The practical utility of ternary nickel-cobalt-manganese oxide-supported platinum catalysts for room-temperature oxidative removal of formaldehyde from the air.

Formaldehyde (FA), a carcinogenic oxygenated volatile organic compound, is present ubiquitously in indoor air. As such, it is generally regarded as a critical target for air quality management. The oxidative removal of FA under dark and room-temperature (RT) conditions is of practical significance. A series of ternary nickel-cobalt-manganese oxide-supported platinum catalysts (Pt/NiCoMnO4) have been synthesized for FA oxidative removal at RT in the dark. Their RT conversion values for 50 ppm FA (XFA) at 5,964 h-1 gas hourly space velocity (GHSV) decrease in the following order: 1 wt% Pt/NiCoMnO4 (100 %) > 0.5 wt% Pt/NiCoMnO4 (25 %) > 0.05 wt% Pt/NiCoMnO4 (14 %) > NiCoMnO4 (6 %). The catalytic performance of 1 wt% Pt/NiCoMnO4 has been examined further under the control of various process variables (e.g., catalyst mass, flow rate, relative humidity, FA concentration, time on stream, and molecular oxygen content). The catalytic oxidation of FA at low temperatures (e.g., RT and 60 °C) is accounted for by Langmuir-Hinshelwood mechanism (single-site competitive-adsorption), while Mars van Krevelen kinetics is prevalent at higher temperatures. In situ diffuse-reflectance infrared Fourier-transform spectroscopy reveals that FA oxidation proceeds through a series of reaction intermediates such as DOM, HCOO-, and CO32-. Based on the density functional theory simulations, the unique electronic structures of the nearest surface atoms (platinum and nickel) are suggested to be responsible for the superior catalytic activity of Pt/NiCoMnO4.

Novel kinetic modeling of photocatalytic degradation of ethanol and acetaldehyde in air by commercial and reduced ZnO: Effect of oxygen vacancies and humidity.

A comprehensive kinetic model has been developed to address the factors and processes governing the photocatalytic removal of gaseous ethanol by using ZnO loaded in a prototype air purifier. This model simultaneously tracks the concentrations of ethanol and acetaldehyde (as its primary oxidation product) in both gas phase and on the catalyst surface. It accounts for reversible adsorption of both compounds to assign kinetic reaction parameters for different degradation pathways. The effects of oxygen vacancies on the catalyst have been validated through the comparative assessment on the catalytic performance of commercial ZnO before and after the reduction pre-treatment (10% H2/Ar gas at 500 °C). The influence of humidity has also been assessed by partitioning the concentrations of water molecules across the gas phase and catalyst surface interface. Given the significant impact of adsorption on photocatalytic processes, the beginning phases of all experiments (15 min in the dark) are integrated into the model. Results showcase a notable decrease in the adsorption removal of ethanol and acetaldehyde with an increase in relative humidity from 5% to 75%. The estimated number of active sites, as determined by the model, increases from 7.34 10-6 in commercial ZnO to 8.86 10-6 mol gcat-1 in reduced ZnO. Furthermore, the model predicts that the reaction occurs predominantly on the catalyst surface while only 14% in the gas phase. By using quantum yield calculations, the optimal humidity level for photocatalytic degradation is identified as 25% with the highest quantum yield of 6.98 10-3 (commercial ZnO) and 10.41 10-3 molecules photon-1 (reduced ZnO) catalysts.

Theoretical investigation of nucleophilic substitution reaction of phenyl carbonyl isothiocyanates with pyridines in gas and polar aprotic solvent.

This study focuses on the mutual interaction of substituents in the nucleophile and substrate - cross interaction constant, ρXY, in the uncatalyzed aminolysis by substituting pyridine with phenyl carbonyl isothiocyanate. The mechanism was found to be a stepwise process with a rate-limiting breakdown of the -NCS leaving group. This stepwise reaction mechanism considers the cross-interaction constant (CIC) with rate-limiting breakdown of tetrahedral intermediate in gas and solvent phases. The corresponding Hammett coefficients are related to the substituents associated with (1) the nucleophiles (X), ρX (-1.93 to -6.54 for the gas phase and 10.5 to 18.9 in the solvent model), and with (2) the substituents associated with the phenyl ring of the substrate (Y), ρY (0.41-3.48 for the gas phase and 1.83 to -10.70 for the solvent model). It also includes the Brønsted coefficient with X, ßX (0.11-1.52 for the gas phase and -2.57 to 3.96 for the solvent model), and CIC values, ρXY (0.69 for the gas phase and 0.87 for the solvent model). In this work, the NBO analysis, reaction potential, reaction electronic flux (REF), dual descriptor, and the structure-energy relationships were considered in interpreting the mechanistic criteria.

Low-temperature oxidative removal of benzene from the air using titanium carbide (MXene)-Supported platinum catalysts.

MXenes are an emerging class of two-dimensional (2D) inorganic materials with great potential for versatile applications such as adsorption and catalysis. Here, we describe the synthesis of a platinized titanium carbide MXene (Pt@Ti3C2) catalyst with varying amounts of platinum (0.1%-2 wt.%) for the low-temperature oxidation of benzene, an aromatic volatile organic compound often found in industrial flue gas. A 1% formulation of Pt@Ti3C2-R allowed near-complete (97%) oxidation of benzene to CO2 at 225 °C with a steady-state reaction rate (r) of 0.119 mol g-1·h-1. This low-temperature catalytic oxidation reaction was promoted by an increase in the lattice oxygen (O*)/Pt2+ species (active sites) of 1%Pt@Ti3C2-R from 45.3/34.6% to 71.0/61.1% through pre-thermal reduction under H2 flow, as revealed by X-ray photoelectron spectroscopy, temperature-programmed reduction, and in situ diffuse reflectance infrared Fourier transform spectroscopy analyses. The cataltyic activity of 1% Pt@Ti3C2-R against benzene was assessed under the control of the key process variables (e.g., catalyst mass, flow rate, benzene concentration, relative humidity, and time-on-stream) to help optimize the oxidation reaction process. The results provide new insights into the use of platinum-based 2D MXene catalysts for low-temperature oxidative removal of benzene from the air.

Thermocatalytic oxidation of a binary mixture of formaldehyde and toluene at ambient levels by a titanium dioxide supported platinum catalyst.

The thermocatalytic oxidative potential of various supported noble metal catalysts (SNMCs) is well-known for hazardous volatile organic compounds (VOCs), e.g., formaldehyde (FA) and toluene. However, little is known about SNMC performance against ambient VOC pollution with low concentration (subppm levels) relative to industrial effuluents with high concentrations (several hundred ppm). Here, the thermocatalytic oxidation performance of a titanium dioxide (TiO2)-supported platinum catalyst (Pt/TiO2) has been evaluated for a low-concentration binary mixture of FA and toluene at low temperatures and in the dark. A sample of TiO2 containing 1 wt% Pt with thermal reduction pre-treatment under hydrogen achieved 100 % conversion of FA (500 ppb) and toluene (100 ppb) at 130 °C and a gas hourly velocity of 59,701 h-1. Its catalytic activity was lowered by either a decrease in catalyst mass or an increase in VOC concentration, relative humidity, or flow rate. In situ diffuse reflectance infrared Fourier transform spectroscopy, density functional theory simulations, and molecular oxygen (O2) temperature-programmed desorption experiments were used to identify possible VOC oxidation pathways, reaction mechanisms, and associated surface phenomena. The present work is expected to offer insights into the utility of metal oxide-supported Pt catalysts for the low-temperature oxidative removal of gaseous VOCs in the dark, primarily for indoor air quality management.

Giant Duckweed (Spirodela polyrhiza) Root Growth as a Simple and Sensitive Indicator of Copper and Chromium Contamination.

Aquatic environment are often contaminated with heavy metals from various industrial sources. However, physicochemical techniques for pollutant detection are limited, thus prompting the need for additional bioassays. We investigated the use of greater duckweed (Spirodela polyrhiza) as a bioindicator of metal pollution. We exposed S. polyrhiza to four pollutants (namely, silver, cadmium, copper, and chromium) and assessed metal toxicity by measuring its frond area and the length of its regrown roots. The plant displayed significant differences in both frond size and root growth in response to the four metals. Silver was the most toxic (EC50 = 23 µg L-1) while copper the least (EC50 = 365-607 µg L-1). Direct comparisons of metal sensitivity and the reliability of the two endpoint assays showed that root growth was more sensitive (lower in terms of 50% effective concentration) to chromium, cadmium, and copper, and was more reliable (lower in terms of coefficient of variation) than those for frond area. Compared to conventional Lemna-based tests, the S. polyrhiza test is easier to perform (requiring only one 24-well plate, 3 mL of medium and a 72-h exposure). Moreover, it does not require livestock cultivation/maintenance, making it more suitable for repeated measurements. Measurements of S. polyrhiza root length may be suitable for assessment when copper and chromium in municipal and industrial wastewater exceed the environmentally permissible levels.

Effects of gas phase composition on competitive adsorption properties of formaldehyde on titanium dioxide-supported platinum in single and mixture compositions.

Titanium dioxide-supported platinum (Pt@TiO2) is regarded as a highly efficient photothermal catalyst to degrade various volatile organic compounds (VOCs). To learn more about the hybrid adsorption/catalysis process of VOCs on Pt@TiO2, their dynamic adsorption behavior on the catalyst surface was studied using the single and multicomponent gas phase of FA (i.e., the latter with four aromatic compounds of benzene, toluene, m-xylene, and styrene (BTXS)) through the control of key operating variables (e.g., VOCs concentration, relative humidity (RH) levels, and dosage). According to the performance evaluation, the doping of TiO2 with Pt metal ions significantly enhanced the FA adsorption capacity (e.g., by 50 % higher than the pristine TiO2) with increased OH (OII) surface active sites (reactivity) and surface porosity. However, in the co-presence of BTXS and water vapor, the adsorption affinity for FA vapor declined by 2 to 3 folds of magnitude with a competitive inhibition of the adsorption interaction on the Pt@TiO2 surface. According to the kinetic and isotherms analysis, a complex, multilayered physicochemical process appears to govern the adsorption of FA molecules onto Pt@TiO2 surface. Overall, the outcomes of this work are helpful to verify the enhanced removal potential of Pt@TiO2 against FA through sequential adsorption and catalytic reaction mechanisms.

Microwave assisted and conventional hydrothermal treatment of waste seaweed: Comparison of hydrochar properties and energy efficiency.

Waste seaweed is a valuable source for converting into value-added carbon materials. In this study, the production of hydrochar from waste seaweed was optimized for hydrothermal carbonization in a microwave process. The produced hydrochar was compared with hydrochar synthesized by the regular process using a conventional heating oven. The results show that hydrochar produced with a holding time of 1 h by microwave heating has similar properties to the hydrochar produced in a conventionally heated oven for 4 h (200 °C and water/biomass ratio 5): carbon mass fraction (52.4 ± 3.9 %), methylene blue adsorption capacity (40.2 ± 0.2 mg g-1) and similar observations on surface functional groups and thermal stability were made between hydrochars produced by both methods. The analysis of energy consumption showed microwave assisted carbonization consume higher energy in compare to conventional oven. The present results suggest that hydrochar made from waste seaweed and using the microwave technique could be an energy-saving technology for producing hydrochar with similar specifications to hydrochar produced by conventional heating methods.

Evaluating ecotoxicological assays for comprehensive risk assessment of toxic metals present in industrial wastewaters in the Republic of Korea.

Toxicity tests represent a rapid, user-friendly and cost-effective means to assess the impact of wastewater quality on aquatic ecosystems. There are not many cases where wastewater management standards are set based on various bio-based ecotoxicity values. Here, we tested a novel multitaxon approach to compare standard water quality indices to toxicity metrics obtained from ecotoxicity tests, conducted using aquatic organisms representing several trophic levels (Aliivibrio, Ulva, Daphnia, and Lemna), for 99 industrial wastewater samples from South Korea. For five wastewater samples, the concentrations of Se, Zn, or Ni exceeded the permissible limits (1, 5, and 3 mg L-1, respectively). All the four physiochemical water quality indices tested were positively correlated with Se and Pb concentrations. The toxicity unit (TU) scores indicated a declining sensitivity to pollutants, in the order Lemna (2.87) >Daphnia (2.24) >Aliivibrio (1.78) >Ulva (1.42). Significant correlations were observed between (1) Cd and Ni, and Aliivibrio, (2) Cu and Daphnia, (3) Cd, Cu, Zn, and Cr and Lemna, and (4) Cu, Zn, and Ni and Ulva. Daphnia-Lemna and Lemna-Ulva were found to be good indicators of ecologically harmful Se and Ni contents in wastewater, respectively. We suggest that regulatory thresholds based on these bioassays should be set at TU = 1 for all the species or at TU = 1 for Aliivibrio and Ulva and TU = 2 for Daphnia and Lemna, if the number of companies whose wastewater discharge exceeds the allowable TU levels is <1 % or 5 % of the total number of industries, respectively. Taken together, these findings could help in establishing a rapid, ecologically relevant wastewater quality assessment system that would be useful for developing strategies to protect aquatic ecosystems.

A Ten-Minute Bioassay to Test Metal Toxicity with the Freshwater Flagellate Euglena agilis.

A chemical analysis of water quality cannot detect some toxicants due to time constraints, high costs, and limited interactions for detection. Bioassays would offer a complementary means to assess pollution levels in water. Euglena is a flagellate green alga and an excellent system for toxicity testing thanks to its ease of culture, rapid growth, and quick response to environmental stresses. Herein, we examined the sensitivity of E. agilis to seven heavy metals by analyzing six end-point parameters: motility, velocity, cell compactness, upward swimming, r-value, and alignment. Notably, the velocity of E. agilis was most sensitive to cadmium (96.28 mg·L-1), copper (6.51 mg·L-1), manganese (103.28 mg·L-1), lead (78.04 mg·L-1), and zinc (101.90 mg·L-1), while r-values were most sensitive to arsenic (12.84 mg·L-1) and mercury (4.26 mg·L-1). In this study, velocity and r-values are presented as useful biomarkers for the assessment of metal toxicity in Euglena. The metals As, Cd, Cu, and Pb were suitable for this test. The advantages of the ecotoxicity test are its rapidity: It takes 10 min to obtain results, as opposed to the typical 3-4 d of exposure time with intensive labor. Moreover, this test can be performed at room temperature under dark conditions.

Mesoporous silica imprinted carbon dots for the selective fluorescent detection of triclosan.

A molecularly imprinted fluorescence sensor built as a mesoporous structured silica imprinted layer on the surface of carbon dots (CDs@m-MIP) was employed for the selective detection of triclosan (TRI). The fluorescence of this CDs@m-MIP was affected sensitively and selectively by TRI via an electron transfer-induced fluorescence quenching mechanism with a detection limit of TRI at 1.08 nM (range 1.72-138 nM) under the optimum setup (e.g., pH, response time, and CDs@m-MIP dose). This approach was used successfully to detect TRI in real water samples (e.g., sewage, river, and tap water). The recoveries of TRI were satisfactory in spiked river and tap water (in 94.7-99.5 %). The outcome of this research is thus expected to help develop highly efficient fluorescent sensing systems towards diverse hazardous compounds including TRI.

Low-temperature oxidative removal of gaseous formaldehyde by an eggshell waste supported silver-manganese dioxide bimetallic catalyst with ultralow noble metal content.

Under dark/low temperature (DLT) conditions, the oxidative removal of gaseous formaldehyde (FA) was studied using eggshell waste supported silver (Ag)-manganese dioxide (MnO2) bimetallic catalysts. To assess the synergistic effects between the two different metals, 0.03%-Ag-(0.5-5%)-MnO2/Eggshell catalysts were prepared and employed for DLT-oxidation of FA. The steady-state FA oxidation reaction rate (mmol g-1 h-1), when measured using 100 ppm FA at 80 °C (gas hourly space velocity (GHSV) of 5308 h-1), varied as follows: Ag-1.5%-MnO2/Eggshell-R (9.4) > Ag-3%-MnO2/Eggshell-R (8.1) > Ag-1.5%-MnO2/Eggshell (7.5) > Ag-5%-MnO2/Eggshell-R (7.2) > Ag-1.5%-MnO2/CaCO3-R (6.8) > MnO2-R (6) > Ag-0.5%-MnO2/Eggshell-R (3.2) > Ag/Eggshell-R (2.6). (Here, 'R' denotes hydrogen-based thermochemical reduction pretreatment.) The temperature required for 90% FA conversion (T90) at the same GHSV exhibited a contrary ordering: Ag/Eggshell-R (175 °C) > Ag-0.5%-MnO2/Eggshell-R (123 °C) > Ag-5%-MnO2/Eggshell-R (113 °C) > MnO2-R (99 °C) > Ag-1.5%-MnO2/Eggshell (96 °C) > Ag-3%-MnO2/Eggshell-R (93 °C) > Ag-1.5%-MnO2/Eggshell-R (77 °C). The eggshell catalyst outperformed the ones made of commercial calcium carbonate due to the presence of defects in the former. The MnO2 co-catalyst enhances the catalytic activities through the capture and activation of atmospheric oxygen (O2) with rapid catalytic regeneration. Also, MnO2 favorably captures the hydrogen of the adsorbed FA molecules to make the oxidation pathway thermodynamically more favorable.

Removal of gaseous benzene by a fixed-bed system packed with a highly porous metal-organic framework (MOF-199) coated glass beads.

The utility of nanomaterial adsorbents is often limited by their physical features, especially fine particle size. For example, a large bed-pressure drop is accompnied inevitably, if fine-particle sorbents are used in a packed bed system. To learn more about the effect of adsorbent morphology on uptake performance, we examined the adsorption efficiency of metal-organic framework 199 (MOF-199) in the pristine (fine powder) form and after its binding on to glass beads as an inert support. Most importantly, we investigated the effect of such coatings on adsorption of gaseous benzene (0.1-10 Pa) in a dry N2 stream, particularly as a function of the amount of MOF-199 loaded on glass beads (MOF-199@GB) (i.e., 0,% 1%, 3%, 10%, and 20%, w/w) at near-ambient conditions (298 K and 1 atm). A 1% MOF-199 load gave optimal performance against a 0.1 Pa benzene vapor stream in 1 atm of N2, with a two-to five-fold improvement (e.g., in terms of 10% breakthrough volume [BTV] (46 L atm [g.MOF-199)-1], partition coefficient at 100% BTV (3 mol [kg.MOF-199]-1 Pa-1), and adsorption capacity at 100% BTV (20 mg [g.MOF-199]-1 (areal capacity: 8.8 × 10-7 mol m-2) compared with those of 3%, 10%, and 20% loading. The relative performance of benzene adsorption was closely associated with the content of MOF-199@GB (e.g., 1% > 3% > 10% > 20%) and the surface availability (m2 [g.MOF-199]-1) such as 291 > 221 > 198 > 181, respectively. This study offers new insights into the strategies needed to expand the utility of finely powdered MOFs in various environmental applications.

Validation of two contrasting capturing mechanisms for gaseous formaldehyde between two different types of strong metal-organic framework adsorbents.

In this research, the adsorption behavior of formaldehyde (FA) onto two types of metal-organic frameworks (MOFs: MOF-199 [M199] and UiO-66-NH2 [U6N]) is investigated against changes in the key process variables (e.g., FA partial pressure (0.5-10 Pa), temperature (30-120 °C), and relative humidity (RH: 0%, 50%, and 100%)). The results revealed that the FA adsorption behavior onto both MOFs is exothermic in nature. Besides, their relative dominance for FA uptake varies interactively with the changes in RH and FA partial pressure levels. As the FA levels increase in dry conditions, their breakthrough volumes (BTV (100% BT)) exhibit contrasting trends: The values of U6N decreased noticeably from 5232 and 3792 L·atm·g-1, while those of M199 increased from 4152 to 5772 L·atm·g-1. The superiority of U6N over M199 in the lower FA level (at<5 Pa) is supported by the Lewis acid-base interactions with amine groups (U6N) in line with kinetic/isotherm studies. Such superiority is also persistent at higher (10 Pa) FA level under all humid conditions in line with its higher moisture stability. However, in dry conditions, the reversal of relative dominance in which M199 exhibits enhanced efficacy for 10 Pa FA uptake (relative to U6N) should reflect its breathing effects with the potent role of pore-diffusion mechanism. This study offers valuable insights into the construction of tunable adsorbents with enhanced adsorptivity toward key targets.

Dynamic anaerobic membrane bioreactor coupled with sulfate reduction (SrDMBR) for saline wastewater treatment.

This study investigated organic removal performance, characteristics of the membrane dynamics, membrane fouling and the effects of biological sulfate reduction during high-salinity (1.0%) and high-sulfate (150 mgSO42--S/L) wastewater treatment using a laboratory-scale upflow anaerobic sludge bed reactor integrated with cross-flow dynamic membrane modules. Throughout the operational period, dynamic membrane was formed rapidly (within 5-10 min) following each backwashing cycle (21-16 days), and the permeate turbidity of <5-7 NTU was achieved with relatively high specific organic conversion (70-100 gTOC/kgVSS·d) and specific sulfate reduction (50-70 gSO42--S/kgVSS·d) rates. The sulfide from sulfate reduction can be reused for downstream autotrophic denitrification. 16S rRNA gene amplicon sequencing revealed that the microbial communities enriched in the sludge were different than those accumulated on the dynamic layer. Overall, this study demonstrates that the anaerobic dynamic membrane bioreactor coupled with sulfate reduction (SrDMBR) shows promising applicability in saline wastewater treatment.

The potential of microplastics as adsorbents of sodium dodecyl benzene sulfonate and chromium in an aqueous environment.

Considering the omnipresence of microplastics (MPs) in aquatic environments, they are expected to exert significatn impacts as carriers for diverse waterborne pollutants. In this work, the adsorptive behavior of two ionic components (i.e., sodium dodecyl benzene sulfonate (SDBS) and Cr(VI)) has been explored against the two types of MPs as model adsorbents, namely poly (ethylene terephthalate) (PET) and polystyrene (PS). The influence of key variables (e.g., pH, particle size, and dose of the MPs) on their adsorption behavior is evaluated from various respects. The maximum adsorption capacity values of SDBS on PET and PS are estimated to be 4.80 and 4.65 mg⋅g-1, respectively, while those of Cr(VI) ions are significantly lower at 0.080 and 0.072 mg⋅g-1, respectively, The adsorptive equilibrium of SDBS is best described in relation to pH and MP size by a Freundlich isotherm. In contrast, the adsorption behavior of Cr(VI) is best accounted for by a Langmuir isotherm to indicate its adsorption across at least two active surface sites.

Kinetic modeling of malondialdehyde reactivity in oil to simulate actual malondialdehyde formation upon lipid oxidation.

The reactivity of malondialdehyde in saturated glycerol triheptanoate oil was studied over a wide temperature range (298.15-453.15 K). With respect to the non-ideal character of a lipid medium, a kinetic model was proposed that described the experimental malondialdehyde data by a reversible hydrolytic cleavage and an irreversible aldol self-condensation reaction. Significant parameter estimates were obtained by using a global one-step non-linear regression procedure. The aldol self-condensation of malondialdehyde showed to be the main degradation route of malondialdehyde in oils. Simulation of the malondialdehyde formation during lipid oxidation of sunflower oil demonstrated that, depending on the heating time, the experimentally obtained malondialdehyde concentrations can substantially underestimate the ongoing lipid oxidation.

Electrochemical pretreatment (EPT) of waste activated sludge: Extracellular polymeric substances matrix destruction, sludge solubilisation and overall digestibility.

Anaerobic digestion (AD) of waste activated sludge (WAS) is widely used for stabilisation, mass reduction and resource recovery. However, AD performance is often hampered by the poor digestibility and slow degradation rate for WAS. A series of bench-scale tests was conducted using innovative electrochemical pretreatment (EPT) method to enhance the destruction of the extracellular polymeric substances (EPS) matrix and anaerobic digestibility. The results showed that the EPS matrix destruction was enhanced by 15-30% after EPT for 0.5 h at voltages of 8-15 V. The highest improvement in hydrolysis rate and overall digestibility was achieved at EPT of 15 V for 1.5 h, which was determined as 59% (from 0.27 to 0.43 d-1) and 28% (from 105 to 134 mL CH4/g VSSadded) respectively, compared with the WAS treatment without EPT. The economic analysis showed 1 h, 12 V EPT was more economically feasible.

Kinetic modeling of heterogeneous esterification reaction using initial reaction rate analysis: data extraction and evaluation of mass transfer criteria.

This data article provides detailed guidance to obtain heterogeneous reaction rate expressions and the corresponding initial reaction rates and their application. Explanation is provided to deal with specific criteria to rule out internal and external concentration gradients, so that the usage of intrinsic catalytic data is guaranteed. Overall, the main goal is to provide an easy tool to evaluate both aforementioned results by simple plug-and-play of available reaction data.

Novel rapid room temperature synthesis of conjugated microporous polymer for metal-free photocatalytic degradation of fluoroquinolones.

The existence of Fluoroquinolones (FQs), non-biodegradable pharmacophores, in the natural environment possesses a serious threat. We herein report a novel, rapid, room-temperature synthesis of semiconducting conjugated microporous polymer (CMP) for the decontamination of four second-generation FQs, Norfloxacin, Enrofloxacin, Ciprofloxacin, and Ofloxacin. The CMP demonstrated impressive gas uptake and FQ adsorption ability. Decreased HOMO-LUMO bandgap resulted in enhanced exciton pair generation on visible-light-illumination. Additionally, a high degree of photocurrent response and suitable redox potentials of the material conjointly endorsed its almost quantitative FQ-degradation efficiency. Ofloxacin showed the best removal efficiency with 0.061 and 0.207 min-1 adsorption and degradation rate constants, respectively, one of the highest values reported. The CMP exhibited equipotent activity for other FQs as well. On increasing the concentration of the FQs or decreasing the incident photo-intensity, quantitative removal efficiencies are observed. Changing the pH of the medium from acidic to alkaline did not impart any change in catalytic activity as well. The reactive species involved viz. O2-, 1O2, etc. and their roles in the degradation process were determined through control and trapping experiments. A plausible in-depth mechanistic pathway was assessed from the FQ degradation intermediates, and the reactive catalytic species substantiating step-by-step break down of the antibiotic backbone.