinsic properties of the holographic optical elements (HOEs) used in this technology. To overcome this limitation, we introduce a method of spatially modulated diffractive optics that can expand the color gamut of HOE-based WG displays. This approach involves spatial modulation using sub-pixelized HOEs, which enables the diffraction of red, green, and blue rays along identical directions. The proposed structure considers both the characteristics of the HOE and the wavelength sensitivity of the observer to optimize the color gamut. Consequently, an expanded color gamut was achieved. The results of the theoretical and experimental analyses substantiate the effectiveness and practicality of this method in enhancing the color gamut of HOE-based WG displays. Thus, the proposed method can facilitate the implementation of more immersive AR displays.

6.
Nat Commun ; 15(1): 2829, 2024 Apr 02.
Article in English | MEDLINE | ID: mdl-38565557

ABSTRACT

In developing an organic light-emitting diode (OLED) panel for a foldable smartphone (specifically, a color filter on encapsulation) aimed at reducing power consumption, the use of a new optically clear adhesive (OCA) that blocks UV light was crucial. However, the incorporation of a UV-blocking agent within the OCA presented a challenge, as it restricted the traditional UV-curing methods commonly used in the manufacturing process. Although a visible-light curing technique for producing UV-blocking OCA was proposed, its slow curing speed posed a barrier to commercialization. Our study introduces a highly efficient photo-initiating system (PIS) for the rapid production of UV-blocking OCAs utilizing visible light. We have carefully selected the photocatalyst (PC) to minimize electron and energy transfer to UV-blocking agents and have chosen co-initiators that allow for faster electron transfer and more rapid PC regeneration compared to previously established amine-based co-initiators. This advancement enabled a tenfold increase in the production speed of UV-blocking OCAs, while maintaining their essential protective, transparent, and flexible properties. When applied to OLED devices, this OCA demonstrated UV protection, suggesting its potential for broader application in the safeguarding of various smart devices.

7.
Water Res ; 253: 121343, 2024 Apr 01.
Article in English | MEDLINE | ID: mdl-38422888

ABSTRACT

A dye-sensitized photocatalysis system was developed for degrading persistent organic contaminants using solid waste (i.e., red mud, RM) and peroxymonosulfate (PMS) under visible light. Complete degradation of acid orange 7 (AO7) was achieved in RM suspension with PMS, where the co-existence of amorphous FeO(OH)/α-Fe2O3 was the key factor for PMS activation. The experimental results obtained from photochemical and electrochemical observations confirmed the enhanced PMS activation due to the Fe-OH phase in RM. DFT calculations verified the acceleration of PMS activation due to the high adsorption energy of PMS on FeO(OH) and low energy barrier for generating reactive radicals. Compared to the control experiment without AO7 showing almost no degradation of other organic contaminants (phenol, bisphenol A, 4-chlorophenol, 4-nitrophenol, and benzoic acid), photo-sensitized AO7* enhanced electron transfer in the FeIII/FeII cycle, dramatically enhancing the degradation of organic contaminants via radical (•OH, SO4•-, and O2•-) and non-radical (dye*+ and 1O2) pathways. Therefore, the novel finding of this study can provide new insights for unique PMS activation by heterogeneous Fe(III) containing solid wastes and highlight the importance of sensitized dye on the interaction of PMS with Fe charge carrier for the photo-oxidation of organic contaminants under visible light.


Subject(s)
Azo Compounds , Benzenesulfonates , Ferric Compounds , Water Pollutants, Chemical , Water Pollutants, Chemical/analysis , Peroxides , Light
8.
J Hazard Mater ; 459: 132207, 2023 10 05.
Article in English | MEDLINE | ID: mdl-37543019

ABSTRACT

Owing to the surge in plastic waste generated during the COVID-19 pandemic, concerns regarding microplastic pollution in aqueous environments are increasing. Since microplastics (MPs) are broken down into submicron (< 1 µm) and nanoscale plastics, their real-time morphological detection in water is necessary. However, the decrease in the scattering cross-section of MPs in aqueous media precludes morphological detection by bright-field microscopy. To address this problem, we propose and demonstrate a differential interference contrast (DIC) system that incorporates a magnification-enhancing system to detect MPs in aqueous samples. To detect MPs in both the stationary and mobile phases, a microfluidic chip was designed, taking into consideration the imaging depth of focus and flow resistance. MPs of various sizes flowing in deionized, tap, and pond water at varying speeds were observed under Static and Flow conditions. Successful real-time morphological detection and quantification of polystyrene beads down to 200 nm at a constant flow rate in water were achieved. Thus, the proposed novel method can significantly reduce analysis time and improve the size-detection limit. The proposed DIC microscopy system can be coupled with Raman or infrared spectroscopy in future studies for chemical composition analysis. ENVIRONMENTAL IMPLICATION: Microplastics (MPs), particularly submicron plastics < 1-µm, can pose a risk to human health and aquatic ecosystems. Existing methods for detecting MPs in the aqueous phase have several limitations, including the use of expensive instruments and prolonged and labor-intensive procedures. Our results clearly demonstrated that a new low-cost flow-channeled differential interference contrast microscopy enables the real-time morphological detection and quantification of MPs down to 200 nm under flowing conditions without sample labeling. Consequently, our proposed rapid method for accurate quantitative measurements can serve as a valuable reference for detecting submicron plastics in water samples.


Subject(s)
COVID-19 , Water Pollutants, Chemical , Humans , Plastics/analysis , Microplastics , Ecosystem , Microscopy , Pandemics , Water Pollutants, Chemical/analysis , Environmental Monitoring , Water/analysis
9.
Opt Express ; 31(12): 19843-19852, 2023 Jun 05.
Article in English | MEDLINE | ID: mdl-37381391

ABSTRACT

In this work, we present a multi-mode resonator based on SU-8 polymer and experimentally verify that the resonator showed mode discrimination can be used as a sensor with high performance. According to field emission scanning electron microscopy (FE-SEM) images, the fabricated resonator shows sidewall roughness which is canonically considered to be undesirable after a typical development process. In order to analyze the effect of sidewall roughness, we conduct the resonator simulation considering the roughness under various conditions. Mode discrimination still occurs even in the presence of sidewall roughness. In addition, waveguide width controllable by UV exposure time effectively contributes to mode discrimination. To verify the resonator as a sensor, we perform a temperature variation experiment, which results in a high sensitivity of about 630.8 nm/RIU. This result shows that the multi-mode resonator sensor fabricated via a simple process is competitive with other single-mode waveguide sensors.

10.
ACS Appl Mater Interfaces ; 15(14): 17867-17878, 2023 Apr 12.
Article in English | MEDLINE | ID: mdl-36988213

ABSTRACT

Reactive chlorine-mediated electrochemical water treatment necessitates selective chlorine evolution reaction (ClER) versus parallel oxygen evolution reaction (OER) in mild pH (7-10), with minimal deployments of precious electrocatalysts. This study reports Ni0.33Fe0.67Oy/TiO2 heterojunction anode prepared by a straightforward sol-gel coating with thermal decomposition at 425 °C. The ClER current efficiency (CE, 70%) and energy efficiency (2.3 mmol W h-1) were comparable to benchmarking Ir7Ta3Oy/TiO2 at 30 mA cm-2 in 50 mM NaCl solutions with near-neutral pH. Correlations of ClER CE of variable NixFe1-xOy/TiO2 (x: 0.33, 0.8-1) with the flat-band potential and p-band center, as experimental descriptors for surface charge density, nominated the outer TiO2 to be the active ClER center. The underlying Ni0.33Fe0.67Oy, characterized as biphasic NiFe2O4 and NiO, effectively lowered the O binding energy of TiO2 by electronic interaction across the junction. The OER activity of Ni0.33Fe0.67Oy superior to the other Fe-doped Ni oxides suggested that the conductive OER intermediates generated on Ni0.33Fe0.67Oy could also facilitate the ClER as an ohmic contact. Stability tests and NH4+ degradation in synthetic and real wastewater confirmed the feasibility of Ni0.33Fe0.67Oy/TiO2 heterojunction anode for mediated water treatments in mild pH.

11.
J Hazard Mater ; 443(Pt A): 130219, 2023 02 05.
Article in English | MEDLINE | ID: mdl-36367474

ABSTRACT

The fate and transport of microplastics (MPs) during deep bed filtration were investigated using combined laboratory experiments and numerical modeling. A series of column experiments were conducted within the designated ranges of six operating parameters (i.e., size of the MP and collector, seepage velocity, porosity, temperature, and ionic strength). A variance-based sensitivity analysis, the Fourier amplitude sensitivity test, was conducted to determine the priority in affecting both the attachment coefficient at the pore scale, and the subsequent stabilized height of the breakthrough curve at the continuum scale, which follows non-monotonic trends with singularity in the size of MP (i.e., 1 µm). Finally, Damkohler numbers were introduced to analyze the dominant mechanisms (e.g., attachment, detachment, or straining) in the coupled hydro-chemical process. The robustness of conceptual frameworks bridges the gap between pore-scale interactions and the explicit MPs removal in the continuum scale, which could support decision-making in determining the priority of parameters to retain MPs during deep bed filtration.


Subject(s)
Microplastics , Sand , Plastics , Filtration , Porosity
12.
Environ Sci Technol ; 56(15): 10829-10837, 2022 08 02.
Article in English | MEDLINE | ID: mdl-35767386

ABSTRACT

Given the widespread use of TiO2, its release into aquatic systems and complexation with dissolved organic matter (DOM) are highly possible, making it important to understand how such interactions affect photocatalytic activity under visible light. Here, we show that humic acid/TiO2 complexes (HA/TiO2) exhibit photoactivity (without significant electron-hole activation) under visible light through ligand-to-metal charge transfer (LMCT). The observed visible-light activities for pollutant removal and bacterial inactivation are primarily linked to the generation of H2O2via the conduction band. By systematically considering molecular-scale interactions between TiO2 and organic functional groups in HA, we find a key role of phenolic groups in visible-light absorption and H2O2 photogeneration. The photochemical formation of H2O2 in river waters spiked with TiO2 is notably elevated above naturally occurring H2O2 generated from background organic constituents due to LMCT contribution. Our findings suggest that H2O2 generation by HA/TiO2 is related to the quantity and functional group chemistry of DOM, which provides chemical insights into photocatalytic activity and potential ecotoxicity of TiO2 in environmental and engineered systems.


Subject(s)
Dissolved Organic Matter , Photochemical Processes , Hydrogen Peroxide , Ligands , Light , Titanium/chemistry
13.
Environ Sci Technol ; 56(9): 5763-5774, 2022 05 03.
Article in English | MEDLINE | ID: mdl-35442651

ABSTRACT

This study reexamined the mechanisms for oxidative organic degradation by the binary mixture of periodate and H2O2 (PI/H2O2) that was recently identified as a new advanced oxidation process. Our findings conflicted with the previous claims that (i) hydroxyl radical (•OH) and singlet oxygen (1O2) contributed as the primary oxidants, and (ii) •OH production resulted from H2O2 reduction by superoxide radical anion (O2•-). PI/H2O2 exhibited substantial oxidizing capacity at pH < 5, decomposing organics predominantly by •OH. The likelihood of a switch in the major oxidant under varying pH conditions was revealed. IO4- as the major PI form under acidic conditions underwent one-electron reduction by H2O2 to yield radical intermediates, whereas H2I2O104- preferentially occurring at pH > 7 caused 1O2 generation through two-electron oxidation of H2O2. PI reduction by O2•- was suggested to be a key reaction in •OH production, on the basis of the electron paramagnetic resonance detection of methyl radicals in the dimethyl sulfoxide solutions containing PI and KO2, and the absence of deuterated and 18O-labeled hydroxylated intermediates during PI activation using D2O and H218O2. Finally, simple oxyanion mixing subsequent to electrochemical PI and H2O2 production achieved organic oxidation, enabling a potential strategy to minimize the use of chemicals.


Subject(s)
Hydrogen Peroxide , Oxidants , Electron Spin Resonance Spectroscopy , Hydroxyl Radical , Oxidation-Reduction , Periodic Acid , Superoxides/metabolism
14.
Adv Mater ; 34(24): e2201608, 2022 Jun.
Article in English | MEDLINE | ID: mdl-35436369

ABSTRACT

Mechanical properties of biological systems provide useful information about the biochemical status of cells and tissues. Here, an artificial tactile neuron enabling spiking representation of stiffness and spiking neural network (SNN)-based learning for disease diagnosis is reported. An artificial spiking tactile neuron based on an ovonic threshold switch serving as an artificial soma and a piezoresistive sensor as an artificial mechanoreceptor is developed and shown to encode the elastic stiffness of pressed materials into spike frequency evolution patterns. SNN-based learning of ultrasound elastography images abstracted by spike frequency evolution rate enables the classification of malignancy status of breast tumors with a recognition accuracy up to 95.8%. The stiffness-encoding artificial tactile neuron and learning of spiking-represented stiffness patterns hold a great promise for the identification and classification of tumors for disease diagnosis and robot-assisted surgery with low power consumption, low latency, and yet high accuracy.


Subject(s)
Algorithms , Neural Networks, Computer , Neurons/physiology , Touch
15.
J Korean Phys Soc ; 80(8): 799-807, 2022.
Article in English | MEDLINE | ID: mdl-35125629

ABSTRACT

The report presents the operation status of and upgrade plan for the 100-MeV proton linac at the Korea Multi-purpose Accelerator Complex (KOMAC). First, an operation history of the 100-MeV linac since its commissioning in 2013, such as operation hours, user services, machine availabilities, and downtimes, is discussed. Second, the status of the beamlines in service or under development is described in a detailed manner. Finally, the Korea Spallation Neutron Source (KSNS), which is part of the upgrade plan for the 100-MeV proton linac to expand its utilization fields, is discussed.

16.
Nano Lett ; 22(2): 733-739, 2022 01 26.
Article in English | MEDLINE | ID: mdl-35025519

ABSTRACT

Inspired by information processing in biological systems, sensor-combined edge-computing systems attract attention requesting artificial sensory neurons as essential ingredients. Here, we introduce a simple and versatile structure of artificial sensory neurons based on a novel three-terminal Ovonic threshold switch (3T-OTS), which features an electrically controllable threshold voltage (Vth). Combined with a sensor driving an output voltage, this 3T-OTS generates spikes with a frequency depending on an external stimulus. As a proof of concept, we have built an artificial retinal ganglion cell (RGC) by combining a 3T-OTS and a photodiode. Furthermore, this artificial RGC is combined with the reservoir-computing technique to perform a classification of chest X-ray images for normal, viral pneumonia, and COVID-19 infections, releasing the recognition accuracy of about 86.5%. These results indicate that the 3T-OTS is highly promising for applications in neuromorphic sensory systems, providing a building block for energy-efficient in-sensor computing devices.


Subject(s)
COVID-19 , Neural Networks, Computer , Humans , SARS-CoV-2 , Sensory Receptor Cells
17.
Medicina (Kaunas) ; 59(1)2022 Dec 28.
Article in English | MEDLINE | ID: mdl-36676688

ABSTRACT

Relapsing polychondritis (RP) is a rare autoimmune disorder that causes inflammation and deterioration of cartilaginous structures such as the ears, nose, joints and laryngotracheobronchial tree. A 42-year-old man receiving treatment for RP underwent open reduction and internal fixation of a femur fracture under spinal anesthesia and with sedation by propofol and remifentanil. The level of sedation was monitored via a bispectral index (BIS), and maintained at between 60 and 80. At the end of the operation, he lost consciousness and displayed weak respiratory effort. During mask ventilation, the patient was judged to have respiratory failure due to high end-tidal CO2 (EtCO2) concentration and respiratory acidosis in an arterial-blood-gas analysis (ABGA). Ventilation through a properly inserted laryngeal-mask-airway or endotracheal intubation were impossible; instead, a surgical tracheotomy was performed. After recovering from respiratory failure with ventilatory support in the intensive care unit (ICU), he experienced the same symptoms three more times, requiring ventilatory support. He was discharged with bilevel positive-airway-pressure (BiPAP), after successful adaptation.


Subject(s)
Anesthesia , Polychondritis, Relapsing , Propofol , Respiratory Insufficiency , Male , Humans , Adult , Polychondritis, Relapsing/complications , Polychondritis, Relapsing/diagnosis , Polychondritis, Relapsing/surgery , Respiratory Insufficiency/etiology , Respiratory Insufficiency/therapy , Respiration , Anesthesia/adverse effects
18.
Adv Sci (Weinh) ; 8(16): e2100586, 2021 Aug.
Article in English | MEDLINE | ID: mdl-34137208

ABSTRACT

Although the organic light-emitting diode (OLED) has been successfully commercialized, the development of deep-blue OLEDs with high efficiency and long lifetime remains a challenge. Here, a novel hyperfluorescent OLED that incorporates the Pt(II) complex (PtON7-dtb) as a phosphorescent sensitizer and a hydrocarbon-based and multiple resonance-based fluorophore as an emitter (TBPDP and ν-DABNA) in the device emissive layer (EML), is proposed. Such an EML system can promote efficient energy transfer from the triplet excited states of the sensitizer to the singlet excited states of the fluorophore, thus significantly improving the efficiency and lifetime of the device. As a result, a deep-blue hyperfluorescent OLED using a multiple resonance-based fluorophore (ν-DABNA) with Commission Internationale de L'Eclairage chromaticity coordinate y below 0.1 is demonstrated, which attains a narrow full width at half maximum of ≈17 nm, fourfold increased maximum current efficiency of 48.9 cd A-1 , and 19-fold improved half-lifetime of 253.8 h at 1000 cd m-2 compared to a conventional phosphorescent OLED. The findings can lead to better understanding of the hyperfluorescent OLEDs with high performance.

19.
Environ Sci Technol ; 55(8): 5382-5392, 2021 04 20.
Article in English | MEDLINE | ID: mdl-33733765

ABSTRACT

This study is the first to demonstrate the capability of Cl- to markedly accelerate organic oxidation using thermally activated peroxymonosulfate (PMS) under acidic conditions. The treatment efficiency gain allowed heat-activated PMS to surpass heat-activated peroxydisulfate (PDS). During thermal PMS activation at excess Cl-, accelerated oxidation of 4-chlorophenol (susceptible to oxidation by hypochlorous acid (HOCl)) was observed along with significant degradation of benzoic acid and ClO3- occurrence, which involved oxidants with low substrate specificity. This indicated that heat facilitated HOCl formation via nucleophilic Cl- addition to PMS and enabled free chlorine conversion into less selective oxidizing radicals. HOCl acted as a key intermediate in the major oxidant transition based on temperature-dependent variation in HOCl concentration profiles, kinetically retarded organic oxidation upon NH4+ addition, and enabled rapid organic oxidation in heated PMS/HOCl mixtures. Chlorine atom that formed via the one-electron oxidation of Cl- by the sulfate radical served as the primary oxidant and was involved in hydroxyl radical production. This was corroborated by the quenching effects of alcohols and bicarbonates, reactivity toward multiple organics, and electron paramagnetic resonance spectral features. PMS outperformed PDS in degrading benzoic acid during thermal activation operated in reverse osmosis concentrate, which was in conflict with the well-established superiority of heat-activated PDS.


Subject(s)
Chlorides , Water Pollutants, Chemical , Chlorine , Hot Temperature , Oxidation-Reduction , Peroxides , Water Pollutants, Chemical/analysis
20.
Water Res ; 191: 116803, 2021 Mar 01.
Article in English | MEDLINE | ID: mdl-33440314

ABSTRACT

This study investigated the influence of adding peroxydisulfate (PDS) to a photoelectrocatalysis (PEC) system using self-doped TiO2 nanotube arrays (bl-TNAs) for organic pollutant degradation. The addition of 1.0 mM PDS increased the bisphenol-A (BPA) removal efficiency of PEC (PEC/PDS) from 65.0% to 85.9% within 1 h. The enhancement could be attributed to the high formation yield of hydroxyl radicals (·OH), increased charge separation, and assistance of the sulfate radicals (SO4·-). The PDS concentration and applied potential bias were influential operating parameters for the PEC/PDS system. In addition, the system exhibited a highly stable performance over a wide range of pH values and background inorganic and organic constituents, such as chloride ions, bicarbonate, and humic acid. Further, the degradation performance of the organic pollutant mixture, including BPA, 4-chlorophenol (4-CP), sulfamethoxazole (SMX), and carbamazepine (CBZ), was evaluated in 0.1 M (NH4)2SO4 solution and real surface water. The degradation efficiency increased in the order of CBZ < SMX < 4-CP < BPA in the PEC and PEC/PDS systems with both water matrices. Compared with the PEC system, the PEC/PDS (1.0 mM) system showed a threefold higher pseudo first-order reaction rate constant for BPA among pollutant mixtures in surface water. This was attributed to enhanced ·OH production and the selective nature of SO4·-. The pseudo first-order reaction rate constants of other pollutants, i.e., 4-CP, SMX, and CBZ increased ca. twofold in the PEC/PDS system. The results of this study showed that the PEC/PDS system with bl-TNAs is a viable technology for oxidative treatment.


Subject(s)
Environmental Pollutants , Nanotubes , Water Pollutants, Chemical , Water Purification , Oxidation-Reduction , Water , Water Pollutants, Chemical/analysis
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