Photodegradation Rate Constant Research Articles

SYNTHESIS OF Ag-MODIFIED TiO2 SOL-GEL FILMS AND ITS APPLICATION AS PHOTOCATALYSTS FOR METHYLENE BLUE DEGRADATION

In the study, the photocatalytic activity of TiO2 films that are created by dip-coating from a sol that contained titanium (IV) isopropoxide, monoethanolamine, and 2-methoxyethanol is demonstrated. Through photo-fixation of Ag (I) ions with varied concentration (10-2 - 10-4 M) in the water phase under UV illumination, the films are subsequently surface-modified with Ag co-catalyst layers. Scanning Electron Microscopy (SEM), X-Ray Photoelectron Spectroscopy (XPS), Ultraviolet-Visible (UV) Spectroscopy, and Electron Paramagnetic Resonance (EPR) techniques are used to physically characterize the samples. Results reveal that the modification of the co-catalyst had no impact on the thickness and porosity of the films. In addition, the study show that the modified TiO2 films had increased photocatalytic activity. All the characterization methods used have shown the formationof surface - bound Ag (I) species and metallic silver nanoclusters. By measuring the Methylene Blue (MB) dye degradation under UV light illumination, as - prepared and Ag -modified TiO2 films are evaluated for their photocatalytic activity, and the impact of the silver precursor concentration during photo-fixation is investigated.The highest catalytic activity is seen for films that have been modified at a concentration of Ag (I) of 10-2 M. Ordered from highest to lowest, the MB photodegradation rate constants are TiO2 < TiO2 /Ag, 10-4 < TiO2 /Ag, 10-3 < TiO2 / Ag, 10-2.

Copper-Based Two-Dimensional Metal-Organic Frameworks for Fenton-like Photocatalytic Degradation of Methylene Blue under UV and Sunlight Irradiation.

To efficiently degrade organic pollutants, photocatalysts must be effective under both ultraviolet (UV) radiation and sunlight. We synthesized a series of new metal-organic frameworks by using mild hydrothermal conditions. These frameworks incorporate three distinct bipyridyl ligands: pyrazine (pyr), 4,4'-bipyridine (bpy), and 1,2-bis(4-pyridyl)ethane (bpe). The resulting compounds are denoted as [Cu(pyz)(H2O)2MF6], [Cu(bpy)2(H2O)2]·MF6, and [Cu(bpe)2(H2O)2]·MF6·H2O [M = Zr (1, 3, and 5) and Hf (2, 4, and 6)]. All six compounds exhibited a two-dimensional crystal structure comprising infinitely nonintersecting linear chains. Compound 3 achieved 100% degradation of methylene blue (MB) after 8 min under UV irradiation and 100 min under natural sunlight in the presence of H2O2 as the electron acceptor. For compound 5, 100% MB degradation was achieved after 120 min under sunlight and 10 min under UV light. Moreover, reactive radical tests revealed that the dominant species involved in photocatalytic degradation are hydroxyl (•OH), superoxide radicals (•O2-), and photogenerated holes (h+). The photodegradation process followed pseudo-first-order kinetics, with photodegradation rate constants of 0.362 min-1 (0.039 min-1) for 3 and 0.316 min-1 (0.033 min-1) for 5 under UV (sunlight) irradiation. The developed photocatalysts with excellent activity and good recyclability are promising green catalysts for degrading organic pollutants during environmental decontamination.

A novel nano-cerium oxide functionalized biochar composite for degradation of organic dye: insight of the photocatalysis mechanism.

Recently, visible-light-driven photocatalysis attracts much concerns in the remediation of environmental organic pollutants. In this study, the cerium doped biochar was fabricated through the hydrothermal method, and served as an efficient photocatalyst towards rhodamine B degradation under visible light irradiation. Almost 100% of rhodamine B was removed by 2.0g·L-1 cerium doped biochar after 60min of visible light irradiation at pH 3, but only about 25.50% and 29.60% of rhodamine B was removed by cerium dioxide and biochar under identical conditions. The degradation process coincided well with the pseudo-first-order kinetic model, and the photodegradation rate constant of cerium doped biochar was 0.0485·min-1, which was respectively 97 and 44 times that of biochar (0.0005·min-1) and cerium dioxide (0.0011·min-1). According to the trapping experiments and electron spin resonance spectroscopy analysis, h+, O2-∙ and ∙OH all participated in the degradation of rhodamine B in the cerium doped biochar photocatalytic systems, and the function of h+ and ∙OH was dominated. Consequently, the biochar could not only be an excellent carrier for supporting cerium dioxide, but also greatly improved its photocatalytic activity. The band gap of cerium doped biochar was narrower than cerium dioxide, which could improve the separation and migration of photogenerated electron-hole pairs under visible-light excitation, thus ultimately enhanced the degradation of rhodamine B. This work provided a deeper understanding of the preparation of biochar-based photocatalyst and its application in the remediation of environmental organic pollution.

Hydraulic retention time governed the micro/nanostructures of titanium-incorporated diatoms and their photocatalytic activity

Titanium-incorporated diatoms are promising biomaterials to photodegrade micropollutants such as pharmaceuticals and personal care products (PPCPs). Hydraulic retention time (HRT) is a key parameter for diatom cultivation and the incorporation of titanium into diatom frustules. This study assessed how HRT governs the micro/nanostructures, titania (TiO2) content and distribution, and the photocatalytic activity of titanium-incorporated diatom frustules. We cultivated a diatom strain Stephanodiscus hantzschii using a feed solution containing titanium(IV) in membrane bioreactors (MBRs) at a solids retention time (SRT) of 10 d and staged HRTs from 24 to 12 and to 6 h. The decrease in HRT reduced the porosity of diatom frustules but increased their silicon and titania contents. When the HRT decreased from 24 to 12 and to 6 h, the specific surface areas of the diatom decreased from 37.65 ± 3.19 to 31.53 ± 3.71 and to 18.43 ± 2.69 m2·g−1 frustules, while the titanium (Ti) contents increased from 53 ± 14 to 71 ± 9 and to 85 ± 13 mg Ti·g−1 frustules. The increase in the influent flow rates of the MBRs with decreasing HRTs likely enhanced nutrient diffusion inside the diatom valve pores, facilitating the uptake and incorporation of silicon and titanium. The titanium-incorporated frustules were effective in removing two representative PPCPs, bisphenol A (BPA) and N,N-diethyl-meta-toluamide (DEET), from water. As photocatalytic activity depends on the amount of titanium, decreasing the HRT substantially increased the photocatalytic activity of the titanium-incorporated frustules. In batch tests under ultraviolet light, frustules from the diatom cultivated at HRTs of 24, 12, and 6 h had the pseudo-first-order removal (mainly through photodegradation) rate constants of BPA of 0.376, 0.456, and 0.683 h−1, respectively. Under the same experimental condition, the pseudo-first-order removal rate constants of DEET by the frustules cultivated at HRTs of 24, 12, and 6 h increased from 0.270 to 0.330 and to 0.480 h−1.

Rational synthesis of two isostructural thiophene-containing metal-organic frameworks toward photocatalytic degradation of organic pollutants

In this work, thiophene moieties (as the crucial functional groups) have been successfully incorporated into the skeleton of metal–organic frameworks (MOFs) by using thienyl-substituted triazole ligands. Reaction of AgCF3SO3 with 3-phenyl-5-(2-thienyl)-1,2,4-triazole (PTTzH) or 3,5-bis(2-thienyl)-1,2,4-triazole (BTTzH) afforded two isostructural MOFs (AgTz-3 and AgTz-4) in gram-scale. AgTz-4 with higher thiophene content showed significantly stronger photocatalytic activity than AgTz-3 with lower thiophene content. Noteworthy, the photodegradation rate constants of AgTz-4 were 0.055 mg·L-1·min-1 for rhodamine B and 0.24 min−1 for salazosulfapyridine, which is comparable or even higher than some MOF-based materials reported in the literature. More importantly, AgTz-4 demonstrated good reusability and stability after four cycles of photodegradation. Our experimental results revealed that the enhanced photodegradation efficiency can be attributed to the increased light absorption capacity and optimized band structure of Ag-MOFs resulting from the introduction of thiophene groups into MOF structures.

2D/2D Bi2MoO6/CoAl LDH S-scheme heterojunction for enhanced removal of tetracycline: Performance, toxicity, and mechanism

In this paper, the two-dimensional (2D) layered CoAl LDH (CoAl) was coupled with Bi2MoO6 (BMO) nanoplate and used for tetracycline (TC) degradation. Based on the results of UV–visible diffuse reflectance spectrum (UV–vis DRS), Motty-Schottky curves, and in situ X-ray photoelectron spectroscopy (XPS), a novel 2D/2D Bi2MoO6/CoAl LDH S-scheme heterojunction photocatalyst was built. The photodegradation rate constant of TC by the optimized sample BMO/CoAl30 was 3.637 × 10−2 min−1, which was 1.26 times and 4.01 times higher than that of Bi2MoO6 and CoAl LDH, respectively. The favorable photocatalytic performance of the heterojunction was attributed to the increased interfacial contact area of the 2D/2D structure. Besides, the transfer of photogenerated electrons from Bi2MoO6 to CoAl LDH under the effect of the built-in electric field (BIEF) reduced the recombination of photogenerated carriers and further improved the photocatalytic performance. The reactive species of h+, ·O2−, and 1O2 exhibited critical roles to degrade TC molecules by reactive radicals capture experiments and electron spin resonance (ESR) tests. The intermediate products of TC degradation and toxicity of intermediates were analyzed by liquid chromatography-mass spectrometer (LC-MS) and Toxicity Estimation Software Tool (T.E.S.T). Additionally, the BMO/CoAl composite photocatalysts showed high stability and environmental tolerance during the testing of cycles and environmental impacts with various water sources, organic contaminants, initial pH, and inorganic ions. This work provides a new protocol for designing and constructing novel 2D/2D S-scheme heterojunction photocatalysts for wastewater treatment.

Effect of dissolved organic matter on sulfachloropyridazine photolysis in liquid water and ice

Dissolved organic matter (DOM) is an ubiquitous component of environmental snow and ice, which can absorb light and produce reactive species (RS) and thus is of importance in ice photochemistry. The photodegradation of sulfachloropyridazine (SCP) without and with DOM present in liquid water and ice were investigated in this study. The photodegradation rate constants for SCP without DOM present was enhanced by 52.5 % in ice relative to liquid water, likely due to the enhanced role of SCP self-sensitized RS in ice. DOM significantly promoted SCP photolysis in both liquid water and ice, which was mainly attributed to roles of singlet oxygen (1O2) and triplet excited-state DOM (3DOM*) generated from DOM. 1O2 production from DOM was significantly enhanced in ice relative to liquid water. Hydroxyl radical (•OH) production from DOM in ice was similar to those in liquid water. Enhancement in 3DOM* production in ice was observed at low DOM concentrations. Suwannee River Fulvic Acid (SRFA) and Elliott Soil Humic Acid (ESHA) exhibited differences in RS production in liquid water and ice, as well as in enhancement of 1O2 and 3DOM* produced in ice relative to liquid water. DOM induced reaction pathways of SCP different from those without DOM present, and therefore affected toxicity of SCP photoproducts. There were differences in photodegradation pathways of SCP as well as in toxicity of SCP photoproducts between liquid water and ice.

Highly Efficient SnIn4S8@ZnO Z-Scheme Heterojunction Photocatalyst for Methylene Blue Photodegradation.

Building heterojunctions is a promising strategy for the achievement of highly efficient photocatalysis. Herein, a novel SnIn4S8@ZnO Z-scheme heterostructure with a tight contact interface was successfully constructed using a convenient two-step hydrothermal approach. The phase composition, morphology, specific surface area, as well as photophysical characteristics of SnIn4S8@ZnO were investigated through a series of characterization methods, respectively. Methylene blue (MB) was chosen as the target contaminant for photocatalytic degradation. In addition, the degradation process was fitted with pseudo-first-order kinetics. The as-prepared SnIn4S8@ZnO heterojunctions displayed excellent photocatalytic activities toward MB degradation. The optimized sample (ZS800), in which the molar ratio of ZnO to SnIn4S8 was 800, displayed the highest photodegradation efficiency toward MB (91%) after 20 min. Furthermore, the apparent rate constant of MB photodegradation using ZS800 (0.121 min-1) was 2.2 times that using ZnO (0.054 min-1). The improvement in photocatalytic activity could be ascribed to the efficient spatial separation of photoinduced charge carriers through a Z-scheme heterojunction with an intimate contact interface. The results in this paper bring a novel insight into constructing excellent ZnO-based photocatalytic systems for wastewater purification.

Visible-light-driven photocatalytic properties of Nb2C/Bi2WO6 hybrids with 2D/2D structure for efficient pollutant removal

Sunlight-driven photocatalysis is a promising method for the efficient removal of pollutants. However, most photocatalysts only adsorb and utilize part of the sunlight. In this work, as a typical MXenes material with broadband adsorption of sunlight, Nb2C nanosheets were obtained by etching Nb2AlC, and the Nb2C/Bi2WO6 hybrids (NB2 and s-NB2) with different coupling interfaces were prepared by in situ growth synthesis and self-assembly method, respectively. In addition, Nb2C nanosheets as co-catalysts were tightly combined with Bi2WO6 nanoflakes to ultimately construct a unique 2D/2D structure, which can reduce the carrier transport distance and increase the interfacial contact area. Moreover, the obtained hybrids exhibited significant improvements in the adsorption capacity and photocatalytic efficiency under visible light irradiation compared with pure Bi2WO6. Furthermore, the photodegradation rate constants for methylene blue (MB) of NB2 and s-NB2 were 0.0945 and 0.0506 min−1, respectively, which were 2.96 and 1.59 times higher than those of pure Bi2WO6. In particular, the hybrids prepared by in-situ growth synthesis (NB2) showed a higher photocatalytic efficiency for the treatment of organic contaminants due to the formed tighter interface. Therefore, this work could provide efficient catalyst configuration with ultrathin 2D/2D structure by using different methods, and demonstrate that Nb2C can serve as an effective co-catalyst for enhanced photocatalytic performance.

Unveil the mechanism of photosensitized fluoroquinolones enhancing chlortetracycline photodegradation under simulated sunlight: Batch experiments and DFT calculation

Fluoroquinolones (FQs), as the most commonly used antibiotics, are ubiquitous in the aquatic environment. The FQs' self-sensitization process could generate reactive oxygen species (ROS), which could react with other coexisting organic pollutants, impacting their transformation behaviors. However, the FQs’ influences and mechanisms on the photochemical transformation of coexisting antibiotics are not yet revealed. In this study, we found ofloxacin (OFL) and norfloxacin (NOR), the two common FQs, can obviously accelerate chlortetracycline (CTC) photodegradation. In the presence of OFL and NOR (i.e., 10 μM), CTC photodegradation rate constants increased by 181.1% and 82.9%, respectively. With the help of electron paramagnetic resonance (EPR) and quenching experiments, this enhancement was attributed to aromatic ketone structure in FQs, which absorbed photons to generate ROS (i.e., 3OFL*, 3NOR*,1O2, and •OH). Notably, 3OFL* or 3NOR* was dominantly contributed to the enhanced CTC photodegradation, with the contribution ratios of 79.9% and 77.3% in CTC indirect photodegradation, respectively. Compared to CTC direct photodegradation, some new photodegradation products were detected in FQs solution, suggesting that 3OFL* or 3NOR* may oxide CTC through electron transfer. Moreover, the higher triple-excited state energy of OFL and NOR over DFT calculation implied that energy transfer from 3OFL* or 3NOR* to CTC was also theoretically feasible. Therefore, the presence of FQs could significantly accelerate the photodegradation of coexisting antibiotics mainly via electron or energy transfer of 3FQs*. The present study provided a new insight for accurately evaluating environmental behaviors and risks when multiple antibiotics coexist.

DOM optical parameters as a tool to understand degradation of phenolic contaminants of emerging concern

Composition and source of dissolved organic matter (DOM) in water influence the rate of production of reactive intermediates (RIs), affecting the photodegradation of phenolic contaminants of emerging concern (PhCECs). However, this relationship has not been fully quantified. Here, for the first time, we propose a mechanism for photodegradation of a surrogate of PhCECs, p-cresol, in different DOM standard solutions under simulated sunlight irradiation. More importantly, the correlation of DOM optical parameters and p-cresol photodegradation kinetic parameters was determined by Pearson correlation. Results showed that indirect photodegradation was the only degradation pathway for p-cresol, mainly through reaction with excited triplet state of dissolved organic matter (3DOM*). Singlet oxygen (1O2) and hydroxyl radical (•OH) hindered degradation of p-cresol by decreasing the steady state concentration of 3DOM*. Moreover, less aromatic and smaller molecular size DOM showed higher steady-state concentration and quantum yield of 1O2, and 3DOM*, resulting in faster p-cresol photodegradation. Finally, 7 out of 8 optical parameters showed strong correlation with the p-cresol photodegradation rate constant. The mechanism and correlations found are a potential tool to predict PhCECs photodegradation in water using DOM optical parameters.

Influence of nitrogen sources on N-doped reduced TiO2 prepared using atmospheric plasma spraying for photocatalytic tetracycline and ciprofloxacin degradation

N-doped reduced TiO2 porous photocatalyst coatings are prepared by atmospheric plasma spraying (APS) technology combined with the geomimetic concept. Unlike traditional photocatalyst preparation methods, this method can be manufactured on a large scale and considerably shortens the preparation time by only 15 min. In this study, acetamide and urea, with one or two nitrogen atoms in the structure, were used as dopants to prepare N-doped TiO2 (T1N and T2N) for photocatalytic antibiotic degradation. Tetracycline (TC, 20 ppm/100 mL) and ciprofloxacin (CIP, 20 ppm/100 mL) were photodegraded under AM1.5G solar simulator illumination. The T1N obtained a higher lattice-nitrogen ratio than T2N, which gave T1N better photocatalytic activity. The rate constants of photodegradation of TC and CIP under simulated solar irradiation are 1.70 and 1.42 (×10−2 min−1), which are more than twice that of T2N and nearly 20 times higher than that of pristine TiO2. Moreover, after 10 rounds of recycling tests, the photocatalyst showed good performance and structural stability. The scavenger test suggested that ̇O2− is the most important reactive species in TC degradation, while ̇OH and h+ play an important role in CIP degradation. The degradation pathways of TC and CIP were proposed. This photocatalyst coating preparation method is suitable for large-scale production and is a time-saving, sustainable, diversified, and future-looking technology.

Investigation of the Effects of Dioctyl Sulfosuccinate on the Photodegradation of Benzo[a]Pyrene in Aqueous Solutions under Various Wavelength Regimes.

Due to the relatively high concentrations of polycyclic aromatic hydrocarbons (PAHs) in oil samples, oil spills in aquatic ecosystems release significant amounts of PAHs. Although remediation efforts often take place during or immediately after an oil spill incident, a portion of the released PAHs remains in the body of water. A natural phenomenon resulting from the direct exposure of PAHs to sunlight is photodegradation. This article investigates the effect of dioctyl sulfosuccinate (DOSS) on the photodegradation of benzo[a]pyrene (BaP), the most toxic PAH in the priority pollutants list of the US Environmental Protection Agency (EPA). DOSS is a surfactant typically used in the remediation of oil spills. Three lamps with maximum emission wavelengths at 350 nm, 419 nm, and 575 nm were individually and simultaneously used to irradiate aqueous solutions of BaP in the absence and the presence of DOSS. When irradiated with the 419 nm lamp or the 575 lamp, BaP showed no photodegradation. Upon irradiation with the 350 nm lamp and with the simultaneous use of the three lamps, the photodegradation of BaP followed first-order kinetics. Independent of the irradiation wavelength, the presence of DOSS increased the half-life of BaP in the aqueous solution. In the case of the 350 nm lamp, the rate constant of photodegradation in the absence and the presence of DOSS varied from (3.79 ± 0.97) × 10-3 min-1 to (1.10 ± 0.13) × 10-3 min-1, respectively. Under simultaneous irradiation with the lamps, the rate constant of photodegradation varied from (1.12 ± 0.35) × 10-3 min (no DOSS) to (3.30 ± 0.87) × 10-4 (with DOSS). Since the largest rate constants of photodegradation were observed in the absence of DOSS, the longer half-lives of BaP in the presence of surfactant were attributed to the incorporation of PAH molecules into the DOSS micelles.

Photodegradation of the insecticide fipronil in aquatic environments: photo-dechlorination processes and products.

Fipronil (FIP) is a phenylpyrazole insecticide that, along with neonicotinoid insecticides, is regularly used worldwide. Photodegradation of FIP in aqueous systems is thought mainly to involve the reaction of desulfinylation to give fipronil desulfinyl (FIP-desulfinyl); however, little is known about further degradation reactions. We investigated FIP photodegradation by analyzing photodegradation products by liquid chromatography and liquid chromatography high-resolution tandem mass spectrometry using an Orbitrap instrument. A wide range of products, including dechlorinated compounds, was detected, and the structures were identified. FIP-desulfinyl has previously been found to be an important and persistent FIP photodegradation product; however, we also found that FIP-desulfinyl was photochemically decomposed to a didechlorinated product via a monodechlorinated product. The main photodegradation pathway was probably similar to that of ethiprole, which has a similar skeleton. The photodegradation rate constant was 22.6 times lower for FIP-desulfinyl (0.00372 min-1) than FIP (0.0839 min-1). The photodegradation rate constant was lower for the newly found didechlorinated product (0.001 min-1 or below) than FIP-desulfinyl, suggesting that the product is persistent in aquatic environments and could be an important indicator of long-term FIP contamination.

Effect of adsorption on ferrihydrite on the photoreactivity of dissolved black carbon for photodegradation of sulfadiazine

The selective adsorption of dissolved black carbon (DBC) on inorganic minerals is a widespread geochemical process in the natural environment, which could change the chemical and optical properties of DBC. However, it remains unclear how selective adsorption affects the photoreactivity of DBC for photodegradation of organic pollutants. This paper was the first to investigate the effect of DBC adsorption on ferrihydrite at different Fe/C molar ratios (Fe/C molar ratios of 0, 7.50 and 11.25, and marked as DBC0, DBC7.50 and DBC11.25) on the photoproduction of reactive intermediates generated from DBC and their interaction with sulfadiazine (SD). Results showed that UV absorbance, aromaticity, molecular weight and contents of phenolic antioxidants of DBC were significantly decreased after adsorption on ferrihydrite, and higher decrease was observed at higher Fe/C ratio. Photodegradation kinetics experiments showed that observed photodegradation rate constant of SD (kobs) increased from 3.99 × 10−5 s−1 in DBC0 to 5.69 × 10−5 s−1 in DBC7.50 while decreased to 3.44 × 10−5 s−1 in DBC11.25, in which 3DBC* played an important role and 1O2 played a minor role, while ·OH was not involved in the reaction. Meanwhile, the second-order reaction rate constant between 3DBC* and SD (kSD, 3DBC*) increased from 0.84 × 108 M−1 s−1 for DBC0 to 2.53 × 108 M−1 s−1 for DBC7.50 while decreased to 0.90 × 108 M−1 s−1 for DBC11.25. The above results might be mainly attributed to the fact that the decrease of phenolic antioxidants in DBC weakened the back-reduction of 3DBC* and reactive intermediates of SD as the Fe/C ratio increased, while the decrease of quinones and ketones reduced the photoproduction of 3DBC*. The research revealed adsorption on ferrihydrite affected the photodegradation of SD by changing the reactivity of 3DBC*, which was helpful to understand the dynamic roles of DBC in the photodegradation of organic pollutants.

Solar-driven photodegradation of synthetic dyes by ternary of titanium oxide-copper oxide-chitosan catalyst

The ternary titanium oxide (TiO2), copper oxide (CuO), and chitosan (TiO2/CuO/Chitosan) photocatalyst (composites) for the photodegradation of synthetic methyl orange (MO) were developed by entrapping copper ions and nanosized TiO2 into chitosan thin films at room temperature. TiO2 Degussa P25 was incorporated with CuO and Chitosan (CS) solution using an ex-situ synthesis method before being immobilized onto glass plates via a dip-coating technique. This study is the first time approach for a combination of a composite comprising two metal oxides to suppress the electron-hole recombination, thus enhancing their catalytic and adsorptive properties. The morphology and surface interactions of the TiO2/CuO/Chitosan composite were determined using techniques such as XRD, FTIR, RAMAN, and SEM-EDX, respectively. The results show the anatase phase and homogenous spherical features of TiO2. The TiO2/CuO/Chitosan composites (0.5 gL-1) exhibited excellent activity for the photodegradation of MO under solar irradiation (λ > 400 nm) at different pH. The decolorization efficiency increased according to pH 9 < pH 7 < pH 6 < pH 3 with the highest degradation efficiency of 85.29% at 1 ppm MO solution, reaching two times greater than the pristine TiO2 nanoparticles (56.55%). Complete degradation of MO was attained at 240 min of solar irradiation with pH 3 using the optimum TiO2/CuO/Chitosan composites of 1:4:1 composition (5 cycles of dip coating) and the photodegradation rate constant is 0.0073 min−1. The physic-chemical study has established the structure, crystalline phase, surface contact, and stability of the catalyst. The photocatalytic improvement under visible irradiation is attributed to band-gap reduction and suspension of electron-hole recombination of the ternary catalyst system. The results of this study offer guidelines for the design of a new synthetic strategy.for the preparation of an efficient photocatalyst for the selective oxidation of synthetic azo dyes compounds.

Convenient synthesis of seaweed-derived porous carbon supported Cu-MoO2 composite as high-performance photocatalyst

The development of a simple and convenient method for synthesizing photocatalysts for the degradation of tetracycline remains a great challenge. In this work, a Cu-MoO2@C composite was successfully synthesized by a high-temperature carbonization of ammonium molybdate infiltrated copper alginate aerogel, which was obtained by curing a mixture of sodium alginate and ammonium molybdate using Cu2+ ions. The photocatalytic properties of the prepared composites were evaluated by the degradation of tetracycline. The results showed that the introduction of Cu nanoparticles on the MoO2@C hybrid could significantly improve the catalytic performance, and the degradation rate of tetracycline reached 92.48 % after 60 min light exposure. Tetracycline's estimated photodegradation rate constant, which was 0.04013 min−1, was 5 times more than that of the composite without Cu loading. Furthermore, the reaction mechanism was explored by electron spin resonance (ESR) test and free radical capture reagent. Intermediate products of tetracycline degradation were analyzed by liquid mass spectrometry (LC-MS).

Optical, structural, electrical and photocatalytic properties of aluminum doped zinc oxide nanostructures

The Al-doped ZnO (Zn1-xAlxO, x = 0.00, 0.02, 0.04, 0.06, and 0.08) nanostructures were synthesized by the chemical vapor deposition technique. Analysis by X-ray diffraction reveals that both undoped and Al-doped ZnO nanostructures are crystallized in a single-phase wurtzite structure with a preferred orientation along the (101) plane. The addition of Al was studied to see how it influenced bond length, crystallite size, unit cell volume, lattice strain, and dislocation density. Field-emission scanning electron microscope imaging showed a significant variation in the morphology with increasing the Al doping level. Absorption spectra in the UV–Visible range revealed that introducing Al3+ ions into the ZnO lattice causes a blue shift in the optical band gap, which was explained according to Burstein-Moss effect and variation of the electronic structure. The direct electrical conductivity measurement showed a transformation between two conduction mechanisms upon variation of the temperature. Transition of the charge carriers from shallow and deep donor levels dominated in the low and high temperature ranges, respectively. The photodegradation rate constants and degradation efficiency were determined as well as the photocatalytic mechanism was described. Upon reaching the x = 0.08 Al doping level, the photocatalytic efficiency of the examined samples increased by 1.7-fold. The obtained results demonstrate that Al doping can tune the electrical, optical, and photocatalytic properties of ZnO nanostructures that make them applicable for many optoelectronic applications.

Bismuth oxychloride microcrystals decorated carbon foams based on waste polyurethane elastomer for enhanced removal of methylene blue

Multicomponent materials containing nanoscale structures, the so-called “nanocomposites” are one of the fastest-growing areas of photocatalytic research. In this study, the nanocomposites of bismuth oxychloride (BiOCl) with porous carbon foam (CF) derived from waste polyurethane (PU) elastomers were developed by a simple hydrothermal method, and the photocatalytic performance of the as-prepared materials was investigated. The structure, morphology and optical properties of the composites were characterized in detail. The photocatalytic activity of the samples was evaluated by studying the degradation of methylene blue (MB) under UV-A irradiation. Even at a high MB concentration (0.5 mmol/L), excellent photocatalytic activity was observed, with an overall removal efficiency of 99.0% in 100 min of irradiation. Kinetic studies were also carried out for the degradation of MB by pristine BiOCl and CF-BiOCl. The photodegradation rate constants were evaluated by fitting the kinetic data with a pseudo-first-order model, and the rate constants of CF-BiOCl composites were higher than that of pristine BiOCl. The enhanced activity of the composites was due to the well-connected heterojunction interface, improved hydrophilicity, more reactive sites, and effective separation of photo-generated charges. Thus, our work combines the valuable waste PU-derived CFs with BiOCl, which provides a strategy to achieve circular economy and environmental remediation objectives.

Quantum and experimental investigation of the application of Crassostrea gasar (mangrove oyster) shell–based CaO nanoparticles as adsorbent and photocatalyst for the removal of procaine penicillin from aqueous solution

The present study was designed to synthesize and characterize calcium oxide nanoparticles (using mangrove oyster shell as a precursor) and apply the synthesized nanoparticles as a photocatalyst to degrade procaine penicillin in an aqueous solution. The photocatalyst exhibited an average band gap of 4.42eV, showed a maximum wavelength of absorbance in the UV region (i.e., 280nm), and is a microporous nanoparticle with a particle diameter of 50nm. The photocatalyzed degradation of the drug was conducted under natural sunlight, and the influence of parameters such as the period of contact, catalyst load, pH, initial drug concentration, and ionic strength was investigated concerning the degradation profile. The results obtained from response surface analysis indicated that an optimum degradation efficiency of about 93% can be obtained at a concentration, pH, and catalyst dosage of 0.125M, 2, and 0.20g respectively, at 0.902 desirabilities. The Langmuir-Hinshelwood, modified Freundlich, parabolic diffusion, pseudo-first-/second-order, and zero-, first-, and second-order kinetic parameters were tested to ascertain the best model that best described the experimental data. Consequently, the Langmuir-Hinshelwood, modified Freundlich, and pseudo-second-order models were accepted based on the minimum error and higher R2 values. Based on the Langmuir-Hinshelwood rate constants for adsorption and photodegradation as well as the evaluated valence bond potential, the degradation of the drug first proceeded through the mechanism of adsorption and followed by the oxidation of the drug by superoxide (generated from the interaction of electrons that generated by through the absorption of UV radiation). The quantum chemical calculation gave evidence that pointed towards the establishment of strong agreement with experimental data and also showed that the carboxyl functional group in the drug is the target site for adsorption and subsequent degradation.