Nitrophenol Compounds Research Articles

In-situ growing of MIL88A(Fe)@active faceted Cu2O core-shell heterostructure for super photocatalytic performance and catalytic reduction of toxic nitrophenol compounds

Herein, well-constructed 2D active (110) and (111) faceted Cu2O nanosheets are in-situ grown on the surface of spindle MIL-88A to form a novel porous MIL88A (Fe)@active faceted Cu2O core-shell heterostructure via a facile solvothermal method. The fabricated heterostructure is optimized to be a promising catalyst for the catalytic reduction of various nitrophenol compounds such as P-nitrophenol and 2,4-dinitrophenols, as well as the removal of methylene blue dye (MB). The optimal M88@Cu2O-2 heterostructure demonstrated an outstanding catalytic performance for reducing nitrophenols, reaching 96.7 % for P-nitrophenol and 96.1 % for 2.4-dinitrophenol. It also achieved excellent photocatalytic activity for MB dye, reaching 95 % through 30 min, compared to 64 % and 72 % for Cu2O and MIL-88A, with rate constants (k) reaching 0.1, 0.038, and 0.04 min−1, respectively. The surprising photocatalytic performance of the prepared structure could be attributed to the following aspects: (i) the growth of the active (111) and (110) facets Cu2O on the surface of MIL-88A, which could provide various surface energies, reactivates, and crystallographic arrangements, all of which impact the photocatalytic efficiency of the designed M88@Cu2O-2 heterostructure, (ii) the construction of an efficient heterojunction between active faceted Cu2O and MIL88A, which resists the recombination of e- and h+, improving the migration and separation of charge carriers, and (iii) the core-shell construction could provide more electron transport channels to significantly enhance the suppression of electron-hole pair recombination in the photocatalytic process. Besides that, the M88@Cu2O-2 core-shell has great photo-electrochemical performance, reaching 17.68 μA/cm2 for the photocurrent test and 73 mA/cm2 for the LSV test when exposed to visible light. Our study will provide a new vision for developing more hierarchical core/shell MOF-based heterostructures with outstanding multifunctional performance for future industrial practice.

Investigation of the Mechanism of Oxidative Potential Increase in Atmospheric Particulate Matter during Photoaging: Important Role of Aromatic Nitrogenous Compounds.

Particulate matter (PM) undergoing various aging processes in the atmosphere changes its toxicity. However, the mechanism of toxicity evolution is not fully clarified currently. This study demonstrates that photoaging promotes an increase in the oxidative potential (OP) of atmospheric PM by about 30%, and the increased OP is mainly attributed to the production of secondary organic compounds, while water-soluble metal ions contribute only 11%. The OP of nonextractable matters (NEMs) of atmospheric PM was mostly increased after photoaging, followed by water-soluble matters (WSMs). NEM can produce quinone-like functional groups and secondary persistent free radicals during photoaging, which are most likely to produce reactive oxygen species (ROS). For WSM, the conversion of low-oxidation humic-like substances (HULIS) to high-oxidation HULIS is the main reason for the increase in OP. Quinones, nitrophenols, and N-containing heterocycles are the OP contributors produced during the conversion process. Among them, quinones are the main secondary oxidizing active compounds, while nitro-phenolic compounds and N-containing heterocyclic compounds may play a catalyst-like role, facilitating the production of oxidizing active compounds and ROS in the newly converted high-oxidation HULIS. This study clarifies the secondary OP generation mechanism and provides new insights into the uncertainty of PM toxicity during atmospheric aging.

Nitrite facilitated transformation of halophenols in ice

This study investigated the expediated transformation of halophenols in the presence of nitrite (NO2−) under slightly acidic conditions in ice, whereas such transformation was negligible in liquid water at 4 °C. We proposed that this phenomenon was attributed to the freeze-concentration effect, incurring a pH drop and the aggregation of NO2− and halophenols within the liquid-like grain boundary layer amid ice crystals. Within this micro-environment, NO2− underwent protonation to generate reactive nitrous acid (HNO2) and nitrosonium ions (NO+) that facilitate the nitration and oxidation of halophenols. When 10 μМ halophenol was treated by freezing in the presence of 5 μМ NO2−, the total yields of nitrated products reached 2.4 μМ and 1.4 μМ within 12 h for 2-chlorophenol (2CP) and 2-bromophenol (2BP), respectively. NO+ drove oxidative coupling reactions, generating hydroxyl polyhalogenated diphenyl ethers (OH-PBDEs) and hydroxyl polyhalogenated diphenyls via C-O or C-C coupling. These two pathways were intricately intertwined. The presence of natural organic matter (NOM) mitigated the formation of nitrated products and completely suppressed the coupling products. This study offers valuable insights into the fate of halophenols in ice and suggests potential pathways for the formation of nitrophenolic compounds and OH-PBDEs in natural cold environments. These findings also open up a new avenue in environmental chemistry research.

Resolving the overlooked photochemical nitrophenol transformation mechanism induced by nonradical species under visible light

Nitrophenols present on the surface of particulates are ubiquitous in the atmosphere. However, its atmospheric photochemical transformation pathway remains unknown, for which the crucial effect of visible light is largely overlooked, resulting in an incomplete understanding of the effects of nitrophenols in the atmospheric environment. This study delves into the photolysis mechanism of 4-nitrophenol (4NP), one of the most abundant atmospheric nitrophenol compounds, on the surface of photoactive particulates under visible light irradiation. Unexpectedly, the nonradical species (singlet oxygen, 1O2) was identified as a dominant factor in driving the visible photolysis of 4NP. The pathways of HONO and p-benzoquinone (C6H4O2) generation were clarified by acquiring direct evidence of C-N and O-H bond breakage in the nitro (-NO2) and hydroxyl (-OH) groups of 4NP. The further decomposition of HONO results in the generation of NO and hydroxyl radicals, which could directly contribute to atmospheric oxidizing capacity and complicate the PM2.5 composition. Significantly, the behavior of 1O2-induced visible photolysis of 4NP was universal on the surface of common particulates in the atmosphere, such as A1 dust and Fe2O3. This work advances the understanding of the photochemical transformation mechanism of particulate-phase atmospheric nitrophenols, which is indispensable in elucidating the role of nitrophenols in atmospheric chemistry.

Formation of halonitromethanes from different nitrophenol compounds during UV/post-chlorination: Impact factors, DFT calculation, reaction mechanisms, and toxicity

As ubiquitous chemical substances in water bodies, nitrophenol compounds (NCs) can form chlorinated halonitromethanes (Cl-HNMs) in the chlorination process. This work chose six typical NCs to explore Cl-HNMs produced during the UV/post-chlorination process, and Cl-HNMs yields from these NCs followed the increasing order of 4-, 2-, 2-amino-3-, 2-methyl-3-, 3-, and 2-chloro-3-nitrophenol. The Cl-HNMs yields increased continually or increased firstly and declined with post-chlorination time. Increasing chlorine dosage favored Cl-HNMs formation, while excessive chlorine dosage decreased Cl-HNMs produced from 2- and 4-nitrophenol. Besides, appropriate UV radiation, acidic pH, and higher precursor concentrations facilitated Cl-HNMs formation. Then, the reaction mechanisms of Cl-HNMs generated from these different NCs were explored according to density functional theory calculation and identified transformation products (TPs), and the main reactions included chlorine substitution, benzoquinone compound formation, ring opening, and bond cleavage. Moreover, the Cl-HNMs generated from 2-chloro-3-nitrophenol were of the highest toxicity, and the six NCs and their TPs also presented ecotoxicity. Finally, two kinds of real waters were used to explore Cl-HNMs formation and toxicity, and they were significantly distinguishable compared to the phenomena observed in simulated waters. This work will give new insights into Cl-HNMs formation from different NCs in water disinfection processes and help better apply the UV/post-chlorination process to water treatments.

Resonance energy transfer aided detection of nitroaromatics in aqueous medium by a luminescent Mn based metal-organic framework

A light brown needle-like crystal of Mn-based metal–organic framework (MOF); [Mn2.5(µ3-OH)(DTDB)2], (DTDB = 2,2′-dithiodibenzoate), compound 1, was synthesized using hydrothermal technique. Compound 1 was systematically characterized by single-crystal X-ray diffraction (SCXRD), powder X-ray diffraction (PXRD), and infrared spectroscopy (IR). Photoluminescence study of compound 1 in an aqueous medium showed intense blue emission centred at 395 nm upon excitation at 310 nm. This emissive property of compound 1 was utilized for selective and sensitive detection of 2,4,6- trinitrophenol (TNP), 2,4- dinitrophenol (DNP) and 4-nitrophenol (NP) in the aqueous medium through luminescence quenching mechanism. As indicated by the good overlap of the absorption spectra of the analytes and the emission spectrum of the compound 1, and manifested as the reduction in luminescence lifetimes, it can be concluded that the resonance energy transfer is the most significant factor for the selective detection of aromatic nitro-phenol compounds. The resonance energy transfer requires the proximity of the donor and acceptor, which was achieved by the molecular level interactions between the ‘S’ atom of the DTDB ligand and phenolic –OH groups of the nitrophenols through non-covalent type interactions like hydrogen bonding and dipolar type interactions. Detection limits for TNP, DNP, and NP with the values of 208 ppb, 156 ppb, and 556 ppb, respectively, were obtained in an aqueous medium. The studies indicate that compound 1 could be helpful for detecting nitrophenol derivatives in water.

Facile fabrication of bifunctional ternary nanocomposite (FCPTNC) as an efficient catalyst for 4-nitrophenol reduction and crystal violet photodegradation

The synthesis of a ternary nanocomposite Fe3O4/CuO-Ppy (FCPTNC) was effectively achieved via hydrothermal and in-situ chemical oxidative polymerisation techniques. FCPTNC was used as a catalyst for reducing the toxic compound 4-nitrophenol to the non-toxic compound 4-aminophenol. Additionally, it was utilised for the visible-light-induced degradation of the crystal violet (CV) dye. FCPTNC underwent characterisation using various techniques, namely X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), ultraviolet–visible diffuse reflectance spectroscopy (UV-DRS), transmission electron microscopy (TEM), vibrating sample magnetometry (VSM), and attenuated total reflectance Fourier-transform infrared spectroscopy (ATR-FTIR). The successful preparation of the nanocomposite was validated through analysis of its structural properties. Moreover, examining its optical properties indicated that the nanocomposite can effectively operate through visible light irradiation. The catalyst demonstrated exceptional catalytic efficacy in eliminating the targeted organic pollutants, namely 4-nitrophenol (4-NP) and crystal violet (CV). The catalyst exhibited a degradation efficiency of 97 % for CV dye within60 min. It achievedthecomplete conversion of 4-nitrophenol into its corresponding amino derivative within15 min. The calculated first-order rate constants for the reduction of 4-NP and photodegradation of CV dye were found to be in the range of 0.53–11.6 × 10−2 min−1 and 3.2–5.6 × 10−2 min−1, respectively. The magnetic catalyst exhibited efficient separation from the reaction media and was successfully recycled for up to fiveconsecutive cycles with negligible loss of catalytic activity. The work demonstrates that the FCPTNC nanocomposite has favourable characteristics, such as facilesynthesis, efficient catalytic activity, and reusability. These findings suggest that the nanocomposite possesses desirable efficiency and durability, rendering it a promising catalyst for environmental applications.

Reaction mechanisms of chlorinated disinfection byproducts formed from nitrophenol compounds with different structures during chlor(am)ination and UV/post-chlor(am)ination

Nitrophenol compounds (NCs) have high formation potentials of disinfection byproducts (DBPs) in water disinfection processes, however, the reaction mechanisms of DBPs formed from different NCs are not elucidated clearly. Herein, nitrobenzene, phenol, and six representative NCs were used to explore the formation mechanisms of chlorinated DBPs (Cl-DBPs) during chlor(am)ination and UV/post-chlor(am)ination. Consequently, the coexistence of nitro and hydroxy groups in NCs facilitated the electrophilic substitution to produce intermediates of Cl-DBPs, and the different positions of nitro and hydroxy groups also induced different yields and formation mechanisms of Cl-DBPs during the chlorination and UV/post-chlorination processes. Besides, the amino, chlorine, and methyl groups significantly influenced the formation mechanisms of Cl-DBPs during the chlorination and UV/post-chlorination processes. Furthermore, the total Cl-DBPs yields from the six NCs followed a decreasing order of 2-chloro-3-nitrophenol, 3-nitrophenol, 2-methyl-3-nitrophenol, 2-amino-4-nitrophenol, 2-nitrophenol, and 4-nitrophenol during chlorination and UV/post-chlorination. However, the total Cl-DBPs yields from the six NCs during chloramination and UV/post-chloramination followed a quite different order, which might be caused by additional reaction mechanisms, e.g., nucleophilic substitution or addition might occur to NCs in the presence of monochloramine (NH2Cl). This work can offer deep insights into the reaction mechanisms of Cl-DBPs from NCs during the chlor(am)ination and UV/post-chlor(am)ination processes.

Effects of cupric ions on the formation of chlorinated disinfection byproducts from nitrophenol compounds during UV/post-chlorination

Cupric ions (Cu2+) are ubiquitous in surface waters and can influence disinfection byproducts (DBPs) formation in water disinfection processes. This work explored the effects of Cu2+ on chlorinated DBPs (Cl-DBPs) formation from six representative nitrophenol compounds (NCs) during UV irradiation followed by a subsequent chlorination (i.e., UV/post-chlorination), and the results showed Cu2+ enhanced chlorinated halonitromethane (Cl-HNMs) formation from five NCs (besides 2-methyl-3-nitrophenol) and dichloroacetonitrile (DCAN) and trichloromethane (TCM) formation from six NCs. Nevertheless, excessive Cu2+ might reduce Cl-DBPs formation. Increasing UV fluences displayed different influences on total Cl-DBPs formation from different NCs, and increasing chlorine dosages and NCs concentrations enhanced that. Moreover, a relatively low pH (5.8) or high pH (7.8) might control the yields of total Cl-DBPs produced from different NCs. Notably, Cu2+ enhanced Cl-DBPs formation from NCs during UV/post-chlorination mainly through the catalytic effect on nitro-benzoquinone production and the conversion of Cl-DBPs from nitro-benzoquinone. Additionally, Cu2+ could increase the toxicity of total Cl-DBPs produced from five NCs besides 2-methyl-3-nitrophenol. Finally, the impacts of Cu2+ on Cl-DBPs formation and toxicity in real waters were quite different from those in simulated waters. This study is conducive to further understanding how Cu2+ affected Cl-DBPs formation and toxicity in chlorine disinfection processes and controlling Cl-DBPs formation in copper containing water.

Comparative analysis of chlorinated disinfection byproducts formation from 4-nitrophenol and 2-amino-4-nitrophenol during UV/post-chlorination

Nitrophenol compounds (NCs) are widely distributed in water environments and regarded as important precursors of disinfection byproducts (DBPs). Herein, 4-nitrophenol and 2-amino-4-nitrophenol were selected as representative NCs to explore chlorinated DBPs (Cl-DBPs) formation during UV/post-chlorination. Dichloronitromethane (DCNM), trichloronitromethane (TCNM), dichloroacetonitrile (DCAN), and trichloromethane (TCM) were formed from 4-nitrophenol and 2-amino-4-nitrophenol during UV/post-chlorination, and the yields of individual Cl-DBPs from 2-amino-4-nitrophenol were higher than those from 4-nitrophenol. Meantime, increasing chlorine contact time, UV fluence, and free chlorine dose could enhance Cl-DBPs formation, while much higher values of the three factors might decrease the yields of Cl-DBPs. Besides, alkaline pH could decrease the yields of halonitromethane (HNMs) and DCAN but increase the yields of TCM. Also, higher concentrations of 4-nitrophenol and 2-amino-4-nitrophenol would induce more Cl-DBPs formation. Subsequently, the possible formation pathways of DCNM, TCNM, DCAN, and TCM form 4-nitrophenol and 2-amino-4-nitrophenol during UV/post-chlorination were proposed according to transformation products (TPs) and density functional theory (DFT) calculation. Notably, Cl-DBPs formed from 2-amino-4-nitrophenol presented higher toxicity than those from 4-nitrophenol. Among these generated Cl-DBPs, DCAN and TCNM posed higher cytotoxicity and genotoxicity, respectively. Furthermore, 4-nitrophenol, 2-amino-4-nitrophenol, and their TPs exhibited ecotoxicity. Finally, 4-nitrophenol and 2-amino-4-nitrophenol presented a high potential to produce DCNM, TCNM, DCAN, and TCM in actual waters during UV/post-chlorination, but the Cl-DBPs yields were markedly different from those in simulated waters. This work can help better understand Cl-DBPs formation from different NCs during UV/post-chlorination and is conducive to controlling Cl-DBPs formation.

Heterogeneous Reactions of Phenol on Different Components of Mineral Dust Aerosol: Formation of Oxidized Organic and Nitro-Phenolic Compounds.

Phenol, a common semi-volatile compound associated with different emissions including from plants and biomass burning, as well as anthropogenic emissions and its derivatives, are important components of secondary organic aerosols (SOAs). Gas and aqueous phase reactions of phenol, in the presence of photochemical drivers, are fairly well understood. However, despite observations showing aromatic content within SOA size and mass increases during dust episodes, the heterogeneous reactions of phenol with mineral dusts are poorly understood. In the current study, surface reactions of phenol at the gas/solid interface with different components of mineral dust including SiO2, α-Fe2O3, and TiO2 have been investigated. Whereas reversible surface adsorption of phenol occurs on SiO2 surfaces, for both α-Fe2O3 and TiO2 surfaces, phenol reacts to form a wide range of OH substituted aromatic products. For α-Fe2O3 surfaces that have been nitrated by gas-phase reactions of nitric acid prior to exposure to phenol, unique compounds form on the surface including nitro-phenolic compounds. Moreover, additional surface chemistry was observed when adsorbed nitro-phenolic products were exposed to gas-phase SO2 as a result of the formation of adsorbed nitrite from nitrate redox chemistry with adsorbed SO2. Overall, this study reveals the extensive chemistry as well as the complexity of reactions of prevalent organic compounds leading to the formation of SOA on mineral surfaces.

PLA/CS-ZnO bionanocomposite for rapid catalytic reduction of nitrophenol compounds as a heterogeneous nanocatalyst.

In this research, a high efficiency and environmentally friendly method to reduce nitrophenol compounds such as 4-nitrophenol (4-NP), 2,4,6-trinitrophenol (2,4,6-TNP) and 2,4-dinitrophenol (2,4-DNP) was used in the presence of poly(lactic acid)/chitosan-ZnO ( PLA/CS-ZnO) bionanocomposite. Using FT-IR, SEM, XRD and UV-Vis techniques, PLA/CS-ZnO bionanocomposite was identified after synthesis. Also, the mechanical properties of the bionanocomposite were investigated using the stress-strain curve. The mentioned bionanocomposite showed a very good efficiency in reducing nitrophenol compounds to aminophenolic compounds, so that under optimal conditions, 100% conversion and selectivity in the reduction of 4-NP, 2,4,6-TNP and 2,4-DNP to 4-aminophenol (4-AP), 2,4,6-triaminophenol (2,4,6-TAP) and 2,4-diaminophenol (2,4-DAP) were observed. UV-Vis absorption spectrum at different times were used to evaluate the progress of the reaction. Furthermore, after the reaction, PLA/CS-ZnO was recovered and used for the next cycle. The results showed that the bionanocomposite can perform ten consecutive cycles without a significant decrease in efficiency. The comparison of catalytic activity with other catalysts showed that the bionanocomposite synthesized in the present research has a higher efficiency in reduction of nitrophenol compounds.

Mixing state and influence factors controlling diurnal variation of particulate nitrophenol compounds at a suburban area in northern China

Nitrophenols have received extensive attention due to their strong light-absorbing ability in the near-ultraviolet-visible region, which could be influenced by the atmospheric processes of nitrophenols. However, our knowledge and understanding of the formation and evolution of nitrophenols are still in the nascent stages. In the present study, the mixing states of four mononitrophenol particles (i.e., nitrophenol, methynitrophenol, nitrocatechol, and methoxynitrophenol), and one nitropolycyclic aromatic hydrocarbon particles (i.e., nitronaphthol (NN)) were investigated using a single-particle aerosol mass spectrometer (SPAMS) in November 2019 in Qingdao, China. The results showed, for the first time, that mononitrophenols and NN exhibit different mixing states and diurnal variations. Four mononitrophenols were internally mixed well with each other, and with organic acids, nitrates, potassium, and naphthalene. The diurnal variation in the number fraction of mononitrophenols presented two peaks at 07:00 to 09:00 and 18:00 to 20:00, and a valley at noon. Atmospheric environmental conditions, including NO2, O3, relative humidity, and temperature, can significantly influence the diurnal variation of mononitrophenols. Multiple linear regression and random forest regression models revealed that the main factors controlling the diurnal variation of mononitrophenols were photochemical reactions during the day and aqueous-phase reactions during the night. Unlike mononitrophenols, about 62–83% of NN were internally mixed with [NH4]+ and [H(NO3)2]-, but not with organic acids and potassium. The diurnal variation of NN was also different from that of mononitrophenols, generally increased from 17:00 to 10:00 and then rapidly decreaed from 11:00 to 16:00. These results imply that NN may have sources and atmospheric processes that are different from mononitrophenols. We speculate that this is mostly controlled by photochemical reactions and mixing with [NH4]+, which may influence the diurnal variation of NN in the ambient particles; however, this requires further confirmation. These findings extend our current understanding of the atmospheric formation and evolution of nitrophenols.

Wildfire plume ageing in the Photochemical Large Aerosol Chamber (PHOTO-LAC).

Plumes from wildfires are transported over large distances from remote to populated areas and threaten sensitive ecosystems. Dense wildfire plumes are processed by atmospheric oxidants and complex multiphase chemistry, differing from processes at typical ambient concentrations. For studying dense biomass burning plume chemistry in the laboratory, we establish a Photochemical Large Aerosol Chamber (PHOTO-LAC) being the world's largest aerosol chamber with a volume of 1800 m3 and provide its figures of merit. While the photolysis rate of NO2 (jNO2) is comparable to that of other chambers, the PHOTO-LAC and its associated low surface-to-volume ratio lead to exceptionally low losses of particles to the walls. Photochemical ageing of toluene under high-NOx conditions induces substantial formation of secondary organic aerosols (SOAs) and brown carbon (BrC). Several individual nitrophenolic compounds could be detected by high resolution mass spectrometry, demonstrating similar photochemistry to other environmental chambers. Biomass burning aerosols are generated from pine wood and debris under flaming and smouldering combustion conditions and subsequently aged under photochemical and dark ageing conditions, thus resembling day- and night-time atmospheric chemistry. In the unprecedented long ageing with alternating photochemical and dark ageing conditions, the temporal evolution of particulate matter and its chemical composition is shown by ultra-high resolution mass spectrometry. Due to the spacious cavity, the PHOTO-LAC may be used for applications requiring large amounts of particulate matter, such as comprehensive chemical aerosol characterisation or cell exposures under submersed conditions.

Nitrophenol compounds photoreduction by MnO2/ZnO thin film with impact on reducing agents

In this work, a thin layer of manganese dioxide/zinc oxide (MnO2/ZnO) was deposited on a glass substrate using a two-stage chemical bath deposition (CBD) method to optimize the photocatalytic activities in the reduction of 2-nitrophenol. The effects of ethanol and butanol as reducing agents on the surface morphology, wettability, thermal insulation, and photocatalytic activities were investigated. At 100 kX magnification, the micrographs clearly showed the MnO2 nanoparticles embedded in the thin film for the single and two-stage CBD, with the particle agglomeration being more pronounced for the two-stage CBD. ZnO has been diffused into MnO2 for both reducing agents, albeit with lower integration. In addition, the images show that the prepared catalyst in butanol gradually granulates with increasing ZnO content compared to ethanol, affecting its particle size and the active surface. The thermal insulation test reveals that the sample with 10 % ZnO reduces the temperature by 4 °C, which improves the durability and stability of the catalyst. The exact composition of the sample demonstrates the optimum photodegradation of 2-nitrophenol with an efficiency of 94.96 % (0.0301 min−1). The measurement of the water contact angle also showed an increase in the contact angle (CA) with a value of 55.6°. Based on the findings, it was found that photocatalysts using butanol as a reducing agent demonstrate higher efficiency in reducing of 2-nitrophenol as compared to ethanol due to its homogeneous distribution and large surface area. This study brought a new direction in impact of reducing agent on void free and dense thin film of the MnO2/ZnO catalyst in reducing of persistent water pollutants under visible light irradiation.

Abatement of Nitrophenol in Aqueous Solution by HOCl and UV/HOCl Processes: Kinetics, Mechanisms, and Formation of Chlorinated Nitrogenous Byproducts

HOCl and UV activated HOCl (UV/HOCl) have been applied for water disinfection and abatement of organic contaminants. However, the production of toxic byproducts in the HOCl and UV/HOCl treatment should be scrutinized. This contribution comparatively investigated the elimination of 4-nitrophenol and the generation of chlorinated byproducts in HOCl and UV/HOCl treatment processes. 61.4% of 4-nitrophenol was removed by UV/HOCl in 5 min with HOCl dose of 60 μM, significantly higher than that by UV (3.3%) or HOCl alone (32.0%). Radical quenching test showed that HO• and Cl• played important roles in UV/HOCl process. 2-Chloro-4-nitrophenol and 2,6-dichloro-4-nitrophenol were generated consecutively in HOCl process; but their formation was less in the UV/HOCl process. Trichloronitromethane (TCNM) was only found in the UV/HOCl process, and its production increased with increasing HOCl dosage. Besides chlorinated products hydroxylated and dinitrated products were also identified in the UV/HOCl process. Transformation pathways involving electrophilic substitution, hydroxylation, and nitration were proposed for 4-nitrophenol transformation in the UV/HOCl process. Wastewater matrix could significantly promote the transformation of 4-nitrophenol to 2-chloro-4-nitrophenol in UV/HOCl process. Results of this study are helpful to advance the understanding of the transformation of nitrophenolic compounds and assess the formation potential of chlorinated byproducts in HOCl and UV/HOCl disinfection processes.

Anthracene and tetraphenylsilane based conjugated porous polymer nanoparticles for sensitive detection of nitroaromatics in water

Conjugated porous polymers (CPPs) are a kind of promising sensing materials for the detection of nitroaromatic compounds, but their sensing applications in aqueous media are limited because of their poor dispersity or solubility in water. In this study, we prepared anthracene and tetraphenylsilane based CPPs named PSiAn by conventional Suzuki coupling and Suzuki-miniemulsion polymerization, respectively. The structure, morphology and porosity of the CPPs were characterized by Fourier Transform infrared spectroscopy (FT-IR), proton nuclear magnetic resonance (1H NMR), transmission electron microscope (TEM) and N2 sorption isotherm, respectively. Both of the CPPs have porous structure which is beneficial for the adsorption and diffusion of the analytes within them. The particle size of PSiAn nanoparticles prepared by Suzuki-miniemulsion polymerization is 10–40 nm from the TEM image, which facilitates the dispersion in the aqueous phase. Combined with the porosity and nanoparticle morphology, PSiAn nanoparticles realized the efficient photoluminescence (PL) sensing of nitroaromatic explosives in aqueous phase. The limit of detection (LOD) and limit of quantitation (LOQ) of PSiAn nanoparticles for 2,4,6-trinitrophenol (TNP) detection in the pure aqueous phase are 0.33 μM and 1.11 μM, respectively. Meanwhile, the good selectivity and anti-interference in presence of other nitro-compounds were observed. Furthermore, the spike/recovery test for the TNP detection in real water samples by PL sensing based on PSiAn nanoparticles indicates the quantitative recovery of TNP from 100.74 % to 101.00 %. The electrochemical test, ultraviolet–visible absorption spectra, excitation and emission spectra, and time-resolved PL spectra were investigated to explore the PL sensing mechanism. As a result, it is found that the fluorescence inner filter effect might be the predominant quenching mechanism during the detection of nitrophenolic compounds such as TNP and 4-nitrophenol (4-NP).

New 5,5-(1,4-Phenylenebis(methyleneoxy)diisophthalic Acid Appended Zn(II) and Cd(II) MOFs as Potent Photocatalysts for Nitrophenols.

Metal-organic frameworks (MOFs) are peculiar multimodal materials that find photocatalytic applications for the decomposition of lethal molecules present in the wastewater. In this investigation, two new d10-configuration-based MOFs, [Zn2(L)(H2O)(bbi)] (1) and [Cd2(L)(bbi)] (2) (5,5-(1,4-phenylenebis(methyleneoxy)diisophthalic acid (H2L) and 1,1'-(1,4-butanediyl)bis(imidazole) (bbi)), have been synthesized and characterized. The MOF 1 displayed a (4,6)-connected (3.43.52)(32.44.52.66.7) network topology, while 2 had a (3,10)-connected network with a Schläfli symbol of (410.511.622.72)(43)2. These MOFs have been employed as photocatalysts to photodegrade nitrophenolic compounds, especially p-nitrophenol (PNP). The photocatalysis studies reveal that 1 displayed relatively better photocatalytic performance than 2. Further, the photocatalytic efficacy of 1 has been assessed by altering the initial PNP concentration and photocatalyst dosage, which suggest that at 80 ppm PNP concentration and at its 50 mg concentration the MOF 1 can photo-decompose around 90.01% of PNP in 50 min. Further, radical scavenging experiments reveal that holes present over 1 and ·OH radicals collectively catalyze the photodecomposition of PNP. In addition, utilizing density of states (DOS) calculations and Hirshfeld surface analyses, a plausible photocatalysis mechanism for nitrophenol degradation has been postulated.

A luminescent anionic Cadmium(II)-MOF for the detection of nitrophenol compounds and metal ions in an aqueous solution

An anionic MOF, namely, {(CH3)2NH2)2[Cd(µ4-PPTA)]·DMF·7H2O}n (1) was synthesized with 4,4′,4″,4‴-(1,4-phenylenbis(pyridine-4,2,6-triyl))tetrabenzoic acid (H4PPTA) and characterized. X-ray results showed that 1 had a four-fold interpenetrating 3D framework with dia topology and the charged balance was provided by dimethylamine cations in the framework. Due to the high emission property and stability of 1 in water, the luminescence detections of nitroaromatic compounds and metal ions were performed with 1. 1 could detect the nitrophenol compounds and metal ions in water via luminescence quenching. The detection limits were 6.84 µM for 4-nitrophenol (NP), 1.85 µM for 2,4-dinitrophenol (DNP) and 2.76 µM for 2,4,6-trinitrophenol (TNP) and 94.4 µM for Al3+, 66 µM for Cr3+, 18.3 µM for Fe3+ and 27.6 µM for Cu2+. The detections of the nitrophenol compounds by 1 were due to hydrogen bonding interaction and resonance energy transfer. Moreover, the detections of metal ions by 1 were assigned to competitive absorption and electrostatic interactions with the anionic framework.

Ultrasound-Assisted Mineralization of 2,4-Dinitrotoluene in Industrial Wastewater Using Persulfate Coupled with Semiconductors.

Oxidative degradation of 2,4-dinitrotoluenes in aqueous solution was executed using persulfate combined with semiconductors motivated by ultrasound (probe type, 20 kHz). Batch-mode experiments were performed to elucidate the effects of diverse operation variables on the sono-catalytic performance, including the ultrasonic power intensity, dosage of persulfate anions, and semiconductors. Owing to pronounced scavenging behaviors caused by benzene, ethanol, and methanol, the chief oxidants were presumed to be sulfate radicals which originated from persulfate anions, motivated via either the ultrasound or sono-catalysis of semiconductors. With regard to semiconductors, the increment of 2,4-dinitrotoluene removal efficiency was inversely proportional to the band gap energy of semiconductors. Based on the outcomes indicated in a gas chromatograph-mass spectrometer, it was sensibly postulated that the preliminary step for 2,4-dinitrotoluene removal was denitrated into o-mononitrotoluene or p-mononitrotoluene, followed by decarboxylation to nitrobenzene. Subsequently, nitrobenzene was decomposed to hydroxycyclohexadienyl radicals and converted into 2-nitrophenol, 3-nitrophenol, and 4-nitrophenol individually. Nitrophenol compounds with the cleavage of nitro groups synthesized phenol, which was sequentially transformed into hydroquinone and p-benzoquinone.