Hydroxyl Radical Formation Research Articles

Capture of single Ag atoms through high-temperature-induced crystal plane reconstruction

The “terminal hydroxyl group anchoring mechanism” has been studied on metal oxides (Al2O3, CeO2) as well as a variety of noble and transition metals (Ag, Pt, Pd, Cu, Ni, Fe, Mn, and Co) in a number of generalized studies, but there is still a gap in how to regulate the content of terminal hydroxyl groups to influence the dispersion of the active species and thus to achieve optimal catalytic performance. Herein, we utilized AlOOH as a precursor for γ-Al2O3 and induced the transformation of the exposed crystal face of γ-Al2O3 from (110) to (100) by controlling the calcination temperature to generate more terminal hydroxyl groups to anchor Ag species. Experimental results combined with AIMD and DFT show that temperature can drive the atomic rearrangement on the (110) crystal face, thereby forming a structure similar to the atomic arrangement of the (100) crystal face. This resulted in the formation of more terminal hydroxyl groups during the high-temperature calcination of the support (Al-900), which can capture Ag species to form single-atom dispersions, and ultimately develop a stable and efficient single-atom Ag-based catalyst.

Photoelectrochemical Conversion of Methane to Ethane and Hydrogen under Visible Light Using Functionalized Tungsten Trioxide Photoanodes with Proton Exchange Membrane.

Developing methane utilization technologies is desired to convert abundant and renewable carbon resources, such as natural gas and biogas, into value-added chemical products. This study provides insights into emerging photoelectrochemical (PEC) technology for the photocatalytic transformation of methane to C2H6 and H2 using visible light at room temperature. The PEC conversion of methane to oxygenates has been investigated in aqueous electrolytes. Herein, we demonstrate the gas-phase PEC methane conversion using a proton exchange membrane (PEM) as a solid polymer electrolyte and a gas-diffusion photoanode for methane oxidation. Tungsten trioxide (WO3), a semiconductor photocatalyst responsive to visible light, is utilized as the photoanode material. Ultraviolet light (∼365 nm) excitation predominantly results in CO2 production with lower C2H6 selectivity in humidified methane. In contrast, visible light (∼453 nm) effectively promotes C2H6 production over the WO3 photoanode, attributed to preferential hydroxyl radical (•OH) formation compared to UV irradiation. Photogenerated holes formed near the valence band maximum of WO3 contribute to •OH formation through a single-electron water oxidation. The photogenerated •OH activates gaseous methane molecules to methyl radicals, subsequently coupled into C2H6 at the gas-electrolyte-semiconductor boundary. H2 is concurrently formed on the cathode electrocatalyst. Improving the selectivity for the dehydrogenative coupling of methane is pivotal for enhancing the energy efficiency in the PEM-PEC system.

Room–temperature hydrogen sensitive Pt–SnO2 composite nanoceramics: Dormancy and a practicable regeneration method

Dormancy has been suggested to be used for metal oxide gas sensors to specifically refer to their response decrease or disappearance after long periods of inactivity at room temperature. In this paper, 1 wt% Pt–SnO2 composite nanoceramics with especially strong responses to hydrogen–containing atmospheres at room temperature, e.g. a response of 11170 to 1 % H2–20 % O2–N2, were successfully prepared through pressing and sintering. A clear dormancy has been observed for them as their responses decreased seriously with time when they were stored in ambient air at room temperature. Commercial ceramic heating plates (Metal Ceramics Heater, MCH) of 10 mm × 10 mm were attached to bars of 1 wt% Pt–SnO2 composite nanoceramics. Dormant bars after 12 months of storage were completely regenerated through a heat–treatment of 200 °C for 10 min by attached MCH ceramic heating plates. According to X-ray photoelectron spectroscopy analyses, the formation of hydroxyl groups on SnO2 in Pt–SnO2 composite nanoceramics and deposition of impurity gases like H2S were proposed responsible for the dormancy, and their removal through mild heat–treatments result in the regeneration. It is suggested that heaters like commercial MCH ceramic heating plates should be included in future room–temperature gas sensors to provide a practicable regeneration from dormancy when needed.

Red Blood Cell Hemoglobin Oxygen Transfer in Deep-Diving Marine Mammals

Objective: Some marine mammals of the order pinniped and cetacean can dive for long durations to forage for food and travel over distances. During these extended dives both pinnipeds and cetaceans experience extreme tissue hypoxia. Numerous adaptations have evolved to allow these species to effciently deliver and utilize oxygen (O2). One genetic difference, which our laboratory has proposed to play an important role in O2 transport effciency in modern hominids, is the inactivation of the CMP-Neu5AC hydroxylase (CMAH) gene. Pinnipeds inactivated Cmah ~ 40 million years ago but, cetaceans still express this N-glycan modifying enzyme. CMAH converts the sialic acid, N-acetylneuraminic acid (Neu5Ac), to its hydroxylated form, N-glycolylneuraminic acid (Neu5Gc). These sialic acids are located at the end of branched sugar chains on the surface of cell membranes. As a result, a change in composition could affect cell membrane charge and hydrophobicity, as well as potentially alter O2 diffusion laterally or across cell membranes. Hypothesis: In this study we hypothesized that O2 transfer from hemoglobin (Hb) in red blood cells (RBCs) to myoglobin (Mb) would differ between cetaceans (CMAH+) and pinnipeds (CMAH-). Methods: This hypothesis was tested using optical absorption spectroscopy to measure O2 exchange between oxygenated Hb in RBC and deoxygenated Mb collected in several species of mustelids and pinniped (CA sea otter, CA sea lion, and walrus) and cetaceans (Bottlenose Dolphin, Beluga, and Orca). Measurements of cell diameters (diffusion length) were also measured. Results: The mean oxygen transfer (O2D/A410) was 47% lower in pinnipeds than cetaceans (p<0.01). The amount of O2 transferred in cetaceans increased with longer reported maximal dive durations. There was a trend for overall RBC diameters to be larger in cetaceans than pinnipeds (p=0.054). Summary: The RBC O2 transfer data in these hypoxia tolerant marine mammals suggest a transfer mechanism that is more effcient in cetaceans in a normoxic environment. Conclusions: More effcient oxygen transfer in cetaceans, who retained the Cmah gene, compared to pinnipeds and mustelids, who did not retain the Cmah gene, suggests that the gene knockout may not be the only factor that facilitates delivery of O2 in these marine mammals. A trend for larger RBC diameters in cetaceans than pinnipeds also suggests that diffusion length is not a main contributing factor. Future experiments to measure oxygen transfer from RBC O2-Hb to Mb under different O2 environments are needed to more closely model what may occur during long duration dives. NSF1929325. This is the full abstract presented at the American Physiology Summit 2024 meeting and is only available in HTML format. There are no additional versions or additional content available for this abstract. Physiology was not involved in the peer review process.

One pot synthesis of multi-functional B doped g-C3N4-praseodymium oxide nanocomposites for colorimetric detection of Hg2+ ion and solar photocatalytic removal of toxic water pollutants

A novel praseodymium oxide-boron co-doped graphitic carbon nitride composite was synthesized via one-step solid-state thermal condensation of urea, orthoboric acid and praseodymium nitrate precursors. The prepared composites were characterized by various methods. All the prepared composites demonstrated multi-functional activities towards peroxidase-mimetic based colorimetric detection of Hg2+ ions and superior photocatalytic efficiency towards photodegradation of textile colorants, photoreduction of hexavalent chromium and nitro aromatics like para-nitro phenol (PNP) and para-nitro aniline (PNA). The superior photocatalytic activity can be attributed to the formation of type II heterojunction which facilitates charge separation and increases the lifetime of photogenerated charge pairs. As evident from the scavenger studies, these charge pairs are involved in the formation of superoxide and hydroxyl radicals. The superior activity of the optimum composite can be attributed to the porous flaky morphology, decreased optical band gap, heterojunction mediated charge separation, and praseodymium oxide's conductive nature. A linear range of about 0.25–800 nM of Hg2+ ions can be detected with a limit of detection (LOD) of 42.4 nM using the colorimetric strategy. The as-synthesized composite is thus a unique, efficient, economically viable, and excellent candidate for detecting and degrading various hazardous water pollutants.

Engineering H2O2 Self-Supplying Platform for Xdynamic Therapies via Ru-Cu Peroxide Nanocarrier: Tumor Microenvironment-Mediated Synergistic Therapy.

Of the most common, hypoxia, overexpressed glutathione (GSH), and insufficient H2O2 concentration in the tumor microenvironment (TME) are the main barriers to the advancment of reactive oxygen species (ROS) mediated Xdynamic therapies (X = photo, chemodynamic, chemo). Maximizing Fenton catalytic efficiency is crucial in chemodynamic therapy (CDT), yet endogenous H2O2 levels are not sufficient to attain better anticancer efficacy. Specifically, there is a need to amplify Fenton reactivity within tumors, leveraging the unique attributes of the TME. Herein, for the first time, we design RuxCu1-xO2-Ce6/CPT (RCpCCPT) anticancer nanoagent for TME-mediated synergistic therapy based on heterogeneous Ru-Cu peroxide nanodots (RuxCu1-xO2 NDs) and chlorine e6 (Ce6), loaded with ROS-responsive thioketal (TK) linked-camptothecin (CPT). The Ru-Cu peroxide NDs (RCp NDs, x = 0.50) possess the highest oxygen vacancy (OV) density, which grants them the potential to form massive Lewis's acid sites for peroxide adsorption, while the dispersibility and targetability of the NDs were improved via surface modification using hyaluronic acid (HA). In TME, RCpCCPT degrades, releasing H2O2, Ru2+/3+, and Cu+/2+ ions, which cooperatively facilitate hydroxyl radical (•OH) formation and deactivate antioxidant GSH enzymes through a cocatalytic loop, resulting in excellent tumor therapeutic efficacy. Furthermore, when combined with laser treatment, RCpCCPT produces singlet oxygen (1O2) for PDT, which induces cell apoptosis at tumor sites. Following ROS generation, the TK linkage is disrupted, releasing up to 92% of the CPT within 48 h. In vitro investigations showed that laser-treated RCpCCPT caused 81.5% cell death from PDT/CDT and chemotherapy (CT). RCpCCPT in cancer cells produces red-blue emission in images of cells taking them in, which allows for fluorescence image-guided Xdynamic treatment. The overall results show that RCp NDs and RCpCCPT are more biocompatible and have excellent Xdynamic therapeutic effectiveness in vitro and in vivo.

Efficient degradation of wastewater by ultra-low platinum doped ZnO lamellar nanoflowers via photoinduced formation of hydroxyl radicals

Photocatalytic degradation technology is a promising strategy for the water treatment, which has many advantages such as saving time, cleanliness and environmental friendliness. In this study, ultra-low amount (0.01 wt%) of nano platinum (Pt) obtained from one-pot reduction method, was doped onto zinc oxide (ZnO) to form a lamellar nanoflower (Pt-ZnO). The characterization of Pt-ZnO was put forwards via scanning electron microscopy, high-angle annular dark-field scanning transmission election microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, liquid chromatography-mass spectrometry, etc. The highest degradation efficiencies of methylene blue (MB), rhodamine B (Rh B), methylene orange (MO), and acid black ATT (ATT) after being treated by Pt-ZnO for about 60 min reached 99.9%, 99.9%, 96.0%, and 97.8% respectively. While the MB and Rh B remained at a degradation efficiency of 99.9% even after being reused 5 times. Surprisingly, Pt-ZnO showed the removal rate of industrial effluent containing acid dyes was 93.9% and the chemical oxygen demand (COD) of wastewater was significantly reduced. Experimental results of LC-MS and free radical scavenging testing indicated MB was mainly split through the continuous open-ring cleavage of C-N bond in N, N-dimethylamine group by ·OH, and finally decomposed into H2O and CO2 achieving the decolorization.

TiO2-Coated Meltblown Nonwoven Fabrics Prepared via Atomic Layer Deposition for the Inactivation of E. coli as a Model Photocatalytic Drinking Water Treatment System

The controlled manufacturing of semiconductor photocatalysts is crucial to their development for drinking water treatment. In this study, TiO2-coated meltblown nonwoven fabrics prepared via Atomic Layer Deposition (ALD) are applied for the inactivation of Escherichia coli (E. coli). It is observed that in the presence of an ultraviolet light-emitting diode (UV-LED) light source (255 nm), 1.35 log E. coli inactivation is achieved. However, exposure to catalyst-coated fabrics in addition to the light source resulted in >4 log E. coli inactivation, suggesting a much higher rate of hydroxyl radical formation on the surface, leading to cell death.

Deconvolution of the Voltammetric Features of a Pt(100) Single-Crystal Electrode.

The Pt(100) single-crystal electrode shows four voltammetric features in acid electrolytes, but the precise corresponding surface phenomena remain unresolved. Herein, a deconvolution of the classical "hydrogen region" from the "hydroxyl and anion region" is attempted by the comparison of voltammetric behavior of Pt(100) and GMLPt(100) electrodes. A systematic study performed on Pt(s)-[n(100) × (111)] and Pt(s)-[n(100) × (110)] electrodes reveals that the feature at EPI = 0.30 VRHE corresponds to pure hydrogen adsorption taking place at (111) step sites vicinal to (100) domains, while the peak at EPII = 0.36 VRHE actually involves hydroxyl replacing hydrogen at (100) domains. An analysis examined for H2SO4, HClO4, CH3SO3H, and HF demonstrates that the specific (H)SO4- adsorption commences at EPIII = 0.40 VRHE and effectively suppresses the formation of hydroxyl at the (100) terrace at higher potentials 0.40 < EPIV < 0.75 VRHE. Non-specifically adsorbing anions (ClO4-, CH3SO3- and F-) would only interact with the hydroxyl phase formed on the Pt(100) terrace in both potential regions.

Single atom Pd anchored-MnO confined in porous carbon matrix for low-level VOCs removal at room temperature

Sustainably removing low-level VOCs at room temperature especially in the presence of water vapor has great demand. Herein, single-atom Pd anchored MnO nanoparticles (Pd/MnO) were confined in the hydrophobic porous carbon matrix. As-synthesized Pd/MnO@C exhibited superior removal capacity for VOCs such as hexanal, pentanal and toluene. Under the WHSV of 450 L/g·h, the 99% removal capacity for 15 ppm hexanal at 30 °C and relative humidity (RH) 50% reached 388.8 mg/g, which was 2.4 times as that of commercial BPL activated carbon. In addition, it exhibited much better regeneration ability at low temperature (105 °C) than activated carbon. In-situ DRIFTS and EPR indicated that water vapor mediated the activation of oxygen to form hydroxyl radicals to decompose VOCs. This paper opens a new way to sustainably remove low-level VOCs at room temperature under humid conditions via the hydrophobic carbon confinement effect and single-atom catalysis.

The Resource Utilization of Poplar Leaves for CO2 Adsorption.

Every late autumn, fluttering poplar leaves scatter throughout the campus and city streets. In this work, poplar leaves were used as the raw material, while H3PO4 and KOH were used as activators and urea was used as the nitrogen source to prepare biomass based-activated carbons (ACs) to capture CO2. The pore structures, functional groups and morphology, and desorption performance of the prepared ACs were characterized; the CO2 adsorption, regeneration, and kinetics were also evaluated. The results showed that H3PO4 and urea obviously promoted the development of pore structures and pyrrole nitrogen (N-5), while KOH and urea were more conductive to the formation of hydroxyl (-OH) and ether (C-O) functional groups. At optimal operating conditions, the CO2 adsorption capacity of H3PO4- and KOH-activated poplar leaves after urea treatment reached 4.07 and 3.85 mmol/g, respectively, at room temperature; both showed stable regenerative behaviour after ten adsorption-desorption cycles.

Technological quality improvement of gluten‐free eggless cakes by the incorporation of untreated and modified hydrocolloids

SummaryThe study examined the impact of untreated β‐glucan (UtβG) and ozonated β‐glucan (OzβG) on the characteristics of batter and gluten‐free eggless cake prepared using finger millet and flaxseed flour by encompassing a comprehensive analysis of physical, rheological, textural, morphological, sensory and nutritional properties. As the β‐glucan level increased, batter density and viscosity demonstrated an upward trend. The frequency sweep test revealed that β‐glucan altered the rheological parameters of batter, with the storage modulus (G′) surpassing the loss modulus (G″), indicating more elastic properties. The inclusion of OzβG resulted in improved physical characteristics and decreased the cake hardness, attributed to the formation of carboxyl and hydroxyl groups. Cakes incorporated with 1.5% OzβG had the highest overall acceptability score. Hence, this study sheds light on the utilisation of untreated and modified oat β‐glucan in the development of gluten‐free eggless cake, potentially aiding the bakery industry in meeting the rising demands for such products.

Wilson Disease: Copper-Mediated Cuproptosis, Iron-Related Ferroptosis, and Clinical Highlights, with Comprehensive and Critical Analysis Update.

Wilson disease is a genetic disorder of the liver characterized by excess accumulation of copper, which is found ubiquitously on earth and normally enters the human body in small amounts via the food chain. Many interesting disease details were published on the mechanistic steps, such as the generation of reactive oxygen species (ROS) and cuproptosis causing a copper dependent cell death. In the liver of patients with Wilson disease, also, increased iron deposits were found that may lead to iron-related ferroptosis responsible for phospholipid peroxidation within membranes of subcellular organelles. All topics are covered in this review article, in addition to the diagnostic and therapeutic issues of Wilson disease. Excess Cu2+ primarily leads to the generation of reactive oxygen species (ROS), as evidenced by early experimental studies exemplified with the detection of hydroxyl radical formation using the electron spin resonance (ESR) spin-trapping method. The generation of ROS products follows the principles of the Haber-Weiss reaction and the subsequent Fenton reaction leading to copper-related cuproptosis, and is thereby closely connected with ROS. Copper accumulation in the liver is due to impaired biliary excretion of copper caused by the inheritable malfunctioning or missing ATP7B protein. As a result, disturbed cellular homeostasis of copper prevails within the liver. Released from the liver cells due to limited storage capacity, the toxic copper enters the circulation and arrives at other organs, causing local accumulation and cell injury. This explains why copper injures not only the liver, but also the brain, kidneys, eyes, heart, muscles, and bones, explaining the multifaceted clinical features of Wilson disease. Among these are depression, psychosis, dysarthria, ataxia, writing problems, dysphagia, renal tubular dysfunction, Kayser-Fleischer corneal rings, cardiomyopathy, cardiac arrhythmias, rhabdomyolysis, osteoporosis, osteomalacia, arthritis, and arthralgia. In addition, Coombs-negative hemolytic anemia is a key feature of Wilson disease with undetectable serum haptoglobin. The modified Leipzig Scoring System helps diagnose Wilson disease. Patients with Wilson disease are well-treated first-line with copper chelators like D-penicillamine that facilitate the removal of circulating copper bound to albumin and increase in urinary copper excretion. Early chelation therapy improves prognosis. Liver transplantation is an option viewed as ultima ratio in end-stage liver disease with untreatable complications or acute liver failure. Liver transplantation finally may thus be a life-saving approach and curative treatment of the disease by replacing the hepatic gene mutation. In conclusion, Wilson disease is a multifaceted genetic disease representing a molecular and clinical challenge.

Identification of plastic-degrading bacteria in the human gut

Environmental pollution caused by the excessive use of plastics has resulted in the inflow of microplastics into the human body. However, the effects of microplastics on the human gut microbiota still need to be better understood. To determine whether plastic-degrading bacteria exist in the human gut, we collected the feces of six human individuals, did enrichment cultures and screened for bacterial species with a low-density polyethylene (LDPE) or polypropylene (PP)-degrading activity using a micro-spray method. We successfully isolated four bacterial species with an LDPE-degrading activity and three with a PP-degrading activity. Notably, all bacterial species identified with an LDPE or PP-degrading activity were opportunistic pathogens. We analyzed the microbial degradation of the LDPE or PP surface using scanning electron microscopy and confirmed that each bacterial species caused the physical changes. Chemical structural changes were further investigated using X-ray photoelectron spectroscopy and Fourier-transform-infrared spectroscopy, confirming the oxidation of the LDPE or PP surface with the formation of carbonyl groups (C=O), ester groups (CO), and hydroxyl groups (-OH) by each bacterial species. Finally, high temperature gel permeation chromatography (HT-GPC) analysis showed that these bacterial species performed to a limited extent depolymerization. These results indicate that, as a single species, these opportunistic pathogens in the human gut have a complete set of enzymes and other components required to initiate the oxidation of the carbon chains of LDPE or PP and to degrade them. Furthermore, these findings suggest that these bacterial species can potentially biodegrade and metabolize microplastics in the human gut.

Enhanced ozonation of nitrobenzene in water using natural iron ores: Efficiencies, mechanisms and stability

Natural minerals show potential for catalytic ozonation in industrial wastewater treatment. In this study, the efficiencies and mechanisms of two natural iron ores in catalytic ozonation processes (COPs) for aqueous nitrobenzene degradation were initially investigated. Compared with single ozonation process, the removal of TOC increased by about 60 % and 35 % in COPs with natural magnetite and pyrite, respectively. Both natural magnetite and pyrite could promote O3 decomposition to form hydroxyl radicals and 1O2. But the inner reaction pathways were different. The natural magnetite facilitated O3 decomposition through the Lewis acids and the electron transfer between Fe(II)/Fe(III) on the catalyst surface, while electron transfer was the only pathway for O3 decomposition by natural pyrite. Continuous flow fixed-bed reactor was adopted to provide better simulation of the practical operation conditions, so that the potential of engineering application could be evaluated. The natural magnetite exhibited excellent catalytic activity and stability during long period continuous operation in fixed-bed reactor. The removal of TOC maintained at 81.9 % under the optimized operating parameters of hydraulic retention time (2.84 h), O3 velocity (0.25 L min−1) and O3 concentration (30 mg L−1). HCO3− and PO43− obviously inhibited the TOC removal efficiencies through radical scavenging and surface –OH occupying. While low concentration of Cl− and SO42− showed negligible effect on the mineralization of aqueous nitrobenzene. After the continuous operation for 672 h, the removal of TOC for nitrobenzene solution in the magnetite-COP system was still stable at about 80 %. The present study demonstrated the engineering application prospect of the natural iron ores in catalytic ozonation treatment of recalcitrant chemical wastewaters.

Characterizing Hydroxyl Radical Formation from the Light-Driven Fe(II)-Peracetic Acid Reaction, a Key Process for Aerosol-Cloud Chemistry.

The reaction of peracetic acid (PAA) and Fe(II) has recently gained attention due to its utility in wastewater treatment and its role in cloud chemistry. Aerosol-cloud interactions, partly mediated by aqueous hydroxyl radical (OH) chemistry, represent one of the largest uncertainties in the climate system. Ambiguities remain regarding the sources of OH in the cloud droplets. Our research group recently proposed that the dark and light-driven reaction of Fe(II) with peracids may be a key contributor to OH formation, producing a large burst of OH when aerosol particles take up water as they grow to become cloud droplets, in which reactants are consumed within 2 min. In this work, we quantify the OH production from the reaction of Fe(II) and PAA across a range of physical and chemical conditions. We show a strong dependence of OH formation on ultraviolet (UV) wavelength, with maximum OH formation at λ = 304 ± 5 nm, and demonstrate that the OH burst phenomenon is unique to Fe(II) and peracids. Using kinetics modeling and density functional theory calculations, we suggest the reaction proceeds through the formation of an [Fe(II)-(PAA)2(H2O)2] complex, followed by the formation of a Fe(IV) complex, which can also be photoactivated to produce additional OH. Determining the characteristics of OH production from this reaction advances our knowledge of the sources of OH in cloudwater and provides a framework to optimize this reaction for OH output for wastewater treatment purposes.

Application of TiO2 Supported on Nickel Foam for Limitation of NOx in the Air via Photocatalytic Processes.

TiO2 was loaded on the porous nickel foam from the suspended ethanol solution and used for the photocatalytic removal of NOx. Such prepared material was heat-treated at various temperatures (400-600 °C) to increase the adhesion of TiO2 with the support. Obtained TiO2/nickel foam samples were characterized by XRD, UV-Vis/DR, FTIR, XPS, AFM, SEM, and nitrogen adsorption at 77 K. Photocatalytic tests of NO abatement were performed in the rectangular shape quartz reactor, irradiated from the top by UV LED light with an intensity of 10 W/m2. For these studies, a laminar flow of NO in the air (1 ppm) was applied under a relative humidity of 50% and a temperature of 28 °C. Concentrations of both NO and NO2 were monitored by a chemiluminescence NO analyzer. The adsorption of nitrogen species on the TiO2 surface was determined by FTIR spectroscopy. Performed studies revealed that increased temperature of heat treatment improves adhesion of TiO2 to the nickel foam substrate, decreases surface porosity, and causes removal of hydroxyl and alcohol groups from the titania surface. The less hydroxylated surface of TiO2 is more vulnerable to the adsorption of NO2 species, whereas the presence of OH groups on TiO2 enhances the adsorption of nitrate ions. Adsorbed nitrate species upon UV irradiation and moisture undergo photolysis to NO2. As a consequence, NO2 is released into the atmosphere, and the efficiency of NOx removal is decreasing. Photocatalytic conversion of NO to NO2 was higher for the sample heated at 400 °C than for that at 600 °C, although coverage of nickel foam by TiO2 was lower for the former one. It is stated that the presence of titania defects (Ti3+) at low temperatures of its heating enhances the adsorption of hydroxyl groups and the formation of hydroxyl radicals, which take part in NO oxidation. Contrary to that, the presence of titania defects in TiO2 through the formation of ilmenite structure (NiTiO3) in TiO2/nickel foam heated at 600 °C inhibits its photocatalytic activity. No less, the sample obtained at 600 °C indicated the highest abatement of NOx due to the high and stable adsorption of NO2 species on its surface.

Effect of pH on the ozonolysis degradation of p-nitrophenol in aquatic environment and the synergistic effect of hydroxy radical.

Density functional theory (DFT) was employed to elucidate the mechanisms for ozonolysis reaction of p-nitrophenol (PNP) and its anion form aPNP. Thermodynamic data, coupled with Average Local Ionization Energies (ALIE) analysis, reveal that the ortho-positions of the OH/O- groups are the most favorable reaction sites. Moreover, rate constant calculations demonstrate that the O3 attack on the C2-C3 bond is the predominant process in the reaction between neutral PNP and O3. For the aPNP + O3 reaction, the most favorable pathways involve O3 attacking the C1-C2 and C6-C1 bonds. The rate constant for PNP ozonolysis positively correlates with pH, ranging from 5.47 × 108 to 2.86 × 109M-1s-1 in the natural aquatic environment. In addition, the formation of hydroxyl radicals in the ozonation process of PNP and the mechanisms of its synergistic reaction of PNP with ozone were investigated. Furthermore, the ozonation and hydroxylation processes involving the intermediate OH-derivatives were both thermodynamically and kinetic analyzed, which illustrate that OH radicals could promote the elimination of PNP. Finally, the toxic of PNP and the main products for fish, daphnia, green algae and rat were assessed. The findings reveal that certain intermediates possess greater toxicity than the original reactant. Consequently, the potential health risks these compounds pose to organisms warrant serious consideration.

Nanosecond-Laser-Induced Breakdown of Aqueous Colloidal Solutions of Dysprosium Nanoparticles: The Influence of Nanoparticle Concentration on the Breakdown Plasma and the Intensity of Physical and Chemical Processes

This paper studies the dynamics of the development of laser breakdown plasma in aqueous colloids of dysprosium nanoparticles by analyzing the time patterns of plasma images obtained using a high-speed streak camera. In addition, the distribution of plasma flashes in space and their luminosity were studied, and the amplitude of acoustic signals and the rate of generation of new chemical products were studied depending on the concentration of dysprosium nanoparticles in the colloid. Laser breakdown was initiated by pulsed radiation from a nanosecond Nd:YAG laser. It is shown that the size of the plasma flash, the speed of motion of the plasma–liquid interface, and the lifetime of the plasma flash decrease with an increasing concentration of nanoparticles in the colloid. In this case, the time delay between the beginning of the laser pulse and the moment the plasma flash reaches its maximum intensity increases with increasing concentrations of nanoparticles. Varying the laser fluence in the range from 67 J/cm2 to 134 J/cm2 does not lead to noticeable changes in these parameters, due to the transition of the breakdown plasma to the critical regime. For dysprosium nanoparticles during laser breakdown of colloids, a decrease in the yield of hydrogen peroxide and an increase in the rate of formation of hydroxyl radicals per water molecule, characteristic of nanoparticles of rare earth metals, are observed, which may be due to the participation of nanoparticles and hydrogen peroxide in reactions similar to the Fenton and Haber–Weiss reactions.

Control of selective SiGe etching by enhanced formation of hydroxyl radicals and by surface passivation in peracetic acid solution

The selective etching of SiGe over Si is a crucial process in the fabrication of advanced 3D semiconductor devices. During the etching process, highly selective SiGe etching is required to obtain precise etch profiles. In this study, the enhancement of the selective SiGe etching in a peracetic acid (PAA) etchant solution by adding hydroxylamine and pentyl acetate was investigated. The addition of hydroxylamine increased the SiGe etching rate and SiGe/Si etching selectivity owing to the more vigorous oxidation of the SiGe surface produced by hydroxyl radicals. The SiGe/Si etching selectivity was also increased through the addition of pentyl acetate owing to the larger decrease in the Si etching rate when compared to that in SiGe. This is due to the stronger passivation effect of pentyl acetate on the Si surface, which suppresses its oxidation more effectively than on the SiGe surface. The SiGe etching rate and SiGe/Si etching selectivity were significantly increased from 223.3 nm/min and 125 to 310.8 nm/min and 557, respectively, through the simultaneous addition of hydroxylamine and pentyl acetate to the PAA etchant solution. Consequently, a mechanism for the selective etching of SiGe on vertically stacked SiGe/Si trench structures using the PAA etchant solution was proposed.